Synopsis

Hebeish’s work has been the subject of more than 580 papers that

have been carried out and published during the last Five decades. The

work addresses many basic and practical aspects of chemical modification

of fibrous textile polymers and their properties as well as the fundamentals

and practices pertaining to synthesis, characterization and application of

various nonfibrous textile auxiliaries. Nature of textile substrates for

example cotton textile could be changed through introducing, in its

macromolecular structure, different amounts of chemical groups in the

monomeric and /or polymeric forms. Such chemical grouping acquires

hydrophilic characteristic or hydrophobic characteristic or both

characteristics, in addition to modifying the basic properties of the fibrous

textile material. Similarly, nature of the newly synthesized nonfibrous

polymeric textile auxiliaries could be modulated (tailored) through

manipulation of the molecular weight of the parent (base) polymer along

with type, form and amount of the introduced chemical moieties. For

example graft copolymers composites and hybrids for use as nonfibrous

textile auxiliaries were obtained through copolymerization of starch,

dextrin, cyclodextrin, chitosan or carboxymethyl cellulose with various

vinyl monomers.

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Chemical reactions involved in the chemical modification of

fibrous textile materials as well as in the synthesis of nonfibrous textile

materials, i.e. textile auxiliaries were performed under a variety of

conditions for the sake of achieving optimization, reaction kinetics and

reaction mechanisms. Certain emphasis was placed on utilization of the

results obtained from the fundamental investigations to develop new,

innovative and / or more efficient techniques for preparation of chemically

modified (chemically finished) textile products with unprecedented

properties. This, indeed, stimulates research which was targeted

particularly towards production of multifunctional cotton products (often

called smart textiles or high performance textile products) through

harnessing nanotechnology and biotechnology in multifinishing process.

Innovative multifinishing agent, namely, chitosan -O- polyethylene

glycol graft copolymer was newly synthesized and characterized using

state –of- the- art facilities. The copolymer together with citric acid in

aqueous medium were applied to cotton to produce medical textiles. One

step process for multifinishing of cotton fabrics was also established. The

process involved effecting simultaneous flame retardancy, grafting and

anticrease finishing.

Research problems chosen for cotton cellulose in the fabric form

are of an applied nature since they are directly related to textile

pretreatment (desizing, scouring, bleaching, mercerizing), dyeing, printing

and finishing. Area of research covers degradative treatments, chemical

modifications via subjecting the cellulose to etherification, esterification,

crosslinking and oxidation reactions as well as grafting on cellulose and

modified celluloses with vinyl monomers. The kinetics and mechanisms

entailed in each procedure were dealt with. The behavior of the chemically

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modified celluloses towards heat transfer printing as well as towards

dyeing with different classes of dyestuffs were examined and interactions

between the dye and the modified cellulose were elicited. In addition,

fundamental principles and detailed information necessary for

establishment of a single-step process by combining two or more of the

chemical processes of cotton and polyester / cotton blends were attained.

The output of the work and its contribution in energy, water and material

saving and, the consequence of this on improving the quality of

environment were clarified. In addition, microstructural differences

between scoured and slack mercerized–restretched cottons were identified.

Furthermore, chemical characteristics of finishes that are critical for

effective soil release properties in durable press-cotton containing fabrics

were defined.

Ionic crosslinking was induced in the molecular structure of cotton

cellulose in the fabric form. To achieve ionic crosslinking the cotton fabric

was first partially carboxymethylated via reaction with monochloroacetic

acid in alkaline medium in order to introduce carboxymethyl groups.

Following this, this modified cotton fabric was subjected to cationization

through reaction with 3-chloro-2-hydroxypropyl trimethyl ammonium

chloride. Ionic crosslinking occurs because of the presence of both

carboxymethyl group and the cationized group. Fabrics so treated enjoyed

ease of care characteristics without losing strength properties.

In addition to the foregoing, Hebeish,s work was extended to

include grafting of chains of vinyl monomers to wool. An important and

difficult problem in this case concerns the site(s) on the protein molecule

at which chemical attachment of the polymer chains occurs and this is

considered in some detail for a number of initiation systems. The influence

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of grafting on the all-important textile properties of wool, notably felting

and permanent set was examined.

Polyamide and polyester fibres were also submitted to grafting

procedures, with the practical objective of enhancing moisture region and

dyeability. Some other problems relating to the dyeing of these fibres were

tackled.

It is as well to highlight our work pertaining to the chemistry of

nonfibrous textile. Studies on synthesis, characterization and application

of several polymeric materials were undertaken. Among these materials

were starch, carboxymethyl cellulose, chitosan, poly(acrylic acid),

poly(methacrylic acid), starch – poly(acrylic acid) composite, starch –

poly(acrylamide) composite, β -cyclodextrin- poly(acrylic acid)

copolymers and β – cyclodextrin- poly(glycidyl methacrylate)

copolymers. Particularly notable was the loading of β – cyclodextrin

copolymers with metal nanoparticles for example, silver nanoparticles

(AgNPs). CMC based hydrogels with and without nano-sized metal

particles were subjected to intensive investigation. Research was also

directed towards synthesis of polymeric materials that are environment –

friendly for use as reducing agent converting the silver ion to silver atom

and stabilizing agent through capping of silver nanoparticles which

represent clusters of silver atom. This was exemplified by the synthesis

and characterization of hydroxylpropyl starch. Hydroxylpropyl starch

plays dual role: reducing and stabilizing agent during the synthesis of

AgNPs. Similarly, investigations into factors affecting graft

copolymerization of β – cyclodextrin with butyl acrylate and utilization of

the obtained copolymers in synthesis of ZnO nanoparticles were

undertaken. The nano-sized ZnO loaded copolymer was then applied to

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cotton fabrics. Also reported was the copolymerization of reactive

cyclodextrin with butyl acrylate. Thus obtained copolymers were loaded

with nano-sized ZnO. These copolymers are used as reactive preformed

polymers which underwent reaction with the hydroxyl groups of cotton

cellulose in alkaline medium via substitution mechanism; similar to

reactive dyes. Cotton fabrics treated with these preformed reactive

polymers displayed multifunctional characteristics, notably, antimicrobial

and water repellency along with improved strength properties.

Thorough investigations into synthesis and characterization of

starch nanoparticles as well as concurrent formation of nanosized

particles of both starch and silver with emphasis on their nanostructural

features and medical applications were reported. Also reported were the

synthesis and characterization of cellulose nanowhiskers and possible

applications of these cellulose nanoparticles before and after chemical

modification in the area of reinforcement and other applications such as in

the synthesis of nanometal particles and processing of novel hybrid

hydrogel. It is worthly to mention that within the framework of our

research plan, electrospun cellulose and cellulose-graft-polyacrylonitrile

copolymer nanofibres containing silver nanoparticles were synthesized for

effective water disinfection.

Our research also addresses technological innovations based on

frontier sciences for development of textile printing. Synthesis,

characterization and application of ultrafine pigment particles form the

base of such development.

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Achievements Within Environmental Scene

Hebeish’s research activities in chemistry of textiles and textile

auxiliaries have been maintained at a high level for Fifty years. These

activities resulted in over 580 papers published in well known scientific

journals of international respect and; he is still publishing vigorously, a

point which will add considerably to his already substantial standing in

science. In addition to the research papers, he is the author or coauthor of

5 books and 13 patents. 105 Ph.D. and M.Sc. theses have also been

supervised by him and several R and D projects implemented under his

direct management. Since 2003 up till now he is the chairman of the

National Compaign for Textile Development which is a multidisciplinary

project aiming at transferring research results to textile industry. All this

testify to his enthusiasm, ability, significant contribution and creativity.

His work is of high scientific merit and he is clearly recognized as a

pioneer and a leading authority in his field.

In the foregoing section, a quick glance at Hebeish’s work

outlining his major research activities in materials science, notably

chemistry of fibrous textiles and nonfibrous textile materials is given. In

the next paragraph major achievements brought about by his studies in the

areas of chemistry and modifications by treatment of naturally occurring

fibres and other biopolymeric materials are briefly summarized.

Particulary notable among the fibrous textile materials are those of

cellulose, wool, polyamide and polyester, whereas the nonfibrous textile

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materials include: starch, CMC, chitosan and cyclodextrin. Special

attention is given to new chemical routes for energy and materials saving.

Nanotechnology and biotechnology are also employed as important

facilities for synthesis of textile materials and textile auxiliaries with

unprecedented properties.

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1. Chemistry of Fibrous Textile Materials

1.1. Cellulose

Cellulose is the polysaccharide part of the cell wall of plants. It

occurs in nature mainly in cotton (seed hairs) and ramie, which contains a

highly pure cellulose. It also occurs as lignocellulose in bast fibres such as

flax and jute and in wood. The quantity of cellulose will vary from over

90% for cotton to more like 70% and 60% for Flax and jute respectively,

the exact values depend on the source of the cotton, flax or jute.

The term cellulose in the strict scientific sense applies only to the

plant cell materials consisting of macromolecules of at least several

hundred to several thousand anhydroglucose units. It is the carbohydrate

part of the cell wall plants, formed out of only glucose molecules

condensed and linked linearly by means of 1,4-glucosidic bonds. Every

bond involves the potential aldehyde group of one glucose and hydroxyl

group of another. Each anhydroglucose unit of the cellulose molecule has

three hydroxyl groups,which are located in position 2,3 and 6. Each

cellulose molecule is ended by an aldehydic group. The chain molecules in

natural cellulose are not all of the same length. The number of

anhydroglucose units, i.e., the degree of polymerization (DP) in different

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chain varies. For this reason one has to deal with averages such as average

molecular weight and average chain length.

Whenever the distance between the various oxygen and hydrogen

atoms in the cellulose molecule reaches 3 A° or less, they interact with

each other to form intermolecular and intramolecular hydrogen bonds. The

involvement of the hydroxyl groups in hydrogen bonding, as well as

dispersion forces determined by the proximity of neighboring atoms,

impart a different reactivity to the three hydroxyl groups available for

chemical reactions.

It is as well to report: (a) that the basic structure of untreated cotton

textiles significantly influences the chemical processes which are carried

out to impart some desirable properties; (b) that the cellulose molecule and

the only reactive function it possesses is provided by the hydroxyl groups,

and (c) that the reaction of chemicals with cellulose is a heterogeneous

reaction and, as a consequence, the reaction rates are slow; this places a

considerable limitation on the type of chemicals which can be considered

for reaction with cellulose.

It is also well-known that pre-treatments of cellulosics, namely;

desizing, scouring, bleaching and mercerizing, are prerequisite for

interaction of cellulose with dyestuff and finishing agents. Nevertheless,

cellulose undergoes certain degradation during these treatments.

Degradation of cellulose during dyeing, printing and finishing is also

possible. Furthermore, the cellulosic goods are subjected to degradation by

different means during use. With these in mind, a research programme has

been undertaken to study these aspects in greater details. For convenience,

Hebeish’s research work in cellulose chemistry can be grouped as follows:

Degradative treatments.

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Mechanisms of degradation of cotton and effects of Mercerization

stretching upon the course of these mechanisms.

Chemical reactions involved in functionalization of cellulose

Vinyl graft copolymerization.

Colouration.

Easy care cotton finishing.

Biotechnology for development of wet processing of cotton textiles

1.1.1. Degradative Treatments

Research in this area was designed to include: (a) effect of short

thermal treatments on molecular degradation, accessibility, reducing and

acidic as well as strength properties of cellulose and modified celluloses;

(b) oxidation of cellulose and cellulose derivatives with sodium chlorite

and sodium hypochlorite, and the mechanisms involved in the oxidation

reactions; (c) susceptibility of cotton and modified cottons to gamma

radiation; (d) changes in the chemical and physical structure of cotton,

alone or in conjunction with polyester, brought about by chemical pre-

treatments such as alkali-boiling, bleaching, mercerizing etc., and their

effects on the interaction of cotton with dyes; and (f) utilization of results

from these fundamental investigations to improve properties of cellulosic

products as well as their preparation (i.e. pre-treatment).

1.1.1.1. Thermal Treatments

The chemical and physical changes in the cellulose structure

brought by short thermal treatments were studied. Reactions occurring

during these treatments viz. (a) oxidation of the functional and reducing

groups to carboxyl groups, (b) oxidation of the cellulose hydroxyls to

aldehydic groups, (c) hydrolysis of glucosidic bond of the cellulose chains

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with resultant increase in the aldehydic group, and (e) decarboxylation

were postulated to account for the variations in copper number, carboxyl

groups, degree of polymerization (DP) and tensile strength. Besides,

changes in accessibility of cellulose by heat treatments were assessed by

dye uptake.

Modified cottons having different degrees of chemical

modification along with blank and control samples were subjected to

thermal treatments. The chemically modified cotton comprised partially

carboxymethylated cotton (PCMC), cyanoethylated cotton (CEC),

polyacrylonitrile-cotton graft copolymers (PAN-cotton copolymer) and

polyacrylamide – cotton graft copolymers (PAam-Cotton copolymer). The

degradation assessed by copper number, carboxyl groups, degree of

polymerization (DP), tensile strength and elongation at break as well as by

monitoring the changes in the modifying groups or the grafted polymers

were undertaken. Results disclosed that: (a) degradation is determined by

previous chemical treatments, (b) PCMC, CEC, poly (AN)-cotton

copolymers and poly (Aam)-cotton copolymers are more susceptible to

degradation than the control sample while the latter is more susceptible to

degradation than the blank, (c) results were interpreted in terms of

chemical and physical changes in the molecular structure of cellulose

brought about by chemical treatments and/or chemical modifications.

Pure viscose, pure polyester and blend of 50% polyester and 50%

viscose as well as polyester and viscose separated from the blend were

thermogravimetrically analyzed before and after these substrates were

thermally treated at 190 C for 1 to 20 minutes. The loss in weight brought

about by thermolysis within temperature varying from 250 C to 450C

was determined. The higher losses in weight of the blend as compared

with the calculated values indicated that the decomposition products of

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viscose catalyzes thermal degradation of polyester. Similarly

decomposition products of polyester act as catalysts for accelerating

degradation of viscose.

1.1.1.2. Hypochlorite, Chlorite and Persulphate Treatments

The oxidation of cotton cellulose with sodium chlorite was studied

under different conditions including concentration of sodium chlorite, pH,

reaction time and temperature. Changes in the chemical structure of the

cellulose was assessed by copper number, carboxyl content, and DP.

Decomposition of sodium chlorite in absence and presence of cellulose

was clarified. Detailed studies on the oxidation of cellulose derivatives,

namely o-methyl cellulose (D.S. 2.625) and partially carboxymethylated

cotton (D.S. 0.12) have also been carried out to visualize the reaction

mechanism. Oxidation of starch with sodium chlorite was also reported.

Based on the basic information obtained, a one- step process for fabric

preparation was devised.

Oxidation of water soluble carboxymethyl cellulose (CMC) with

sodium hypochlorite have been studied under a variety of conditions. The

influence of degree of polymerization (DP) and degree of substitution

(DS) of CMC on the rate of oxidation was also investigated. It was shown

further that oxidized CMC exhibited intrinsic viscosity which decreases

with increasing chlorine consumption; the decrease in the initial stages of

oxidation was much higher than the later stages. The drop in the intrinsic

viscosity of high viscosity CMC was greater than for those having low

viscosity. Highly substituted CMC (DS 3) was made soluble by oxidation.

Based on these findings, it was postulated that the hypchlorite

simulataneously attacks the glucosidic linkages and the hydroxyls of the

CMC and that some glucosidic linkages are more susceptible to oxidation

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than the others. In addition, rheological properties studies revealed that the

oxidized CMC samples are characterized by pseudoplastic behaviour. A

point of practical significance is the use of oxidized CMC as a thickner in

reactive dyes printing pastes produces printed goods whose over-all

properties were comparable with those obtained when sodium alginate

was used. Indeed this goal could be achieved after detailed systematic

study on the reaction of reactive dyes with CMC under different

conditions.

Poly(AN)-, Poly(Aam)- and Poly(methacrylic acid)-cotton

copolymers having different graft yields were oxidized using sodium

hypochlorite under different conditions. The extent and rate of oxidation

were studied with respect to copper number, carboxyl content, nitrogen

content and chlorine consumption. The effect of oxidation on the strength

properties of cotton before and after graft copolymerization was also

examined. It was found that introduction of the graft in the molecular

structure of cotton exerted a considerable influence on the behaviour

towards hypochlorite oxidation, being dependent upon amount and nature

of the graft as well as the oxidation conditions. By and large the cotton

copolymer is more susceptible to oxidation than the ungrafted cotton.

Involvement of poly (Am) graft in a reaction with hypochlorite was

postulated to explain the higher chlorine consumption observed with

poly(Am)-cotton copolymers. All the cotton copolymers under

investigation displayed higher deterioration than the ungrafted cotton.

The bevaviour of cotton graft copolymers towards persulphate

oxidation was also extensively studied and compared with that of

ungrafted cotton. It was disclosed that the extent and rate of oxidation

expressed as oxygen consumption, copper number and carboxylic content

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– depend essentially upon the amount and nature of the grafted polymer as

well as the conditions of the oxidation reaction.

1.1.1.3. Acid Treatments

After being prepared, the aforementioned cotton copolymers

having different graft yields were studied with respect to hydrolytic

susceptibility using 0.5 N HCl for varying length of time at different

temperatures. Results of carboxylic group, copper number, nitrogen

content and tensile strength concluded that the PAN-copolymers and the

PAam-cotton copolymers also played higher hydrolytic susceptibility than

the blank (ungrafted cotton) and the control sample (cotton fabric treated

with the initiator used in synthesis of the graft copolymers). The apposite

holds true for poly(methauric acid)-cotton copolymers. The latter were

more resistant to acid degradation than the blank and control sample.

1.1.1.4. Gamma Radiation

Etherified cotton having different amounts and nature of ether

content were synthesized and exposed to gamma radiation at different

doses. While cyanoethylated cotton and carbamoylethylated cotton

exhibited higher resistance to gamma radiation particularly whent they

acquired appreciable amounts of the ether group, partially

carboxymethylated cottons were less resistance. The cyanoethyl and the

carbamoylethyl groups seem to impede oxidation of the cellulose

hydroxyls and/or glucosidic bonds against radiolysis.

1.1.1.5. Pretreatment

Loomstate cooton fabrics contain both natural impurities such as,

fats, waxes, pectins, residual mote and natural colouring matter as well as

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added matter, viz. sizing materials applied to the warp threads for efficient

performance in weaving. Effective removal of these impurities through

pretreatment is a pre-requisite for production of properly bleached, dyed,

printed and finished fabrics. The pretreatment usually involves three

stages, namely, desizing to remove the size, scouring to remove fats,

waxes, pectins and residual mote and, oxidative treatment to destroy the

colouring matter. The conventional processes, even the continuous one,

for the pretreatment are exceptionally intensive in energy, material and

space requirements. A logical approach to conserving energy, equipment

utilities, manpower, etc. is to shorten the sequence by combining the

pretreatment operations.

To achieve the above goal, intensive investigation into the use of

hydrochloric acid, sulphuric acid and potassium persulphate as desizing

agents and potassium persulphate along with sodium hydroxide as a

technological base for combined desizing-scouring process were

undertaken. The three stages involved in the pretreatment of starch sized

cotton fabrics were also shortened in a single stage process using a

mixture of oxidants together with nonionic wetting agent or a formulation

containing of hydrogen peroxide, sodium hydroxide, magnesium sulphate,

chelating agent and wetting agent. This one-stage process for desizing,

scouring and bleaching were carried out under a variety of conditions.

Fabric samples so treated were analyzed for loss in fabric weight,

wettability, degree of polymerization and strength properties. Free radical

mechanism was postulated where hydrogen peroxide decomposed to yield

perhydroxyl anion (HOO-) and perhydroxyl free radical (HOO.). The

sizing materials on the fabrics, starch in case of all cotton fabric and PVA

in case of the cotton/polyester blend fabric, undergo degradation under the

action of decomposition products of hydrogen peroxide. These oxidizing

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species, in particular, the perhydroxyl free radicals destroy also the natural

colouring matters. Sodium hydroxide removes the fats and waxes from

cotton via converting them to soap and hydrolyzing the small amount of

esters present. In addition, sodium hydroxide removes the pectic substance

from cotton through conversion to soluble salts. These impurities as well

as the degraded sizing materials seem to exist in a dispersed state due to

the presence of the wetting agent. The latter seems also to prevent

reabsorption of these non-fibrous materials on the fabrics.

1.1.2. Mechanisms of degradation of Cotton and Effects of

Mercerization-Stretching upon the Course of these

Mechanisms

When cotton cellulose is subjected to mercerization treatments, the

molecular structure of the cellulose is modified in such a way that

although it undergoes higher chemical degradation yet it retains higher

strength as compared to unmercerized cotton. It is believed that there must

be differences in microstructural features between native cotton and

mercerized-restretched cottons that account for this behaviour. Clear

understanding of the phenomenon that accompanying the increased rates

of molecular degradation and increased extent of strength retention will be

useful in providing basis for new routes to improve balance in properties

in chemically modified cotton fabrics.

The work presented in this section was undertaken with a view to

measure the fundamental changes occurring as a consequence of acid,

hypochlorite, heat, ultraviolet and weathering degradative treatments of

cotton, and to determine the effect of mercerization-restretching of yarns

upon these fundamental changes in order to identify the structural features

that are critical to the improved retention of strength in mercerized-

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restrethed yarns. To achieve this, scoured cotton yarn was mercerized

using skien mercerizing machine on which the amount of yarn shrinkage

or restreching could be accurately measured. Tension on the yarn was

adjusted so as to give different mercerized-re-stretched yarns (90 to 103 %

of the original length). The mercerized cotton yarns so obtained together

with the scoured yarn were analyzed for copper number, carboxyl content,

degree of polymerization, iodine sorption and strength properties before

and after being subjected to the aforementioned degradative treatments.

Infrared spectroscopy and X-ray analysis as well as chemical

microscopical analysis were also used to clarify microstructural

differences among scoured and slack mercerized-restretched cottons.

Given below are summaries of these studies along with main conclusions

arrived at therefrom.

1.1.2.1. Effect of different Degradative Treatments on Cotton and

Slack Mercerized-Restretched Cottons

Scoured ply yarn was slack mercerized followed by restretching

the cotton yarn to 90, 94, 96, 100 and 103 % of original length in the

mercerizing solution. Practically there was no change in neither the

chemical structure of cotton cellulose nor in yarn number, twist variation

and evenness of the yarn, but there were considerable changes in the fine

structure of cotton with resultant increase in strength and decrease in

elongation at break.

The scoured and five mercerized cotton yarns were subjected to

acid, hypochlorite, heat, ultraviolet and weathering degradative treatments.

Degradation of cotton cellulose was assessed by copper number, carboxyl

content, degree of polymerization (DP), iodine sorption as well as strength

and related properties. Studies of these degradative treatments with respect

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to cotton and the five mercerized cotton yarns reveal the following

features:

The mercerized yarns retain higher strength in spite of higher

degradation as compared to scoured yarn.

The strength of mercerized yarns after treatment is dependant of the

magnitude of stretching; the higher the magnitude of stretching the

higher the strength.

The magnitude of stretching has no significant effect on copper

number, carboxyl content and iodine sorption of the degraded

mercerized cottons. On the contrary, there is a tendency that the DP is

higher the higher the magnitude of stretching.

The degradative treatments studied have practically no effect on twist,

yarn numbers and evenness of the scoured and mercerized cottons,

indicating that the decrease in yarn strength is due to chemical

degradation rather than changes in twist, yarn number and/or evenness.

The average distances between centers of crystallites in mercerized

cotton after any of the degradative treatment in question are much

shorter than their mates in scoured cotton, indicating that the

frequency of successive regions of high lateral order is much more in

mercerized cottons as compared to scoured cotton.

Plotting the DP of degraded yarns against the corresponding tensile

strength reveals that the curve of scoured cotton does not overlay on

those of mercerized cottons. The curves of mercerized cottons, on the

other hand, overlay irrespective of the magnitude of tension except in

one case.

The plots of DP with tensile strength also show that the strength of

scoured cotton yarn whose DP was reduced by the treatment to DP

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below 1000 decreases sharply whereas with mercerized cotton yarns

no sharp decrease in strength was observed.

The strength decreases as the percentage of bonds broken increases

irrespective of the degradative treatment within the range studied.

However, for a given substrate, the type of the degradative treatment

determines the magnitude of the strength loss since at equal

percentages of bonds broken, the strength varies considerably with the

type of degradative treatment.

For a given percentage of bonds broken, strength of mercerized cotton

yarns is greatly higher than that of scoured cotton.

For a given percentage of bonds broken, the strength of the highly

stretched yarn (i.e. slack mercerized then re-stretched under high

tension) is significantly higher than those re-stretched at lower tension.

1.1.2.2. Infrared spectroscopy and X-ray Analysis

The changes in the microstructure of scoured cotton yarn brought

about by slack mercerization followed by restretching the yarn (90-103 %

of original length) in the mercerizing solution was assessed by infrared

soectroscopy and X-ray analysis.

X-ray analysis showed that the largest changes in micro-structure

of the mercerized cottons have been the increase in cellulose I content

with increased restreching of the yarns.

The above conclusion has been confirmed by X-ray analysis of

these cottons after acid and hypochlorite treatments as well as through

infrared spectroscopy using the infrared ratio a1373/a2900 cm-1.

That conclusion suggests that the stretching has an effect on the

crystal structure and/or favours recrystallization.

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1.1.2.3. Structural Differences Between Scoured Cotton and Slack

Mercerized-Restretched Cottons

Scoured ply cotton yarn (substrate I) was slack mercerized

(substrate II) and slack mercerized followed by restreching to 94%

(substrate III) and 103 % of the original length (substrate IV). These

substrates were given an acid pretreatment (0.5 N HCl, 60C, 15 min.).

The four substrates and their corresponding HCl treated substrates

(substrate I-H, II-H, III-H and IV-H) were reacted under similar conditions

with N,N-diethylaziridinium chloride to yield diethylaminoethyl (DEAE)-

cottons. In addition, DEAE-cottons of substrates I,I-H, II and II-H were

hydrolyzed with 0.5 N HCl at 80C for 0.5, 1,2,3,5, and 7 hours and the

ratio of substituents in the D-glucopyranosyl units of these DEAE-cottons

as well as in those of DEAE-hydrocelluloses were determined. Nitrogen,

chemical microscopical and X-ray analyses were used to assess the

structural differences among the substrates. The results obtained lead to

following conclusion.

There is a considerable difference between the reactivity of

scoured cotton and slack mercerized-restrtched cottons due to difference

in the microstructures between the substrates in question. These

microstructural differences are reflected on availability, accessibility and

state of order of the cellulose hydroxyls in the scoured and mercerized

cottons.

1.1.2.4. Characterization of Microstrucural Differences Between

Scoured Cotton and Slack Mercerized-Restretched Cottons

Further studies were undertaken with a view: (a) to establish the

reproducibility of the reaction between forms of cotton and

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diethylaziridinium chloride (DAC), (b) to clarify microstructural

differences between the diethyl aminoethyl (DEAE) cottons and the

unmodified cottons and (c) to characterize microstructural differences

among scoured cotton and mercerized cottons. To achieve the goal,

experiments were designed to establish reproducibility of the said reaction

with scoured cotton yarn (substrate I), slack mercerized cotton (substrate

II), Slack mercerized –restretched 94 % (substrate III) and slack

mercerized-restrtched 103 % of original length (substrate IV).

The work was then extended to include study of compositions and

structures of the hydrolyzates (i.e., hydrocellulose and solubilized

fractions) resulting from hydrolysis of the modified cottons with 2.5 N

HCl under reflux for 1/3, 2/3, 1, 2, 3, 5 and 7 hours. Studies of rates of

hydrolysis of the cellulose, rates of removal of substituted glucoses and

rates of removal of individual types of substituted glucose units were

considered as a means to provide information regarding: (a) distribution of

DEAE substituents throughout the structure of cellulose, (b) nature of

accessible regions of hydroxyl groups at C-2, C-3 and C-6 of the

glucopyranosyl units in the cellulose elementary fibril. Main conclusions

arrived at from these studies are given below.

1.1.2.4.1. Reproducibility of the Reaction

Reaction of cotton cellulose with DAC is reproducible within the

experimental factor of 0.04 % N regardless of the cellulosic materials

used in this work.

Determination of the distribution of DEAE substituents among 2-0-,

3-0- and 6-0- positions of the D-gluco-pyranosyl units in any of the

substrates used confirms reproducibility of the reaction provided that

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gas liquid chromatography was carried out immediately after

silylation.

1.1.2.4.2. Microstructure of DEAE Cottons versus unmodified

cottons

Changes in microstructures of scoured and mercerized cottons

(substrates I-IV) brought about by introduction of DEAE substituents

using conditions established for each substrate to acquire almost equal

amount of DEAE groups were assessed by X-ray analysis. Specifically,

the DS’s of DEAE cottons amount of 0.036, 0.041 and 0.038 for

substrates I, II, III and IV respectively. These modified substrates and their

corresponding unmodified cottons were also analyzed for moisture regain,

loss in weight and degree of polymerization upon acid hydrolysis. The

results obtained lead to the following conclusion:

No substantial changes in the original structures of the scoured and

mercerized cottons occur by introduction of DEAE substituents. Thus

the DEAE cottons would serve as good replicas of the original

substrates while the latter bear the DEAE tags.

1.1.2.4.3. Microstructural Differences Among Scoured and

Mercerized Cottons

In order to gain more information about microstructural differences

among scoured cotton and slack mercerized –restretched cotton, it is a

must to examine distribution of DEAE substituents in the cellulose

structure, nature of accessible regions and selective accessibilities of

hydroxyl groups at C-3 and C-6 relative to C-2 of the D-glucopyranosyl

units in DEAE scoured cotton and DEAE mercerized cottons. When this

was done, results obtained lead to the following:

22

Studies concerning rates of hydrolysis of the cellulose and rates of

removal of substituted glucose units in the four substartes under

investigation made it evident that despite the higher resistance of

scoured cotton (substrate I) to acid hydrolysis, it has lost much of its

DEAE substituents by virtue of their poor distribution throughout the

cellulose structure.

Slack mercerized cotton (substrate II), on the other hand, retains much

of the DEAE substituents despite its higher susceptibility to acid

hydrolysis because of better distribution of the DEAE substituents

throughout the structure of cellulose.

Slack mercerization followed by re-stretching to 94% of the original

length of cotton yarn (substrate III) enhances the resistance of

substrate II to acid hydrolysis while decreasing the distribution of the

DEAE substituents throughout the cellulose structure.

The above situation becomes more apparent when slack mercerization

was followed by re-stretching to 103 % of original length (substrate

IV).

1.1.2.4.4. Nature of Accessible Regions

Differences between structural nature of accessible regions of

scoured cotton (substrate I), slack mercerized cotton (substrate II) and

slack mercerized – restretched cottons (substrate III and IV) were also

assessed. This was done by consideration of DEAE substituents at 2-0-, 3-

0- and 6-0- positions of the D-glucopyranosyl units and their removal

from the original DEAE cottons as a function of duration of acid

hydrolysis. The results obtained provide the following indications:

Slack mercerization of scoured cotton decreases the highly ordered

segments of the cellulose elementary fibril meanwhile it increases the

23

availabity of the hydroxyl groups at C-2 and C-6 positions of the D-

glucopyranosyl units.

The rate constants increase significantly by applying stretch in

consequence with slack mercerization.

The above effect turns to the opposite when slack mercerization was

followed by re-stretching.

The rate constants for removal of 2-0- or 6-0- substituted glucoses

from either the sensitive or crystalline segment of the elementary fibril

of cellulose decreases significantly by slack mercerization.

The rate constants increase significantly by applying in consequence

with slack mercerization.

Neither slack mercerization nor mercerization restretching exerts

considerable influence on the rate constants for the removal of the 3-0-

substituted glucose units from the two types of segments.

1.1.2.4.5. Selective Accessibility

The selective accessibility of the hydroxyl groups at C-3 and C-6

relative to C-2 of the D-glucopyranosyl units in DEAE scoured cotton

(substrate I) and DEAE mercerized cottons (Substrate II-IV) were

determined after different duration of acid hydrolysis for the solubilized

portions and the insoluble portions. Results obtained with the solubilized

portion provide the following indication.

Slack mercerization releases the 0(3)H from its involvement with

0(6)H…0(1) hydrogen bonding. The opposite holds true when stretch

was applied in consequence with slack mercerization, but with the

certainly that the groups at C-3 in slack mercerized-restrtched cottons

(Substrates III and IV) are less constrained than in scoured cotton

(substrate I).

24

Results of the insoluble portion, on the other hand, provide the

following indication:

Slack mercerization enhances the 0(3)H …0(5) as well as 0(6)……

0(1) hydrogen bonding. In contrast, slack mercerization followed by

restretching decreases these hydrogen bonding.

1.1.3. Chemical Reactions Involved in Functionalization of Cellulose

This area of research and developmental work was undertaken

with the primary objective of creating active centers in the cotton cellulose

molecule to make it more reactive and to modify the basic properties of

cellulose. For this purpose, reaction of cellulose with N-

methylolacrylamide and its derivatives under the influence of acid

catalyst, with acrylamide as well as with urea followed by methylolation,

with alkoxy adducts of acrylamide and with hexahydro-1,3,5-triacryloyl-s-

triazine and with 2,4-dicholoro-6-(p-nitroanilino)-s-triazine followed by

reduction of nitro group to amino group were carried out under different

conditions. Mechanisms involved in these reactions were elicited, and

ability of these reactive centers to facilitate and accelerate dyeing and

finishing reactions with cotton cellulose were studied. Continuous and

semi-continuous methods for chemical modification of cotton via partial

carboxymethylation were studied. A novel approach for introducing the

carboxymethylation reaction in the wet processing of cotton fabrics as a

means of sensitization (increasing reactivity) of cotton was also

investigated. Chemical modification of cotton via partial

carboxymethylation was successfully introduced in the pretreatment

processes of cotton fabric and, as a result, desizing and mercerizing could

be omitted.

25

Thorough investigations into factors affecting chemical reactions

inducing modification of flax cellulose were performed. Grey flax fibres

were bleached under different conditions using different bleaching

scheme. Conditions appropriate to produce bleached flax without serious

degradation of the fibre substance were chosen for preparation of bleached

flax fibres. These flax fibres were used as a starting materials for chemical

modification of flax cellulose via partial carboxymethylation,

cyanoethylation, carbamoylethylation, acetylation, crosslinking and vinyl

graft polymerization. All these reactions were carried out under different

conditions with emphasis on kinetics and mechanisms of these reactions.

Similar research programme was carried out using jute fibers. Particularly

notable was the contribution of jute constituents, namely, water soluble

matters waxes, pectin, lignin, hemicelluloses and α-cellulose in the vinyl

graft copolymerization reaction of the jute fabrics.

1.1.4. Vinyl Graft Copolymerization

Considerable research and technical work were and still are being

performed on grafting of vinyl monomers onto cellulosic in different

laboratories throughout the world. The wide range of available vinyl and

other monomers suggests that grafting is a powerful method for producing

substantial modification in fibre properties. This field of research has

evoked considerable academic and industrial interest. Thus it is clear that

the chemical combination of synthetic polymers with cellulose, i.e.,

cellulose graft copolymer opens up exciting possibilities for the cellulose

industry particularly in the textile field. One of the essential reasons for

this is that the grafting process involves modification of cellulose through

creation of branches of synthetic polymers that confer certain desirable

properties on cellulose without destroying its intrinsic properties.

26

Hebeish’s studies on chemical modification of cellulose via graft

polymerization with vinyl monomers had two-fold objective:

a) Understanding the kinetics and mechanisms of grafting, and,

b) Building up basic information needed for improvements to be

made in properties of products.

To achieve the goal, grafting reactions were studied with respect to

the following aspects: (i) nature of the cellulose substrate; (ii) feasibility of

a number of initiators which have been suggested or actually used for

vinyl polymerization onto cellulose and modified celluloses; (iii) proof of

grafting, whenever required, and some properties of cellulose graft

copolymers. In addition, the subject was reviewed and a compilation of

the literature in the form of comprehensive monograph was made to define

the present state of knowledge of grafting onto cellulose and modified

celluloses.

1.1.4.1. Nature of the substrate

The effect of the fine structure of cellulosic substrates on their

grafting reactions with acrylonitrile and other vinyl monomers using the

ceric ion redox system for initiation was studied. Seven substrates,

namely, native cotton, hydrocellulose, cottons swollen with NaOH,

ethylendiamine and zinc chloride, viscose and ramie were chosen to

represent a wide range of crystallinity and accessibility. The grafting

reactions were performed under different conditions including time and

temperature as well as type of initiator. The relation between substrate

accessibility and graft yields was studied. The decay of free radical

activity of the ceric-oxidized cellulose was also studied, with particular

reference to time and temperature of storage, presence of air and substrate

accessibility. In addition, number average molecular weight of grafted

27

polyacrylonitrile was determined in selected cases. Moisture regain of

polyacrylonitrile–cellulose graft copolymers was also studied.

Grafting of slack mercerized cotton yarns followed by stretching

upto 103% of original length of the yarn was examined. Results obtained

indicated that the graft yield is lower the higher the magnitude of

stretching.

The behavior of chemically modified celluloses brought about by

etherification, esterification, crosslinking and oxidation, towards grafting

was shown to depend upon the influence of the newly created or

introduced groups on properties of cellulose. Among these are: (a)

variation in the physical structure (perhaps the cellulose is held in an open

state); (b) swelling of cellulose; (c) availability and accessibility of the

cellulose hydroxyls to reaction; (d) reactivity of the cellulose hydroxyls in

the presence of the newly created or introduced groups; (e) specific

localization of the newly created or introduced groups on the

anhydroglucose unit of cellulose; (f) the type of reaction between the

cellulose and initiator (whether specific or non-specific); (g) reactivity of

the introduced group with initiator; and (h) affinity of the monomer to

modified cellulose.

In general, if the introduced groups increase the magnitude of (a),

(b), (c) and (d) or if they act as additional sites for grafting i.e., (g),

grafting would be greatly enhanced. Among the modified cotton which

constituted examples of this partially carboxymethylated cotton (PCMC),

cyanoethylated cotton, carbamoylethylated cotton and cellulose

carbamate. Conversely, lower grafting would occur if the introduced

groups adversely affect the reactivity of cellulose hydroxyls. The same

situation would be encountered if the groups of chemically modified

28

cellulose take place at the carbon atom in the anhydroglucose unit of

cellulose, the hydroxyl groups of which are liable to react specifically with

the initiator. These were exemplified by grafting on acetylated cellulose,

crosslinked cellulose, as well as acrylamidomethylated cellulose and its

reaction product with mercaptoethanol or hydrogen sulphide.

1.1.4.2. Initiation System

The feasibility of different initiation systems to induce grafting

onto cellulose and modified celluloses was studied. The graft yield relied

on the nature of the initiator as well as on structural changes occurring in

the cellulose by its chemical modification. Also studied was the effect of

nature of monomer, monomer mixtures and conditions of the grafting

reactions on the magnitude of grafting vis-à-vis homopolymerization.

The initiation systems used included interalia, the following: Ceric

ion (Ceiv); Ceiv- cellulose thiocabonate; pentavalent Vanadium;

Dimethylaniline (DMA) – Benzyl chloride (BC); Manganese IV; cellulose

tri carbonate - Crvi; cellulose thiocarbonate – potassium bromate; Ferrous

cellulose thiocarbonate – persulfate; Ferrous cellulose thiocarbonate –

hydrogen peroxide; azobisisobutyronitrile (AIBN); dimethylaniline

(DMA)–Cu+2 ion; hydrogen peroxide; Fe+2–hydrogen peroxide; hydrogen

peroxide–thiourea dioxide; Fe+2 thiourea dioxide–hydrogen peroxide;

hydrogen peroxide–thiourea dioxide; Fe+2 thiourea dioxide–hydrogen

peroxide; hydrazine hydrate–Cu+2; decomposition of aryl diazonium

group; cellulose thiocarbonate – Ferric nitrate; and ; gamma radiation.

Among the vinyl monomers used mention is made of the

following: acrylonitrile, acrylamide, methyl methacrylate, methyl acrylate,

29

ethyl acrylate, allyl acrylate, acrylic acid, methacrylic acid and glycidyl

methacrylate.

1.1.5. Colouration

Colouration of cellulosic occurs either through dyeing or printing

including heat transfer printing. When a fiber is immersed in a dyebath,

dyeing takes place in three stages, namely, (a) transportation of the dye

from solution to surface of the fibre; (b) adsorption of the dye at the fibre

surface and; (c) diffusion of the dye from the surface to the initiator of the

fibre. The stage (a) is governed by the movement of dye liquor relative to

individual fibres. The remaining two stages depend on the nature of the

fibre and the dye molecule. Some or all of the following forces will

contribute to the total adsorption: (i) electrostatic attraction between

charged sites in the substrate and ionic substance; (ii) attraction by

induction between ionic substances and a nonconducting substrate; (iii)

polar Van der Waal’s forces (hydrogen bonds); (iv) non-polar Van der

Waal’s forces and (v) chemical forces.

The affinity of a dye for a fibre will depend on: (a) the

hydrophobic – hydrophilic nature of the fibre; (b) the hydrophobic –

hydrophilic nature of the dye; (c) the possibility of close packing between

dye and the surface in the fibre and; (d) the accessibility of the fibre to

dyes.

Dyeing maybe considered from two aspects, namely, (i) the

thermodynamic aspect, which deals with the distribution of dye between

fibre and dyebath when equilibrium has been established and; (ii) kinetic

aspect which is concerned with dyeing process in action.

30

1.1.5.1. Dyeing of Cotton Cellulose

In Hebeish’s work, dyeing of cotton cellulose was undertaken with

a view (a) to study the mode of interaction of direct dyes with cotton

cellulose; (b) to improve the dyeability of cotton and viscose by making

use of redox system; (c) to expedite chemical fixation of reactive dyes via

introduction of latent alkaline catalyst in the molecular structure of cotton

cellulose and; (d) to examine the effect of the mercerization stretching on

the dyeability of cotton cellulose.

Results of the mode of interaction of the dye molecule with cotton

cellulose indicated that the overall fastness properties of the dyeings were

a manifestation of the physical and chemical structures of the dye used.

The fastness to washing relied to a large extent on the involvement of the

dye molecules with cellulose as well as intermolecular hydrogen bonding

between cellulose and water. Characteristic fading curves (C. F.) revealed

that dyes capable of intermolecular hydrogen bonding and these with no

hydroxyl or amino groups exhibited C. F. curves of positive slope. On the

contrary, dyes that form intermolecular hydrogen bond with cellulose

molecule acquired C. F. curves of negative slope. The visible spectra of

these dyes indicated that light fastness increased as λmax decreased.

Presence of redox system during dyeing of cotton cellulose and viscose

with direct dyes acted in favour of dye fixation. Evidences were given to

assure that dyeing involved covalent bonds between cellulose and dye by a

free radical mechanism in addition to their conventional enhancement via

physical forces.

Built-in alkaline catalyst in the molecular structure of cotton

cellulose could be achieved by reacting cotton fabrics with carbon

31

disulphide to yield sodium cellulose thiocarbonate. The latter was found

amenable to dyeing with reactive dyes in absence of alkaline catalyst.

The effect of mercerization stretching on dyeing of cotton with a

direct dye was investigated. At higher magnitude of stretching, lower dye

uptake was observed.

1.1.5.2. Dyeing of Chemically Modified Celluloses

Research in this area was undertaken with a view of studying the

effects of changes in the chemical and physical structure of cellulose

brought about by etherification, esterification, grafting, crosslinking and

oxidation on the dyeability of cellulose. Studied also was the effect of the

nature of the dyes (configuration, molecular size, substituents, etc.) on its

affinity for the modified cellulose. Furthermore, fading characteristics of

the dyeing were studied. Modified celluloses with additional functional

groups were dyed with dyestuffs of no or little affinity for cellulose and

the contribution of the additional functional groups in the cellulose

molecule in fixation of these dyes as well as in fixation of substantive and

reactive dyestuffs were clarified. Partially etherified and esterified

celluloses used comprise partially acetylated cellulose, PCMC,

cyanoethylated cellulose, crosslinked cellulose, carbamoylethylated

cellulose and cellulose graft copolymers. Several reactive and direct dyes

were employed.

These aforementioned studies may be exemplified by the research

that was directed towards studying the behavior of cotton and crosslinked

cottons before and after mercerization to reactive dyes. It was found that

crosslinking reduces significantly the susceptibility of cotton to reactive

dyes. Mercerization enhances dyeability of all substrates but enhancement

32

was much greater in case of non-crosslinked cotton. Different colour

designs with different patterns and properties can be conferred on a given

cotton fabric by making use of local crosslinking and/or mercerizing

followed by dyeing.

1.1.5.3. Printing of Cotton Fabrics

Hebeish’s research and developmental work had four-fold

objective: (a) technical feasibility of some thickeners in printing cotton

fabrics with reactive dyes; (b) development of new thickeners based on

polysaccharides as substitute for sodium alginate; (c) studying

stabilization and structure of emulsions; (d) improvement of the colour

strength of printed fabrics through application of the principles of

chemical modification of cotton; and (e) chemical modification of cotton

to make it amenable to heat transfer printing.

As an example of the above, mention is made of the following.

Hexahydro- 1, 3, 5- tri acryloyl-s-triazine (Fixing agent) was incorporated

in printing pastes of some direct, acid and reactive dyes. Dye fixation was

substantially higher in the presence than in the absence of the fixing agent

in case of direct dyes after soaping. Moreover, prints obtained with these

dyes in the presence of the fixing agent retain most of the colour after

extraction with dimethyl formamide (DMF); in contrast with prints in its

absence where complete colour removal was observed. The acid dyes

could only be fixed in the presence of fixing agent provided that the dye

acquired the substituent with labile hydrogen. A considerable

enhancement in dye fixation could be achieved with reactive dyes in the

presence of fixing agent. It was postulated that the fixing agents acts as

binder between the dye and cellulose and/or its decomposition products

(essentially N-methylol acrylamide derivatives) polymerize within the

33

cellulose matrix, thereby impeding removal of the dye during soaping and

DMF extraction.

Emphasis was placed on development of new thickeners for

reactive printing to replace sodium alginate which is universally

recognized as the best thickener for reactive printing. In this regard

research was designed to cover all factors affecting reactions with starch

as well as carboxymethyl cellulose (CMC) to make both polymeric

materials suitable for reactive printing. Thus, CMC was subjected to

oxidation, cyanoethylation and vinyl graft copolymerization using acrylic

acid, methacrylic acid and acrylamide. The copolymerization products

were used as thickeners for reactive printing in the form of composite

which represents all the copolymerization products or in the form of graft

copolymer where the homopolymer was removed from the products of the

copolymerization reaction. Similarly, starch and oxidized starches were

subjected to some reactions and its modified form or its composites or

copolymers were used successfully to prepare pastes for reactive printing.

Particularly notable is the success of using starch-polyacrylamide

composites on industrial scale.

1.1.5.4. Heat Transfer Printing

It is well known that heat transfer printing is ideally suitable for

fabrics made of thermoplastic textile fibres such as polyester and

polyamide. During the transfer printing operation the disperse dyes

sublime and diffuse into the softened synthetic fibres. As a result, the dye

is permanently embedded in the fibres.

In order to render cotton cellulose amenable for heat transfer

printing, cotton either alone or in conjunction with polyester was subjected

34

to the following chemical modification: (a) it was reacted with various

crosslinking agents, based on N-methylol compounds; (b) it was reacted

with acrylonitrile in presence of alkali under different conditions to yield

cyanoethylated products having different amounts of cyanoethyl groups,

(c) it was first cyanoethylated followed by crosslinking and (d) it was graft

copolymerized with various vinyl polymers. Cyanoethylated cotton and

PCMC-polystyrene graft copolymers were found to be the best substrate

amenable for heat transfer printing. Printing with very good fastness

properties could be obtained with these substrates. Explanation of the

success of some chemical modifications and failure of the others were

provided.

The feasibility of simultaneous cure/transfer print of melamine

formaldehyde-treated all cotton fabric and 50/50 polyester/cotton fabric

was studied using aluminum chloride, aluminum sulphate, magnesium

chloride, magnesium sulphate, barium chloride, ammonium chloride,

ammonium hydrogen phosphate and ammonium dihydrogen phosphate

catalysts.

1.1.6. Easy Care Cotton Finishing

Cotton occupies excellent position among textile fibres all over the

world. This pre-eminence is due to a happy combination of properties such

as abundance, fine cross-section, high strength and durability, ability to

absorb moisture, easy dyeability, etc. However, cotton has certain

drawbacks the most out standing of which are low wrinkle resistance and

inability to maintain shape or creases, especially in moist weather. In order

to obviate such defects, it is a must to produce what is called

"stabilization" of the fibre structure. This could be achieved by treating the

cotton fabrics with various finishing agents. The latter are either di-or

35

polyfunctional compounds which are able to react with cotton cellulose

most probably via covalent crosslinking. Thus the crosslinking finishes

include those treatments used to give cotton fabrics easy care properties,

i.e., shape-holding properties, wrinkle resistance, wash-wear and durable

press properties as well as dimensional stability.

Several studies on crosslinking of cellulose with di-or

polyfunctional N-methylol compounds were undertaken in order to

overcome serious problems associated with easy care and durable press

finishing treatments. Among these problems are great loss in the strength

and related properties, balance between wet/dry crease recovery and

tensile strength, free formaldehyde in the finished products and greater

susceptibility of the latter to soiling and their lower levels of soil removal.

Rot proofing properties of easy care cotton was also studied. Of the

numerous studies that have been carried out to tackle problems associated

with easy care cotton finishing, soil and soil release are particularly

notable as summarized below.

1.1.6.1. Soiling and Soil Release

In this context, research was undertaken with a view to define the

chemical characteristics of finishes that are critical for effective soil

release properties in durable press cotton-containing fabric with hope to

provide information on mechanisms of soil release. For this purpose,

cotton and cotton/polyester blend fabrics were chemically modified

before the crosslinking treatments according to the following: (a) partial

carboxymethylation by reacting cotton cellulose with monochloroacetic

acid in presence of sodium hydroxide; (b) cyanoethylation by reacting

cotton cellulose with acrylonitrile using sodium hydroxide as a catalyst in

aqueous and nonaqueous media: (c) partial alkaline hydrolysis of

36

cyanoethylated cotton to obtain cotton bearing cyanoethyl along with

carboxyethyl groups; (d) partial carboxymethylation of cotton prior to

cyanoethylation to obtain cotton bearing cyanoethyl along with

carboxymethyl; (e) carbamoylethylation by reacting cotton cellulose with

acrylamide in aqueous and nonaqueous media under the catalytic

influence of sodium hydroxide; (f) graft polymerization of acrylonitrile

either alone or together with methacrylic acid (MAA) onto cotton and

blend fabrics (g) graft polymerization of acrylamide either alone or

together with MAA onto cotton and blend fabrics; (h) graft

polymerization of styrene either alone or together with MAA onto cotton

and blend fabrics and, (i) graft polymerization of glycidyl methacrylate

either alone or together with MAA onto cotton and blend fabrics.

Grafting was induced by the Fe2+-thioureadioxide-H2O2 redox system or

the mutual irradiation technique.

In addition, water soluble cellulose derivatives, tetraoxalyl urea,

laboratory prepared poly(acrylic acid) as well as conventional soil release

finishes were independently incorporated during the crosslinking

treatments of the unmodified cotton and cotton/polyester blend fabrics.

Crosslinking formulation consisted of DMDHEU and MgCl2.6H2O and

crosslinking treatment was carried out in absence and presence of

nonionic softener. Soiling and soil release characteristics of the cotton

and modified cottons before and after crosslinking treatments were

evaluated. Aqueous soil and nonaqueous oily soil were used. For aqueous

soil, carbon black and water were mixed with a dispersing agent: for oily

soil, carbon black was mixed with mineral oil. Beside this, most of

samples before and after crosslinking were tested for hydrophilicity,

measured by water absorbency, water-rise, water imbibition and water

37

regain as well as tensile strength, elongation at break and wash-and-wear

rating.

1.1.6.2. Output of Research Pertaining to Soiling and Soil Release

The forgoing summary as well as details of these studies

particularly those concerning the hydrophilicity of cotton, cotton/polyester

blend and their corresponding modified samples before and after

crosslinking treatments lead to the same point. Although blending of

cotton with polyester alters the susceptibility of cotton to soiling and its

ability to release the soil, the point that introduction of additional

hydrophilization or even intensified hydrophilization cannot solely

determine the ability of cotton and blend fabrics to release the soil. The

same holds true for additional hydrophobicity and/or hydrophilicity.

Topochemical vis-à-vis topophysical aspects should be considered. The

fibres undergo physical changes during the chemical modification

treatments prior to crosslinking treatments. There are also changes in the

physical as well as the chemical structure of the fibres during the

crosslinking treatments. All these changes are governed by the nature and

amount of structural soil release finishes introduced in the molecular

structure of the fibres or included therein. The changes which the fibres

undergo are also influenced by conditions used for introduction of

structural soil release finishes and techniques employed for introduction of

additives with potential soil release properties. Such changes together with

chemical characteristics of the soil release finishes determine the affinity

of the soil for modified fibres or carbon black alters the soiling and the soil

release characteristics of the fabrics. Similarly, incorporation of

conventional softener in the crosslinking formulation exerts a considerable

influence on the soiling and soil release properties of cotton-containing

durable press fabric.

38

1.1.7. Biotechnology for Development of Wet Processing of

Cotton Based TextilesBiotechnology can be defined as the use of living organisms or

their cellular, subcellular or molecular constituents to manufacture and

establish processes. It is not an industry in itself, but an important

technology with unlimited fascinating applications. It will also have a

large impact on many different industrial sectors in the future.

The mediation of chemical reactions by catalytic proteins

(enzymes) is a central feature of living systems. Living cells make

enzymes although the enzymes themselves are not alive. Living cells can

be encouraged to make more enzymes than they would normally make.

Living cells can also be encouraged to make a slightly different type of

enzymes (protein engineering) with improved characteristics of

specificity, stability and performance in industrial processes. These

enzymes usually operate under mild conditions of pH and temperature.

Many enzymes exhibit great specificity and stereoselectivity.

Needless to say that biotechnology is not new. The enzymatic

removal of starch sizes from woven fabrics has been in practice during

almost the whole 20th century and the fermentation vat is probably the

oldest known dyeing process. The new impetus given to biotechnology in

the last few years is unequivocally due to the very rapid developments in

genetic manipulation technologies (genetic engineering) which introduces

the possibility of tailoring organisms. The latter are used for optimization

of established or novel metabolites of commercial importance. These

tailored organisms are also used of transferring genetic material (genes)

from one organism to another.

39

Furthermore, biotechnology offer the potential for new industrial

processes that require less energy and are based on renewable raw

materials. Biotechnology is not, therefore, concerning with biology, but it

is a truly interdisciplinary subject involving the integration of natural

sciences along with engineering sciences. Major advances in microbial

technology and genetics allow recently the broad range of enzymatic

application in the industrial sectors. Enzymatic processes have been

increasingly incorporated in textiles over the last years. Cotton, wool, flax

or starches are natural materials used in textiles that can be processed with

enzymes. The latter have been used in desizing, scouring, polishing,

washing, degumming, peroxide degradation in bleaching bath as well as

for decolourization of dyehouse, wastewater, bleaching of released

dyestuff and inhibiting dye transfer. Furthermore, many new applications

are under development such as modification of natural and synthetic

fibres, enzymatic dyeing, finishing, etc.

Most of textile processes are heterogeneous where auxiliaries as a

dye, enzyme, softener or oxidant have to be taken from the solution to the

fibers. These processes require the presence of surface-active agents, ionic

force "balancers", buffers, stabilizers and others which are characterized

with high turbulence and mechanical agitation in the textile bathes. Hence

a good understanding of major protein interactions within textile processes

is a must in order to anticipate trouble shooting possibilities when

enzymes are used. It can be expected that an enzyme protein can interact

with all chemical agents in solution due to the large variety of side chains

or the outer amino acids in the large 3D structure of the protein. It is

understandable that proteins (enzymes) are composed by amino acids with

a variety of side chains ranging from non-polar aliphatic and aromatic to

acidic, basic and neutral polar. This, indeed, allows to a globular 3D

40

protein to create in the active site all ranges of micro-environments for

catalysis.

1.1.7.1. Establishment of Biotreatment Appropriate for Processing

of Cotton-Based Textiles

With the above in mind, Hebeish’s research work was undertaken

with a view to establish environmentally sound conditions for purification

(i.e. pretreatment or preparation) of 100% loomstate cotton fabrics and

cotton/polyester blend fabrics. Another objective was to study the effect of

biopolishing of these fabrics before and after the latter were crosslinked.

To achieve the goal, four different types of cotton-based fabrics, namely,

loomstate cotton fabrics (Substrate I), mercerized loomstate cotton fabrics

(Substrate II), loomstate cotton/polyester (50/50) blend fabrics (Substrate

III) and, Mercerized loomstate cotton/polyester (35/65) blend fabrics

(Substrate IV) were biodesized using α-amylase enzyme. After that they

were bioscoured using alkaline pectinase enzyme under a variety of

conditions in order to set up optimization of bioscouring. Thus obtained

bioscoured substrates were subjected to bleaching through in situ

generated peracetic acid as the resultant of reacting

tetracetylethylenediamine (TAED) with hydrogen peroxide (H2O2).

Reaction of TAED with H2O2 was carried out under different conditions in

order to establish the best condition for bleaching with this

environmentally friendly bleaching system.

The so abstained bioscoured bleached substrates were given

enzymatic treatment using cellulase enzyme to effect biopolishing of these

substrates; these substrates were then subjected to easy care finishing by

crosslinking adjacent cellulose chains using dimethylol

dihydroxyethyleneurea (DMDHEU). In another series of experiments the

41

said bioscoured –bleached substrates were similarly crosslinked followed

by biopolishing.

Measurements of the technical properties were made of the four

substrates before and after being subjected to bioscouring, bioscouring

followed by bleaching, biopolishing of the bioscoured-bleached substrates.

Technical properties that were monitored include: nitrogen content, loss in

fabric weight, tensile strength and elongation at break, tear strength,

whiteness index, surface roughness and wrinkle recovery angle (WRA).

Scanning electron micrograph was also examined. The properties were

taken as a measure for fabric performance.

Summaries and conclusions arrived at from the aforementioned

studies are given under.

1.1.7.2. Establishment of Optimal Conditions for Bioscouring

Optimization studies of bioscouring disclosed that the four

substrates could be successfully scoured by either alkaline pectinase in

single use or in admixture with cellulase enzyme. Results of bioscouring

using different binary mixture of alkaline pectinase and cellulase enzyme

concluded that the performance of the bioscoured cotton-based fabrics is a

manifestation of (a) type and nature of the fabric, (b) kind and nature of

the enzymatic system, (c) properties measured for assessment of fabric

performance and (b) interrelationship of measured properties and their

dependence of each other. When alkaline pectinase/cellulase mixture are

used, care must be taken because remarkable decrease in tensile strength

was observed due to the attack of the cellulase enzyme on both cotton and

polyester components. Inclusion of EDTA in the bioscouring treatment

resulted in improvement of fabric performance. The same holds true upon

42

addition of -cyclodextrin to the bioscouring system based on either

alkaline pectinase alone or in admixture with cellulase enzyme.

1.1.7.3. New Development in Scouring and Bleaching

Optimal conditions for bleaching by in situ formed peracetic acid

of the bioscoured substrates under investigation were established.

Concurrent bioscouring and bleaching (which is considered by all means

a new development) of the four substrates could be achieved. Also

practiced were the conventional scouring using NaOH followed by

bleaching using H2O2 and other bleaching processes vis-à-vis our new

development. The comparison revealed unequivocally that the

environmentally sound technology brought about by current development

is by far the best. The new development involves a single-stage process

for full purification (preparation) of cotton textiles. Beside the advantages

of the new development with respect to major technical fabric properties,

it is ecofriendly and reproducible; points which advocate the new

development for mill trials.

1.1.7.4.Most Appropriate Strategy for Bioscouring

The effect of bioscouring of the four cotton-based substrates could

be realized by comparing their technical properties before and after

biopolishing. The latter had practically no effect on wrinkle recovery

angle (WRA), surface roughness, and tear strength. On the other hand,

strength properties and whiteness index decreases after biopolishing as a

consequence of enzymatic hydrolysis and residual enzyme on the

substantially of the substrate. Residual enzyme, expressed as N%, was

substantially higher after than before biopolishing. Bioscouring of the four

substrates had very marginal effect on N%, strength properties and

43

whiteness index; meanwhile it had a strong tendency to improve surface

roughness. A comparison between biopolishing of the four substrates

before crosslinking (pre-crosslinking) and biopolishing of the same

substrates followed by crosslinking (post-crosslinking) revealed marginal

differences in N%, WRA and whiteness index, a point which validates the

argument that cellulase enzyme could not break down the DMDHED

crosslinking within the molecular structure of cotton fabrics. Pre-

crosslinking caused higher losses in strength properties than post-

crosslinking. Examination carried out using scanning electron microscopy

(SEM) revealed that almost smooth fibre surfaces were observed with pre-

crosslinking as compared with post-crosslinking. Other fibre

characteristics were highlighted by making use of SEM.

1.1.7.5. Approaches for Application of Enzymatic Treatment and

Reactive Dyeing

In this respect, the work addresses three approaches. The first

approach is based on two- step process where a systematic investigation

was undertaken on factors affecting biotreatment of cotton fabrics using

cellulase enzyme and, the onset of this on the dyeing properties of the

fabrics when the latter where dyed using mono- and bifunctional reactive

dyes. In the second approach, one- bath process for biotreatment and

dyeing was established through controlling sequence of addition of the

ingredients of both enzymatic biotreatment and reactive dyeing. The third

approach refers to a post treatment process where dyeing was carried out

first then thus obtained dyeings were treated with cellulase enzyme.

Enzymatic effect was expressed as variation in the enzyme activity, loss in

fabric weight, wrinkle recovery angle, tensile strength, elongation at break

and colour strength in addition to overall fastness properties for selected

44

samples. Results obtained with the three processes reveal that the two-step

process is by far the best then comes the one step-process. The pos-

treatment process occupies the last position in this order. Differences

among the three processes were explained in terms of the environment

created during applications of each of these processes and, to what extent

does this environment acts in favour of the interaction of the enzyme

and/or the dye with the cotton fabrics.

1.1.7.6. Innovative Technology for Multifunctionalization of Cotton

Fabrics

Innovative technology for preparation of multifunctionalized

cotton fabrics with high technical performance was established. The

innovation entailed the following consecutive sequence: cotton fabrics

were subjected to cellulase biotreatment followed by reactive dyeing then

easy care finishing treatment. pH was adjusted at 7 before commencing

dyeing and finishing. No washing or drying was involved in the sequence.

The so obtained fabrics displayed high technical performance as

monitored by color strength, wrinkle recovery angle, retained strength in

addition to softness and smoothness. Anchoring the enzyme to the cotton

fabric ought to be taken as one of the reasons accounting for such high

performance. It is believed that the enzyme protein molecules are fixed

and immobilized within the molecules structure of cotton via their

attachment to the cellulose hydroxyls by the finish molecules. The latter

acts as bridges connecting the protein molecules of the enzyme with the

cellulose macromolecules of the cotton fabric.

45

1.2. Wool

Wool is a natural fibre of animal origin. Raw wool may contain

between 30 and 70% of impurities. The latter are wool fat, suint, dirt,

mineral matter and burrs. When all impurities have been removed, keratin

remains. Keratin has the following average composition: carbon (50%),

oxygen (22 to 25%), nitrogen (16 to 17%), hydrogen (7%) and sulphur (3

to 4%).

Keratin belongs to the group of compounds classed as proteins

which are the ultimate stage of complexity of organic matter before it

becomes living tissue. Proteins are giant molecules built up by the

condensation of a number of comparatively simple alpha amino acids. The

final product of this condensation is a very large molecule known as a

peptide. More complex amino acids appear as side chains of the main

skeleton. Glycine is the simplest alpha amino acid, but as many as more

than thirty others have been isolated from proteins.

Long chain keratin molecules are organized in crystalline and

amorphous regions. Unstretched and stretched wool fibres correspond to

two forms known as alpha and beta keratin respectively. A unique feature

of keratin is the existence of cysteine linkages or the disulphide bonds.

Wool is the oldest and most universally used textile fibres. It

possesses excellent properties such as provide warmth, natural felting

tendency, soft and lofty feel, resiliency, crease resistance at low

humidities, good setting properties, excellent draping characteristics, high

46

moisture sorbability, etc. However, wool has certain drawbacks the most

outstanding of which are excessive shrinkage during washing, poor crease

resistance at higher humidity, very high ability to felting and poor

permanent set.

Chemical modification of wool through grafting with different

vinyl monomers promises to be a potential powerful method for producing

substantial modification in wool properties. Hence, a research programme

was put forward to study the basic aspects of vinyl graft polymerization

onto wool. General kinetics and mechanisms of the grafting reactions were

studied in details with a number of initiators to provide basis for new

routes to improve balances in properties of chemically modified wool

fabrics. The effects of structural changes in wool brought about by

reduction, acetylation, alkylation and dinitrophenylation on the

susceptibility of wool towards grafting was discussed.

Feasibility and efficiency of different initiators, viz, ceric ion,

manganese (IV), dimethylaniline-benzyl chloride mixture, periodate ion,

cupric sulphate-hydrazine hydrate, ditertiary azobisisobutyronitrile and

different oxidants (hydrogen peroxide, ditertiary butyl peroxide, ferric ion)

along with thiourea as co-catalyst were investigated. Ability of thiourea

alone to induce vinyl graft polymerization onto wool in aqueous acidic

medium was also studied. The dependence of grafting on monomer

reactivity, conditions of polymerization reactions additives, solvents,

water/solvent was clarified.

Grafting of chains of vinyl monomers on wool was studied. An

important and difficult problem in this case concerns the site(s) on the

protein molecule at which chemical attachment of the polymer chains

occurs and this was considered in some detail for a number of initiation

47

systems. The influence of grafting on the all-important textile properties of

wool, notably felling and permanent set was examined.

Combined dyeing and grafting as well as dyeing through grafting

of vinyl sulphone dyes were examined and reactions involved elucidated.

Proof of grafting was provided and properties of the grfated products were

evaluated. In addition, the subject was reviewed.

Permanent set of wool fabrics under the action of

monoethanolamine sulaphate alone or together with hydrogen peroxide

and methyl methacrylate was also investigated. In addition, improving the

dyeability of wool by making use of redox systems was studied.

48

1.3. Polyamide

The term polyamide indicates that the fibre molecules contain

many CONH-groups. These have been formed from intermediates which

are not themselves of a fibrous nature.

The bulk of polyamide fibre commercially available is based either

on nylon 66, derived from hexamethylene diamine and adipic acid, or

nylon 6, derived from caprolactam; small amounts of nylon 11 are made

from W-amino-undercanoic acid. The number refers to the number of

carbon atom in the repeating unit of the molecule. Positive identification

of nylon 66 or 6 depends on the fact that nylon 66 melts at 250 C, while

nylon 6 melts at 210 C.

The various types of polyamide fibres differ slightly in physical

properties and in their capacity to take up dye. In addition to high strength

and abrasion resistance, polyamide fibres have good resistance to

chemicals and to wet processing. Another important property is

thermoplasticity, which enables the fibre to be heat-set.

Chemical modification of polyamide fibres, in particular via graft

copolymerization, appears to be very fascinating field for research with

unlimited future possibilities for improving their properties. Bearing this

in mind, studies were undertaken to investigate the basic aspects of graft

copolymerization of vinyl monomers to nylon. Thus, detailed studies of

grafting reactions initiated by a variety of chemical activation technique

were presented. The kinetics and mechanisms entailed in each procedure

49

were dealth with. Factors affecting the efficiency of each system in

achievement of grafting were also put into perspective. In addition,

reactions of cyanuric chloride and its derivatives with polyamide fibres in

nonaqueous medium was studied. The work was further extended to

include studies on dyeing and the fading characteristics of polyamide

substrates.

1.3.1. Polyamide Copolymers

Different polyamide copolymers were synthesized by making use

of various vinyl monomers, namely, methyl methacrylate (MMA), and

methacrylic acid (MAA). The copolymerization reaction was effected by

several initiators, viz., pentavalent vanadium, azobisisobutyronitrile,

dimethylaniline/Cu+2 system, thiourea-potassium bromate redox system,

dimethylaniline-benzylchloride-acetic acid system. The copolymerization

reaction was investigated in every initiation system under a variety of

conditions. Variables studied, among others, were nature and

concentration of both monomer and initiator, medium of the

copolymerization reaction notably ratio of the solvent-water mixture and

coplymerization temperature, time and pH, as well as incorporation of

cupric sulphate or ferric sulphate in case of azobisizobutronitrile-induced

graft copolymerization. Studies of copolymerization reaction was not

confined to the graft yield but was extended to homopolymer formation

and total conversion. Kinetics and copolymerization mechanism involved

with each of the said initiation systems were postulated.

1.3.2. Reaction with Cyanuric Chloride and its Derivatives

Critical factors affecting dyeing of polyamide (nylon 6) with newly

synthesized azo dyes were studied. Utilization of redox systems to

50

improve the colour strength of dyeings for acid dye was made. Fading

characteristcs of some monoazo dyes on polyamide films were examined.

1.3.4. Factors Affecting Dyeing

Nylon 6- in the fabric form- was dyed with seventy eight newely

synthesized dyestuffs under a variety of conditions, including

concentrations of the dye and carrier as well as duration and temperature

of dyeing. Dyes were prepared by coupling N-(o-hydroxphenyl)

benzenesulphonamide; N-(hydroxyphenyl) benzene-sulphonamide; N(m-

hydroxyphenyl) p-toluenesulphonamide; N-(o-hydroxyphenyl) p-

chlorosulphonamide or n-(m- hydroxyphenyl) p- chlorosulphonamide,

with diazotized amines. The latter included ortho-, meta- and para-

nitroaniline; ortho-, meta- and para-chloroaniline; ortho-, meta- and para-

aminobenzoic acid; ortho-, meta- and para-toulidine as well as α- and -

naphthylamine. Results of these studies led to the following:

The colour strength is improved by increasing dye concentration,

duration and temperature of dyeing. However, the magnitude of this

improvement depends upon type and position of the group on the

amine as well as the type of diazonium salt.

The type and position of the group on the amine together with type of

diazonium salt control the nature of the dye.

Nature of the dye determines not only whether or not dyeing with

these dyes necessitates a carrier but also the concentration of the

carrier required for optimal colour strength.

Differences in colour strength observed upon using the dyes under

investigation were attribuated to differences between these dyes in

forces of adsorption and affinity to the fibre.

51

Washing fastness of the dyeings obtained with the said dyes was

generally good.

Light fastness depends essentially on the nature of the dye which

governs state of aggregation of the dye molecules inside the fibre.

Raising the temperature from 30 to 60C caused significant

improvement in colour strength. The some holds true for duration of

dyeing up to 60 min. In addition to association of the dye with nylon-6

by salt-like bond, a free radical mechanism was suggested.

1.3.5. Improved Dyeability

Redox systems based on potassium, sodium or ammonium

peroxodisulphate or potassium periodate as oxidant and glucose, thiourea,

sodium thiosulphate or potassium pyrosulphite as reductant were

incorporated in the dyeing bath of nylon-6 under a variety of conditions.

An acid dye namely kiton Scarlet 4 R was used. The colour strength and

dye fixation enhanced outstandingly in presence of the redox system,

depending upon and concentration of the redox components. Raising the

dyeing temperature from 30 to 60 C caused significant improvement in

colour strength. Beside association with nylon-6 buy salt-like bond, a free

radical mechanism was suggested.

1.3.6. Fading Characteristics

The absorption spectra of seven different monoazo dyes at

different concentrations in water and in methanol as well as their

absorption of cellulose diacetate (CDA) and polyamide (PA) films were

examined.

It was found that the extent of dye aggregation in methanol is

greater than in water despite the higher dielectric constant of water,

52

reflecting the anomalous behaviour of water. However, structural

characteristics and concentration of the dye determine the state of dye

molecules in water and methanol. Some of the dyes examined had greater

tendency to aggregate while the others were probably present in

monodispersed form. On the contrary, all the dyes seem to have a strong

tendency to aggregate on the CDA and PA films indicating that

involvement of the dye in an interaction with the substrate alters the

structural characteristics of the dye and, therefore, its ability to aggregate.

In accordance with this were the results of studies dealing with evaluation

of the light fastness of the same dyes on both films using day light as well

as a light fastness tester for different exposure periods.

The fading rate curves and the characteristics fading curves of

seven azo dyes on polyamide (PA) and cellulose diactate (CDA) films

were examined. Fading was enhanced by prolonging the time of

irradiation and decreased by increasing dye concentration on the substrate,

irrespective of the nature of the latter or the dye used. However, the

magnitude of fading was governed by structural characteristics of both dye

and substrate. The results obtained suggested that dyes of higher ability to

aggregate forming large and uniform particles were more resistant to

fading than those forming smaller and/or a non-uniform size of dye

aggregates. Similarly, substrates of higher polarity and porosity acted in

favour of association of dye molecules, thereby impeding fading. These

suggestions were, indeed, substantiated by measurements of the extinction

y/x ratio after different irradiation periods.

Polyamide (PA) and cellulose diacetate (CDA) films were dyed

with a simple azo dye 4-hydroxy - nitroazobenzene, at nearly the same

concentrations and were exposed to artificial daylight for 200 h. the

53

absorption spectra before and after exposure were taken and the fading

rate curves plotted; in this way, the spectrum fading curves were obtained.

The shade became bluer on fading: that is, the hue of the dye moved

towards the blue end of the spectrum. The implication of this is that the

dye molecules are present on the substrates as a mixture of small

aggregates and monodisperse molecules. the aggregates dye (short

waveband) decreased more than the monodisperse dye (longer wave-

band); in accordance with our results pertaining to water insoluble azoic

dyes.

54

1.4. Polyester

Polyester fiber is a synthetic linear polymeric ester formed by

reacting a bifunctional acid with a bifunctional alcohol. The acid is

terephthalic acid or its dimethyl ester while the alcohol is ethylene glycol.

The raw material for these chemicals is petroleum. The starting material

for ethylene glycol is ethylene, which is manufactured by cracking

petroleum. Ethylene is oxidized to afford ethylene glycol.

Terephthalic acid is made from para-xylene which must be free

from ortho and meta isomers. The para xylene is oxidized with nitric acid

to terephthalic acid which may be esterified with methanol to dimethyl

terephthalate. The terephthalic acid or its ester and ethylene glycol are

polymerized in vacuo at high temperature. The polymer is extruded in the

form of a ribbon from the autoclave onto a casting wheel. The ribbon of

polymer solidifies on the wheel and is then cut into chips for easy

handling and these re conveyed by suction to the spinning building.

The polyester fiber possesses excellent mechanical, aesthetic,

resilience and crease retention properties. Most of the mineral and organic

acids, oxidizing and reducing agents, alcohols, ketones, soaps and

detergents have no serious chemical action on polyester fibre.

Nevertheless, polyester fiber is difficult to dye and has very poor ability to

sorb water. It is also a subject to static build-up and pilling during wear.

Research carried out by us on polyester, fibers had four-fold

objective: (a) investigation into the major aspects of free radical graft

55

copolymerization of poly (ethylene terephthalate) fibre (PET) and PET

blends; (b) improvements in functional characteristics of PET by grafting;

(c) dyeing of PET and fading characteristics of the dyeing, and (d) heat

transfer printing of PET.

1.4.1. Graft Copolymerization onto PET

The research work presented in this area was undertaken with a

view to build up basic information on the graft polymerization reactions of

vinyl monomers with PET fibres. Studies of the general kinetics of the

reactions using different monomer and monomer mixtures under a variety

of conditions were performed. Furthermore, major properties of the poly

(ethylene terephthalate) fibres before and after polymerization with vinyl

monomer were examined to see the imparted properties as a result of such

modification.

i.Copolymerization with methyl vinyl pyridine: A number of our

research papers were targeted toward graft copolymerization of PET

with 2-methyl -5-vinyl pyridine (MVP) monomer. In one case,

radiation induced grafting of MVP to PET fibres was investigated

under different conditions employing a post- radiation technique. Over

a range of a total dose of 1-10 Mard, increasing the total dose from 1

upto 3 Mard was accompanied by a significant enhancement in the

extent and rate of grafting. Further increase in the total dose caused a

decrease. The same situation was encountered with respect to MVP

concentration (5% - 10%) and polymerization temperature (75 0C – 90 0C). MVP concentration of 8% and a temperature of 85 0C constituted

the optimal. Addition of copper sulphate at a concentration of 0.05

m.mole/l offset grafting. The effect of the said parameters on

homopolymerization occurring during grafting was also investigated.

56

Polymerization of MVP in presence of poly (ethylene

terephthalate) fibres (PET) using benzoyl peroxide (BP) as initiator

caused a substantial increase in the weight of fibres. The mechanism of

this polymerization is believed to be grafting by vinyl addition to PET

radical formed under the influence of B.P. The graft yield increased by

increasing B.P. and MVP concentrations upto a certain limit then

decreases. Maximum grafting occurred at 85 0C. Incorporation of Cu+2,

Fe+3 or Li ion polymerization system enhanced the graft yield

outstandingly. Addition of acetic or oxalic acid to the reaction

decreased the magnitude of grafting. The same situation was

encountered when a water/solvent mixture was used as reaction

medium. Solvents employed were methanol, ethanol, propanol and

butanol. Also studied was the polymerization reaction with respect to

homopolymer, total conversion, and graft efficiency. Graft

polymerization of MVP on unstretched poly (ethylene terephthalate)

fibers (PET) using H2O2 as initiator was investigated under different

conditions. The extents and rates of grafting, homopolymer and total

conversion were dependent upon concentration of initiator and

monomer as well as on the polymerization temperature. Stretching the

PET fibres prior to grafting reduced appreciable the susceptibility of

the fibres towards grafting, being dependent on the magnitude of

stretching. Graft polymerization of MVP onto polyester/wool blended

fabric was carried out using benzoyl peroxide as initiator. The graft

polymerization reaction was conducted under a variety of conditions,

including initiator and monomer concentrations, time and temperature

of polymerization. The graft reaction proceeded initially at a fast rate

and decreased with time to a slower rate. The grafted samples show

improved dyeability toward acid dye, increased density, and decreased

57

moisture regain as compared with the untreated blend. Furthermore, a

tentative mechanism for initiation of grafting was suggested.

ii.Copolymerization with Methyl Methacrylate: Presence of

poly(ethylene terephthalate) fibres (PET) during polymerization of

methyl methacrylate (MMA) using H2O2 as initiator resulted in a

substantial constant increase in the weight of the fibres after repeated

extraction with acetone. Fractional precipitation curves of the

extracted PET-MMA polymerization product and a physical mixture

of PET and PMMA were different, indicating that the interaction of

MMA with PET involved grafting. The magnitude of grafting relied

on H2O2 and MMA concentrations and pH, time and temperature of

polymerization. Incorporation of Cu++ or Fe++ ions in the

polymerization medium caused a decrement in grafting irrespective of

the metallic ions concentrations. Using methylene chloride as a

swelling agent for the fibres failed to enhance the susceptibility of the

latter towards grafting. On the contrary terechloroethane was quite

promising in this regard. The homopolymer formed during grafting

was also reported.

iii.Copolymerization with Acrylic Acid: Graft polymerization of acrylic

acid to poly(ethylene terephthalate) fibres using H2O2 as initiator was

only possible in benzyl alcohol as reaction medium. The effect of

initiator , monomer concentrations, reaction time and temperature as

well as addition of metallic salts to the polymerization medium were

studied. Addition of copper sulphate to the polymerization medium

decreased the rate of grafting and no leveling off of grafting could be

achieved even after 5 hours. The ferrous ammonium sulphate

functioned similarly but to lesser degree, and leveling off of grafting

58

occurred after 4 hours. This contrasted with grafting in absence of

metallic salts where grafting leveling off after 1 hour. Action of initial

graft formation as diffusion barrier is believed to account for this.

iv.Copolymerization with Glycidyl Methacrylate: Fe+2 - H2O2 redox

system initiated polymerization reactions of glycidyl methacrylate

(GMA) from aqueous solution with poly(ethylene terephthalate) fibres

were investigated. The polymer add-on is greatly influenced by H2O2

concentration, as well as reaction time and temperature. At 65 0C, the

polymerization reaction showed an induction period of about 120

minutes, in contrast with reactions at 750, 850, and 950C where no

induction period was observed though the polymer add-on was quite

low at 750C during the initial stages of the reaction. Using dimethyl-

formamide (DMF) alone or mixed with water as polymerization

medium offset the polymerization reaction. Incorporation of

thioureadioxide in polymerization system decreased the polymer add-

on significantly. Poly(GMA)-PET fibers showed improved moisture

regain.

v.Copolymerization with Acrylic Acid/Styrene Mixture: Graft

polymerization of acrylic acid/styrene mixtures on poly(ethylene

terephthalate) fibres using H2O2 as initiator was investigated under

different conditions including acrylic acid/styrene ratio, monomer

mixtures concentration, initiator concentration, polymerization

temperature, pH of polymerization medium, addition of metallic salts

and use of solvent/water mixture instead of aqueous medium. It was

found that the rate and extent of grafting for acrylic acid/styrene

mixtures were much higher than those of single monomers, indicating

a synergistic effect. Maximum percent grafting occurred when acrylic

59

acid/styrene mixture at ratio of 70:30 was used. Increased the

monomer mixture concentration from 2% to 40% was accompanied by

a significant enhancement in percent grafting. No grafting took place

at 65 0C even after 4 hours. Raising the polymerization temperature to

750C expedited grafting; the magnitude of the latter increased by

increasing temperature upto 95 0C. Addition of copper sulphate and

ferrous ammonium sulphate to the polymerization system offset

grafting. The opposite holds true for lithium chloride provided that its

concentration did not exceed 15 m.mole/l. Methyl alcohol/water

(20:80) constituted the optimal medium for polymerization.

1.4.2. Properties of PET Graft Copolymers

Grafting of PET with MVP was carried out using gamma rays and

benzoyl peroxide independently for the initiation of grafting. The poly

(MVP)-PET graft copolymers were analyzed for density, moisture regain,

and dyeability. Radiation-induced grafting yielded copolymers with

densities and moisture regain appreciably higher than those produced by

benzoyl peroxide. The same results were obtained when acid dyes were

used. The behavior of (MVP)-PET graft copolymer towards some reactive

dyes was also studied. The extent and rate of dyeing were dependent on

pH of the dyebath, nature of the dye and the magnitude of grafting.

Dyeing occurred through formation of salt linkages between the pyridine

moieties and the solubilizing groups (usually sulphonate groups) in the

dye molecule.

Grafting of the PET component in polyester/cotton blend fabric

with MVP has been disclosed to increase tensile strength, elongation at

break, moisture regain and dye uptake and to decrease electrical

resistivity.

60

Further, the alkylation reaction of poly(MVP)-PET graft

copolymers with different alkaylating agents was studied .

Monochlororacetic acid has proved to be the best as far as degree of

alkylation and enhancement in electrical conductivity caused thereby are

concerned. Kinetic investigation revealed that alkylation follows a second-

order reaction, and the apparent activation energy is 15.23 cal/mole.

Polymerization of glycidyl methacrylate (GMA), methyl

methacrylate (MMA) and acrylic acid (AA)/styrene (St) mixtures with

poly(ethylene terephthalate) fabric (PET) to different polymer add-on was

performed. Moisture regain, dyeability and soiling properties of the

modified PET were examined. It was found that introduction of

poly(GMA) in PET structure brings about (a) improved moisture regain,

(b) enhanced dyeing with disperse dyes, (c) affinity and possible dyeing

with acid, direct and reactive dyes, (d) improved aqueous and nonsqucous

oily soil resistance and (f) decreased ease of soil removal. The magnitude

of moisture regain, dyeability and soiling properties were dependent upon

the percent polymer add-on. Polymerization of MMA with PET improved

the dyeability of the PET with the disperse dye as well as resistance to

nonaqueous oily soil while decreasing the resistance to aqueous soiling

and ease of both aqueous and nonaqueous soil removal. In case of PET

polymerized with poly (AA/St) there was a considerable enhancement in

moisture regain, dyeing with the disperse dye and resistance to aqueous

and nonaqueous oily soiling. On the other hand, both aqueous and

nonaqueous soil release characteristics of PET were imparted by

polymerization of the latter with AA/St mixture.

1.4.3. Dyeing of PET and Modified PETAs already indicated, copolymerization of PET with certain vinyl

monomers enhances the dyeability of PET. With this in mind, work was

61

elaborated and extended to include further studies on the dyeability of

PET copolymers. Novel method for dyeing of PET and its blends was also

devised. In addition, the effect of pH control on dyeing of PET and the

fading characteristics of the dyeings were examined.

1.4.3.1. Improved Dyeing by Vinyl Grafts

Samples of polyester fabric were independently graft polymerized

to different levels with methyl methacrylate (MMA), styrene (St.),

methacrylic acid (MAA) or a St/MAA mixture at ratio of 40/60. These

samples and control sample prepared under conditions similar to those of

grafting, as well as the ungrafted sample were dyed with a disperse dye in

the presence and absence of carrier. Examination of the dyeing properties

revealed that the color strength of the grafted samples were much higher

than the ungrafted and control samples. Nevertheless, the nature and

amount of the graft determined the magnitude of colour strength. It was

also shown that the control sample acquired higher colour strength than

the ungrafted sample and that the colour strength in the presence of a

carrier is substantially higher than in its absence, irrespective of the

substrate used. Furthermore, the results obtained with samples grafted

with poly (MMA) were very promising even at a low temperature dyeing

(70 -80 0C) and in absence of a carrier, indicating the potentiallity of graft

polymerization with MMA in improving the dyeability of polyester fabric.

1.4.3.2. Low Temperature Dyeing

Presence of polyester, polyester/cotton blend and cotton fabrics in

a system containg a disperse dye, vinyl monomer and hydrogen peroxide

permitted dyeing of these substrates at 85 C. Neither grafting nor

homopolymerization occurred. The colour strength was governed by

62

nature and concentration of the monomer, concentration of the dye and

hydrogen peroxide, as well as duration and temperature of dyeing.

Increasing monomer and dye concentrations caused significant

enhancement in the colour strength. The same holds true for duration (30 –

105 minutes) and temperature (65 – 85 C). With respect to the monomers,

the colour strength followed the order: Methyl

methacrylatestyreneMethacrylic acidAcrylic acid Acrylamide.

The mechanism through which the monmer function was elicited.

In addition, the suitability of continuous method for dyeing using the vinyl

monomer was reported.

1.4.3.3. pH Control

Dyeing of polyester materials with disperse dyes at a high

temperature in the absence of carriers and at different range of dye bath

pH was studied. It was found that the behavior of the dye as well as the

magnitude of dye uptake at different pH values were greatly affected by

nature and position of the substituents of the dye. Substituents, which form

lyonium ions in acidic medium produce higher dye uptake in alkaline

medium and those which form lyate ions in alkaline medium bring about

higher dye uptake in acidic medium. Substituents which are not able to

form neither lyonium ions nor lyate ions yield practically the same dye

uptake over a wide range of pH values.

1.4.3.4. Fading Characteristics

Characteristic fading curves of some monazo dyes on polyester

films were examined. The slopes of these curves were dependent upon

both the physical as well as the chemical properties of the dyes. Only for

those dyes, which were capable of forming intramolecular hydrogen bonds

63

negative slopes were shown, whereas for the other dyes the slopes were

positive.

1.4.3.5. Heat Transfer Printing

The suitability of coloured alginate films in heat transfer printing

of polyester fabric was examined. The colour strength of the polyester

prints depended on the dye concentration in the film, temperature and, to

some extent, the time of transfer. The prints acquired excellent washing

fastness and at least four prints having comparable colour strength could

be achieved by using the same film.

In another investigation, the feasibility of coloured CMC films in

heat transfer printing of polyester and nylon fabrics was examined. The

colour strength of the prints depended essentially upon disperse dye

concentration in the film and temperature of transfer. Increasing the time

of transfer had also a favourable effect on colour strength of the prints, but

this effect was not as significant as those obtained upon increasing the dye

concentration in the film or raising the temperature of transfer. The CMC

films could be used several times and the prints acquired excellent

washing fastness.

64

2. Chemistry of Nonfibrous Textile Materials

2.1. Starch

Starch is a polysaccharide found in seeds, fruits, tubers, roots and

stem pith of plants. It occurs usually in the form of discrete granules. The

size, shape and striations of these granules determine the origin of starch

and therefore, its variety.

Chemically, starch molecule is constructed from α-D-

glucopyranose units jointed in the 1:4 position. Nevertheless, starch is

made up from two types of polysaccharides having different structures,

namely amylose and amylopectin. Amylose is a linear molecule of degree

of polymerization of ca. 200-300. It is largely crystalline. When dispersed

in -water, amylose tends to gel and is precipitated after standing for long

periods. The phenomenon occurs on cooling a cooked starch paste when

gelation takes .place. This process is known as retrogradation. Amylose

combines with iodine to give deep blue colour. It is in the form of a helix

with six glucose units per turn, inside which is just enough space to

accommodate an iodine molecule.

Amylopectin, on the other hand, has extensive branched chain

65

structure. The linear branch elements consists of 20-30 glucose units in α-

1,4-glucoside linkage, which are linked as α-1,6-glucoside at the branch.

Amylopectin contains only very few reducing group, because the branched

chains start out in each case from an aldehyde end group of the side chain.

It is practically amorphous, and has a largely globular structure. It is

capable of considerable expansion by hydration, with hardly a tendency to

retrogradation. Amylopectin does not give starch-iodine blue colour but a

purple and sometimes reddish brown colour; depending upon the source of

starch.

Hebeish’s research work on starch was designed to include : (a)

gelatinization of starch at room temperature under the influence of urea;

(b) chemical modification of starch through grafting, carboxymethylation,

carbamoylethylation/ carboxyethylation, cyanoenthylation and oxidation;

(c) mechanisms of reactions involved in gelatinization and chemical

modification; and (d) properties of the modified starches. In addition,

studies on starch and starch derivatives have been discussed from the point

of their utilization inwarp sizing along with other sizing agent.

2.1.1. Gelatinization of Starch

Addition of urea to starch slurry caused gelatinization of starch at

room temperature. The time required for gelatinization, type of gel

formed, rheological properties and apparent viscosity of starch suspension

in urea solutions were determined. Suspensions of starch in urea solutions

did not show any fermentations and retrogradation during 8 weeks storage.

The Urea seems to interact with starch to form adducts or urea starch

complexes. The urea starch complex, acquires very high affinity to water

thereby causing swelling and gelatinization of starch.

66

2.1.2. Starch Copolymers

The ability of potassium permanganate to induce graft

copolymerization of acrylonitrile (AN) onto starch was investigated. The

graft yield depends on monomer and initiator concentrations as well is

reaction time and temperature. Chemical analysis of the reaction product

of starch and (AN) in presence of potassium permanganate revealed that

the latter acted as initiator for polymerization of AN and as oxidizing

agent for starch. Proof for grafting was provided through infrared analysis

and solubility properties of the reaction product.

Graft copolymerization of acrylamide onto starch using ferrous

starch thiocarbonate-persulphate redox system was investigated under a

variety of conditions. The graft yield, expressed as nitrogen percent, was

significantly favoured in acidic medium as well as by increasing the

presulphate concentration, acrylamide concentration, and polymerization

temperature. Carbon tetra-chloride constituted the optimal medium for

polymerization. Grafting was also favoured in either, higher or lower

liquor ratios.

Graft copolymerization of acrylamide onto rice starch was

investigated under different conditions using potassium persulphate,

benzoyl peroxide or potassium permanganate as initiator. Grafting was

characterized by two rates regardless of the initiator used. The first rate

occurred during the initial stages of polymerization while the second

during the later stages. The first rates of grafting for the three initiators

were very close indicating the insignificant effect of the nature of the

initiator on grafting during the initial stages of the reaction. On the other

hand, the second rates of grafting exhibited the order: potassium

persulphate> benzoyl peroxide> potassium permanganate, reflecting the

role played by the nature of initiator during the later stages of the reaction.

67

Substantial differences in solubility were observed between

polyacrylamide-starch graft copolymers and unmodified starch as well as

among copolymers prepared using the three initiators. Although the

copolymers acquired higher solubility percent than the unmodified starch,

yet the solubility was determined by nature of initiator, graft yield,

structural changes in the copolymer occurring during grafting and the

temperature of solubility measurement.Copolymers prepared using

benzoyl peroxide or potassium persulphate showed lower viscosity than

the unmodified starch. The opposite was the case with respect to

copolymer prepared using potassium permanganate.

When starch was treated with KMnO4 solution, MnO2 was

deposited overall the starch. The amount of MnO2 deposited relied on the

KMnO4 concentration. Subjecting the MnO2-containing starch to a

solution consisting of monomer, (methacrylic acid, MAA) and acid (citric,

tartaric, oxalic or sulphuric acid) resulted in formation of poly (MAA)-

starch graft copolymer. The magnitude of grafting, expressed as meq.-

COOH/100g starch, was determined by amount of MnO2 deposited, MAA

concentration, temperature and duration of polymerization as well as kind

and concentration of the acid. Incorporation of cations such as Fe+3, Cu+2

and Li+1 had a significant effect on grafting. A tentative mechanism for

grafting of starch with MAA using MnO2-acid system was elucidated.

Solubility and viscosity properties of poly-acrylamide-starch graft

copolymer were examined and compared with those of nongrafted starch.

When the solubility was measured at low temperature, no difference in the

solubility percent between nongrafted and grafted starches was observed.

On the other hand, the solubility of the polyacrylamide-starch graft

copolymer was higher than that of the nongrafted starch when the

solubility was measured at high temperature. Furthermore, increasing the

68

nitrogen content of the copolymer causes an enhancement in the solubility

percent. With respect to viscosity, it was disclosed that grafting of starch

with acrylamide reduces substantially the viscosity of starch.

2.1.3. Starch Composites

Starch was polymerized independently with acrylamide, acrylic

acid, methacrylic acid and acrylonitrile (AN) using potassium

persulphate(K2S2O8) as initiator. The products of the polymerization

reaction, namely, the starch composite, consist of free (intact) starch,

grafted starch, homopolymer and Oxidized starch. The ratios of these

composite constituents were found to differ considerably depending upon

the nature of monomer as evidenced by differences in viscosity curves

(amylograph-viscogaph) as well as sizeability of the composites and their

ease of removal from cotton yarns during desizing. Also studied was the

dependence of the extent of polymerization (grafting and

homopolymerization) of AN to starch on K2S2O8 and AN concentrations,

polymerization temperature, starch/AN ratio and starch + AN/liquor ratio;

and the onset of these factors on the a parent viscosity of the composite

obtained thereof.

Preparation of poly (AA)-starch composite was achieved by

polymerization of acrylic acid monomer using the hydrolyzed starch

thiocarbonate-potassium bromate as redox initiation system. Influences of

the polymerization time and temperature, concentrations of potassium

bromate, acrylic acid, and thiocarbonation components (CS2 and NaOH)

as well as partial preneutralization of AA on total conversion, graft yield,

homopolymer and grafting efficiency were extensively studied. The

viscosity of poly (AA)-starch composite produced under a variety of

reaction conditions was also studied. Tentative mechanisms signifying

69

different chemical events that probably occur throughout the whole course

of the thiocarbonation and polymerization reactions along with the

hydrolyzed starch were also reported.

Polymerization of acrylic acid (AA) with native and hydrolyzed

maize starches was achieved via the potassium bromate-thiourea dioxide

redox system. Factors affecting the efficiency of the said redox system

and, in turn, the polymerization process were studied. The polymerization

reaction was monitored via determination of the total conversion percent

of AA. The Poly(AA)-starch composite was evaluated by calculating the

polymer yield, namely, the graft yield, grafting efficiency, homopolymer

and total conversion. Tentative mechanism was described to clarify

different chemical events occurring throughout the whole course of

polymerization process.

On a limited industrial scale, Poly(acrylic acid)-hydrolyzed starch

composite was used as sizing agent for cotton/polyester (35:65) yarns

(count No. 40/1) under different conditions. Parameters studied embrace:

(a) the size solution concentration (9.0-12.5%) and (b) the yarn

withdrawing speed in the sizing machine (30-70 m/min.). The sizing effect

was controlled by measuring the size add-on/the size solution and water

pick-up, the viscosity, as well as, the sized yarn properties (tensile

strength, elongation at break and the elongation differences). Results

obtained led to the following conclusions: (a) the composite can be

successfully used independently without any additives as sizing agent for

cotton/polyester yarns, (b) the concentration of composite in the slasher

can be 9% which is much less than the conventional sizing agent (13-

14%), and (c) the speed of the sizing machine could be increased to 70

m/min. instead of 40 m/min. in the conventional case.

70

2.1.4. Starch hybrids2.1.4.1. Development of New Starch Hybrids through Successive

Polymerization and Etherification

New starch hybrids were synthesized via introduction of ether

groups in the molecular structure of poly(MAA)-starch graft copolymer,

poly(MAA)-starch composite, poly(Aam)-starch graft copolymer, or

poly(Aam)-starch composite. The copolymers and the composites were

prepared by polymerization of starch with ether methacrylic acid (MAA)

or acrylamide (Aam). The composite refers to the polymerization products

including graft copolymer, homopolymer, oxidized starch brought about

under the influence of initiator and, intact starch. On the other hand, the

copolymers refers to the polymerization after removal of homopolymer.

Polymerization was conducted using Na2S2O4/K2S2O8. At this end, the

MAA starch based products, i.e., composite and the copolymer were

subjected to etherification with acrylamide in alkaline medium. While

Aam starch based products were subjected to carboxymethylation using

monochloroacetic acid in strong alkaline medium. Results obtained signify

that: (1) the composite is less susceptible to etherification than the

copolymer, (2) the magnitude of the polymer in the form of graft or

homopolymer adversely affects the etherification reduction, (3) before

etherification the composite, the copolymer and the native starch exhibit

non-Newtonian thixotrobic behavior whereas after etherification these

products are characterized by non-Newtonian pseudoplastic behavior and,

(4) the apparent viscosity decreases as the rate of shear increases

irrespective of the nature of starch products examined. The results are

interpreted in terms of variation of the accessibility of starch graft and/or

the homopolymer in vicinity of starch molecules towards the etherfication

reaction, i.e. carbamoylethylation and carboxymethylation.

71

2.1.4.2. New Starch Hybrids via Etherification of Poly

(Acrylamide)-Starch Copolymers with Acrylamide

Novel starch hybrids containing acrylamide (Aam) moieties in

monomeric (i.e carbamoylethyl groups) and polymeric (poly acrylamide)

forms were synthesized. Thus, starch was first polymerized with

acrylamide to yield poly (Am)-starch composite and poly (Aam)-starch

graft copolymer which represent the total polymerization products before

and after removal of the homopolymer, respectively. The composite and

the copolymer were then carbamoylethylated via reaction with Aam.

Beside the carbamoylethyl groups, carboxyethyl groups were inevitably

formed during carbamoylethylation. This and the onset of such

modification on the rheloigical properties of the so synthesized starch

hybrids signify the following. a) The extents of carbamoylethylation of

the composite and the copolymer were much lower than native starch; b)

The magnitude of poly(Am) content in the form of graft or homopolymer

adversely affects the carbamoylethylation reaction; c) Before

carbamoylethylation, the composite, the copolymer and native starch

exhibited non-Newtonian thixotropic behavior. , d) After

carbamoylethylation the etherified products were characterized by

pseudoplastic behavior. The apparent viscosity of starch, starch composite

and starch copolymer decreased significantly after carbamoylethylation

but with the certainty that the apparent viscosity increased by increasing

the carbamoylethyl and carboxyethyl groups in these starch hybrids.

2.1.4.3. New Route for Novel Polycarboxylic Starch Hybrid

Starch was polymerized with methacrylic acid (MAA) to different

magnitudes of poly (MAA) using potassium persulphate/sodium

thiosulphate redox initiation system. The polymerization products are

72

referred to as "composite". The latter consists of poly (MAA)-starch graft

copolymer, poly (MAA) in the form of homopolymer, oxidized starch

brought about under the influence of the initiator and intact starch. At this

end, the composite, the copolymer, and the untreated (native) starch were

subjected to carboxymethylation under different conditions and the

rheological properties of these starch – based products before and after

carboxymethylation examined. Results obtained disclosed that the

susceptibility of these products toward carboxymethylation follows the

order: native starch > Copolymer > composite. Meanwhile, these products

exhibits non- Newtonian thixotropic behavior before carboxymethylation

and; their rheology signifies the order: Composite > copolymer > native

starch; whereas after carboxymethylation these products are characterized

by non-Newtonian Pseudoplastic behavior. For a given rate of shear, the

apparent viscosity follows the order: native starch > composite >

copolymer >carboxymethyl composite >carboxymethyl starch

>carboxymethyl copolymer; in contrast with Pseudoplasticity which

reveals an opposite order. It was also shown that the apparent viscosity

increases by increasing poly (MAA) in the copolymer and composite and

that redrying of the copolymer and the composite after normal

precipitation and drying causes a considerable enhancement in the

apparent viscosity of these products.

2.1.5. Oxidation of Starch

Thorough investigation into the oxidation of starch using different

oxidizing agents as well as gamma rays were preformed. Of these mention

is made of the following.

Egyptian rice and maize starches were treated with sodium

hypochlorite at different concentrations. The oxidized starches so obtained

73

were monitored for carboxyl content and rheological properties. 1n

addition, the extent and rate of the oxidation reaction was assessed by

monitoring the chlorine consumption. Results indicated that the extent

and rate of oxidation of rice starch, expressed as chlorine consumption, are

much higher than those of maize starch. The opposite holds true for the

carboxyl content. Pastes of rice and maize starches before and after

oxidation exhibit non-Newtonian thixotropic behavior but their apparent

viscosity decrease by increasing the hypochlorite concentration. At any

event, however, the apparent viscosity of rice starch is substantially higher

than that of maize starch. Storing the pastes for 24 hr adversely affect the

apparent viscosity particularly with oxidized starches prepared using

higher hypochlorite concentration.

Maize and rice starches were independently oxidized with sodium

chlorite in absence and presence of formaldehyde. The treatment was

carried out under different conditions including sodium chlorite and

formaldehyde concentrations and duration. The treated starch samples

were monitored for carboxyl and carbonyl contents as well as apparent

viscosity at different rates of shear. Results obtained indicated that with

both starches the percent chlorite decomposed increases as the

formaldehyde concentration increases within the range studied. The same

holds true for the duration of oxidation. The apparent viscosity. of starch

before and after oxidation decreases as the rate of shear increases. Maize

starch is more susceptible to oxidation than rice starch. When applied as

sizing agents for cotton textiles, oxidized starches derived from maize and

rice starch display better performance than the unoxidized starch, but with

the superiority of the sizeability and desizeability of oxidized maize

starch.

74

Sodium hypochlorite was used along with starch sizing

formulation in a textile mill. Cotton Warps were sized with this size and

compared with those sized with similar sizing formulation but in absence

of the hypochlorite. Warp performance on the loom showed an average

breakage/hour of 2.44 and 2.89 for warp yarns sized in presence and

absence sodium hypochlorite, respectively.

The use of potassium persulphate instead of the hypochlorite in

oxidation of starch during sizing operation in a textile mill was found

more appropriate from both the technical as well as economic point of

view. Warp yarns sized in presence of persulphate exhibited greater

abrasion resistance and tensile strength.

Oxidation of starch with hydrogen peroxide was investigated in

highly alkaline media .Similar studies were performed with-respect to

polyvinyl alcohol. The results obtained were taken to form a base for

simultaneous desizing, scouring and bleaching of cotton fabric the warp of

which was sized with starch, and of polyester/cotton blend fabric sized

with polyvinyl alcohol.

Maize and rice starches were gamma irradiated in the presence of

air over a range of radiation doses from 10 to 250 KGY. Structural

changes in the starch molecules brought about by irradiation were

evaluated in terms of carbonyl and carboxyl groups as well as apparent

viscosity and solubility. Significant enhancement of the carbonyl and

carboxyl groups as well as the solubility, along with decrease in apparent

viscosity, particularly at higher radiation doses were observed. Of

particular interest were the results of apparent viscosity at different rates

of shear. The apparent viscosity of unirradiated starch decreased as the

rate of shear increased. Application of these oxidized starches to cotton

75

fabric was also carried out to evaluate the suitability of such modified

starches as sizing agents.

Ultrafine structures of low, medium, and highly oxidized starches,

symbolized as LOS, MOS, and HOS, respectively, were thoroughly

investigated. These oxidized starches were obtained by treatment of native

starch (NS) with three different concentrations of sodium perborate (SPB).

Thus obtained products were studied with respect to major chemical and

fine physical characteristics vis-a-vis those of NS (a) acidic and reduced

groups creation along with mode of association, (b) significant increase in

solubility, and (c) outstanding decrease in apparent viscosity.

Thermogravimetric analysis (TGA) revealed thermal stability of the said

substrates follows order: HOS>MOS>LOS>NS. Scanning electron

micrographs (SEM) showed polygonal or irregular shape with particle size

ranging from 2 to 20 l. After oxidation, the starch surface became rough

and the edges lost their definiteness completely. In conclusion, SPB is an

efficient oxidant to produce oxidized starches with useful characteristics,

which advocate them to wide applications in textile sizing and medicinal

domains

2.1.6. Starch Ethers

Synthesis and characterization of several starch ethers were the

subject of several researches of current work. Particularly notable are the

cyanoethyl starch (CES) and carboxylmethyl starch (CMS).

2.1.6.1. Cyanoethyl Starch

In one study, rice starch was cyanoethylated by reacting it with

acrylonitrile in presence of sodium hydroxide at different concentrations

of acrylonitrile and reaction temperatures. The effect of cyanoethylation

76

on the rheological and solubility properties of starch was examined. It was

found that the extent of the cyanoethylation reaction increased by

increasing acrylonitrile concentration provided that the latter was not less

than 8 ml acrylonitrile per 10 g starch. A temperature of 50°C constituted

optimal temperature for cyanoethylation. Regardless of the extent of

cyanoethylation, cyanoethyl starches were characterized by pesudoplastic

behavior. Cyanoethylated starch having smaller amounts of cyanoethyl

groups had higher viscosity than those of relatively larger amounts. On the

other hand, the cyanoethyl starches were soluble in water regardless of the

extent of cyanoethylation.

In another study, cyanoethyl starch containing 4.53 wt-% nitrogen

was prepared and its rheological properties were examined and compared

with those of alkali treated starch before and after storing for varying

lengths of time. Cyanoethyl starch offered advantages in terms of higher

stability to storage, higher apparent viscosity and improved film forming

properties as compared with alkali treated starch.

In a third study, rice starch was reacted with acrylonitrile in

presence of sodium hydroxide under different conditions including

liquor/starch ratio. sodium hydroxide concentration and acrylonitrile

concentration as well as reaction time and temperature. The reaction

products were analyzed for nitrogen and carboxylic contents and the

results obtained were used for calculation of the degree of substitution

(D.S.), reaction efficiency (R.E.) and total extent of etherification.

Reaction products refered to mixed starch ethers, namely, cyanoethyl

starch, carbamoylethyl starch, and carboxyethyl starch. Due to analytical

difficulties to differentiate between the first two ethers, they were looked

upon as cyanoethyl starch. The D.S. of the latter and the R.E. of

cyanoethylation were greatly favored at temperature not exceeding 40°C

77

using lower liquor ratios for reaction time up to 4 h provided that certain

acrylonitrile and sodium hydroxide concentrations were used. Kinetics and

mechanisms of the cyanoethylation reaction and other reaction associated

with were also elucidated.

2.1.6.2. Carboxymethyl Starch (CMS)

Maize starch was reacted with monochloroacetic acid in presence

of sodium hydroxide. The reaction involved is known as

carboxymethylation. The latter was carried out under a variety of

conditions. For every set of conditions carboxmethylation was studied

with respect to the extent of the reaction expressed as degree of

substitution (DS) and reaction efficiency (RE). Results indicated that

starch: water ratio of 1:2.5, sodium hydroxide (8N) duration (0.5- 3h) and

temperature (60-70°C) act in favour of both DS and RE. The DS increases

by increasing concentration of monochloroacetic acid and, is governed by

the reaction medium, it follows the order: iospropanol >cyclohexan>

dimethyl formamide> methanol> acetone> water. Isopropanol: water

mixture (80:20) constitutes the most favourable medium for the

carboxymethylation reaction under the conditions used. A scheme of

reactions involved during carboxymethylation of starch is additionally

reported.

Similarly, preparation of carboxymethyl starch using

monochloroacetic acid and sodium hydroxide was investigated: under

different conditions. The carboxymethylation reaction was studied with

respect to the degree of substitution (D.S.) of the carboxymethyl starch

and the reaction efficiency (R.E.).of carboxymethylation. Variables

studied included concentration of reactants and liquor ratio. Of particular

interest were the results obtained at 100°C for 1 hr; carboxymethyl starch

78

of D.S. 0.436 with R.E. of ca. 79% could be achieved using solid

reactants/liquor ratio of 1: 1.

In the third study, research was designed to tailor materials of

specific utilization, namely sizing of cotton textiles by making use of

maize starch and rice starch. Hence both starches were subjected

independently to oxidation with potassium persulphate to obtain starches

with different molecular sizes. The original starches and the oxidized

starches were then partially carboxymethylated with monochloroacetic

acid under the catalytic influence of sodium hydroxide. In this way the

molecular, structure of starch, i.e., the molecular weight of the polymeric

backbone and substituents present thereon, could be controlled. Results

signify the following: (a) persulphate oxidation yields mixed type

"(acidic/reducing) of oxidized starch since the latter contains both

carbonyl and carboxyl groups; (b) the extent of oxidation relies on the

severity of the conditions used but it is certain that maize starch is more

susceptible towards oxidation than rice starch due mainly to structural

differences; (c) oxidation of starch prior to carboxymethylation enhances

the amenability of starch to carboxymethylation regardless of the kind of

starch used and; (d) when applied as sizing agents, carboxymethyl starches

derived from oxidized starches proved to be the best and the original

starch the least while oxidized starches stood in mid-way position.

The fourth study was concerned with import- substitute materials

with respect to CMS. To achieve this, carboxymethyl starch was prepared

by reacting starch with monochloroacetic acid in presence of sodium

hydroxide under a variety of conditions. Results obtained indicated that

the carboxyl content of CMS increases by increasing the material to liquor

ratio; NaOH concentration upto 4N, monochloroacetic acid concentration,

79

and time and temperature of the reaction. Based on these results,

conditions for preparation of CMS with comparable properties to the

imported CMS were established.

2.1.7. Starch Phosphate Monoesters

Starch phosphates were studied with a view of clarifying

dependence of their characteristics on factors affecting their synthesis.

Factors examined include concentrations of urea and phosphoric acid as

well as reaction time, temperature and pH of the reaction medium. On the

other hand, the properties embrace acidity, nitrogen content, viscosity,

swellability and solubility. Results indicated that incorporation of urea in

the reaction mixture (starch, phosphoric acid and sodium pyrophosphate)

variably alters the acidity but with the certainty that the value of the

acidity still far behind that obtained in absence of urea. On the other hand,

increasing the phosphoric acid concentration brings about a substantial

increment in both acidity and nitrogen content. Both acidity and nitrogen

content increase also by raising" the temperature from 110 to 150°C, and

by increasing the reaction time from 0.5 to 1.5h. Highest acidity, and

nitrogen content are obtained at the lowest pH; increasing the pH causes a

sharp decrement in the acidity and nitrogen content. Furthermore, the

results indicate that viscosity, swellability and solubility properties of the

so obtained modified starches rely largely on factors controlling the

condition of the treatment. The latter yields various esterified starches

such as starch phosphate, starch ammonium phosphate, starch carbamate

and crosslinked starch. The magnitude of each of these esters in the

reaction products was determined which, in turn, are the essential deciding

factors for the said properties of the esterified starch in question.

80

2.1.8. Reactive Starches

Starch and different hydrolyzed starch samples were subjected to

two independent reactions, namely, grafting with acrylamide using K2S2O8

as initiator and oxidation with K2S2O8 under the grafting condition but in

absence the monomer. Copper number and carboxylic group

measurements showed that both grafting and oxidation decrease

outstandingly the copper number of the hydrolyzed samples and diminish

completely the copper number of the hydrolyzed samples and those of the

original starch sample. On the contrary, grafting and oxidation cause

significant enhancement in the carboxylic content, indicating partial

conversion of the aldehydic to carboxylic groups under the oxidative

action of K2S2O8; but it is certain that higher amounts of carboxylic groups

are created in absence than in presence of acrylamide. Polymerization

studies showed that the hydrolyzed starch samples are much more

susceptible than the original starch sample toward grafting with

acrylamide only during the initial stages of the reaction. Preliminary

experiments describing introduction of methylol groups into the molecular

structure of .grafted sample and application of the methylolated product to

cotton fabric were also reported.

Similar studies have dealt with preparation of different hydrolyzed

carboxymethyl starches (CMS) and their copolymerization with

acrylamide as a base for production of starch-based reactive

carbohydrates. Furthermore, reactivity of starch, oxidized starches and

CMS could be induced in the molecular structure of starch through

introduction of 1) pendant double bonds via acrylamide- methylation, 2)

epoxy groups through grafting with glycidyl methacrylate, 3) methylol

groups via reacting of starch carbamate with formaldehyde.

81

2.1.9. Multimodification of starch for development of new materials

Herein, the idea is to tailor starch based polymeric materials with

new and improved characteristics by controlling the molecular size of

starch molecules and substituents present thereon. In combination with

this a precise determination of the nature and amount of the substituent

particularly whether they are in monomeric form or polymeric form or

both. With this in mind, numerous research and development efforts were

undertaken to synthesize and characterize innovative polymeric materials.

Structural modification to maize and rice starch molecules could be

accomplished through detailed studies including, inter alia, the following

investigations.

(1) Acid hydrolysis of starch to control the molecular size of starch.

(2) Oxidation of starch as another means for controlling the molecular

size of starch.

(3) Cyanoethylation of starch, hydrolyzed starches and oxidized starches.

(4) The combined effect of hydrolysis and cyanoethylation as well as

those of oxidation and cyanoethylation and grafting of starch with

vinyl monomers.

(5) Grafting of acrylamide onto carboxymethyl starch derived from

native, hydrolyzed and oxidized starches.

(6) Acetylation of native starch and hydrolyzed and oxidized starches

derived thereof then subjecting the so obtained acetylated starches to

grafting with methacrylic acid.

(7) Graft copolymerization of different vinyl monomers onto

carbamoylethyl starches derived from native, hydrolyzed and oxidized

starches using potassium persulphate as initiator.

82

(8) Polycarboxylic acid starch hybrids, polyacrylamide–carboxymethyl

starch hybrids and starch composites were synthesized, characterized

and found certain applications as shown in the foregoing sections.

(9) Cation-exchange starches containing carboxyl groups were

synthesized according to the following step: (a) starch was crosslinked

using epichlorohydrin , then (b) graft copolymerized with acrylonitrile

(AN) and (c) the poly (AN) – starch graft copolymer was subjected to

alkaline hydrolysis. The so synthesized copoloymer bears carboxyl

and cyanoethyl groups and was successfully used as cation –

exchanger.

(10) Another approach for preparation of cation – exchange starches

involved synthesis of poly(glycidyl methacrylate) GMA – starch graft

copolymers followed by their reaction with orthophosphoric acid

(H3PO4).

(11) Poly (GMA)–starch graft copolymer was reacted with

diethylenediamine under a variety of conditions to yield anion –

exchange starches. Anion – exchange starches were also synthesized

through the following steps : (a) cyanuric chloride was reacted with p-

nitroaniline to yield 2 [p-nitroanilino] 4,6- dichloro-s-triazine (b) the

latter compound was then reacted with starch and (c) reduction of

aromatic amine groups on the starch molecules was effected using

thiourea dioxide.

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2.2. Chitosan

Chitosan is the deacetylated derivative of chitin, which is the

second most abundant polysaccharide found on earth next to cellulose.

Chitin is the main component in the shells of crustaceans such as shrimps,

crab and lobster. It is also found in exoskeletons of insects and in the cell

wall of some fungi. Chitin has the same backbone as cellulose, but it has

an acetamide group on the C-2 position instead of hydroxyl group and its

molecular weight, purity and crystal morphology are dependent on its

source. Chitin is poly [β-(1-4)-2-acetamido-2-deoxy-D-glucopyranose.

Chitosan is the N-deacetylated derivative of chitin, and most of its

glycopyronose residues are 2-amino-2-deoxy-D-glucopyronose. Chitosan

is commonly prepared by deacetylating α-chitin using 40-50 % aqueous

alkali at 100 – 160 °C for few hours. The resulting chitosan has a degree

of deacetylation up to 0.95. The solubility in dilute aqueous acids is

obtained at an extent of deacetylation of 60%. In contrast with most of

naturally occurring polysaccharides such as cellulose, dextran and

carrageenan which are neutral or acidic in nature, chitin and chitosan are

examples of highly basic polysaccharides. Their unique properties include

polyoxysalt formation, ability to form films, chelate metal ions and optical

structural characteristics.

Hebeish’s work on chitosan had three-fold objective. The first was

to develop chitosan based products which lead ultimately to greater

utilization of chitosan particularly in chemical finishing of cotton textiles.

The second comprised synthesis, characterization and application in

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medical fields of water soluble chitosan-O- polyethylene glycol (PEG)

copolymer and chitosan – N- PEG copolymer. The third was pertaining to

the synthesis of selective chitosan adducts which would help to verifying

the structure – function relationship of these derivatives.

To achieve the goal facile procedures for controlling the molecular

mass of chitosan were established. Concurrently, it was equally important

to design versatile synthetic routes for introducing the desired substituents

in the molecular structure of the so obtained chitosan substrates. Chitosan

molecular mass control could be achieved through systematic

investigation of the conditions affecting hydrolysis and oxidation of

chitosan using HC1 and H2O2 respectively. When the chitosan samples of

certain molecular masses were available, the different substituents could

be introduced through subjecting these chitosan samples independently

under different conditions to carboxymethylation, carbamoylethylation,

acrylamidomethy-lation and grafting with acrylamide. Application of

these tailored chitosan based materials to cotton fabric -alone and in

admixture with other finishes - were also reported.

The work was further extended to develop innovative

multifinishing system for preparation of new cotton products that can be

used in the field of medical textiles. The innovation is based on synthesis

and characterization of water soluble chitosan-O-PEG as well as chitosan-

N-PEG graft copolymerization. With the former copolymer, the synthesis

was carried out by reacting N-phthaloyl chitosan with polyethylene glycol

monomethyl ether iodide (MPEGI) in the presence of silver oxide.

Phthaloyl chitosan was prepared by reacting phthalic anhydride with

chitosan to protect its amino groups during copolymerization. Chitosan-N-

PEG copolymer, on the other hand, was synthesized by reaction of

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chitosan with MPEG aldehyde. The latter was prepared by chemical

oxidation of MPEG with dimethyl sulphoxide (DMSO) and acetic

anhydride.

Thorough investigations into factors affecting the synthesis of the

aforementioned chitosan tailored products and copolymers along with

complete examination of their structure using sophisticated tools such as

IR, 1H-NMR, TGA, X-ray, and chemical analysis were undertaken. Major

outputs arrived at from these studies are summarized below.

2.2.1. Acid Hydrolysis

Chitosan was subjected to HCl hydrolysis using different HCl

concentrations for different lengths of time at different temperatures. The

hydrolysis caused a decrement in apparent viscosity and nitrogen content

and an increase in copper number and carboxyl content; the magnitude of

variation in these properties depends on severity of hydrolysis. However,

the increase in carboxyl groups was unexpectedly very high by virtue of

the reaction of HCl with chitosan forming chitosan hydrochloride.

Hydrolysis was characterized by an initial fast rate followed by slower rate

most probably due to the removal of the most accessible domains of

chitosan in the initial stages of hydrolysis. At any event, however, it is

certain that by HCl hydrolysis, chitosan substrates having different

apparent viscosity values and, therefore, different molecular masses could

be achieved.

2.2.2. Oxidation

Chitosan was oxidized with H2O2 using different concentrations,

durations, temperatures, and pH’s. Results obtained indicated that the

severity of oxidation reaction determine the magnitude of the decrease in

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apparent viscosity and nitrogen percent as well as the increase in copper

number and carboxyl content. It was also disclosed that the pH determines

the site (i.e. at C3 and C6 hydroxyls, the amine group at C2 and at the 1-4

glucosic linkage) on the chitosan molecule on which the H2O2 attack

occurs. It was further concluded that the oxidation of chitosan with H2O2

results in chitosan substrates having different apparent viscosities and,

therefore, different molecular masses.

2.2.3. Carboxymethylation

Carboxymethylation of chitosan was performed under different

conditions including concentrations of both monochloroacetic acid and

sodium hydroxide, temperature and duration of carboxymethylation as

well as material to liquor ratio. Hydrolyzed and oxidized chitosans were

also used as starting materials to shed insight on the role of the nature of

chitosan in the carboxymethylation reaction. The latter was carried out in

isopropanol/water mixture (70:30) to avoid dissolution of the resultant

carboxymethyl chitosan in the reaction medium. The carboxymethylation

reaction was followed through monitoring the degree of substitution (DS)

as a measure of the extent of the reaction, the nitrogen percent to trace

changes, if any, in the amine groups, and the apparent viscosity to clarify

the effect of carboxymethylation on the molecular mass of the chitosan

substrates. Results obtained revealed also that the DS follows the order:

original chitosan> hydrolyzed chitosan> oxidized chitosan.

Carboxymethylation was accompanied by decrement in both molecular

mass and nitrogen content of the chitosan substrates and the magnitude of

such decrement was governed by factors affecting the carboxymethylation

reaction. IR spectra of the three chitosan substrates before and after

carboxymethylation were described.

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2.2.4. Carbamoylethylation

Chitosan and hydrolyzed chitosan were reacted independently with

acrylamide under different conditions including concentration of both

acrylamide and sodium hydroxide and temperature and duration of the

etherification reaction. The essential reaction product was carbamoylethyl

chitosan. In combination with this was carboxyethyl chitosan which was

inevitably formed via alkaline hydrolysis of the carbamoylethyl chitosan

during the etherification reaction. It was further shown that acid

hydrolysis of chitosan prior to carbamoylethylation decreased the

susceptibility of chitosan to carbamoylethylation.

2.2.5. Acrylamidomethylation

Chitosan and hydrolyzed chitosan were reacted with N-

methylolacrylamide in presence of NH4C1 as a catalyst. The extent of the

reaction, expressed as meq. double bond /100g sample and percent

nitrogen, was found to depend on the concentration of both N-

methylolacrylamide and catalyst and reaction time and temperature. The

most appropriate conditions for acrylamidomethylation of chitosan and

hydrolyzed chitosan were found to be the same. Nevertheless, the extent

of the reaction for chitosan is much greater than hydrolyzed chitosan

indicating that pre-acid hydrolysis decreases the susceptibility of chitosan

to acrylamidomethylation significantly.

2.2.6. Graft Copolymerization of Acrylamide Onto Chitosan and

Hydrolyzed Chitosan

Graft copolymerization of acrylamide onto chitosan and

hydrolyzed chitosans using ceric ammonium nitrate as initiator was

studied-under a variety of conditions including concentration of both

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monomer and initiator, polymerization time and temperature and material

to liquor ratio. The extent of the graft copolymerization reaction,

expressed as graft yield percent and nitrogen percent, was found to rely on

these parameters. Indeed thorough investigation of the latter gave rise to

optimal conditions for graft copolymerization of acrylamide onto chitosan.

It was also found that hydrolyzed chitosan displayed much lower

graftability than the chitosan. Acid hydrolysis prior to grafting most

probably attacks the accessible domains of chitosan and, in so doing,

converts them to very short degraded chains which are removed during

washing. That is, the hydrolyzed chitosan lacks the most accessible

domains which are behind the greater susceptibility of the original

chitosan towards the grafting reaction.

2.2.7. Utilization of Tailored Chitosan Adducts as Chemical Finishes

Chitosan and chemically modified chitosans were applied, as

chemical finishes, to cotton fabric. They were used alone or together with

a conventional finishing agent, namely, Knittex FLC conc, (dihydroxy

ethylene urea/melamine formaldehyde derivatives). The modified

chitosans used were: hydrolyzed chitosan, oxidized chitosan,

carboxymethyl chitosan, carboxymethyl hydrolyzed chitosan,

carboxymethyl oxidized chitosan, carbamoylethyl

chitosan,carbamoylethyl hydrolyzed chitosan, acrylamidomethyl

hydrolyzed chitosan, chitosan grafted with poly (acrylamide) and

hydrolyzed chitosan grafted with poly (acrylamide).

Involvement of these chitosan based finishes in interaction with

cotton cellulose and /or Knittex FLC could be realized through monitoring

the nitrogen percent of the finished cotton fabric. It was disclosed that the

interactions of Knittex FLC - which most probably involves chemical

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reactions with cotton cellulose are much greater in absence than in

presence of chitosan based finishes. Similarly incorporation of Knittex

FLC, in the chitosan finishing bath detract from the ability of the chitosan

finish to interact with cotton cellulose.

In absence of Knittex FLC, chitosan based .finishes claimed

different but significant improvement in tensile strength of the fabric. This

is probably due to extra strength of chitosan film which, in turn, is

governed by molecular mass of the chitosan finish, nature and distribution

of substituents and mode of association of the finish with cotton fabric. In

presence of Knittex FLC, on the other hand, the tensile strength remained

almost intact in case of carboxymethyl hydrolyzed chitosan finish while

decreasing marginally in case of other chitosan based finishes but in no

case the tensile strength is lower in absence than in presence of the

chitosan based finish. Also no striking change occurred with respect to

elongation at break regardless of the finish used. Crease recovery was as

high as 2800 upon using carbamoylethyl hydrolyzed chitosan plus Knittex

FLC. The fabric so treated exhibit a tensile strength of 66 Kgf compared

with 58 Kgf for similarly treated fabric but in absence of the chitosan

finish. This, indeed, may be regarded as a breakthrough in easy care

finishing of cotton and deserve mill trials.

2.2.8. Synthesis and Application of Chitosan-O-PEG Graft

Copolymer

The synthesis was carried out by reacting N-phthaloyl chitosan

with polyethylene glycol monomethyl ether iodide (MPEGI) in the

presence of silver oxide. Phthaloyl chitosan was prepared by reacting

phthalic anhydride with chitosan to protect its amino groups during

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copolymerization.

Bleached and dyed cotton fabrics were treated under different

condition with chitosan-O-PEG using citric acid (crosslinking agent) and

sodium hypophosphite (SHP) as catalyst. Results conclude that using a

finishing formulation containing 1% (chitosan-O-PEG), 5% citric acid,

and 3% SHP for fabric treatment then curing the latter at 160 °C for 2

minutes constitutes the most appropriate condition for application of

chitosan-O-PEG to the cotton fabric.

2.2.9. Synthesis and Application of Chitosan-N-PEG Graft

Copolymer

Chitosan-N-PEG copolymer was synthesized by reaction of

chitosan with MPEG aldehyde. The latter, was prepared by chemical

oxidation of MPEG with dimethyl sulphoxide (DMSO) and acetic

anhydride.

Bleached and dyed cotton fabrics used for surgical gowns and

drapes manufacture were subjected to multifinishing treatments under

different conditions thereby optimization of the treatment could be

achieved as follows: the cotton fabric was padded to 100% wet pick up in

a treating bath containing 2% chitosan-N-PEG graft copolymer, 3% citric

acid as crosslinking agent and 1% SHP as a catalyst and cured at 160 °C

for 2 minutes.

Beside nitrogen analysis, sophisticated techniques, namely, FTIR,

H-NMR, TGA, X-ray, and SEM were used to characterize the chitosan-O-

PEG as well as chitosan-N-PEG graft copolymers before and after

application to cotton fabric.

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2.2.10. Performance Properties of Chitosan-O-PEG and Chitosan-N-

PEG Copolymers

Cotton fabrics treated as described above with chitosan-O-PEG

and chitosan-N-PEG copolymers exhibited following features.

(1) The treated fabric displayed more smoothness than untreated

fabrics; this was concluded by measuring roughness degree of the

surface which is inversely proportional stiffness degree.

(2) The treated fabrics fell short with respect to air permeability, pore

size and tensile strength as compared with the untreated fabrics.

(3) Bursting strength of the treated fabric was higher than untreated

fabric.

(4) The treated fabric displayed very high activity against E.coli and

S.aureaus.

(5) The treated fabric had durability for biological activity

(antibacterial activity) even after 20 laundering cycles.

By and large current results conclude that the use of chitosan-O-

PEG as well as chitosan-NPEG graft copolymers in presence of citric acid

(crosslinking) and SHP (catalyst) represent a novel route for production of

medical textiles especially those employed in surgical gowns and drapes.

2.3. Carboxymethyl Cellulose (CMC)Carboxymethyl cellulose (CMC) is one of the most important

cellulose derivatives with wide spread application in different disciplines.

CMC is the result of reacting cellulose with monochloroacetic acid in

presence of sodium hydroxide. It is soluble in water provided that its

carboxyl groups are in the sodium form. Based on the molecular weight,

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degree of substitution, degree of purity and the origin of cellulose used for

the CMC preparation, there are numerous type of CMC.

In Hebeish's work especial attention was given to preparation,

characterization and application of CMC. For preparation of CMC various

agricultural wastes, namely rice straw, sugar cane bagasse, cotton stalks

and wood manufacturing wastes, were subjected to pulping by one-and

two-stage alkali boiling. Cellulosic pulps obtained were

carboxymethylated in nonaqueous medium, under-identical conditions.

Degree of substitution (DS) and rheological properties of the CMC were

found to rely on the plant source and degree of purity of cellulose. Higher

degree of purity was accompanied by higher DS and lower apparent

viscosity. Examination of the rheograms of CMC solutions indicated non-

Newtonian thixotropic behavior, irrespective of the cellulosic starting

material used for the preparation of CMC.

Synthesis of CMC using raw cotton stalks (without pulping) as a

staring material was investigated and found feasible. It involved treatment

of grinded cotton stalks with monochloroacetic acid and sodium hydroxide

under certain conditions, isolation of the impurities via treatment with

water and filtration and precipitation of CMC from the filtrate. The yield

and DS of CMC was found to increase by increasing the etherifying

agent's concentration. The opposite held true for the apparent viscosity.

CMC solutions exhibited non-Newtonian pseudoplastic behavior.

Conditions appropriate for aqueous carboxymethylation were developed.

Cellulose pulp (250 g) was introduced in a shredder then 250 g NaoH in

300 ml water were added after shredding for 90 min. The reaction mixture

was then transferred from the shredder to stoppered glass container and

kept therein for 3 days, after which the reaction products were air dried

and grinded. The work was further extended to investigate the

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reproducibility of this aqueous carboxymethylation process using bagasse

and rice straw pulps. Results obtained indicated that the process is

practically reproducible, particularly when bagasse pulp was used.

Carboxymethylation of cellulose and hydrolyzed celluloses was

studied under identical conditions. The cellulose was obtained by

purification of cotton linters whereas hydrolyzed celluloses were obtained

by subjecting the purified linters to sulphuric acid at different

concentrations. The extent of hydrolysis was determined by copper

number while that of carboxymethylation by degree of substitution (D.S).

It was found that the extent of hydrolysis increased by increasing the acid

concentration in the range studied (0.75:4 N H2SO4). It was also found that

the extent of carboxymethylation increased as the extent of hydrolysis

increased, i.e. the hydrolyzed celluloses were more susceptible to

carboxymethylation than their original cellulose. All the CMC samples

were soluble in water.

Pastes of CMC samples derived from cellulose before and after

hydrolysis with 0.75 N H2SO4 displayed non-Newtonian pseudoplastic

behavior while those prepared after hydrolysis of cellulose with 1.5, 3, and

4N H2SO4 were characterized by non-Newtonian thixotropic behavior. The

apparent viscosity of these pastes decreased by increasing the extent of

hydrolysis as well as the rate of shear. Storing the pastes for one week had

practically no significant effect on rheological properties.

Jute waste fibers have been used as the starting material for the

preparation of carboxymethyl cellulose (CMC) and the dependence of the

properties of CMC on the purity of starting material as well as on the

concentration of etherifying agents has been investigated. It was observed

that the degree of substitution (DS) of CMC increases with the increase in

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the degree of purity of the starting cellulosic material; it follows the order:

α-Cellulose > holocellulose > dewaxcd and pectin-free jute > dewaxed

jute. DS also increases with increase in the concentration of etherifying

agents i.e. (mononochloroacetic acid and sodium hydroxide). On the other

hand, the solubility of CMC is governed not only by DS and the purity of

the starting material but also by the concentration of the etherifying agents

used. It was further reported that the theological properties of CMC are

characterized by non-Newtonian pseudoplastic behaviour with the

exception of very few samples which exhibit thixotropic behaviour. The

purity of the starting material as well as the DS of CMC determine the

theological properties. The measuring temperature as well as storing of the

CMC pastes before commencing the measurements have no significant

effect on the rheological properties. The apparent viscosity was found to

depend on the degree of purity of the cellulosic samples, DS and duration

of storing before measurement.

Cellulose, obtained from flax shaves was first oxidized to different

extents using sodium hypochlorite. This cellulose and the oxidized

cellulose derived thereof were then carboxymethylated under identical

conditions. While the extent of the oxidation was expressed as chlorine

consumption, the extent of carboxymethylation was (expressed as degree

of substitution (DS). Rheological properties of the carboxymethyl

cellulose and carboxymethyl oxidized cellulose were also measured before

and after their pastes were stored for three days. Results of these studies

indicate that pre-oxidation of cellulose reduces its susceptibility towards

carboxymethylation; the higher the extent of oxidation the lower the extent

of carboxymethylation.

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Pastes of CMC derived from the unoxidized cellulose and highly

oxidized celluloses exhibit non-Newtonian pseudoplastic behavior, while

those derived from mildly oxidized celluloses are characterized by non-

Newtonian thixotropic behavior. The results indicate further that the

apparent viscosity of these pastes decreases by increasing the extent of

oxidation as well as the rate of shear. Storing of these pastes for 3 days

increases the apparent viscosity, suggesting that they undergo coagulation

during storing.

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2.4.Nanotechnology for Development of Functional Finishes

Nanotechnology deals with small and small-sized materials of

dimensions in the range of few nanometers to less than 100 nanometers.

Today nanoscale materials represent real and widespread possibilities for

interesting fundamental science as well as useful technologies. The

interest in nanoparticles of these typical sizes is due to the fact that the

magnetic, optical and electronic behaviors of bulk materials can be

modified when their size approaches the nanometer scale.

Nanomaterials have a large surface area and, therefore, higher

chemical reactivity than the same mass of material produced in a larger

form. In some cases materials that are inert in their larger form are reactive

when produced in their nanoscale form. In short, nanotechnology aims to

tailor and design nanoscale structures with defined functionalities.

Nanoparticles are synthesized as per two manufacturing

techniques, namely, the top down approach and the bottom up approach.

The principle behind the top-down approach is the take of a bulk piece of

materials and then modify it into the wanted nanostructure and,

subsequent stabilization of the resulting nanosized particles by addition of

colloidal protecting agent. Cutting, grinding and etching are typical

fabrication techniques which have been developed to work on the

nanoscale. The sizes of the nanostructures which can be produced with top

down technique are between 10–100 nm. On the contrary, bottom-up or

self-assembly refers to construction of a structure atom-by-atom,

molecule-by-molecule or cluster-by-cluster. Colloidal dispersion used in

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the synthesis of nanoparticles is a good example of bottom-up approach.

The size of the nanostructures which can be obtained with the bottom-up

approach spans the full nanoscale. According to this bottom-up approach,

metallic nanoparticles can be obtained by two methods, viz. the physical

method, which is based on mechanic subdivision of metallic aggregation

and, chemical method which is based on nucleation and growth of metallic

atoms. Of the several methods described in the literatures for the synthesis

of metallic nanoparticles by the bottom-up approach, the chemical

reduction method seems to be the most commonly used.

There are a series of chemical reductants that have been used for

preparation of noble metal nanoparticles which include, inter alia,

hydrogen gas, hydrazine, sodium borohydride, ethylene glycol,

formaldehyde, sodium citrate, glucose and dextrin. Without stabilizer

metal nanoparticles which are formed by reduction tend to form

aggregation so the stabilizer is necessary to prevent metal nanoparticles

aggregation. A variety of stabilizers, e.g., donor ligands, polymers and

surfactants are used to control the growth of the primarily formed

nanoparticles and to prevent them from agglomeration. Polymers such as

polyacrylamide, chitosan, heparin and starch are reported to act as both

reducing and stabilizing agent.

Nanotechnology has real commercial potential for the textile

industry. Reasons for this are that the conventional methods used to impart

different properties to fabrics often do not lead to permanent effects, and

will lose their functions after laundering or weaving. In combination with

this are the low chemical usage, low energy costs and less change in

physical and mechanical properties achieved using nanotechnology in

textile and apparel. It is as well to note that the properties imparted to

textiles using nanotechnology include water repellant, soil resistance,

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wrinkle resistance, anti-bacteria, anti-static, UV-protection, flame

retardant, self-cleaning, improvement of dyeability, etc.

With the above in mind, Hebeish’s work was targeted towards

developments of nanotechnology in textiles. The target had two-fold

focus: (1) Upgrading existing functions and performance of textile through

intensive investigations into synthesis, characterization and application of

metal nanoparticles as new textile finishes using the bottom-up approach.

Similarly, but employing the top-down approach, a great deal of research

and practice were devoted to synthesis and characterization of nanosized

pigment as nanocolorant for improved textile printing. (2) Developing

smart and intelligent textile with unprecedented functions through

preparation of innovative multifunctional auxiliaries with salient

properties. Given below are summarizes of and conclusions arrived at

from some of these studies .

2.4.1. Synthesis and Characterization of Silver Nanoparticles

Despite the availability of hydroxypropyl starch (HPS) as

commercial water soluble starch derivatives, synthesis of HPS through

hydroxypropylation of maize starch was systematically studied in our

work. The synthesis was carried out under different conditions including

concentrations of alkali, propylene oxide, DS of HPS and silver nitrate,

pH, temperature and duration of the hydroxypropylation reaction. This

was done with a view to have tailored HPS products which can better

serve as a reducing and stabilizing agent during the preparation of silver

nanoparticles.

Factors affecting the reduction efficiency and stability as well as

shape and size of the formed silver nanoparticles were studied. The

formation of silver nanoparticles was monitored via color and UV- visible

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spectral analysis. The resultant silver nanoparticles colloidal solutions

were evaluated by making use of Transmission Electron Microscopy

(TEM) to determine size and size distribution.

Based on the results, optimum conditions for preparation of silver

nanoparticles colloids with excellent size and size distribution ranged from

6-8 nm were established. Silver nanoparticles colloidal solutions

synthesized using these optimum conditions are stable and remains

without aggregation for more than six months.

The output of this research stimulated preparation of well

stabilized silver nanoparticles solution of a concentration of 1620 ppm

with a diameter of 9-18 nm. Silver nanoparticles solution with such unique

characteristics is unequivocally feasible for industrial applications.

Solution containing 1620 ppm silver nanoparticles was diluted to

50 ppm and 100 ppm. The diluted solutions were applied to cotton fabrics

in presence and absence of a binder to impart antibacterial properties to

the fabrics. Solution containing 50 ppm silver nanoparticles induce

excellent and durable bactericidal activity to cotton fabrics provided that

1% binder is added to this solution. Particularly noteable is the successful

mill trials which resulted in 5 tons of cotton fabric that acquired permanent

antibacterial properties.

2.4.2. Bio-synthesis of Silver Nanoparticles

Development of reliable and eco-friendly process for synthesis of

metallic nanoparticles is an important step in the field of application of

nanotechnology. One of the options to achieve this objective is to use

natural processes such as biological systems. Our work was undertaken

with a view to produce silver nanoparticles (AgNPs) using fungi and

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harnessing AgNPs in antimicrobial finishing of cotton based textile. That

is, the work addresses bio-synthesis of AgNPs using fungi secreted

enzymes and proteins and, the use of thus obtained AgNPs in cotton

finishing.

In this work four different fungal strains were screened for their

ability to produce extracellular silver nanoparticles using their medium

filtrates and biomass filtrates. Considering the UV-vis intensity,

wavelength, TEM and particle size distribution, the most promising results

have been obtained using the biomass filtrate of the fungus Fusarium

solani (sample removed after 72h incubation). Therefore, the fungus F.

solani could be advocated as candidate for use in preparation of silver

nanoparticles. Further studies were carried out using the most promising

fungus F. solani in order to evaluate the effect of other factors on

production of AgNPs with suitable size and concentration for industrial

application. Variables studied include biomass concentration, pH of

reaction medium, reuse of biomass, AgNO3 concentration and ratio of

AgNO3 concentration to biomass filtrate concentration.

Having established the most appropriate conditions for the use of

nanobiotechnology in preparation of AgNPs as described above, the

output of this calls for preparation of well-stabilized silver nanoparticles

solution with concentration of 2160 ppm and a mean diameter range of 8-

15 nm. Silver nanoparticles solutions with such unique characteristics are

unequivocally feasible for industrial applications.

At any event, however, the so obtained silver nanoparticles as

finishing agent were applied to cotton based textiles and finally evaluation

of antimicrobial properties of the treated fabrics was made. The results

provided some insight as to which parameters may have impact on

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reduction of silver ions to silver. Antimicrobial activity was observed

when silver nanoparticles were incorporated in cotton fabrics. The work

demonstrates the possible use of biologically synthesized silver

nanoparticles and its incorporation in fabrics to impart sterilization.

2.4.3. Ultra-Fine Characteristics of Starch Nanoparticles

Starch nanoparticles (St-NPs) were synthesized using native maize

starch (NS) with and without surfactant. The synthesis was carried out as

per the solvent displacement method after being modified. Modification

involved the use of aqueous alkaline medium as the solvent and ethanol as

the organic nonsolvent. This was done with a view to assure easier and

more reproducible St-NPs preparation without consuming more solvent.

The modified method for preparation of St-NPs was evaluated;

investigation into factors affecting it were made in order to discover the

optimum conditions for such preparation. Factors studied included

concentration of starch as well as concentration of surface-active agent,

namely, Tween 80, which was added before precipitation. World-class

facilities was used for evaluation of the obtained St-NPs such as

transmission electron microscopy, particle size analyzer (PS),

polydispersity index (PdI), Fourier transform infrared (FT-IR)

spectroscopy and, X-ray diffraction (XRD). The results indicate that there

are no changes of the chemical structure of St-NPs as indicated by FT-IR

and the crystallinity pattern is converted from A-type to amorphous (V-

type). The data obtained indicate also that the smallest, highly distributed

particles of St-NPs size with good PdI are obtained in the presence of 20

% Tween 80 (based on weight of NS).

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2.4.4.Concurrent Formation of Nanosized Particles of Both Starch

and Silver with Emphasis on Their Nanostructural Features

Green innovative strategy was developed to accomplish silver

nanoparticles through formation of starch-silver nanoparticles (St-AgNPs)

in the powder form. Thus, St-AgNPs were synthesized through concurrent

formation of the nanosized particles of both starch and silver. The alkali

dissolved starch acts as reducing agent for silver ions and as stabilizing

agent for the formed AgNPs. The chemical reduction process occurred in

water bath under high-speed homogenizer. After completion of the

reaction, the colloidal solution of AgNPs coated with alkali dissolved

starch was cooled and precipitated using ethanol. The powder precipitate

was collected by centrifugation, then washed, and dried; St-AgNPs

powder was characterized using state-of-the-art facilities including UV-vis

spectroscopy, Transmission Electron Microscopy (TEM), particle size

analyzer (PS), Polydispersity index (PdI), Zeta potential (ZP), XRD, FT-

IR, EDX, and TGA. TEM and XRD indicate that the average size of pure

AgNPs does not exceed 20nm with spherical shape and high concentration

of AgNPs (30000 ppm).The results obtained from TGA indicates that the

higher thermal stability of starch coated AgNPs than that of starch

nanoparticles alone. In addition the data obtained from EDX which reveal

the presence of AgNPs and the data obtained from particle size analyzer

and zeta potential determination indicate good uniformity and high

stability of St-AgNPs).

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2.4.5. More Insight on Characterization of Nano-sized Particles of

Silver Powder and Their Evaluation for Different Medical

Applications

Powdered silver nanoparticles and highly concentrated solutions of

AgNPs using alkali dissolved starch which act the dual role: as reduction

for Ag+ and stabilizer for AgNPs formed thereof. AgNPs colloidal

solution having different concentrations (60, 125 and 250 ppm) was

prepared from stock solution having high concentration of AgNPs (30000

ppm). The AgNPs colloidal solutions were used for treatment of cotton

fabrics as per the pad-dry-cure technique. Cotton fabrics loaded with these

three different concentrations of AgNPs colloidal solutions were evaluated

for various medical applications, namely, antimicrobial, wound healing,

anti-inflammatory as well as toxicity. The antimicrobial efficacy of

dressing containing 250 ppm AgNPs was more effective against

microorganisms including bacteria and fungi than that of dressing

containing 60 and 125 ppm as indicated by the inhibition zone. The wound

healing of dressing containing the highest content of AgNPs (250 ppm)

acquire the greatest potent healing, which is nearly similar to the

controlled cream (Dermazin). It was also found that wound healing is

intimately linked to inflammation in normal circumstances as various

inflammatory mediators are secreted to modulate the healing process

within wounds. The obedema percent of 250 ppm AgNPs was nearly the

same as appeared in the case of standard drug (indomethacin). The MIC)

for the produced AgNPs on subsequent experiments was ≤ 10 μg/mL. The

antimicrobial wound dressing of AgNPs treated cotton fabrics is proposed

to have promising potential in smart textiles, medical purposes as well as

in various biological fields.

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2.4.6. Development of New system based on Crosslinked Starch

Nanoparticles for Drug (diclofenac sodium) Delivery

Herein we present a manifold study aiming at development of a

promising and controlled release transdermal delivery system to enhance

the therapeutic efficiency of diclofenac sodium (DS). The system is based

on crosslinked starch nanoparticles which were synthesized using native

starch (NS) and oxidized starches derived thereof. The oxidized starches

comprised low, medium and highly oxidized starches that could be

abbreviated as LOS, MOS and HOS, respectively. Crosslinking was

effected by reacting starch with sodium tripolyphosphate (TPP) at

different concentrations. Crosslinked starch nanoparticles loaded with DS

were synthesized according to the nanoprecipitation method using

different DS concentrations.

A two-level factorial design were practiced for prediction of

optimized formulation for DS loaded crosslinked starch nanoparticles. At

this end, the optimized formulation was applied to LOS, MOS and HOS.

The formulated nanospheres were assessed systematically by monitoring

drug loading, enacapsulation efficiency, transmission electron microscopy

(TEM), particle size analyser, polydispersity index (PDI) and zeta

potential for shape and surface characteristics and in vitro release studies.

Physicochemical characterization and analysis of the formulated

nanosphares were also exercised using Fourier transform infrared

spectroscopy (FT-IR), X-ray diffraction (XRD) and differential scanning

caliorimetry (DSC) to determine the physical nature (crystallinity),

thermal behaviour and possible occurrence of interaction between DS and

the crosslinked starch nanoparticles. Interaction of crosslinked starch

nanoparticles with DS causes profound changes in the crystalline structure

of DS; DS is completely converted to amorphous structure. Application of

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experimental In vivo targeting efficiency of the optimum formula of NS,

LOS, MOS and HOS crooslinked with TPP and loaded with DS were

examined histopathologically in skin irritation of healthy rats.

Obviously, then, the essential target of the work could be

successfully achieved. Application of experimental design allowed the

optimization of different factors to yield spherical nanoparticles with small

particle size, low polydispersity indix and high entrapment efficiency and

sustained release for DS drug. The histophathological studies on rat skin

advocate the use of the designed transdermal DS loaded crosslinked starch

and medium oxidized starch nanoparticles formulations as they are safe

and non-irritant to rat skin. This would render the designed formulation a

safe, highly effective, controlled and convenient mean of therapy with the

non-steroidal anti-inflammatory drug (NSAIDs).

2.4.7. Modulation of the Nanostructural Characteristics of Cellulose

Nanowhiskers

Modulation of nanostructural characteristics of cellulose

nanowhiskers (CNW) was achieved via synthesis of the latter from native

cotton cellulose using three different sulfuric acid concentrations. Of

these, 60% (w/w) sulfuric acid was found the most adequate. When this

particular concentration was used at 60 oC for 60 min. to extract CNW

from the native cotton cellulose, the resultant CNW display salient

features. Specifically, thus obtained CNW are characterized by 57% yield

(based on dry weight of cellulose), size diameter of 10 – 25 nm and size

length of 80 – 200 nm, degree of crystallinity of 90% while maintaining

the crystalline structure of cellulose I, similar functionality and typical

profile like the native cotton cellulose but with significantly different

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thermal behavior. Indeed, these characteristics advocate the CNW in

question as a good candidate in the area of reinforcement and other

applications.

2.4.8. Development of Cellulose Nanowhiskers – Polyacrylamide

Copolymer as Highly Functional Precursor in Synthesis of

Nanometal Particles

The chief objective of current studies was to innovate new

precursor for use in different applications especially in green synthesis of

nanometal particles. The innovation involved creation of copolymer

prepared through graft polymerization of cellulose nanowhiskers (CNW)

with acrylamide (AAm) under different conditions for the sake of

copolymer optimization. Thus prepared CNW – PAAm copolymers were

fully characterized and the most promising and appealing copolymer was

used as a novel precursor in green synthesis of silver and copper

nanoparticles. The experimental procedures adopted were as follows.

Egyptian cotton fibers in the sliver form were purified by subjecting them

to two successive treatments, namely alkali – and perborate treatments.

CNW was prepared from the purified cotton as per the acid (H2SO4)

hydrolysis method. In a next step, CNW were copolymerized with AAm

under different conditions and the CNW – PAAm copolymers obtained

were fully characterized using world – class tools, then, the most highly

functional copolymer was selected and used through detailed

investigations as precursor in green synthesis of Ag and Cu nanoparticles.

Results of the above studies reveal that the weight of CNW is

about 57% of the initial dry weigh of cotton. Copolymers with the highest

graft yield is obtained using AAm concentration of 0.07 mole/l. The

crystal nature of CNW as cellulose I remains unaltered after

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copolymerization but the crystallinity decreases, being dependent upon the

magnitude of grafting. Copolymer with high graft content exhibits lower

crystallinity. TEM micrographs illustrate the nanosize and size

distribution of the polydispersed copolymer but only DLS could determine

these properties with respect to AAm graft. TGA indicates that the

copolymer is much more thermally stable than CNW. The CNW – PAAm

copolymer was used successfully as highly functional, effective and

adequate precursor in green synthesis of silver and copper nanoparticles as

shown by UV-vis spectral analysis and TEM micrographs. A salient

feature is that a multi-branched shape and hyperbranched shape like – tree

involving AgNPs and PAAm graft of the copolymer are formed. CuNPs as

a candidate was successfully harnessed in conductive fabric application

through homogeneous deposition for CuNPs onto the cotton fabric after

loading.

2.4.9. Synthesis, Characterization and Application of Nanosized

Carbamoylethyl Cellulose Whiskers

The main target of current studies was to develop a new-innovation

strategy for synthesis of nanosized carbamoylethyl cellulose (NCEC) and

application of the latter in preparation of silver and copper nanoparticles.

The innovation is based on conversion of cellulose nanowhiskers (CNW)

to effective precursors through their carbamoylethylation. Thus NCEC

with degree of substitution (DS) of 0.8 has been prepared successfully via

semi dry etherification of CNW with acrylamide. FTIR spectra of the

NCEC exhibit the existence of new peaks, which confirmed the

introduction of CH2CH2CONH2 moieties in the molecular structure of

CNW brought about by the carbamoylethylation. XRD patterns and TEM

analysis demonstrated that the newly synthesized NCEC has lost its

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crystalline structure, despite their small size which attained the value of

37.84 nm with a majority of 80.6% as depicted from DLS analysis. NCEC

displayed also higher thermal stability than CNW. In short,

carbamoylethylation of CNW resulted in the accomplishment of new

product with salient properties. Particularly notable is the amenability of

NCEC to dissolve in hydrophilic solvent.

Being rich in terminal reducing groups in addition to the amide

groups, NCEC would certainly function as a strong reducing agent. In

combination with this is the polymeric nature of NCEC. Such

characteristics would advocate NCEC to serve as stabilizing and reducing

agent in the synthesis of metallic nanoparticles when e.g. AgNPs were

prepared as per the chemical reduction method in the presence of NCEC.

AgNPs acquired spherical shape even upon using higher concentration of

AgNO3 to produce colloidal solution containing AgNPs at concentration

of 2000ppm. The tendency of AgNPs at this latter concentration towards

aggregation is unlimited. On the other hand, the stability of CuNPs

colloidal solution was limited indicating lower capping potency of NCEC

with respect to CuNPs vis-à-vis AgNPs. As a consequence, AgNPs are the

most highly preferable nanosized particles for application in the realm of

smart conductive textile.

2.4.10. Processing and Properties of Novel Hybrid Nanogels

A hydrogel is a network of hydrophilic polymers that can swell in

water and hold large amount of water ranging from 10% to thousands of

times of the weight of xerogels while maintaining the structure. A three –

dimensional network is formed by crosslinking polymer chains.

Crosslinking can be provided by covalent bonds, hydrogen bonding, van

der waals interactions and/or physical entanglement. Hydrogels are very

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sensitive to environmental stimulus, which is manifested by a sharp phase

transition; a feature which is important for their application particularly in

pharmaceutical field. Indeed manipulation of hydrogel structure has

produced stimuli–sensitive hydrogels, which change their swelling degree

or undergo phase transition in response to minimal changes in

environmental conditions. Current work addresses the synthesis and

characterization of novel hybrid nanogels which are temperature

responsive. The synthesis involves preparation of cellulose nanowhiskers

(CNW) followed by inserting them in a polymerization system containing

N-isopropyl acrylamide (NIPAm) monomer and bismethylene amine

(BMA) crosslinker, potassium persulphate (KPS), initiator and water.

In this way CNW – PNIPAm hybrid nanogel is formed.

Modulation of the properties of this hydrogel could be made through

varying the factors affecting the structure of the hydrogel. Factors studied

encompass CNW% : NIPAm% ratio, concentration of both the crosslinker

and initiator as well as temperature – responsive for swelling behavior of

the hybrid nanogels. Conclusions arrived at from these studies are

summarized below.

i. CNW produced through sulfuric acid hydrolysis are well stabilized

polydispersed nanoparticles with size diameter ranging from 10-25nm

with a length range of 80-200nm.

ii. Incorporation of CNW into PNIPAm enhances the values of

Equilibrium swelling ratio (ESR) provided that the concentration of

CNW are within 10% using CNW : PNIPAm ratio 10:90 and 25%

using CNW : PNIPAm ratio of 25:75.

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iii. ESR of the formed hydrogels displays a very fast increase by

increasing the crosslinker (BMA) concentration from 1% to 3% then

decreases upon further increase in the concentration up to 6%.

iv. ESR exhibits high values within a very narrow range (1% - 1.5%) of

initiator (KPS) concentration then decreases thereafter.

v. The hydrogels exhibit good swelling behavior and display

hydrophilicity at temperature lower than 320C; above this temperature

the hydrogels become hydrophobic (as evidenced by the low value of

ESR) similar to least critical solvent temperature (LCST) of pure

PNIPAm. This means that the CNW–PNIPAm nanocomposite

hydrogel is very sensitive to temperature stimuli.

vi. FTIR and TGA were employed to verify the ultrafine structure of the

hydrogels under investigation.

vii. Morphology of CNW–PNIPAm hybrid nanogels as revealed by SEM

indicates: (a) the morphology exhibits a homogeneous, well –

proportional network structure and dense architecture without apparent

microscopic phase separation of the polymeric constituents, (b) the

hydrogel are covered by highly connected irregular pores with size

ranging from 0.5 – 1.2 µm, (c) the pores are spherical in shape with

circular interactions and, (d) the distribution of the pores over the

hydrogel appears more even and homogeneous throughout the surface

area.

2.4.11. Carboxymethyl Cellulose (CMC) Hydrogel Containing

Metallic Nanoparticles

Here, our research was targeted to accomplish superabsorbent

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hydrogel through reacting (crosslinking) CMC with epichlorohydrin.

Characteristics of the formed hydrogel were found to rely on concentration

of epichlorohydrin, curing time and curing temperature. Characterization of

the hydrogel was made using IR analysis and SEM. In situ formation of

nanoparticles during the formation of the hydrogel was also performed. The

hydrogel containing AgNPs was characterized using UV-vis spectroscopy,

spectrophotometer, SEM, EDX, TEM and antibacterial test. Indeed current

research is by all meens considered as a novel endeavor because it brings

into focus a new route for synthesizing hydrogel containing AgNPs which

promote CMC hydrogel for antibacterial and medical applications.

In another series of experiments, epichlorohydrin was replaced by

other crosslinkers to convert the water soluble CMC to hydrogel. Thus three

polycarboxylic acids, namely, maleic acid, succinic and citric acid were

independently used to introduce crosslinks in the molecular structure of

CMC. Experimentally, CMC was dissolved in aqueous solution with

continuous mechanical stirring until a homogenous viscous mixture was

obtained. The polycarboxylic acid was then added dropwise to the CMC

solution while continuously stirring whereby a paste was formed. This paste

was transferred to Petri dish for drying and curing. The experimental was

extended to conduct one-step process for preparation of CMC hydrogels in

combination with ZnO nanoparticle. The hydrogels were prepared using

different concentrations of each of the said acids at different curing

temperature and time and the onset of this on the swelling ratio of the

hydrogel was investigated. Characterization of the hydrogel was performed

using FTIR, SEM and EDX analysis. Hydrogels containing ZnO

nanoparticles display significant antibacterial activity when G +ve and G –

ve bacteria were employed in the bioassay test.

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2.4.12. Cyclodextrin Copolymers–Nanosized Composites for

Production of Smart Cotton Textiles

Cyclodextrin (CD) is obtained from the enzymatic

degradation of starch; an enzyme named: cyclodextrin glucanotransferase

interacts with soluble starch by cyclization to produce cyclodextrins. The

properties of cyclodextrin are directly derived from its typical ring structure

made of six, seven or eight glycopyranose units, corresponding,

respectively, to α -, β and γ cyclodextrin. Cyclodextrin acquires a conical

(torus)-shaped structure. The exterior of this conical shaped oligmer is

hydrophilic whereas the interior constitutes a hydrophobic cavity whose

dimensions are especially well adapted not only to aliphatic but also to an

even greater extent aromatic parts of molecules to form supramolecules,

also called inclusion compounds.

A part from these naturally occurring cyclodextrins, many

cyclodextrin derivatives have been synthesized. These derivatives are

usually produced by amination, esterification, etherification, or grafting of

cyclodextrin through its primary and secondary hydroxyl groups. The most

notable feature of cyclodextrins is their ability to form solid inclusion

complexes (host–guest complexes) with a very wide range of solid, liquid

and gaseous compounds by a molecular complexation. In these complexes,

a guest molecule is held within the cavity of cyclodextrin host molecule.

Complex formation is a dimensional fit between host cavity and

guest molecule. The lipophilic cavity of cyclodextrin molecules provides a

microenvironment into which appropriately sized nonpolar moieties can

enter to form inclusion complexes. No covelant bonds are broken or formed

during formation of the inclusion complex.

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Hebeish's research studies given in this section were undertaken

with a view to synthesize multifunctional finishing agents based on

cyclodextrin, followed by utilization of these agents in production of

multifunctionalized cotton textile, or what is called smart cotton products.

The latter acquire, inter alia, antibacterial activity, ease of care

characteristics and slow release of fragrance. To achieve the goal, a green

strategy based on harnessing nanotechnology was devised, being dependent

on research and developmental work that were designed to include three

approaches. The first approach involved detailed systematic studies

pertaining to synthesis of β- cyclodextrin – polyacrylic acid graft

copolymers (βCD–g-PAA) and their utilization as green precursor in the

synthesis of silver nanoparticles (AgNPs). In the second approach, novel

finishing agents for cotton textiles, namely, monochlorotriazinyl – β-

cyclodextrin grafted to different extents with polyacrylic acid (MCT-βCD-

PAA) were synthesized. On the other hand, the third approach comprised

the following successive sequence of treatments: i) treatment of cotton with

3- chloro -2- hydroxypropyl trimethyl ammonium chloride to synthesize

cationized cotton, ii) treatment of cationized cotton with MCT-βCD-g-

PAA), iii) thus obtained modified cotton was treated with nanosilver

colloids followed by, iv) treatment with the perfume. These three

approaches are, to some extent, elaborated as given under.

2.4.12.1. β-Cyclodextrin-Poly(acrylic acid) Graft Copolymer as

Green Precursor for Synthesis of Silver Nanoparticles

In this context beta cyclodextrin grafted with polyacrylic acid (βCD-

g-PAA) was newly synthesized and used to perform dual actions, viz

reducing agent and stabilizing agent during the preparation of silver

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nanoparticles. Fixation of this copolymer on cotton fabric was affected

using epichlorohydrin.

The AgNPs were monitored via color and UV- visible spectral

analysis. Meanwhile thus obtained silver nanoparticles colloids were

evaluated by making use of Transmission Electron Microscopy (TEM) to

determine size and size distribution of these nanoparticles. Such monitoring

and evaluation revealed that reduction of Ag+ to Ag°, coalesces of the latter

to form cluster and the size of this cluster depends on the type and

concentration of alkali, the graft yield of the copolymer, the concentrations

of both silver nitrate and copolymer and the means of heating: thermal,

ultrasonic or microwave. Thermal method is by far more effective than the

microwave and ultrasonic methods. Silver nitrate nanoparticles with size of

10-15nm and spherical shape are obtained irrespective of the method used

but with the certainty that the uniformity of the silver nanoparticles obtained

by the thermal and microwave methods is more than that of the ultrasonic

method.

Application of AgNPs colloidal solution(s) was carried out as per

two techniques. In one technique the cotton fabric was first treated with the

colloidal solution then treated with the finishing formulation solution

containing the copolymer along with epichlorohydrin in alkaline medium.

In the second technique, fabric was treated with the finishing formulation

followed by the nanosilver colloidal solution. Surface characteristic of the

treated fabrics vis-à-vis the untreated fabric as well as their antibacterial

activity before and after several washing were thoroughly investigated. The

innovative formulation in question results in fabrics with excellent and

durable bactericidal properties.

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2.4.12.2.Reactive Preformed Polymers

In this context, novel finishing agents for cotton textiles, namely,

monochlorotriazinyl-β-cyclodextrin grafted to different extents with

polyacrylic acid (MCT-βCD-g-PAA) were synthesized. They are, indeed,

reactive preformed polymers which can be grafted to cotton cellulose

through a substitution mechanism. For convenience these novel finishes will

be referred to as the copolymer. Synthesis of the copolymer involved

copolymerization of reactive cyclodextrin (MCT-βCD) with acrylic acid

(AA) using potassium persulphate as initiator. Factors affecting

copolymerization, expressed as graft yield and carboxyl content, were

studied and appropriate conditions for synthesis of the copolymers are

established. The copolymer was characterized by FTIR Spectroscopy and

fabrics were treated with perfume, specifically, jasmine oil, to achieve

ultimately multifunctionalized cotton fabrics. The latter acquired interalia,

ease of care characteristics and perfume release. The residual / perfume and

its smell lasted for at least 5 weeks. Images of SEM microscopy of the

fabrics before and after multifinishing were also presented.

2.4.12.3. Cotton Cellulose Bearing Cationized Groups, Triazinyl -β-

Cyclodextrin Moieties and PAA Moieties for Incorporation of

AgNPs and Perfume

In this regard, multifunctionalization of cotton textile was effected

through the following successive sequences of treatments: 1) treatment

involving reaction of cotton cellulose with 3-Chloro-2-hydroxypropyl

trimethyl ammonium chloride (known commercially as Quat-188) to

synthesize cationized cotton, 2) treatment of this cationized cotton with

reactive cyclodextrin graft copolymerized with polyacrylic acid (MCT-β-

CD-g-PAA) to obtain cotton bearing cationic and cyclodextrin moieties, 3)

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treatment of the so modified cotton with nanosilver colloids followed by 4)

treatment with the perfume. The first three treatments were carried out using

different concentrations of Quat-188, reactive copolymer and silver

nanoparticles. We have made use of the cyclodextrin moieties as a "host" to

accommodate perfume molecules "guest" through inclusion of the perfume

in the cyclodextrin cavities. FTIR, antibacterial activity test and crease

recovery were used to characterize and evaluate the said modified cotton

before and after treatment with nanosilver colloids.

Results obtained conclude that : (a) silver nanoparticles adsorption

was much greater on cotton bearing both cationic and cyclodextrin moieties

than on cationized cotton, (b) antibacterial activity (gram +ve and gram –

ve) was realized and found to be dependent on the content of AgNPs in the

cotton sample, (c) cationization was accompanied by improvement in crease

recovery and further improvement was observed by further modification of

cationized cotton using reactive cyclodextrin copolymer and , (d) inclusion

of perfume in the cyclodextrin cavities allowed the fabric to release pleasant

smell for 7 weeks.

2.4.12.4.In Situ Formation of AgNPs

In addition to the three approaches described above, the studies were

extended to include in situ formation of nano-sized silver particles which

was performed as per two approaches. In the first approach cationized

cotton fabric was treated with silver nitrate followed by reduction of the

latter by βCD-g-PAA or MCT-βCD-g-PAA. The second approach involved

treatment of cotton fabric reacted (grafted) with MCT-βCD-g-PAA with

silver nitrate followed by reduction of the latter with either βCD-g-PAA or

sodium borohydride. In both approaches reduction of the silver ions gave

rise to silver nanoparticles formed in situ.

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Conclusions arrived at from these studies are: (1) MCT-βCD-g-PAA

failed to induce reduction of silver ions to silver nanoparticles (2) βCD-g-

PAA, on the other hand, succeeded to induce such reduction and prove to be

better than a conventional reducing agent such as sodium borohydride, (3)

in situ formation of silver nanoparticles were uniformly distributed within

the grafted copolymer network of the fabric and, therefore the latter

exhibited stronger antibacterial activity, (4) the in situ formation of the

silver nanopartieles in the fabric was proved by XRD whereas SEM image

verified surface characteristics and the uniform distribution of the nanoscale

silver particles, and (5) the treatments involved in the in situ formation of

nanosilver particles brought about improvement in fiber-fabric resilience.

2.4.13. Development of Silver-Containing Nanocellulosics for Effective

Water Disinfection

Electrospun cellulose nanofibers and cellulose-graft-

polyacrylonitrile (Cell-g-PAN) copolymer nanofibers containing silver

nanoparticles (AgNPs) were synthesized for effective water disinfection.

Surface morphology, AgNPs content, physical distribution of AgNPs, levels

of silver leaching from the fibers in water and antimicrobial efficacy were

studied. Scanning electron microscope images revealed that AgNPs in

cellulose nanofibers were more evenly dispersed than in Cell-g-PAN

copolymer nanofibers, but with the certainty that Cell-g-PAN copolymer

nanofibers had higher AgNPs content. This was confirmed by energy

dispersive X-ray analysis and atomic absorption analysis. Both cellulose

nanofibers and Cell-g-PAN copolymer nanofibers containing AgNPs had

excellent antimicrobial activity against Escherichia coli,Salmonella typhi,

and Staphylococcus atoms, with cellulose-nAg nanofibers killing between

91 and 99 % of bacteria in a contaminated water sample and Cell-g-PAN-

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nAg copolymer nanofibers killed 100 %. Neither Cell-g-PAN copolymer

nanofibers nor cellulose nanofibers leached silver into water.

2.4.14. Nanotechnology in Textile with Contribution to Pigment

Printing

Our research presented here is the subject of a monograph carrying

the above tittle. Apart from an overview pertaining to major realms of

nanotechnology in textile processing, our original work addresses

technological innovations based on advanced and frontier sciences for

development of textile printing. Special emphasis is placed on

nanotechnology for the progress of pigment printing. Thus, synthesis,

characterization and application of ultrafine pigment particles from the base

of such development and progress. Synthesis involves miniaturization of

pigment nanoparticles under a variety of conditions. Ultrasonic is also

employed as a substitute of mechanical disintegration of the pigment using

homogenizer stirring. Miniaturization of the pigment is carried out with and

without dispersing / stabilizing agent. The latter includes polyvinyl

pyrrolidone (PVP) and polyethylene glycol (PEG). These pigments are

studied to clarify the impact of nature of the nano-sized pigment particles on

size and particle distribution of the pigment. Size, shape and particle size

distribution of the ultrafine pigment particles were monitored through

transmission electron microscopy (TEM). Meanwhile, printed fabrics (i.e.

cotton, cyanoethylated cotton, partially carboxymethylated cotton and

polyester/ cotton blend fabrics) were evaluated for cotton strength (K/S) and

overall fastness properties.

Given below are a summary of and conclusion arrived at form the

aforementioned studies:-

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1. The size, shape and particle size distribution rely on time and

temperature of stirring. The nanoscale pigment size decreases

significantly by prolonging the stirring time from 10 to 60 min. the

opposite holds true for raising the temperature from 80 0C to 100

0C.

2. The above finding and those connected with changes in shape and

particle size distribution could be explained in terms of

disintegration of the pigment to much smaller sizes of large surface

area which favour the possibility of aggregation and agglomeration.

3. Increasing the pigment concentration from 0.25 to 3gm/100ml water

increases the pigment particle size from 21.9 nm to 27.1 nm. Most

probably higher pigment concentration protect its particle size from

the action of mechanical and thermal enegies involved in

miniaturization. In combination with this is the greater tendency of

the nanoparticles to aggregate / agglomerate when higher pigment

concentrations were used.

4. Incorporation of PVP or PEG at different concentrations during

miniaturization of the pigment at different times causes:

(a)disaggregation of the pigment particles, (b) higher disintegration

and, in turn, smaller nano-sized pigment particles, (c) uniform and

narrow ultrafine pigment particle distribution and (d) very little or

no evidence of aggregation/agglomeration of the pigment

nanoparticles particularly at higher PVP concentration. PVP or

PEG performs dual function (i) as dispersing agent thereby keeping

the nanoscale pigment particles dispersed and (ii) as a capping,

coating and/or encapsulating agent to prevent coalesce of pigment

particles.

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5. Miniaturization in presence of PVP or PEG using ultrasonic based

technology yield ultrafine pigment particles with much smaller sizes

and more uniform particle distribution than those obtained using the

homogenizer with vigorous stirring.

6. Pigment Green, Pigment Blue and Pigment Orange exhipit particle

sizes of 65, 95 and 134 nm, respectively, before miniaturization.

After miniturization in presence of PVP these pigments display

particle sizes of 16.2, 29.2 and 12 nm respectively. This reflects the

impact of nature of the pigment on size of the nanopigment particles

after miniaturization.

7. Printability of the pigment nanoparticles is determined by size,

shape and particle distribution which, in turn, are a manifestation of

the condition of miniaturization. By and large, higher colour

strength (K/S) is obtained by the smaller nanopigment particles. On

the other hand, the overall fastness properties are not significantly

affected by maniturization irrespective of the condition used.

8. Printing in absence of binder using Pigment Green nanoparticles

after miniaturization yield colour strength which is about 130%

higher than before miniaturization. This percentage decreases

significantly in presence of binder.

9. printability, expresses as colour strength and fastness properties of

the nano-sized pigment particles differ substantially on cotton fabric,

polyester/cotton blend fabric, partially carboxymethylated cotton

fabric and cyanoethylated cotton fabric. This reflects impact of the

nature of textile substrate used for printing.

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3. Chemical Routes for Environment Protection Via

Energy and Material Saving

A perusal at our work that has been published over the last three

decades and summarized briefly in the foregoing paragraphs, would reveal

that a great deal of our research activities were directed towards

establishment of conditions and/or development of techniques as well as

synthesis of new auxiliaries with a view to reduce energy, labour , time, and

cost in the wet processing of textiles. In addition to their original targets,

our efforts may form the basis of a potential means for environmentally

sustainable industrial technologies.

By and large our efforts comprise: 1) combination of two or more of

the wet processes of textiles; 2) chemical modification of cotton to enhance

its susceptibility towards dyeing and finishing; 3) enhancement of fixation

of reactive dyes on cotton textile; 4) synthesis of reactive carbohydrates to

substitute conventional ones; 5) recycling of water-soluble starch sizes as

per the ultrafiltration technology and; 6) multifunctionalization of cotton.

Major finding and conclusions arrived at from these research efforts follow.

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3.1. Combined process

3.1.1.Combined pretreatment

In common practice, bleaching of linen fabric comprises scouring

using sodium hydroxide and reducing agent and bleaching using three

successive agents: sodium hypochlorite, sodium chlorite and hydrogen

peroxide. According to our research, on the other hand, unscoured linen can

be bleached using H2O2/ urea system. Our research focuses on the following

combined pretreatments:

Degradative effect of stabilized H2O2 in highly alkaline medium on

starch and polyvinyl alcohol (PVA) led to one-step process for desizing,

scouring and bleaching of starch-sized cotton fabric and PVA-sized

polyester/cotton fabric.

Devised treating formulations for loomstate cotton and

polyester/cotton fabrics resulted in size removal and improved whiteness

with minimum degradation of fibre.

A novel pre-paratary process for cotton fabric using urea-activated

H2O2 as technical basis for simultaneous desizing, scouring and bleaching

of cotton fabric.

- Combined desizing and scouring.

- Combined desizing and mercerizing.

- Combined desizing, scouring and bleaching.

Executive summary of the above combined pretreatments is

reported in the book “ Development in Textile Chemistry and Chemical

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Technology , Special Contribution” by A. Hebeish, ASRT, July 1994,

Cairo, Egypt.

3.1.2. Combined dyeing and finishing

Traditionally, dyeing and easy care finishing of cotton textiles are

carried out separately and in succession. Our research efforts devoted to

establish innovative single-step process for dyeing and finishing involves

one of the following approaches.

Methylolated dye was newly synthesized and applied to cotton fabric

along with N-methylol finishing agent in one step dyeing and finishing

process using acid – based catalytic system.

Reactive dye along with monomethylol urea, dimethylol urea or N-

methylolacrylamide and alkaline catalyst were applied to cotton fabric

as per the pad-dry-cure method. Thus obtained fabrics exhibited

outstanding crease recovery, reasonable loss in tensile strength and

preserved fastness properties.

Simultaneous dyeing and finishing of acrylamidomethylated cotton

using nucleophilic dyestuffs as well as reactive dyes with excellent

dye fixation and wash - wear properties could be achieved.

3.2. Improving Chemical Reactivity of CottonWe have undertaken this work with a view to create active centres

in cellulose molecule and modify the basic properties of cotton. Thus

certain chemically modified cottons were synthesized, characterized and

used as the basis for enhancing the reactivity of cotton cellulose. Among

these modified cotton, mention is made of the following:

3.2.1. Acrylamidomethylated Cotton (AMC)

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AMC was used for concurrent dyeing and wash -wear finishing as

described above

3.2.2. Cotton Bearing Aromatic Amino Groups

This modified cotton displayed flame retardancy and easy care

properties when it was treated with tetrakis; hydroxymethyl phosphonium

chloride (THPC) along with reactant resin and / or urea.

3.2.3. Cellulose Carbamate

Reaction of carbamate with P- nitroaniline followed by reduction,

diazotization and coupling resulted in a set of different colours.

3.2.4. Other Modified Cottons

Methylolated cellulose carbamate, diethylaminoethylated cotton,

cotton graft copolymers and other. Modified cotton were used for

increasing the chemical reactivity of cotton towards reactive dyes.

3.2.5. Heat Transfer Printing

Cyanoethylated cotton and polystyrene graft -copolymers were the

best for transfer printing with very good fastness properties

3.3. Enhancement of Reactive Dye Fixation Research work has been carried out to overcome the problems

associated with application of reactive dyes on cotton fabrics as follows:

Use eco-friendly compounds such as chitosan and polyacryiamide

dextrin hybrid for aftertreatment of reactive dyeings.

Optimize the application of these compounds through modulation of

technical parameters affecting the after treatment.

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The structures of both chitosan and the hybrid permit formation of salt

linkage between cotton and these compounds along with covalent

bonds between reactive dye and cellulose hydroxyl leading to

enhanced dye fixation and this relies on dyeing conditions, after

treatment conditions and nature of the dye.

The after treatments represent a means for ecological dyeing due to

reduced amounts of salts, lower temperature and the use of eco-

friendly compounds.

3.4. Reactive carbohydrate polymeric productsConventionally, carbohydrate materials such as starch and water

soluble CMC are used as temporary finishes for cotton textiles. Removal

of these finishes during washing increases the pollution load.

Our research activities brought into focus novel reactive

carbohydrates which were successfully applied as permanent finishes to

cotton fabrics as given under.

Graft copolymerisation of CMC and hydrolyzed CMC with acrylamide

followed by methylotation resulted in reactive finishes for cotton when

applied using pad-dry-thermo fixation method.

Starch and hydrolyzed starches have been modified as described above

for CMC and applied to cotton fabric. Durability of the finish has been

studied systematically.

CMC bearing pendant double bonds were prepared via reaction with

N-methylolacrylamide under acid conditions.

Reactive sizes including methylolated polyacrylamide-dextrin

copolymer and methylolated polyacrylamide-PVA copolymer as

permanent size and finishing agent respectively.

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3.5. New Reclaimable sizes for Improved High Speed

Weaving and Reduced Pollution

Our research and technical efforts were strongly directed towards

development of new starch –based sizes which were characterized by the

following features; 1) they were water soluble, 2) they were reclaimable

for re-use as sizing agent thereby reducing pollution, 3) they were as

efficient as the best commercial reclaimable sizes of high weaveablitiy.

and) they were thermally stale. Stated in other words our work had two

fold objectives:

To improve the environment through minimal pollution by removing

for reuse the sizing agent from finishing plants' waste water.

To enhance the technical properties of textile warps for superior

weaving on modern high speed weaving machines.

Experimental study to compare between cotton yarns sized with two

commercial and three reclaimable sizes was preformed.

Among the five sizing agents used, polycarboxylic starch composite

prepared at our NRC proved to be the best candidate for industrial

application.

3.5.1. Recycling of Water-Soluble Starch Sizes

Textile pollution is caused by discharging the waste water

produced by textile wet processing. Minor air pollution results from

spinning, weaving and some finishing process.

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Recovery of sizing agents from waste water can be achieved by ultra-

filtration process. Parameters controlling the efficiency of this process

has been extensively studied.

Recovery of starch sizes need to induce solubilization of starch

without affecting its molecular mass. This could be achieved via

derivatization of starch before being used as size base materials.

Soluble poly (acrylic acid) -starch composite could be recovered from

the desize effluent by making use of ultra-filtration technique. A

detailed study of the factors affecting the ultra-filtration process was

also undertaken.

3.5.2. Introduction of Ultrafiltration Technology to Textile Industry

in Egypt

Within the framework of our research plan, an ultrafiltration unit

was installed for the first time in one of the biggest companies for

spinning and weaving in Egypt. Preparation of starch based sizes was

preformed through polymerization of starch, carboxymethyl starch or

grafting of carboxymethyl starch with vinyl monomers such as acrylic

acid, acrylamide or butyl acrylate as described previously under starch

composites and starch hybrids.

Needless to say that the pollution of environment raised from

textile contributes much to the total industrial pollution. The major part of

the textile pollution is mainly caused from discharging the wastewater

which is produced during the different textile wet processes. On the other

hand, air pollution caused by spinning, weaving and some finishing

processes constitute the minor part.

128

From the typical wet processes used in cotton fabric manufacturing,

the desizing alone causes more than 50% of the textile pollution load.

To minimize this percent of pollution, different methods have been

proposed, one of them is recovering the sizing agents from water. The

latter can be achieved by mean of the ultrafiltration method.

The ultrafiltration operation is a pressure driven membrane process by

which macromolecular solutes (sizing agent) are concentrated by

means of transferring the solvent (water) through the membrane pores

while the sizing molecules (macromolecules) retained. The separation

of the sizing agents molecules from water molecules by the

ultrafiltration (UF) process depends on many parameters such as:

a) The nature and the data of the membrane (molecular weight cut off,

material, water flux, pH and thermal stability)

b) The size and physico-chemical properties of the sizing agent (solute).

c) Operating conditions (applied pressures, temperature, the

concentration of the feed solution, the operating time and the Reynolds

number of the feed flow).

The main factors which can be measured during the process are the

permeate flux and the rejection, because the understanding of the

mechanism involved in the ultrafiltration of the macromolecular

solution is complicated.

Textile sizes are high molecular weight polymers. If these polymers

can be removed from the fabric in the same form as they were applied

to the warp, then the recovery of the size from desizing effluent by

means of ultrafiltration becomes feasible. In this process, a

semipermeable micropores membrane performs the separation. Water

and low molecular weight solutes pass through the membranes and are

129

removed as permeate. The feed stream flows parallel to the membrane

surface discharging of permeate leads to raising up the concentration

of the charge "desizing effluent". The regenerated (concentrate) will be

reused as sizing agent and the purified effluent (permeate) will be used

in the desizing process. These changes depend on the stability of the

sizing agents at the operating conditions of the ultrafiltration process.

The ultrafiltration has successfully recovered polyvinyl alcohol,

carboxymethyl cellulose, polyacrylate. Polyvinyl alcohol is the

preferred size for reuse due to its high stability because the others

suffer from degradations during the ultrafiltration recovery. With

starch sizes the problem is great. Normally starch sizes is not

'recoverable because of the need for degradation prior to removal in

desizing. The trend now is modifying the starch to be recoverable from

the sized yarns. The modification of starch can be achieved via

etherification, esterification, oxidation, graft polymerization , and

water soluble composite formation. The latter are the subject of this

work.

Hence poly(acrylic acid)-starch composite sized cotton fabric was

desized and recovery of the composite was undertaken. The desizing

was effected only by water (90°C). The recovery of composite from

the desize effluent was done by making use of the ultrafiltration

technique (UP). In the latter, factors studied were process time (h) and

the regenerate and permeate concentrations, the rate of flux (1/h.m2)

and the rejection%. The effect of the different processes (sizing,

desizing, UF recovery) on the viscosity of composite was studied in

comparison with the virign solution. Results obtained indicated that

the desizing effluent can be recovered successfully by means of the UP

technique.

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3.6. Multifunctionalization of Cotton A current nanotechnology—based research program has been started to

achieve saving resources, control of pollutants, develop innovative

textile products with new functionalities and to satisfy the requirements

of the textile consumer.

The reactive copolymers bearing β-Cyclodextrin (CD) were prepared

and applied to cotton in presence of metal nanoparticles.

The chemistry of grafting cotton with reactive copolymer based on CD

moiety and poly(butyl acrylate) and its role in the finishing of cotton

were reported. The onset of this application of cotton fabric performance

as well as antimicrobial and air permeability properties were examined.

A full characterization of grafted fabrics and metal nanoparticles by

electron microscopy and physical means has been carried out.

The so treated cotton fabrics exhibit antibacterial properties which

withstands several washing cycles and acquire improved air permeability

leading to comfortable garments made thereof.

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4. Conclusion

Over the last fifty years, we have been involved in research and

development pertaining to the chemistry of fibrous and nonfibrous textile

materials. Of the textile materials investigated mention is particularly

made of cellulose, wool, polyamide and polyester. It is certain, however,

that great attention is given to cotton cellulose. Research area of cotton

cellulose covers degradative treatments, mechanisms of degradation of

cotton and effects of mercerization restretching upon the course of these

mechanisms, chemical reactions entailed in functionalization of cellulose,

vinyl graft copolymerization, coloration, easy care cotton finishing and,

biotechnology and nanotechnology for development of wet processing of

cotton textiles.

Particularly notable are the chemistry and modification of cotton

cellulose when it was submitted to partial carboxymethylation,

cyanoethylation, carbamoylethylation, crosslinking and / or

copolymerization with vinyl monomers such as acrylonitrile (AN),

acrylamide(Aam), acrylic acid (AA) and glycidyl methacrylate (GMA).

The chemistry of cotton cellulose and thus obtained modified cottons

before and after being subjected to degradative treatments using different

oxidants, gamma radiation, thermal heating and acid hydrolysis are

studied. This is done in order to identify microstructural features brought

about by such degradative treatments and the onset of this on the

mechanical, physical and chemical properties of cotton.

132

We have also studied the effect of different degradative treatments

on cotton and slack mercerized-restretched cotton yarns with a view to

have clear understanding of the phenomenon: when cotton is subjected to

mercerization treatments, the molecular structure of the cellulose is

modified in such a way that although it undergoes higher chemical

degradation, yet it retains higher strength as compared to unmercerized

cotton. It is believed that there must be differences in microstructural

features between native and mercerized – restretched cotton that account

for this. Consequently we have measured the fundamental changes

occurring as a result of acid, hypochlorite, heat, Ultra- violet and

weathering degradative treatments of cotton. The effect of mercerization-

restretching of yarns upon the fundamental changes are determined in

order to identify the structural features that are critical to the improved

retention of strength on mercerization-restretched cotton yarns. Tension on

the yarns was adjusted so as to give different mercerized – restretched

yarns (90, 94, 96, 100 and 103% of the original length). Cotton and

mercerized cotton yarns were analyzed for copper number, carboxyl

content, degree of polymerization, iodine sorption and strength properties

before and after being subjected to the said degradative treatments.

Infrared spectroscopy as well as chemical microscopical analysis were

also used to clarify microstructural differences among scoured and slack

mercerized-restretched cotton.

Based on the forgoing, following conclusions may be reported:

1) The magnitude of stretching has no effect on copper number, carboxyl

content and iodine sorption of the degraded mercerized cottons. On the

contrary, higher stretching is accompanied by higher tensile strength.

133

2) The average distances between centres of crystallites in mercerized

cottons after any of the degradative treatments in question are much

shorter than their mates in scoured cotton, indicating that the frequency

of successive regions of high lateral order is much more in mercerized

cotton as compared to scoured cotton.

3) Plots of DP with tensile strength signify that scoured cotton yarn

whose DP was reduced by the degradative treatment to DP below 1000

decreases sharply whereas with mercerized cotton no sharp decrease in

strength was observed.

4) For a given percentage of bond broken, the strength of the highly

stretched yarn is significantly higher than those restretched at lower

tensions.

5) X-ray and infrared analysis showed that the largest changes in

microstructure of mercerized cottons has been the increase in cellulose

I content with increased restretching of the yarns. Stretching has an

effect on crystal structure and/or favours recrystallization.

6) There is a considerable difference between the reactivity of scoured

cotton and slack mercerized-restretched cottons due to difference in the

microstructure between the substrates in question. Reaction of cotton

and mercerized-restreched cotton with N, N-diethylaziridinum chloride

to yield diethylaminoethyl (DEAE)-cottons followed by acid

hydrolysis of DEAE cottons were performed. Results made it evident

that despite the higher resistance of scoured cotton to acid hydrolysis,

it has lost much of its DEAE substituents by virtue of their poor

distribution through the cellulose structure. On the contrary slack

mercerized cotton retains much of the DEAE substituents despite

higher susceptibility to acid hydrolysis because of better distribution of

the DEAE substituents throughout the structure of cellulose.

134

7) Slack mercerization enhances the O (3)H…O(5)……….O(1) hydrogen

bonding. In contrast, slack mercerization followed by stretching

decreases this hydrogen bonding.

Our work on chemical modification of cellulose via graft

polymerization with vinyl monomers had two – fold objective: (a)

understanding the kinetics and mechanisms of the graft copolymerization

reaction and, (b) building up basic information needed for improvements

to be made in the properties of products. Hence, the grafting reactions

were studied with respect to the following aspects (i) nature of cellulose

substrates, (ii) feasibility of a number of initiators to induce grafting of

vinyl monomers onto cellulose and modified celluloses, (iii) proof of

grafting and, (iv) major properties of the cellulose graft copolymers. In

addition, we have reviewed the subject and compilation of the literature

including our own work was made and published by international

publishing house. Needless to say that we were and still are pioneer in the

grafting area. We were the first to introduce it to the Egyptian researchers.

Our work on grafting is flourishing specially with respect to nonfibrous

textile materials as may be realized from paragraphs to be presented later.

Colouration comprises dyeing and printing. In this context we have

undertaken the research with a view (a) to study the mode of interaction of

direct dyes with cotton cellulose, (b) to improve the dyeability of cotton

and viscose by making use of redox systems, (c) to expedite chemical

fixation of reactive dyes via introduction of latent alkaline catalyst in the

molecular structure of cotton cellulose, (d) to examine the effect of

mercerization stretching on dyeability of cotton cellulose, (e) to develop

thickeners as substitute of sodium alginate in reactive printing and, (f) to

render cotton amenable for heat transfer printing. Research results provide

135

clear understanding, plausible clarification and facile verification for all

these colouration-related issues as executively summarized in current

document.

Easy care and durable process cotton finishing, known also as

crosslinking finishes, involve treatments of cotton fabrics with di- or

polyfunctional compounds which are able to react with cotton cellulose

most probably via covalent crosslinking. As a result the cotton fabrics

exhibit shape holding properties, wrinkle resistance, wash- and- wear and

durable press properties as well as dimensional stability. However, such

finishing is associated with a number of problems which were the subject

of extensive research world-wide. We have kept abreast with this research

and reported novel approaches for tackling the following problems (a)

great loss in strength and related properties, (b) balance between wet/dry–

wrinkle recovery against tensile strength, (c) free formaldehyde released

from the finished cotton products and, (d) greater susceptibility of the

finished products to soiling and their lower levels of soil removal.

Of the numerous studies we have carried out, emphasis was placed

on soiling and soil release with a view to define the chemical

characteristics of finishes that are critical for effective soil release

properties in durable press cotton-containing fabric with hope to provide

information on mechanisms of soil release. For this purpose different

chemical groups (moieties) in the monomeric form or polymeric form or

both with various hydrophilicity/hydrophobicity characteristics were

introduced in the molecular structure of cotton and cotton polyester fabrics

via chemical modifications before the crosslinking finish. In addition,

water soluble cellulose derivatives, laboratory prepared polycarboxylic

136

acid and conventional soil release finishes were independently

incorporated in the crosslinking formulation.

Research results disclose that although blending of cotton with

polyester alters the susceptibility of cotton to soiling and its ability to

release the soil, the point that introduction of additional hydrophilization

or even intensified hydrophilization cannot solely determine the ability of

cotton and blend fabrics to release the soil. The same holds true for

additional hydrophobicity and/or hydrophilicity. Topochemical vis-à-vis

topophysical aspects should be considered as previously outlined.

Harnessing biotechnology for development of wet processing of

cotton and polyester/cotton blend fabrics was the subject of several of our

studies. The idea is to substitute harsh chemicals used in different wet

processes of the said fabrics with appropriate enzymes for the sake of

energy, water and materials conservation and, therefore, environmental

protection. Meanwhile the chemical, physical and mechanical properties

of the processes fabrics are maintained. Thus intensive research brought

into focus: (1) an appropriate biotreatment based on environmentally

sound conditions for pretreatment (purification) of cotton-based fabrics,

(2) investigation into factors affecting biopolishing before and after

crosslinking of the fabrics in question, (3) optimal conditions for

bioscouring were established, (4) new development in scouring and

bleaching of the cotton and blend fabrics whereby these two processes

were concurrently performed, (5) most appropriate strategy for

bioscouring could be achieved, (6) enzymatic treatment and reactive

dyeing could be applied as per three approaches and, (7) innovative

technology for multifunctionaization of cotton fabrics through cellulose

biotreatment, reactive dyeing and easy care finishing.

137

Wool was subjected to grafting of chains of vinyl monomers. An

important and difficult problems in this case concerns with site(s) on the

protein molecule at which chemical attachment of the polymer chains

occurs and this is considered in some detail for a number of initiation

systems. The impact of grafting on all-important textile properties of wool

notably felting and permanent set was examined.

Polyamide and polyester fibres were also submitted to grafting

procedures, with the practical objective of enhancing moisture region and

dyeability. Some other problems relating to the dyeing of these fibres were

tackled.

Equally brought into focus was our work concerned with the

chemistry of nonfibrous textile materials. Studies on synthesis,

characterization and application of many polymeric materials were

undertaken. Among these materials were starch, carboxymethyl cellulose

(CMC), chitosan and β-cyclodextrain. Apart of their different etherfication

products, these materials arouse much attention when they were graft

copolymerized with various vinyl monomers. This is exemplified by

starch-poly(AA) composite, starch-poly(Aam) composite, β-cyclodextrin-

poly(GMA) copolymers. Particularly notable was the loading of β-

cyclodextrin copolymers with metal nanoparticles, for example, silver

nanoparticles. CMC based hydrogels with and without nano-sized metal

particles were the subject of intensive investigation concerning their

synthesis, characterization and application especially in the medical

domains. Research was also directed towards synthesis of polymeric

materials that are environment-friendly for use as reducing agent

converting the silver ion to silver atom and stabilizing agent through

capping of silver nanoparticles which represent clusters of silver atom.

138

This was exemplified by the synthesis and characterization of

hydroxylpropyl starch. Hydroxylpropyl starch plays dual role: reducing

and stabilizing agent during the synthesis of AgNPs. Similarly,

investigations into factors affecting graft copolymerization of β-

cyclodextrin with butyl acrylate and utilization of the obtained copolymers

in synthesis of ZnO nanoparticles were undertaken. The nano-sized ZnO

loaded copolymer was then applied to cotton fabrics. Also reported was

the copolymerization of reactive cyclodextrin with butyl acrylate. Thus

obtained copolymers were loaded with nano-sized ZnO. These copolymers

were used as reactive preformed polymers which underwent reaction with

the hydroxyl groups of cotton cellulose in alkaline medium via

substitution mechanism; similar to reactive dyes. Cotton fabrics treated

with these preformed reactive polymers displayed multifunctional

characteristics, notably, antimicrobial and water repellency along with

improved strength properties.

Thorough investigation into synthesis and characterization of

starch nanoparticles as well as concurrent formation of nanosized particles

of both starch and silver, with emphasis on their nanostructural features

and medical applications are reported. Also reported are the synthesis and

characterization of cellulose nanowhiskers and possible applications of

these cellulose nanoparticles before and after chemical modification in the

area of reinforcement and other applications such as in synthesis of

nanometal particles and processing of novel hybrid nanogel.

It is worthy to mention that within the framework of our research

plan, electrospun cellulose nanofibers and cellulose-graft-polyacrylonitrile

copolymer nanofibers containing silver nanoparticles were synthesized for

effective water disinfection.

139

Our research also addresses technological innovations based on

frontier science for development of textile printing. Synthesis,

characterization and application of ultrafine pigment particles constitute

the base of such development.

140

5. Innovation

Advancing insight into structural features and reactivity of fibrous

and nonfibrous textile materials has created novel types of materials.

Innovation of such materials has necessitated conducting basic and applied

research pertaining to the chemical modification treatments of fibrous

materials, e.g., cellulose, wool and polyester and, nonfibrous materials,

e.g., starch, chitosan and cyclodextrins. That is, the reactions involved in

the modification treatments have been studied from both academic and

practical point of view, i.e., from concept to implementation. General

kinetics, mechanism and optimization of the reactions entailed in each

modification were postulated and verified. In concomitant with this was

the application of the results leading to optimization and modernization of

the textile processing and, therefore, development of new and/or improved

textile products. Highlights could be represented by the following

innovations.

1) Development of one-step process for preparation of loomstate cotton

fabrics using sodium chlorite at pH 8.

2) Combination of processes, namely, desizing, scouring and bleaching

in one process for preparation (pretreatment) of cotton and

polyester/cotton blend fabrics using, for example, stabilized hydrogen

peroxide in highly alkaline medium.

3) In starch mercerization – restretching of the cotton yarns, the latter

should be restretched to maximum 100% of their original length.

141

Lower than 100% restretching is not economically accepted beside

decrease in yarn strength and lusters. On the other hand, stretching to

103% of the original length of the yarns causes partial conversion of

cellulose II to cellulose I. We have shown for the first time that yarns

slack mercerized followed by restretching to 103% of their original

length fall short in reactivity, luster and structural uniformity although

they display higher tensile strength.

4) Introduction of partial carboxymethylation in the wet processing of

loomstate cotton fabrics resulted in omittion of desizing and

mercerization processes beside producing chemically modified cotton

fabrics with better properties compared to desized and mercerized

fabrics.

5) Continuous and semi-continuous methods were devised for

production of chemically modified cottons, notably, partially

carboxymethylated cotton.

6) A reactive dye was invented. Unlike the conventional halogen or

sulphatoethyl sulphone-based reactive dyes, the new dye reactivity is

based on N-methylol groups. This allows it to react with cellulose

textiles in presence of acid catalyst which is also used to catalyze

reaction of N-methylol crosslinking agents with the cellulosics.

Combined dyeing and easy care finishing can, therefore, be carried

out in single step process, opposite to conventional reactive dyes

which react with cellulose in alkaline medium and their easy care

finishing is carried out separately and in succession.

7) Of the many reactive printing thickeners developed to substitute

sodium alginate thickener (the universely accepted thickener for

printing cellulosics with reactive dyes) mention should be strongly

made of starch-polyacrylamide composite. This composite proves to

142

be the best since it was successfully applied on industrial scale.

Equally effective is the starch- poly butyl acrylate composite.

8) To render cotton fabrics amenable for heat transfer printing,

numerous modified cottons were synthesized through crosslinking,

etherification, esterification and vinyl graft copolymerization using

different monomers. Among these modified cottons, cyanoethylated

cotton and partially carboxymethylated cotton – polystyrene graft

copolymers were the most amenable for heat transfer printing.

9) Development of fast catalytic system (mixed catalyst) for crosslinking

stimulated industrial production of easy care cotton finishing at a

curing temperature range as low as (100 0 – 120 0C).

10) Chemical characteristics of finishes that are critical for effective soil

release properties in durable press cotton – containing fabrics were

defined to serve as basics for designing and production of new soil

release finishes.

11) Biotechnology was used for development of the wet processing of

cotton and cotton/polyester blend fabrics with possible substitution of

harch chemicals by enzymes as well as to involve the enzymatic

treatment in multifunctionalization of cotton fabrics.

12) Vinyl graft copolymerization onto fibrous and nonfibrous textile

materials brought about products, for example, (a) wool graft

copolymers with no felling; (b) polyester – and polyamide graft

copolymers with increased water and dye absorption; (c) starch graft

copolymers and starch –poly(vinyl) composites with rheological

properties suitable for use as sizing agents as well as thickeners for

printing; (d) cyclodextrin graft copolymers loaded with nanosilver

particles for application in smart cotton production and (e) chitosan

143

graft copolymers for production of medical textiles and products for

other purposes.

13) Functional textile fabrics were produced on industrial scale by

treatment of cotton fabrics with chitosan having different molecular

weights in presence of ammonium citrate. Fabrics produced acquired

antibacterial activity.

14) Low temperature dyeing (65 – 85 0C) of polyester, polyester/cotton

blend and cotton fabrics could be realized in a system containing

disperse dye, vinyl monomers and hydrogen peroxide. Neither

grafting nor homopolymerization occurred.

15) Hydrogels based on CMC loaded with either silver or ZnO

nanoparticles and hydrogels based on cellulose nanoparticles

(cellulose nanowhiskers, CNW) loaded with silver nanoparticles were

synthesized and characterized. Condition for synthesis and application

of these products in medical domains were established. Also

established were the synthesis of starch nanoparticles and silver

nanoparticles concurrently. Their use in medical domains was also

practiced. On the other hand, cellulose nanofibers and cellulose-

polyacrylonitrile graft copolymer nanofibers loaded with silver

nanoparticles were successfully synthesized, characterized and used

in water disinfection.

16) Recovery of water soluble starch size using the ultrafiltration unit was

introduced for the first time in Egypt. Starch-polyacrylic acid

composite was prepared on industrial scale and used in sizing of warp

cotton yarns and after weaving the fabrics was desized using hot

water. The water containing the removed size was ultrafiltrated to

yield 95% reclaimable sizing material.

144

17) Chemical routes were established for environmental protection

through energy, water and materials conservation. They include (a)

combined wet processes such as combined desizing, scouring and

bleaching as well as combined dyeing and finishing; (b) enhancement

of cotton reactivity and/or cotton susceptibility towards dyeing and

finishing; (c) synthesis of reactive carbohydrates as permanent

finishes to substitute the conventional ones used therein as

temporarily finishing and; (d) recycling of the water soluble starch

sizes as per the ultrafiltration technology.

18) The complete chain of innovation was exercised in production of

antibacterial garments as per the client (company) request. Based on

our research in the field of nanotechnology, the most appropriate

conditions for synthesis of silver nanoparticles (AgNPs) were

established and used for preparation of an amount of AgNPs large

enough to treat 5 tons of textile fabrics. Thus treated fabrics were

converted into garments and exported to one of EU countries after

being submitted to the necessary testing and analysis. Results of the

latter were in full agreement with those made by the European

exporter.

19) Innovation based on the top-down approach of nanotechnology was

practiced for development of textile printing. Synthesis,

characterization and application of ultrafine (nano) pigment particles

constitute the base of such development.

Obviously, then, the academic and applied research and

developmental activities presented in current document were conducted

within environmental scene. The chemistry and modifications of fibrous

and nonfibrous textile materials were notably performed under

predetermined and controlled conditions for the sake of energy, water,

145

chemicals, and materials saving which, in turn, mentain good quality of

the environment. Meanwhile, modulation of reactions involved in

chemistry and modifications of fibrous and nonfibrous materials brought

into focus the following: (a) understanding the kinetics and mechanisms of

chemical reaction involved in the modification treatments; (b) provision of

the package of technological knowledge which is useful for industrialists

and researchers and (c) help introducing new and novel technology to the

textile and other industries. Emphasis was placed on harnessing frontier

sciences such as nanotechnology and biotechnology for producing smart

apparel, domestic and technical (medical) textile products.

Summing up, research output contributes to existing knowledge

and strengthens the scientific ground on which an effective technical

service can be offered. It also enables the concerned scientists to define

possible research needs in the field of chemistry of fibrous and nonfibrous

textile materials. On the other hand, technology development includes: (i)

optimization and modernization of textile processing; (ii) development of

new, improved and more efficient technologies for production of

chemically modified polymers with unique characteristics; (iii)

development of products with new and unprecedented and interesting

properties and; (iv) energy and materials saving with significant

improvement in the quality of environment.

146

References

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2. M. Kamel, A. Kantouch and A. Hebeish, "Chemical Modification of Cotton Febrics", Paper Presented at the '2nd Cotton Technology and Economic Conference, U.A.R. Chem. Soc.', Alexandria, Egypt.(1964), 25

3. M. Kamel, A. Kantouch and A. Hebeish, "A Novel Application of the Padding Methods for Effecting the Carboxymethylation of Cotton", Textile Praxis International, 19, (1964) 1114

4. M. Kamel, A. Kantouch and A. Hebeish, "Study of the Different Factors Which Affect the Partial Carboxymethylation of Cotton Fabrics Using Padding Methods", Textile Praxis International, 20, (1965) 577

5. A. Hebeish and P. C. Mehta, "Grafting of Acrylonitrile on Cellulosic Materials by Tetravalent Cerium", Textile Research Journal, 37, 10 (1967) 911-913

6. M. Kamel, A. Kantouch and A. Hebeish, "Study on Partially Carboxylated Cotton: Part III: Chemical Behaviour of Partially Carboxymethylated Cotton", Indian Journal of Technology, 5, (1967) 58

7. M. Kamel, A. Kantouch and A. Hebeish, "Studies of Partially Carboxymethylated Cotton: Part IV: Degradation of Cotton", Indian Journal of Technology, 5, (1967) 324

8. A. Hebeish and P. C. Mehta, "Grafting of Acrylonitrile to Different Cellulosic Materials by High Energy Radiation", Textile Research Journal, 38, 10 (1968) 1070 - 1071

9. A. Hebeish and P. C. Mehta, "Cerium-Initiated Grafting of Acrylonitrile onto Cellulosic Materials", Journal of Applied Polymer Science, 12, 7 (1968) 1625-1647

10. A. Y. Kulkarni, A. Hebeish and P. C. Mehhta, "Studies on Ceric Ion Initiated Graft Polymerization on Cellulosic Materials: Part II:" Paper Presented at the '9th Technol, Conf., SITRA', India.(1968), 36

147

11. A. Hebeish and P. C. Mehta, "Molecular Weight and Moisture Regain of Polyacrylonitrile Cellulose Graft Copolymers", Textile Research Journal, 39, 1 (1969) 99 - 100

12. A. Hebeish and P. C. Mehta, "Grafting of Vinyl Monomers and Their Binary Mixtures to Cellulose Using Ceiv as Initiator", Cellulose Chemistry and Technology, 3, (1969) 469

13. A. Hebeish, "Various Aspects of Easy Care Cotton Finsihing", L’Industrie Textile, 991, (1970) 415

14. A. Kantouch, A. Hebeish and M. H. El-Rafie, "Use of Sodium Chlorite in Simultaneous Desizing and Bleaching", Textilveredlung, 5, (1970) 200-220

15. A. Kantouch, A. Hebeish and M. H. El-Rafie, "Graft Copolymerization of Vinyl Monomers on Modified Cotton: Part I: Grafting of Vinyl Monomers on Partially Carboxymethylated Cotton", Europian Polymer Journal, 6, 12 (1970) 1575-1586

16. A. Kantouch, A. Hebeish and M. H. El-Rafie, "Action of Sodium Chlorite on Cellulose and Cellulose Derivatives", Textile Research Journal, 40, 2 (1970) 178-184

17. A. Bendak, A. Kantouch and A. Hebeish, "Grafting of Acrylonitrile and Methyl Methacrylate on Wool Fibres by the Ceric Ion Method", Kolorisztikal Ertesito, 13, (1971) 106

18. A. Hebeish, "Basic Aspects of Grafting Vinyl Monomer onto Cellulose", Kolorisztikal Ertesito, 13, 1/2 (1971) 12

19. A. Hebeish and A. Bendak, "Radiation Induced Grafting of Vinyl Monomers on Wool", Teintex, 10, (1971) 719

20. A. Hebeish, A. Bendak and A. Kantouch, "Grafting of Wool with Vinyl Monomers by Using Trichloroacetic Acid–Bis(Acetonylacetonato)-Copper(II) Cocatalyst", Journal of Applied Polymer Science, 15, 11 (1971) 2733-2741

21. A. Hebeish, A. Kantouch, A. Bendak and A. El-Torgoman, "Chemical Modification of Polyester/Cotton Blends: Part I: Partial Carboxymethylation", American Dyestuff Reporter, 60, (1971) 40

22. A. Hebeish, A. Kantouch and M. H. El-Rafie, "Graft Copolymerization of Vinyl Monomers on Modified Cotton: Part II: Grafting of Acrylonitrile and Methylmethacrylate on Acetylated Cotton", Journal of Applied Polymer Science, 15, 1 (1971) 11-24

23. A. Hebeish, A. Kantouch and M. H. El-Rafie, "Graft Copolymerization of Vinyl Monomers on Modified Cotton: Part IV: Ceric Induced Grafting on Vinyl Monomers on Cellulose Bearing Different Substituents", Journal of Applied Polymer Science, 15, 8 (1971) 1921-1939

148

24. A. Hebeish, R. A. Mashoor and M. Kamel, "Effect of Pretreatment on Some Physical and Chemical Properties of Cellulose before and after Dyeing During Irradiation: Part 1: Effect of Pretreatments on the Photodegradation of Cotton", American Dyestuff Reporter, 62, 2 (1971) 39 - 44

25. M. Kamel, A. Hebeish and I. Abd El-Thalouth, "Action of Sodium Hypochlorite on Carboxymethylated Cellulose", Textile Research Journal, 41, 5 (1971) 450 - 454

26. M. Kamel, A. Hebeish and I. Abd El-Thalouth, "Chemical Modification of Cellulose Ethers with a View of Making Them Suitable for Printing and Other Purposes", Egy. Patent, 10511. (1971)

27. M. Kamel, A. Hebeish, K. Atya and I. Abd El-Thalouth, "Investigation on Possible Use of Carboxymethylated Cellulose in Reactive Dyes Print Pastes", Cellulose Chemistry and Technology, 5, (1971) 371

28. A. Kantouch, A. Hebeish and A. Bendak, "Ceiv Initiated Graft Polymerization of Methyl Methacrylate on Wool Fibres", Europian Polymer Journal, 7, 2 (1971) 153-163

29. A. Kantouch, A. Hebeish and M. H. El-Rafie, "Graft Copolymerization of Vinyl Monomers on Modified Cotton: Part III: Grafting of Acrylonitrile and Methyl Methacrylate on Cyanoethylated Cotton by the Ceric Ion Method", Journal of Applied Polymer Science, 15, 4 (1971) 1007-1019

30. A. Hebeish, A. Abid and M. Shams, "Catalysts for Easy Care Cellulose Finishing", Paper Presented at the '2nd International Science Symposium For Dyeing and Finishing', Alex., Egypt, March.(1972), 2, 36

31. M. Kamel, A. Hebeish and R. A. Mashoor, "Effect of Pretreatments on Some Physical and Chemical Properties of Cellulose before and after Dyeing During Irradiation: Part 2: Photosensitization in Presence of Direct Dyes", American Dyestuff Reporter, 61, 9 (1972) 92

32. A. Kantouch, S. H. Abdel-Fattah and A. Hebeish, "Mniv-Initiated Graft Copolymerization of Methyl Methacrylate on Wool Fibres", Polymer J. (Jappan), 3, (1972) 675-680

33. A. Kantouch, A. Hebeish and A. Bendak, "Graft Copolymerization of Methyl Methacrylate on Wool by Periodate Ions", Textile Research Journal, 42, 1 (1972) 7-9

34. A. Kantouch, A. Hebeish and M. H. El-Rafie, "Graft Copolymerization of Vinyl Monomers on Modified Cotton: Part

149

V: Grafting to Crosslinked Cellulose ", Textile Research Journal, 42, 1 (1972) 10-13

35. A. Bendak and A. Hebeish, "Wool Graft Copolymers Initiated by Azobisisobutyronitrile", Journal of Applied Polymer Science, 17, 6 (1973) 1953-1962

36. I. G. Bercsenyi, M. I. Khalil, A. Kantouch and A. Hebeish, "Studies on the Structure of Emulsions Stabilized by Nonionic Emulsifiers: Part I: Effect of the Type of Emulsifier", Kolorisztikal Ertesito, 15, (1973) 234

37. A. Hebeish, I. Abd El-Thalouth and M. Kamel, "Flow Properties of Oxidized Cmc : A Possible Base for Reactive Dyes Print Pastes", American Dyestuff Reporter, 62, 2 (1973) 28

38. A. Hebeish, A. Kantouch, A. Bendak and S. H. A. Fattah, "Vinyl Graft Copolymerization onto Wool", Paper Presented at the '2nd

International Wool and Man-Made Fibres Conference', Alex., Egypt, April.(1973), 36

39. A. Hebeish, A. Kantouch, M. I. Khalil and M. H. El-Rafie, "Graft Copolymerization of Vinyl Monomers on Modified Cotton: Part VI: Vinyl Graft Copolymerization Initiated by Manganese (IV)", Journal of Applied Polymer Science, 17, 8 (1973) 2547-2556

40. M. Kamel, A. Hebeish, M. Allam and A. Al-Aref, "Creation of Reactive Centers on Cotton: Part II", Journal of Applied Polymer Science, 17, 9 (1973) 2725-2738

41. S. H. Abdel-Fattah, A. Kantouch and A. Hebeish, "Mniv-Initiated Graft Copolymerization of Methyl Methacrylate on Wool Fibres: Part II: Effect of Kind of Acids", Journal of Chemistry (Egypt), 17, 3 (1974) 311

42. I. G. Bercsenyi, A. Hebeish, A. Kantouch and M. I. Khalil, "Studies on the Structure of Emulsions Stabilized by Nonionic Emulsifiers: Part II: Stability and Structure of Emulsions Using a Blend of Nonionic Emulsifiers", Kolorisztikal Ertesito, 16, (1974) 73

43. A. Hebeish, S. H. Abdel-Fattah and A. Bendak, "Redox-Initiated Vinyl Graft Copolymerization onto Wool with Thiourea as the Reductant: Part II: Fe3+-Thiourea Co-Catalyst Induced Graft Copolymerization of Methyl Methacrylate on Wool and Modified Wool Fibres", Die Angewandte Makromolekulare Chemie, 37, (1974) 11-25

44. A. Hebeish and A. Bendak, "Redox-Initiated Vinyl Graft Copolymerization onto Wool with Thiourea as the Reductant: Part I: Grafting of Methyl Methacrylate with the Hydrogen Peroxide–

150

Thiourea Catalyst System", Journal of Applied Polymer Science, 18, 5 (1974) 1305-1317

45. A. Hebeish, M. I. Khalil and M. H. El-Rafie, "Graft Polymerization of Vinyl Monomers on Modified Cotton: Part VII: Grafting by Chain Transfer", Die Angewandte Makromolekulare Chemie, 27, (1974) 149

46. M. Kamel, A. Hebeish and A. Al-Aref, "Creation of Reactive Centers on Cotton: Part IV: Reaction of Acrylamidomethylated Cotton with Some Sulfur Compounds", Journal of Applied Polymer Science, 18, 11 (1974) 3463-3474

47. M. Kamel, A. Hebeish and A. Z. Morsi, "Behaviour of Chemistry Modified Cellulose Towards Some Reactive Dyes", Journal Society Dyers and Colourits, 90, (1974) 352

48. A. Kantouch, M. I. Khalil, I. G. Bercsenyl and A. Hebeish, "Studies on the Structure of Emulsions Stabilized by Nonionic Emulsifiers: Part III: Effect of Oil Chain Length on W.O. Emulsions", Kolorisztikal Ertesito, 16, (1974) 140

49. A. Bendak, S. H. Abdel-Fattah and A. Hebeish, "Redox Initiated Graft Copolymerization onto Wool with Thiourea as the Reductant: Part III: Ditertiary Butyl Peroxide-Thiourea Co-Catalyst", Die Angewandte Makromolekulare Chemie, 43, (1975) 11-28

50. A. Bendak, M. I. Khalil, M. H. El-Rafie and A. Hebeish, "Graft Polymerization of Methacrylate onto Wool Using Dimethylaniline–Benzyl Chloride Mixture as Initiator", Journal of Applied Polymer Science, 19, 2 (1975) 335-351

51. M. H. El-Rafie and A. Hebeish, "Graft Copolymerization of Nylon 6 with Methyl Methacrylate Using Dimethylaniline/Cu2+ Ion System", Journal of Applied Polymer Science, 19, 7 (1975) 1815-1827

52. M. H. El-Rafie, M. I. Khalil and A. Hebeish, "Azobisisobutyronitrile-Induced Vinyl Graft Polymerization onto Nylon 66", Journal of Applied Polymer Science, 19, 6 (1975) 1677-1684

53. A. Hebeish, A. Kantouch, A. Bendak and S. H. Abdel-Fattah, "Vinyl Graft Copolymerization onto Wool", Paper Presented at the '2nd International Wool and Man Made Fibers Conference', Alexandria, Egypt, April.(1975),

54. M. Kamel, A. Hebeish and I. Abd El-Thalouth, "Technological Evaluation of Oxidized Cmc as Printing Pastes for Reactive Dyes", American Dyestuff Reporter, 64, 3 (1975) 22

151

55. M. Kamel, A. Hebeish and A. Al-Aref, "Creation of Reactive Centers on Cotton: Part V: Simultaneous Dyeing and Finishing of Acrylamidomethylated Cotton Fabrics", Textile Research Journal, 45, 2 (1975) 131-135

56. M. H. El-Rafie, A. Wally and A. Hebeish, "Dimethylaniline-Cu2+

Ion System Initiated Graft Polymerization of Methyl Methacrylate on Viscose Fibres", Journal of Applied Polymer Science, 14, 12 (1976) 2903 - 2909

57. A. Hebeish, "New Catalyst System for Easy-Care Cotton Finishing", Journal of Applied Polymer Science, 20, 10 (1976) 2631-2642

58. A. Hebeish, E. Allam, A. Hamza, M. Shasm and M. M. Kamel, "Effect of Finishing with N-Methylol Compounds on the Properties of Dyed Polyester Cotton Blend", Kolorisztikal Ertesito, 19, (1976) 308

59. A. Hebeish, M. H. El-Rafie and A. Waly, "Thiourea-Potassium Bromate Redox System Initiated Graft Polymerization of Methyl Methacrylate and Methacrylic Acid on Nylon 6", Journal of Applied Polymer Science, 14, 12 (1976) 2895 - 2902

60. A. Hebeish, S. H. A. Fattah and M. H. El-Rafie, "Thiourea-Induced Graft Polymerization of Methyl Methacrylate onto Wool in Aqueous Acidic Medium", Journal of Applied Polymer Science, 20, 12 (1976) 3449-3452

61. A. Hebeish, A. Kantouch, A. Bendak and A. El-Torgoman, "Chemical Modification of Polyester/Cotton Blend: Part III: Acetylation", Kolorisztikal Ertesito, 18, (1976) 214

62. A. Hebeish and A. Schliefer, "Free Formaldehyde in Fabrics Treated with N-Methylol Finishing Agents", Textile Research Journal, 46, (1976) 465

63. M. Kamel, A. Hebeish and I. Abd El-Thalouth, "Chemical Modification of Cmc Via Cyanoethylation to Make It Suitable for Cellulosic Fabric Printing and Other Purposes", Egyptian Patent, 661. (1976)

64. M. M. Kamel and A. Hebeish, "Behavior of Cellulose Grafted with Poly(Methyl Methacrylate) and Polyacrylonitrile toward Some Direct and Reactive Dyes", Journal of Applied Polymer Science, 20, 9 (1976) 2407-2418

65. I. Abd El-Thalouth, H. L. Hanna and A. Hebeish, "Oxidation of Carboxymethyl Starch with Sodium Hypochlorite", Textile Research Journal, 47, 3 (1977) 209-211

152

66. S. H. Abdel-Fattah, A. Kantouch and A. Hebeish, "Permanent Set of Wool by Monoethaiolamine Sulphite", Kolorisztikal Ertesito, 19, (1977) 23

67. S. H. Abdel-Fattah, S. E. Shalaby, E. A. Allam and A. Hebeish, "Benzoyl Peroxide-Induced Graft Polymerization of 2-Methyl-5-Vinylpyridine onto Polyester/Wool Blend", Journal of Applied Polymer Science, 21, 12 (1977) 3355-3365

68. A. Hebeish, "Studies on Chemically Modified Celluloses", Paper Presented at the 'Chemistry Workshop “Chemical Modification of Cotton”, Sponsored by National Research Center and American Chemical Society', Cairo, Nov. 28 - Dec., 8.(1977),

69. A. Hebeish, E. Allam, A. Hamza, M. Shams and M. Kamel, "Concurrent Dyeing and Finishing of Polyester Cotton Blend", Kolorisztikal Ertesito, 19, (1977) 28

70. A. Hebeish, M. H. El-Rafie, M. I. Khalil and A. Bendak, "Graft Copolymerization of Vinyl Monomers onto Modified Cotton: Part VIII: Dimethylaniline/Benzyl Chloride Induced Grafting of Methyl Methacrylate onto Partially Carboxymethylated Cotton", Journal of Applied Polymer Science, 21, 7 (1977) 1901-1910

71. A. Hebeish, M. H. El-Rafie, M. I. Khalil and A. Bendak, "Grafting of Nylon 66 with Methyl Methacrylate Using Dimethylaniline-Benzyl Chloride-Acetic Acid Initiating System", Journal of Applied Polymer Science, 21, 7 (1977) 1965-1970

72. A. Hebeish, M. M. Kamel, M. H. El-Rafie, E. A. El-Alfy and M. Kamel, "Evaluation of Simultaneous Dyeing and Finishing of Cotton Fabric in Alkaline Medium: Part I: Mode and Mechanisms of the Reaction", Kolorisztikal Ertesito, 19, 9-10 (1977) 295

73. A. Hebeish, A. Kantouch, A. Bendak, A. Z. Morsi and A. El-Torgoman, "Effect of Pretreatment on Dyeing of Cotton with Reactive Dyes: Part II: Light Fading", Cellulose Chemistry and Technology, 11, (1977) 539

74. A. Hebeish, A. Kantouch, A. Bendak, A. Z. Morsi and A. El-Torgoman, "Effect of Pretreatment on Dyeing Properties of Polyester/Cotton Blended Fabrics", Cellulose Chemistry and Technology, 11, (1977) 675

75. A. Hebeish, A. Kantouch, A. Z. Morsi, A. Bendak and A. El-Torgoman, "Effect of Pretreatment of Cotton Dyeing with Reactive Dyes: Part I", Cellulose Chemistry and Technology, 11, (1977) 531

76. A. Hebeish, A. Z. Morsi, M. I. Khalil and F. Abdel-Mohdy, "Dyeing of Chemically Modified Cellulose: Part III: Effect of Chemical Modification of Cellulose on Light Fastness of Some Direct Dyes", Kolorisztikal Ertesito, 19, (1977) 167

153

77. A. Hebeish, A. Z. Moursi, M. I. Khalil and F. A. Abdel-Mohdy, "Dyeing of Chemically Modified Cellulose: Part II: Effect of Chemical Modification of Cellulose on the Dyeing Properties of Some Direct Dyes", Journal of Applied Polymer Science, 21, 8 (1977) 2191-2199

78. M. Kamel, A. Hebeish, M. M. Kamel and R. Mashour, "Acid Catalyzed Reactive Dye for Cotton: Part I: Preparation and Application", American Dyestuff Reporter, 66, 11 (1977) 44-47

79. I. Rusznak, A. Hebeish, E. Allam and N. El-Shinawy, "Behaviour of Polyester/Viscose Blends During Therma Treatment", Kolorisztikal Ertesito, 19, (1977) 99

80. I. Abd El-Thalouth and A. Hebeish, "Cyanoethylated Carboxymethyl Cellulose Pastes for Reactive Dyes", American Dyestuff Reporter, 67, 4 (1978) 24

81. M. A. El-Kashouti, I. Abd El-Thalouth, L. A. Abdou and A. Hebeish, "Utilization of Hexahydrate-1.3.5triacryloyl-S-Triazine in Cotton Printing", Cellulose Chemistry and Technology, 12, (1978) 233

82. H. L. Hanna, I. Abd El-Thalouth and A. Hebeish, "Reaction of Cyanuric Chloride and Its Derivatives with Polyamide Fibres in Non-Aqueous Medium", Die Angewandte Makromolekulare Chemie, 67, (1978) 151

83. A. Hebeish, S. H. Abdel-Fattah and M. H. El-Rafie, "Redox-Initiated Graft Copolymerization onto Wool with Thiourea as Reductant: Part IV: Grafting of Vinyl Sulfone Dyes onto Wool Using Thiourea–H2o2 Redox System", Journal of Applied Polymer Science, 22, 8 (1978) 2253-2264

84. A. Hebeish, N. Y. Abou-Zeid, E. A. El-Alfy and A. Waly, "Studies on Cellulose Carbamate: Part II: Reaction of Cellulose Carbamate with Crosslinking Agent", Cellulose Chemistry and Technology, 12, (1978) 671 - 684

85. A. Hebeish, N. Y. Abou-Zeid, A. Waly and E. A. El-Alfy, "Graft Copolymerization of Vinyl Monomers on Modified Cotton: Part X: Hydrogen Peroxide Induced Grafting of Styrene on Cellulose Carbamate", Die Angewandte Makromolekulare Chemie, 70, (1978) 87 - 99

86. A. Hebeish and A. T. El-Aref, "Improvement of Cellulose Properties Via Chemical Modification", Kolorisztikal Ertesito, 4, (1978) 180

87. A. Hebeish, M. H. El-Rafie, A. Waly and A. Z. Moursi, "Graft Copolymerization of Vinyl Monomers on Modified Cotton: Part IX: Hydrogen Peroxide–Thiourea Dioxide Redox System Induced

154

Grafting of 2-Methyl-5-Vinylpyridine onto Oxidized Celluloses", Journal of Applied Polymer Science, 22, 7 (1978) 1853-1866

88. A. Hebeish, M. M. Kamel, M. H. El-Rafie, E. A. El-Alfy and M. Kamel, "Simultaneous Dyeing and Easy Care Finishing in Alkaline Medium: Part II: Technological Evaluation", Cellulose Chemistry and Technology, 12, (1978) 317

89. A. Hebeish, A. Kantouch and F. K. Soliman, "Studies on Partially Carboxymethylated Cotton: Part V: Novel Application of Partial Carboxymethylation in the Wet Processing of Cotton Fabrics", Cellulose Chemistry and Technology, 12, (1978) 289

90. A. Hebeish, A. Kantouch and F. K. Soliman, "Studies on Partially Carboxymethylated Cotton: Part VI: Behaviour of Partially Carboxymethylated Cotton Towards Bleaching. Dyeing and Easy Care Finishing", Cellulose Chemistry and Technology, 12, (1978) 301

91. A. Hebeish, S. Shalaby and M. El-Shahid, "Graft Polymerization of 2-Methyl-5-Vinyl Pyridine on Poly (Ethylene Terephthalate) Fibres Using H2o2 as Initiator", Die Angewandte Makromolekulare Chemie, 66, (1978) 139

92. A. Hebeish, S. E. Shalaby, E. Allam and M. F. El-Shahid, "Chemical Modification of Polyester/Cotton Blends. III. Grafting with 2-Methyl-5-Vinylpyridine", Journal of Applied Polymer Science, 22, 3 (1978) 847-850

93. A. Hebeish, S. E. Shalaby and A. M. Bayazeed, "Graft Copolymerization of 2-Methyl-5-Vinyl Pyridine to Poly(Ethylene Terephthalate) Fibres Using a Post-Radiation Technique", Journal of Applied Polymer Science, 22, 11 (1978) 3335-3342

94. A. Hebeish, A. Waly, A. Z. Moursi and M. H. El-Rafie, "Preparation of Chemically Modified Cotton Via Introduction of Aromatic Amino Groups", Journal of Applied Polymer Science, 22, 9 (1978) 2713-2716

95. A. Hebeish, A. I. Waly, N. Y. Abou-Zeid and E. A. El-Alfy, "Studies on Cellulose Carbamate: Part I: Reaction of Cellulose Carbamate with Aromatic Amines", Textile Research Journal, 48, 8 (1978) 468-472

96. S. E. Shalaby, A. M. Bayazeed and A. Hebeish, "Factors Affecting Polymerization of 2-Methyl-5-Vinylpyridine in Poly(Ethylene Terephthalate) Fibers Using Benzoyl Peroxide as Initiator", Journal of Applied Polymer Science, 22, 5 (1978) 1359-1375

97. A. Baghash, A. Hebeish and A. El-Hadidy, "Utilization of Light Microscope in Predicating Cotton Strength and Fibre Damage", Cellulose Chemistry and Technology, 13, (1979) 195

155

98. M. A. El-Kashouti, M. M. Kamel and A. Hebeish, "Heat Transfer Printing of Cotton and Polyester/Cotton Blends", Cellulose Chemistry and Technology, 13, (1979) 307

99. N. El-Shinawy, E. Allam and A. Hebeish, "Graft Polymerization of Acrylonitrile on Linen", Cellulose Chemistry and Technology, 13, (1979) 665

100. A. Hebeish, I. Abd El-Thalouth and M. El-Kashouti, "Novel Method for Heat Transfer Printing Using Sodium Alginate Film", Egy. Patent, 327. (1979)

101. A. Hebeish, I. Abd El-Thalouth and M. El-Kashouti, "Novel Thickening Agent for Cotton Yarn Sizing and Other Purposes", Egy. Patent, 72. (1979)

102. A. Hebeish, I. Abd El-Thalouth, M. El-Kashouti and S. H. Abdel-Fattah, "Graft Polymerization of Acrylonitrile on Starch Using Potassium Permanganate as Initiator", Die Angewandte Makromolekulare Chemie, 78, (1979) 101 - 107

103. A. Hebeish, E. Allam, A. T. El-Aref and M. R. El-Zairy, "Technological Evaluation of Concurrent Dyeing and Finishing of Polyester/Cotton Blend", Cellulose Chemistry and Technology, 13, (1979) 93

104. A. Hebeish, A. M. Bayazeed and S. E. Shalaby, "Dyeing Properties of Poly(Methyl Vinyl Pyridine)-Poly(Ethylene Terephthalate) Graft Copolymers", Journal of Applied Polymer Science, 23, 10 (1979) 3051-3059

105. A. Hebeish, A. T. El-Aref, E. Allam and Z. El-Hilw, "Studies of Some Basic Aspects in Easy Care Cotton Finishing: Part I: Nature of Substrate and Methods of Application", Die Angewandte Makromolekulare Chemie, 80, (1979) 177

106. A. Hebeish, A. T. El-Aref, E. A. El-Alfy and M. H. El-Rafie, "Effect of Short Thermal Treatment on Cotton Degradation", Journal of Applied Polymer Science, 23, 2 (1979) 453-462

107. A. Hebeish, A. T. El-Aref and M. H. El-Rafie, "Graft Copolymerization of Vinyl Monomers onto Modififed Cotton: Part XI: Cerium Induced Grafting of Methyl Methacrylate onto Allylated Cotton", Die Angewandte Makromolekulare Chemie, 78, (1979) 195

108. A. Hebeish, M. A. El-Kashouti and M. M. Kamel, "Heat Transfer Printing of Cotton and Polyester/Cotton Blends", Egyptian Patent, 189. (1979)

109. A. Hebeish, M. H. El-Rafie, M. M. Kamel and A. T. El-Aref, "Improving Soil-Release Properties of Easy-Care Cotton Via

156

Chemical Modification", Journal of Applied Polymer Science, 24, 9 (1979) 2071-2072

110. A. Hebeish, M. Kamel, S. A. Amin, M. S. Affifi and F. M. Tera, "Reflection Spectra of Simple Mono-Azo Dyestuffs on Polyamide Fabric and Their Relations to the Association and Light Fastness Properties of the Dyes", Kolorisztikal Ertesito, 21, 3 (1979) 126-133

111. A. Hebeish, M. Kamel, S. A. Amin, M. S. Affifi and F. M. Tera, "The Relation between Light-Fastness and Physical Properties of Simple Mono-Azo Dyestuffs", Textile Research Journal, 49, 5 (1979) 260

112. A. Hebeish and M. M. Kamel, "Catalysts for Easy Care Cotton Finishing", Kolorisztikal Ertesito, 1, (1979) 34

113. A. Hebeish, E. M. Khalil, A. Waly and M. H. El-Rafie, "Behaviour of Chemically Modified Cellulose Towards Dyeing: Part IV: Dyeability of Poly(Methyl Vinyl Pyridine)-Cellulose Graft Copolymers before and after Treatment with Epichlorohydrin", Journal of Applied Polymer Science, 23, 10 (1979) 3061-3069

114. A. Hebeish, A. Z. Moursi, A. Waly and M. H. El-Rafie, "Dyeing of Chemically Modified Cellulose: Part IV: Dyeing of Oxidized Celluloses with Some Reactive and Direct Dyes", Journal of Applied Polymer Science, 24, 2 (1979) 385-394

115. A. Hebeish, F. A. Nassar, N. A. Ibrahim and A. M. Islam, "Studies of Some Basic Aspects in Easy Care Cotton Finishing: Part II: Influence of Urea Pad on Free Formaldehyde and Strength of Crosslinked Cotton", Die Angewandte Makromolekulare Chemie, 81, 1 (1979) 95 - 107

116. A. Hebeish, F. A. Nassar, N. A. Ibrahim and A. M. Islam, "Studies of Some Basic Aspects in Easy Care Cotton Finishing: Part III: Catalysts", Die Angewandte Makromolekulare Chemie, 82, 1 (1979) 11 - 25

117. A. Hebeish, F. A. Nassar, N. A. Ibrahim and A. M. Islam, "Studies of Some Basic Aspects in Easy Care Cotton Finishing: Part IV: Effect of Acid Scavengers on Free Formaldehyde in and Strength of Crosslinked Cotton", Die Angewandte Makromolekulare Chemie, 82, 1 (1979) 27 - 37

118. A. Hebeish, S. Shalaby and A. Bayazeed, "Vinyl Graft Copolymerization onto Poly (Ethylene Terephthalate) Fibres", Kolorisztikal Ertesito, 21, (1979) 2

119. A. Hebeish, S. Shalaby and A. Bayazeed, "Some Properties of Poly (Methyl Vinyl Pyridine)-Poly (Ethylene Terephthalate) Graft

157

Copolymers with Special Reference to Dyeing Properties", Journal of Applied Polymer Science, 23, 10 (1979) 3051 - 3059

120. A. Hebeish, M. Tawfik, M. H. El-Rafie, I. Abd El-Thalouth, A. T. El-Aref, E. Allam and A. Waly, "Mechanisms of Degradation of Cotton and Effects of Mercerization Stretching Upon the Course of These Mechanisms. Part II. Hypochlorite Treatments", Cellulose Chemistry and Technology, 13, (1979) 717

121. A. Hebeish, A. Waly, E. A. El-Alfy, N. Y. Abou-Zeid, A. T. El-Aref and M. H. El-Rafie, "Behaviour of Chemically Modified Cellulose Towards Dyeing: Part VI: Dyeing of Methylolated Cellulose Carbamate with Different Classes of Dyestuffs", Cellulose Chemistry and Technology, 13, (1979) 327 - 340

122. A. Hebeish, A. Waly and M. A. El-Kashouti, "Durable Flame Resistance Via Reaction of Cotton Cellulose Bearing Aromatic Amino Groups with Tetrakis(Hydroxymethyl)Phosphonium Chloride", Journal of Applied Polymer Science, 23, 6 (1979) 1803-1810

123. A. Hebeish, A. Waly, M. Tawfik, N. Y. Abou-Zeid, S. Shalaby and M. H. El-Rafie, "Mechanism of Degradation of Cotton and Effects of Mercerization Stretching Upon the Course of These Mechanisms. Part I. Acid Degradation", Cellulose Chemistry and Technology, 13, (1979) 543 - 564

124. M. Kamel, A. Hebeish, M. M. Kamel and R. Mashoor, "Acid Catalyzed Reactive Dye for Cotton: Part II: Light Fading", American Dyestuff Reporter, 68, 7 (1979) 31 - 33

125. S. Shakra, H. L. Hanna and A. Hebeish, "Effect of Ph Control on Dyeing of Polyester Materials with Disperse Dyes", Die Angewandte Makromolekulare Chemie, 75, (1979) 53-62

126. M. H. El-Rafie, E. M. Abdel-Bary, A. El-Hussini and A. Hebeish, "Dyeing of Chemically Modified Cellulose: Part VIII: Behaviour of Cellulose Graft Copolymers Towards Dyeing with Different Classes of Dyestuffs", Die Angewandte Makromolekulare Chemie, 88, (1980) 193

127. M. H. El-Rafie, S. H. Abdel-Fattah, E. M. Khalil and A. Hebeish, "The Cupric Sulphate-Hydrazine Hydrate System as an Initiator for Vinyl Graft Polymerization onto Wool", Die Angewandte Makromolekulare Chemie, 87, (1980) 63-74

128. A. Hebeish, E. M. Abdel-Bari, M. H. El-Rafie and A. El-Hassini, "Graft Polymerization of Vinyl Monomers onto Modified Cotton: Part XIII: Grafting of Methyl Methacrylate onto Partially Carboxymethylated Cotton Using Fe2+/H2o2 Redox System", Cellulose Chemistry and Technology, 14, (1980) 159

158

129. A. Hebeish, E. M. Abdel-Bary, A. Waly and S. Bedewy, "Graft Polymerization of Vinyl Monomers onto Modified Cotton: Part XV: Initiation by Decomposition of Aryl Diazonium Groups", Die Angewandte Makromolekulare Chemie, 86, (1980) 47

130. A. Hebeish, E. A. El-Alfy, A. Waly and N. Y. Abou-Zeid, "Graft Copolymerization of Vinyl Monomers onto Modified Cotton: Part XII: Grafting of 1,1-Dihydroperfluoroheptyl Acrylate onto Cellulose Carbamate Using Hydrogen Peroxide as Initiator", Journal of Applied Polymer Science, 25, 2 (1980) 223-233

131. A. Hebeish, M. El-Kashouti and I. Abd El-Thalouth, "Novel Method for Preparation of Viscous Material Suitable for Sizing without Using Energy", Egy. Patent, 305. Nov., (1980)

132. A. Hebeish, M. H. El-Rafie, E. M. Abdel-Bary and A. El-Hussini, "Graft Copolymerization of Vinyl Monomers onto Modified Cotton: Part XVII: Continuous and Semi – Continuous Methods for Grafting of Partially Carboxymethylated Cotton with Acrylamide", Die Angewandte Makromolekulare Chemie, 88, (1980) 89

133. A. Hebeish, A. Waly, E. M. Khalil and M. H. El-Rafie, "Graft Polymerization of Vinyl Monomers onto Modified Cotton: Part XIV: Poly (Methyl Vinyl Pyridine) – Partially Carboxy-Methylated Cotton Graft Copolymers as a Base for Flame Resistance Cotton", Cellulose Chemistry and Technology, 14, (1980) 169

134. A. Hebeish, A. Waly, A. Z. Moursi and F. A. Abdel-Mohdy, "Dyeing of Chemically Modified Cellulose: Part VII: Dyeability of Cellulose Bearing Aromatic Amino, Nitro, and Acrylamidomethyl Groups", Journal of Applied Polymer Science, 25, 3 (1980) 457-467

135. I. Abd El-Thalouth, M. El-Kashouti and A. Hebeish, "Heat Transfer Printing of Polyester Using Coloured Alginate Films", Die Angewandte Makromolekulare Chemie, 91, (1981) 99

136. I. Abd El-Thalouth, M. A. El-Kashouti and A. Hebeish, "Chemical Modification of Starch: Part III: Improved Rheological Properties of Starch through Aqueous Cyanoethylation", Die Angewandte Makromolekulare Chemie, 85, (1981) 173

137. I. Abd El-Thalouth, M. A. El-Kashouti and A. Hebeish, "Modification of Rice Starch through Thermal Treatment with Urea", Starch - Stärke, 33, 9 (1981) 306-310

138. N. Y. Abou-Zeid, W. Anwar and A. Hebeish, "Dyeing of Chemically Modified Cellulose: Part VII: Behaviour of Methylolated Carbamoylethylated Cellulose Towards Different

159

Classes of Dyestuffs", Cellulose Chemistry and Technology, 15, (1981) 321 - 330

139. N. Y. Abou-Zeid, W. Anwar and A. Hebeish, "Graft Copolymerization of Vinyl Monomers onto Modified Cotton: Part XVI: Grafting of Acrylonitrile and Methacrylate onto Methylolated Carbamoylethyl Cellulose Using Ceric Ammonium Sulphate as Initiator", Cellulose Chemistry and Technology, 16, 1 (1981) 59 - 66

140. E. El-Alfy and A. Hebeish, "Ce+4 Induced Polymerization of Allyl Methacrylate with Cotton Cellulose", Journal of Polymer Science: Part A-1: Polymer Chemistry, 19, 12 (1981) 3137-3143

141. M. A. El-Kashouti, I. Abd El-Thalouth and A. Hebeish, "Utilization of Cmc Films in Transfer Printing", Cellulose Chemistry and Technology, 15, (1981) 305

142. M. H. El-Rafie, M. A. El-Kashouti, A. El-Hussini and A. Hebeish, "Heat Transfer Printing of Partially Carboxymethylated Cotton Graft Copolymers", Cellulose Chemistry and Technology, 15, (1981) 199

143. M. H. El-Rafie, M. A. El-Kashouti, F. El-Sisi and A. Hebeish, "Dyeing of Chemically Modified Cellulose: Part X: Dyeing of Cotton Graft Copolymers with Some Direct, Basic and Reactive Dyes", Cellulose Chemistry and Technology, 15, (1981) 427

144. M. F. El-Shahed, S. E. Shalaby and A. Hebeish, "Improving Antistatic Properties of Poly(Methylvinylpyridine)–Poly(Ethylene Terephthalate) Graft Copolymers Via Alkylation", Journal of Applied Polymer Science, 26, 4 (1981) 1129-1134

145. A. Hebeish, I. Abd El-Thalouth and M. A. El-Kashouti, "Chemical Modification of Starch: Part II: Cyanoethylation", Journal of Applied Polymer Science, 26, 1 (1981) 171-176

146. A. Hebeish, I. Abd El-Thalouth and M. E. Kashouti, "Gelatinization of Rice Starch in Aqueous Urea Solutions", Starch - Stärke, 33, 3 (1981) 84-90

147. A. Hebeish, N. Y. Abou-Zeid, E. A. El-Kharadly, A. T. El-Aref, E. Allam, S. Shalaby and E. A. El-Alfy, "Mechanism of Degradation of Cotton and Effects of Mercerization-Stretching Upon the Course of These Mechanisms: Part V: Weathering", Journal of Applied Polymer Science, 26, 8 (1981) 2713-2725

148. A. Hebeish, E. Allam, A. Bendak, N. Y. Abou-Zeid, M. Tawfik, M. H. El-Rafie and S. H. A. Fattah, "Mechanism of Degradation of Cotton and Effects of Mercerization-Stretching Upon the Course of These Mechanisms: Part IV: Ultraviolet Treatment", Cellulose Chemistry and Technology, 15, (1981) 535 - 550

160

149. A. Hebeish, E. Allam, E. A. El-Alfy, N. Y. Abou-Zeid and A. Waly, "Behaviour of Chemically Modified Cellulose Towards Dyeing: Part XIII: Dyeability of Poly (Glycidyl Methacrylate). Containing Cotton with Different Dyes", Textilveredlung, 16, 11 (1981) 448 - 450

150. A. Hebeish, E. Allam and A. T. El-Aref, "Effect of Mercerization-Stretching on Dyeing of Cotton with a Direct Dye", Textilveredlung, 16, 5 (1981) 174

151. A. Hebeish, M. H. El-Rafie, M. A. El-Kashouti and F. El-Sisi, "Graft Copolymerization of Vinyl Monomers onto Modified Cotton: Part XXI: Cu2+-Hydrazine Hydrate Redox System Induced Grafting of Methyl Methacrylate on Periodate Oxidized Cellulose", Die Angewandte Makromolekulare Chemie, 93, (1981) 97

152. A. Hebeish, M. H. El-Rafie and F. El-Sisi, "Graft Copolymerization of Vinyl Monomers onto Modified Cotton: Part XXII: Ceric-Induced Grafting of Acrylonitrile on Cellulose Bearing Nitrogen Containing Groups", Die Angewandte Makromolekulare Chemie, 95, (1981) 149

153. A. Hebeish, M. H. El-Rafie and M. I. Khalil, "Effect of Mercerization-Stretching on Vinyl Graft Polymerization of Cotton", Die Angewandte Makromolekulare Chemie, 101, (1981) 1

154. A. Hebeish, M. M. El-Rafie, M. A. El-Kashouti and F. El-Sisi, "Graft Copolymerization of Vinyl Monomers on Modified Cotton: Part XVIII: Grafting of Methyl Methacrylate and Acrylonitrile on Cotton Treated with N-Methylol Crosslinking Agents Using Tetravalent Cerium as Initiator", Journal of Applied Polymer Science, 26, 12 (1981) 3995-4009

155. A. Hebeish and N. A. Ibrahim, "Utilization of Phosphorous Containing Compounds in Textile Chemical Processing: Part 1", Kolorisztikal Ertesito, 24, 5-8 (1981) 175

156. A. Hebeish, S. E. Shalaby and A. M. Bayazeed, "Graft Polymerization of Methyl Methacrylate on Poly(Ethylene Terephthalate) Fibers Using H2o2 as Initiator", Journal of Applied Polymer Science, 26, 10 (1981) 3253-3269

157. A. Hebeish, S. E. Shalaby and A. M. Bayazeed, "H2o2-Induced Graft Polymerization of Acrylic Acid on Poly(Ethylene Terephthalate) Fibers", Journal of Applied Polymer Science, 26, 10 (1981) 3245-3251

158. A. Hebeish, A. Waly and F. A. Abdel Mohdy, "Dyeing of Chemically Modified Cellulose. Part XI. Fading Characteristics of Cellulose Bearing Aromatic Amino Groups and

161

Acrylamidomethylated Cellulose Dyed with Some Direct and Reactive Dyes", Cellulose Chemistry and Technology, 15, (1981) 629

159. A. Hebeish, A. Waly, E. M. Abdel-Bary and S. Bedewy, "Graft Copolymerization of Vinyl Monomers onto Modified Cotton: Part XIX: Grafting of Methyl Methacrylate on Tertiary Aminized Cotton Using Bisulphite-Hydrogen Peroxide Redox System", Cellulose Chemistry and Technology, 15, (1981) 441

160. A. Hebeish, A. Waly, E. M. Abdel-Bary and S. Bedewy, "Graft Copolymerization of Vinyl Monomers onto Modified Cotton: Part XX: Grafting of Methyl Methacrylate on Cellulose Containing Sulphonic Acid Groups Using Fe2+-Hydrogen Peroxide Redox System", Cellulose Chemistry and Technology, 15, (1981) 505

161. A. Hebeish, A. Waly and F. A. Abdel-Mohdy, "Dyeing of Chemically Modified Cellulose. Part X. Behaviour of Cellulose Copolymerized with Poly (Methyl Methacrylate) and Poly Styrene, Poly (Methyl Vinyl Pyridine) Towards Dyeing with Some Direct and Reactive Dyes", Die Angewandte Makromolekulare Chemie, 95, (1981) 55

162. A. Hebeish, N. Y. A. Zeid, S. Shalaby, A. T. El-Aref, A. Waly, I. Abd El-Thalouth and M. Tawfik, "Mechanism of Degradation of Cotton and Effects of Mercerization-Stretching Upon the Course of These Mechanisms: Part III: Heat Treatment", Die Angewandte Makromolekulare Chemie, 99, (1981) 93 - 116

163. M. I. Khalil, S. S. Aggour, M. H. El-Rafie and A. Hebeish, "Graft Polymerization of Methyl Methacrylate onto Nylon 6 Using Pentavalent Vanadium as Initiator", Die Angewandte Makromolekulare Chemie, 96, (1981) 59

164. M. I. Khalil, M. H. El-Rafie and A. Hebeish, "Pentavalent Vanadium Ion-Induced Grafting of Methyl Methacrylate onto Cotton Cellulose", Journal of Applied Polymer Science, 26, 1 (1981) 149-157

165. M. A. Morsi, E. M. Abdel-Bary, M. A. El-Tamboly and A. Hebeish, "Aqueous and Nonaqueous Vinyl Graft Polymerization in Partially Carboxymethlated Cotton", Cellulose Chemistry and Technology, 15, (1981) 193

166. S. Shakra, H. L. Hanna and A. Hebeish, "Some Fading Characteristics of Various Monoazo Dyes on Polyester", Die Angewandte Makromolekulare Chemie, 93, (1981) 75-81

167. I. Abd El-Thalouth, M. A. El-Kashouti and A. Hebeish, "Novel Method for Heat Transfer Printing of Polyester", Acta Polymerica, 33, 6 (1982) 385

162

168. F. I. Abdel-Hay, M. I. Khalil and A. Hebeish, "Polymerization of Allyl Methacrylate with Wool Fabric Using Different Initiators", Journal of Applied Polymer Science, 27, 4 (1982) 1249-1258

169. N. Y. Abou-Zeid, A. Waly, E. A. El-Alfy and A. Hebeish, "Fe2+/Thioureadioxide/H2o2-Induced Polymerization of Glycidyl Methacrylate and Its Mixtures with Acrylamide, Acrylonitrile, Butylmethacrylate, or Styrene with Cotton Fabric", Journal of Applied Polymer Science, 27, (1982) 2105 - 2117

170. E. Allam, A. T. El-Aref, M. Abou-Amer, A. Hebeish and Z. El-Hilw, "Studies of Some Basic Aspects in Easy Care Cotton Finishing: Part V: Crosslinking of Partially Carboxymethylated Cotton Using the Pad-Wet-Batch Method", Kolorisztikal Ertesito, 24, 6 (1982) 295-303

171. A. T. El-Aref, E. Allam, M. Abou-Amer, Z. El-Hilw and A. Hebeish, "Behavior of Chemically Modified Cellulose Towards Dyeing: Part XIV: Behavior of Cotton and Crosslinked Cottons before and after Mercerization Towards Some Reactive Dyestuffs", Journal of Applied Polymer Science, 27, 3 (1982) 871-878

172. M. A. El-Kashouti, I. Abd El-Thalouth and A. Hebeish, "Transfer Printing of Chemically Modified Polyester/Cotton Blend", Acta Polymerica, 33, (1982) 221

173. H. L. Hanna, S. Shakra and A. Hebeish, "Solvent Pretreatment to Modify Polyester Dyeability", American Dyestuff Reporter, 71, 4 (1982) 24-28

174. A. Hebeish, I. Abd El-Thalouth and F. K. Soliman, "Effect of Sodium Hydroxide on Some Important Properties of Cotton Fabrics", Cellulose Chemistry and Technology, 16, 5 (1982) 485

175. A. Hebeish, N. Y. Abou-Zeid and N. Anwar, "Chemical Modification of Cotton through Reaction with Alkoxy Adducts of Acrylamide and Hexahydro-1.3.5-Triacryloyl-S-Triazine in Nonaqueous Medium", Die Angewandte Makromolekulare Chemie, 91, (1982) 77 - 97

176. A. Hebeish, N. Y. Abou-Zeid, E. El-Kharadly, S. Shalaby, S. H. Abdel-Fattah, E. A. El-Alfy and H. I. Nasr, "Chemical Factors Affecting Soiling and Soil Release from Cotton Containing Durable Press Fabrics: Part II: Cotton Cellulose Grafted with Poly (Acrylic Acid) and Poly (Methacrylic Acid)", Cellulose Chemistry and Technology, 16, 4 (1982) 383 - 391

177. A. Hebeish, E. Allam, A. Bendak, S. Shakra and L. A. Abdou, "Chemical Factors Affecting Soiling and Soil Release from Cotton Containing Durable Press Fabrics: Part VII: Application of

163

Conventional Soil-Release Finishes During Crosslinking of Cotton Fabric", Cellulose Chemistry and Technology, 16, (1982) 405 - 409

178. A. Hebeish, S. A. Amin, F. A. Nassar, N. A. Ibrahim and H. L. Hanna, "Chemical Factors Affecting Soiling and Soil Release from Cotton Containing Durable Press Fabrics: Part III: Application of Cmc During the Crosslinking Treatment", Cellulose Chemistry and Technology, 16, (1982) 405

179. A. Hebeish, M. H. El-Rafie, A. T. El-Aref, M. I. Khalil, I. Abd El-Thalouth, M. El-Kashouti and M. M. Kamel, "Chemical Factors Affecting Soiling and Soil Release from Cotton Containing Durable Press Fabrics: Part VI: Effect of Introduction of Carboxymethyl Groups in the Cotton Component of Polyester/Cotton Blend", Journal of Applied Polymer Science, 27, 10 (1982) 3703-3719

180. A. Hebeish, M. H. El-Rafie, M. M. Kamel, I. Abd El-Thalouth, A. T. El-Aref, M. H. El-Kashouti and M. I. Khalil, "Chemical Factors Affecting Soiling and Soil Release from Cotton Containing Durable Press Fabrics: Part I: Cotton Cellulose Bearing Carboxymethyl Substituents", Cellulose Chemistry and Technology, 16, (1982) 287

181. A. Hebeish, H. L. Hanna and S. Shakra, "Improved Dyeability of Polyester Pretreated with Carriers", American Dyestuff Reporter, 71, 3 (1982) 24-28

182. A. Hebeish and N. A. Ibrahim, "Studies of Some Basic Aspects in Easy Care Cotton Finishing: Part VIII: Crosslinking of Cotton Using Urea Phosphate as Catalyst", Kolorisztikal Ertesito, 24, (1982) 305 - 311

183. A. Hebeish and N. A. Ibrahim, "Utilization of Phosphorous Containing Compounds in Textile Chemical Processing: Part 2", Kolorisztikal Ertesito, 24, 1 (1982) 118

184. A. Hebeish and N. A. Ibrahim, "Studies of Some Basic Aspects in Easy Care Cotton Finishing: Part VI: Urea Nitrate Catalyzes Crosslinking of Cotton", Textile Research Journal, 52, 2 (1982) 116-122

185. A. Hebeish and N. A. Ibrahim, "Studies of Some Basic Aspects in Easy Care Cotton Finishing: Part VII: Urea Oxalate as a Catalyst for Crosslinking", Acta Polymerica, 33, 6 (1982) 381 - 384

186. A. Hebeish, N. A. Ibrahim, F. A. Nassar, H. L. Hanna and S. A. Amin, "Chemical Factors Affecting Soiling and Soil Release from Cotton Containing Durable Press Fabrics: Part IV: Inclusion of

164

Cmc in Crosslinking Polyester/Cotton Blend", Kolorisztikal Ertesito, 24, (1982) 325

187. A. Hebeish, S. Shalaby and A. Bayazeed, "H2o2-Induced Graft Polymerization of Acrylic Acid/Styrene Mixtures on Poly(Ethylene Terephthalate) Fibers", Journal of Applied Polymer Science, 27, 1 (1982) 197-209

188. A. Hebeish, S. E. Shalaby and A. M. Bayazeed, "Vinyl Graft Polymerization-Induced Modification of Some Properties of Poly(Ethylene Terephthalate) Fabric", Journal of Applied Polymer Science, 27, 10 (1982) 3683-3690

189. N. A. Ibrahim and A. Hebeish, "The Problem of Free Formaldehyde in Cellulosic-Containing Durable Press Fabrics", Kolorisztikal Ertesito, 24, (1982) 313

190. M. I. Khalil, F. I. Abdel-Hay and A. Hebeish, "Polymerization of Allyl Methacrylate with Nylon 6 Using Benzoyl Peroxide as Initiator", Die Angewandte Makromolekulare Chemie, 103, 1 (1982) 143-152

191. M. I. Khalil, S. S. Aggour and A. Hebeish, "Behaviour of Nylon Graft Copolymers Towards Disperse, Acid and Direct Dyes", Textilveredlung, 17, 6 (1982) 263

192. M. I. Khalil, O. I. Aglan and A. Hebeish, "Behaviour of Cellulose Graft Copolymers Towards Persulphate Oxidation: Part III: Poly(Acrylonitrile) Graft Copolymers", Journal of Applied Polymer Science, 27, 7 (1982) 2377-2386

193. M. I. Khalil, O. I. Aglan and A. Hebeish, "Behaviour of Cellulose Graft Copolymers Towards Persulphate Oxidation: Part I: Methyl Methacrylate Graft Copolymers", Acta Polymerica, 33, 7 (1982) 437

194. M. I. Khalil, E. A. El-Alfy, M. H. El-Rafie and A. Hebeish, "Graft Polymerization of Methyl Methacrylate on Cellulose Carbamate and Modified Cotton Derived from It", Cellulose Chemistry and Technology, 16, 5 (1982) 465 - 472

195. M. I. Khalil, M. H. El-Rafie, A. Bendak and A. Hebeish, "Graft Polymerization of Methyl Methacrylate onto Wool Using Dimethylaniline/Copper(II) System", Journal of Applied Polymer Science, 27, 2 (1982) 519-526

196. S. Shakra, N. A. Ibrahim and A. Hebeish, "Mode of Interaction of Direct Dyes with Cotton Cellulose", Kolorisztikal Ertesito, 24, 1 (1982) 133

197. A. Waly, N. Y. Abou-Zeid, E. A. El-Alfy and A. Hebeish, "Polymerization of Glycidyl Methacrylate, Methacrylic Acid, Acrylamide and Their Mixtures with Cotton Fabric Using Fe2+-

165

Thioureadioxide-H2o2 Redox System", Die Angewandte Makromolekulare Chemie, 103, (1982) 61 - 76

198. F. A. Abdel Mohdy, M. I. Khalil and A. Hebeish, "Comparative Investigations in Esterification of Cellulose Obtained with Acetic and Trifluoroacetic Anhydrides", Cellulose Chemistry and Technology, 17, (1983) 569 - 573

199. E. El-Kharadly and A. Hebeish, "Reaction of Acrylamidomethylated Cellulose with Some Amino Compounds", Cellulose Chemistry and Technology, 17, (1983) 461 - 466

200. M. H. El-Rafie, E. M. Khalil, S. A. Abdel-Hafiz and A. Hebeish, "Behaviour of Chemically Modified Cotton Towards Thermal Treatment: Part II: Cyanoethylated Cotton", Journal of Applied Polymer Science, 28, 1 (1983) 311-326

201. M. H. El-Rafie, E. M. Khalil, S. A. Abdel-Hafiz and A. Hebeish, "Behaviour of Chemically Modified Cotton Towards Thermal Treatments: Part IV: Poly(Acrylamide)/Cellulose Graft Copolymers", Cellulose Chemistry and Technology, 17, (1983) 629

202. M. H. El-Rafie, E. M. Khalil, S. A. Abdel-Hafiz and A. Hebeish, "Behaviour of Chemically Modified Cotton Towards Thermal Treatments: Part III: Poly (Acrylonitrile)- Cellulose Graft Copolymers", Acta Polymerica, 34, 1 (1983) 231

203. A. Hebeish, N. Y. Abou-Zeid, E. El-Kharadly, S. E. Shalaby, E. A. El-Alfy, S. H. Abdel-Fattah, A. M. Bayazeed and H. Nasr, "Chemical Factors Affecting Soiling and Soil Release from Cotton Containing Durable Press Fabrics: Part VIII: Grafting of Polyester/Cotton Blend Fabrics with Carboxyl-Containing Polymer", Journal of Applied Polymer Science, 28, 3 (1983) 1179-1193

204. A. Hebeish, N. Y. Abou-Zeid, A. Waly and E. A. El-Alfy, "Chemical Factors Affecting Soiling and Soil Release from Cotton Containing Durable Press Fabrics: Part XV: Copolymerization with Mixtures of Vinyl Monomers", American Dyestuff Reporter, 72, 10 (1983) 25-32

205. A. Hebeish, A. Bendak, E. Allam, L. A. Abdou and S. Shakra, "Chemical Factors Affecting Soiling and Soil Release from Cotton Containing Durable Press Fabrics: Part V: Incorporation of Conventional Soil-Release Finishes During the Crosslinking Treatments of Polyester/Cotton Blend", Kolorisztikal Ertesito, 25, 1 (1983) 3

166

206. A. Hebeish, M. A. El Kashouti and I. Abd El-Thalouth, "New Approaches for Heat Transfer Printing Nylon 6", American Dyestuff Reporter, 72, 2 (1983) 24-26, 28

207. A. Hebeish, E. El-Alfy, A. Waly and N. Y. Abou-Zeid, "Chemical Factors Affecting Soiling and Soil Release from Cotton Containing Durable Press Fabrics: Part XIII: Polymerization of Styrene and Glycidyl Methacrylate", American Dyestuff Reporter, 72, 8 (1983) 49 - 50, 67 - 73

208. A. Hebeish, E. Elkharadly, S. H. Abdel Fattah and H. Nasr, "Chemical Factors Affecting Soiling and Soil Release from Cotton Containing Durable Press Fabrics: Part XIV: Grafting with Polyacrylamide", American Dyestuff Reporter, 72, 9 (1983) 48-55, 64

209. A. Hebeish, E. A. El-Kharadly and N. A. Ibrahim, "Effect of Catalysts on Rot-Proofing Cotton Containing Durable Press Fabrics", American Dyestuff Reporter, 72, 10 (1983) 42-45, 52

210. A. Hebeish, M. H. El-Rafie, N. Y. Abou-Zeid, M. M. Kamel, A. Waly, A. T. El-Aref and I. S. Fraag, "Mechanisms of Degradation of Cotton and Effects of Mercerization-Stretching Upon the Course of These Mechanisms: Part VI: Structural Differences between Scoured Cotton and Slack-Mercerized/Stretched Cottons", Die Angewandte Makromolekulare Chemie, 111, (1983) 69 - 84

211. A. Hebeish, E. M. Khalil, M. H. El-Rafie and S. A. Abdel-Hafiz, "Behaviour of Chemically Modified Cotton Towards Thermal Treatments: Part I: Partially Carboxymethlated Cotton", Die Angewandte Makromolekulare Chemie, 112, (1983) 107

212. A. Hebeish, S. Shalaby, A. Waly and A. Bayazeed, "Polymerization of Glycidyl Methacrylate with Poly(Ethylene Terephthalate) Fibres Using Ferrous-Ion/Hydrogen Peroxide Redox System", Journal of Applied Polymer Science, 28, 1 (1983) 303-310

213. A. Hebeish, A. Waly, N. Y. Abou-Zeid and E. A. El-Alfy, "Chemical Factors Affecting Soiling and Soil Release from Cotton Containing Durable Press Fabrics: Part XVI: Copolymerization of Cotton with Polyacrylonitrile", American Dyestuff Reporter, 72, 7 (1983) 15 - 17, 19 - 21

214. N. Y. Abou-Zeid, A. Higazy and A. Hebeish, "Graft Copolymerization of Styrene, Methylmethacrylate, and Acrylonitrile onto Jute Fibres", Die Angewandte Makromolekulare Chemie, 121, 1 (1984) 69 - 87

167

215. A. Bayazeed, E. A. El-Alfy and A. Hebeish, "Novel Method of Low Temperature Dyeing of Pet and Its Blends", American Dyestuff Reporter, 73, 6 (1984) 24, 26, 28-29

216. E. A. El-Alfy, A. Esmael, F. Mahmoud, A. M. R. Ibrahim and A. Hebeish, "Synthesis and Application of Some New Azo Dyes: Part I: Dyes Prepared by Coupling of N-(O-Hydroxyphenyl)Benzene Sulphonamide with Diazotized Amines", Tinctoria, 81, 9 (1984) 264

217. A. Esmael, E. A. El-Alfy, F. Mahmoud, A. M. R. Ibrahim and A. Hebeish, "Synthesis and Application of Some New Azo Dyes: Part II: Dyes Prepared by Coupling of N-(M-Hydroxylphenyl)Benzene Sulphonamide with Diazotized Amines", Kolorisztikal Ertesito, 24, (1984) 156

218. H. L. Hanna, N. A. Ibrahim and A. Hebeish, "Combined Dyeing and Easy Care Finishing of Cotton Fabric Using Solubilized Vat Dyes and N-Methylol Crosslinking Agents", American Dyestuff Reporter, 73, 10 (1984)

219. A. Hebeish, I. Abd El-Thalouth, M. A. El-Kashouti and M. I. Khalil, "Chemical Factors Affecting Soiling and Soil Release from Cotton Containing Durable Press Fabrics: Part XI: Cotton Bearing Carboxymethyl Together with Cyanoethyl Groups", Acta Polymerica, 35, 2 (1984) 170-175

220. A. Hebeish, A. Bayazeed, B. I. A. Gawad, S. K. Basily and S. El-Bazza, "Action of Hydrogen Peroxide in Strongly Alkaline Solutions on Rice Starch", Starch - Stärke, 36, 10 (1984) 344-349

221. A. Hebeish, A. Bendak, L. A. Abdou, S. Shakra and E. Allam, "Chemical Factors Affecting Soiling and Soil Release from Cotton Containing Durable Press Fabrics: Part XXV: Inclusion of Different Copolymers", Kolorisztikal Ertesito, 26, (1984) 314-371

222. A. Hebeish, S. T. El Sheltawi, H. I. Nasr and K. Haggag, "The Dependence of Soiling and Soil Release on Structural Changes in Cotton Induced by Hypochlorite Oxidation and Crosslinking", Tinctoria, 81, (1984) 365

223. A. Hebeish, E. A. El-Alfy, A. Waly, N. Y. Abou-Zeid and M. H. Abo-Shosha, "Chemical Factors Affecting Soiling and Soil Release from Cotton Containing Durable Press Fabrics: Part XXIII: Polymerization of Styrene and Glycidyl Methacrylate with Pet/Cotton (Polyethylene Terephthalate/Cotton) Blends", American Dyestuff Reporter, 73, 8 (1984) 37-43

224. A. Hebeish, A. T. El-Aref, A. Bayazeed, M. M. Kamel and M. H. El-Rafie, "Chemical Factors Affecting Soiling and Soil Release from Cotton Containing Durable Press Fabrics: Part XVIII:

168

Carbamoylethlation of Cotton / Polyester Blend Fabric", Tinctoria, 81, 10 (1984) 289

225. A. Hebeish, A. T. El-Aref, M. M. Kamel and M. H. El-Rafie, "Chemical Factors Affecting Soiling and Soil Release from Cotton Containing Durable Press Fabrics: Part X: Carbamoylethylation of Cotton", Acta Polymerica, 35, 1 (1984) 99-103

226. A. Hebeish, E. El-Kharadly, S. H. Abdel-Fattah, K. Haggag and M. H. Abo-Shosha, "Chemical Factors Affecting Soiling and Soil Release from Cotton Containing Durable Press Fabrics: Part XXII: Grafting of Polyester / Cotton Blends with Poly Acrylamide", American Dyestuff Reporter, 73, 7 (1984) 32, 34-38

227. A. Hebeish, M. H. El-Rafie, A. T. El-Aref, A. Bayazeed and M. M. Kamel, "Chemical Factors Affecting Soiling and Soil Release from Cotton Containing Durable Press Fabrics: Part XVII: Cyanoethylation of Cotton/ Polyester Blend Fabric", Tinctoria, 81, 6 (1984) 166

228. A. Hebeish, M. H. El-Rafie, A. T. El-Aref and M. M. Kamel, "Chemical Factors Affecting Soiling and Soil Release from Cotton Containing Durable Press Fabrics: Part IX: Cotton Bearing Cyanoethyl Substituents", Acta Polymerica, 35, 1 (1984) 93-98

229. A. Hebeish, K. El-Zoghby and S. Haleem, "Food Stain Removal from Cotton and Pet/Cotton Fabrics", American Dyestuff Reporter, 73, 2 (1984) 36-39

230. A. Hebeish, N. A. Ibrahim, S. A. Amin and H. L. Hana, "Chemical Factors Affecting Soiling and Soil Release from Cotton Containing Durable Press Fabrics: Part XII: Inclusion of Different Additive Compounds in Crosslinked Cotton", Acta Polymerica, 35, 4 (1984) 316-320

231. A. Hebeish, A. Waly, N. Y. Abou-Zeid, E. A. El-Alfy and M. H. Abo-Shosha, "Chemical Factors Affecting Soiling and Soil Release from Cotton Containing Durable Press Fabrics: Part XXI: Copolymerization of Polyester/Cotton Blend with Poly (Acrylonitrile)", American Dyestuff Reporter, 73, 4 (1984) 31-37

232. A. Hebeish, A. Waly, N. Y. Abou-Zeid, N. A. Ibrahim, M. H. El-Rafie, A. T. El-Aref and A. Bayazeed, "Mechanisms of Degradation of Cotton and Effects of Mercerization-Stretching Upon the Course of These Mechanisms: Part VII: Characterization of Microstructural Differences between Scoured Cotton and Slack Mercerized-Stretched Cottons", Die Angewandte Makromolekulare Chemie, 120, (1984) 119 - 148

169

233. A. Bayazeed, E. A. El-Alfy and A. Hebeish, "Polyester Dyeing Improved by Vinyl Grafts", American Dyestuff Reporter, 74, 3 (1985) 38-40

234. A. Bayazeed, M. H. El-Rafie and A. Hebeish, "Ferrous Cellulose Thiocarbonate/Persulphate Redox System Induced Graft Polymerization of Methacrylic Acid onto Cotton Fabric", Acta Polymerica, 36, 2 (1985) 353

235. E. A. El-Alfy, F. Mahmoud, A. M. R. Ibrahim and A. Hebeish, "Synthesis and Application of Some New Azo Dyes: Part III: Dyes Prepared by Coupling of N-(O-Hydroxyphenyl)-P-Toluenesulphonamide with Diazotized Amines", Kolorisztikal Ertesito, 27, 5-6 (1985) 120

236. E. A. El-Alfy, A. Waly and A. Hebeish, "Graft Copolymerization of Perfluoroheptyl Methacrylate/Glycidyl Methacrylate Mixtures with Cotton Fabric Using Ferrous Thioureadioxide/Hydrogen Peroxide Redox System", Die Angewandte Makromolekulare Chemie, 130, (1985) 137

237. M. H. El-Rafie, E. M. Khalil, S. A. Abdel-Hafiz and A. Hebeish, "Graft Copolymerization of Cotton Fabric with Different Vinyl Monomers Using Ferrous Cellulose Thiocarbonate/Hydrogen Peroxide Redox System", Acta Polymerica, 36, 12 (1985) 688

238. A. Hebeish, "Textile Industry and Environmental in Egypt (Case Study on Clean Technologyies for Textile Finishing in North Africa)", Paper Presented at the 'International Symposium o Clean Technologies ', Karlsruhe, Germany, Oct. 7-18.(1985),

239. A. Hebeish, I. Abd El-Thalouth, K. Haggag, M. El-Kashouti and M. I. Khalil, "Chemical Factors Affecting Soiling and Soil Release from Cotton Containing Durable Press Fabrics: Part XIX: Introduction of Cyanoethyl Groups Along with Carboxymethyl Groups in Cotton/Polyester Blend Fabric", Tinctoria, 82, (1985) 41

240. A. Hebeish, I. Abd El-Thalouth, M. A. Ibrahim and M. R. Elzairy, "Cyanoethylated Starch Thickeners as Substitutes for Sodium Alginate in Printing with Reactive Dyes", Starch - Stärke, 37, 11 (1985) 373-382

241. A. Hebeish, I. I. Abdel-Gawad, I. K. Basily and S. El-Bazza, "Degradation of Poly(Vinyl Alcohol) in Strongly Alkaline Solutions of Hydrogen Peroxide", Journal of Applied Polymer Science, 30, 6 (1985) 2321-2327

242. A. Hebeish, N. Y. Abou-Zeid, A. Waly, E. A. El-Alfy and M. H. Abo-Shosha, "Chemical Factors Affecting Soiling and Soil Release from Cotton Containing Durable Press Fabrics: Part XXIV: Copolymerization of Pet/Cotton Blend with Vinyl

170

Monomers Mixtures", American Dyestuff Reporter, 74, 5 (1985) 36-39

243. A. Hebeish and S. El Bazza, "Single-Stage Process for Desizing, Scouring, and Bleaching of Cotton Fabric", Die Angewandte Makromolekulare Chemie, 134, 1 (1985) 37

244. A. Hebeish and S. El-Bazza, "Novel Method for Desizing, Scouring and Bleaching Polyester/Cotton Blends", American Dyestuff Reporter, 74, 10 (1985) 33-36, 40

245. A. Hebeish and S. El-Bazza, "Single-Stage Desizing, Scouring and Bleaching Process Versus Conventional Processes", Kolorisztikal Ertesito, 27, 12 (1985) 17

246. A. Hebeish and S. El-Bazza, "Novel Approch for Desizing, Scouring and Bleaching of Polyester/Cotton Blend Fabric", American Dyestuff Reporter, 74, 10 (1985) 74

247. A. Hebeish, S. T. El-Sheltawi and K. Haggag, "Behaviour of Thermally Treated Cotton and Crosslinked Cotton Fabrics Towards Soiling and Soil Release", Kolorisztikal Ertesito, 27, 5-6 (1985) 140

248. A. Hebeish, N. A. Ibrahim, H. L. Hanna, S. A. Amin and M. I. Khalil, "Chemical Factors Affecting Soiling and Soil Release from Cotton Containing Durable Press Fabrics: Part XX: Inclusion of Different Additives in the Finishing of Cotton/Polyester Blend Fabrics", Tinctoria, 82, 2 (1985) 129 - 134

249. A. Hebeish, A. Waly and A. M. Hassanien, "Chemical Modification of Cotton Via Treatment with Carbohydrazide", Cellulose chemistry and technology, 19, 5 (1985)

250. A. Hebeish, A. H. Zahran and A. M. K. El-Naggar, "Behavior of Cyanoethylated Cotton Towards Gamma Radiation", Journal of Applied Polymer Science, 30, 10 (1985) 4057-4067

251. A. Hebeish, A. H. Zahran, A. M. Rabie and A. M. El-Naggar, "Synthesis of Poly(Acrylic Acid)- and Poly(Styrene)-Cyanoethylated Cotton Graft Copolymers Using Gamma Radiation", Die Angewandte Makromolekulare Chemie, 134, 1 (1985) 37

252. N. A. Ibrahim, K. Haggag and A. Hebeish, "Improving the Dyeing Properties of Textiles Via Utilization of Redox Systems: Part I: Dyeing of Wool and Wool/Polyacrylic Blend Fabrics with Acid Dye", Die Angewandte Makromolekulare Chemie, 131, 1 (1985) 15 - 24

253. N. A. Ibrahim, K. Haggag and A. Hebeish, "Improving the Dyeing Properties of Textiles Via Utilization of Redox Systems: Part II:

171

Dyeing of Nylon 6 with Acid Dye", Die Angewandte Makromolekulare Chemie, 132, 1 (1985) 53 - 60

254. N. A. Ibrahim and A. Hebeish, "Dependence of Soiling and Soil Release of Easy-Care Cotton on Factors Controlling the Finishing Treatment", Die Angewandte Makromolekulare Chemie, 130, 1 (1985) 111-124

255. F. M. Tera, L. A. Abdou, M. N. Michael and A. Hebeish, "Fading Characteristics of Some Monoazo Dyes on Cellulose Diacetate and Polyamide Films: Part I", Polymer Photochemistry, 6, 5 (1985) 361-374

256. F. M. Tera, L. A. Abdou, M. N. Michael and A. Hebeish, "Fading Characteristics of Some Monoazo Dyes on Cellulose Diacetate and Polyamide Films: Part II", Polymer Photochemistry, 6, 5 (1985) 375-383

257. I. Abd El-Thalouth, M. R. Elzairy and A. Hebeish, "Rheological Properties of Some Printing Pastes", American Dyestuff Reporter, 75, 5 (1986) 32-41, 47

258. N. Y. Abou-Zeid, A. Waly, A. Higazy and A. Hebeish, "Fe+2/Thioureadioxide/Hydrogenperoxide-Induced Polymerization of Various Vinyl Monomers with Flax Fibres", Die Angewandte Makromolekulare Chemie, 143, (1986) 85 - 95

259. A. Bayazeed, S. Farag and A. Hebeish, "Graft Polymerization of Acrylamide onto Starch Using Ferrous-Starch Thiocarbonate-Persulphate Redox System", Starch - Stärke, 38, 8 (1986) 268-272

260. E. A. El-Alfy, S. S. Aggour, M. H. Mardini and A. Hebeish, "Improved Cotton Dyeability Via Introducing Diethyl Amino Ethyl Groups into the Molecular Structure", American Dyestuff Reporter, 75, 5 (1986) 22, 24-29, 48

261. E. A. El-Alfy, S. S. Aggour, M. H. Mardini and A. Hebeish, "Improving the Dyeability of Cotton Fabric Via Introduction of Diethylaminoethyl Groups in the Molecular Structure of Cotton Cellulose", American Dyestuff Reporter, 75, 5 (1986) 922

262. K. El-Zoghbi, S. Halim and A. Hebeish, "Effect of Some Deodorants on Color and Strength of Cotton-Based Textiles", American Dyestuff Reporter, 75, 5 (1986) 42-43, 47

263. A. Hebeish, I. Abd El-Thalouth, M. A. Ibrahim and M. R. El-Zairy, "Technical Feasibility of Some Thickeners in Printing Cotton with Reactive Dyes", American Dyestuff Reporter, 75, 2 (1986) 22-29, 43

264. A. Hebeish, E. A. El-Alfy, A. Esmael and A. M. R. Ibrahim, "Synthesis and Application of Some New Azo Dyes: Part VI: Dyes Prepared by Coupling of N-(M-Hydroxyphenyl)-P-Chloro-

172

Benzene Sulphonamide with Diazotized Amines", American Dyestuff Reporter, 75, 10 (1986) 22-25, 28

265. A. Hebeish, M. H. El-Rafie, E. M. Khalil and S. S. Abd El-Hafiz, "Effect of Degradative Treatment on Cotton Graft Copolymers: Part I: Behavior of Poly (Acrylonitrile) Cotton Graft Copolymer Towards Hypochlorite Treatments", Cellulose Chemistry and Technology, 20, 9 (1986) 523

266. A. Hebeish, M. H. El-Rafie, E. M. Khalil and S. A. Abdel-Hafiz, "Effect of Degradative Treatments on Cotton Graft Copolymers: Part V: Behavior of Poly(Acrylamide)-Cotton Graft Copolymers toward Acid Treatments", Journal of Applied Polymer Science, 31, 6 (1986) 1645-1653

267. A. Hebeish, M. H. El-Rafie, E. M. Khalil and S. A. Abdel-Hafiz, "Effect of Degradative Treatments on Cotton Graft Copolymers: Part IV: Hydrolytic Susceptibility of Poly(Acrylonitrile)-Cotton Graft Copolymers", Journal of Applied Polymer Science, 32, 4 (1986) 4453-4464

268. A. Hebeish, M. H. El-Rafie, E. M. Khalil and S. A. Abdel-Hafiz, "Effect of Degradative Treatment on Cotton Graft Copolymers: Part II: Hypochlorite Oxidation of (Poly Acrylonitrile) Cotton Graft Copolymers by Hypochlorite Treatments", Cellulose Chemistry and Technology, 20, (1986) 625 - 629

269. A. Hebeish, N. A. Ibrahim and M. H. El-Rafie, "One-Step Dyeing and Finishing of Polyester/Cotton Fabrics Using Reactive Dyes and Crosslinking Agents", American Dyestuff Reporter, 75, 3 (1986) 32 - 35

270. A. Hebeish, H. I. Nasr, L. A. Abdou, S. T. El Sheltawi and K. Haggag, "Effect of Structural Changes of Cotton by Acid Hydrolysis and Crosslinking on Soiling and Soil Release", Journal of Applied Polymer Science, 31, 1 (1986) 197-208

271. A. Hebeish, A. Waly and A. M. Hassanien, "Improving Cotton Dyeing and Other Properties by Emulsion Polymerization with Glycidyl Methacrylate", American Dyestuff Reporter, 75, 4 (1986) 26-34

272. A. Hebeish, A. H. Zahran and A. M. K. El-Naggar, "Oxidative Susceptibility of Partially Carboxymethylated Cotton to Gamma Radiation", Journal of Applied Polymer Science, 31, 1 (1986) 273-282

273. A. Hebeish, A. H. Zahran and A. M. K. El-Naggar, "Effect of Gamma Radiation on Carbamoylethylated Cotton", Polymer Photochemistry, 7, 3 (1986) 187-198

173

274. A. Hebeish, A. H. Zahran, A. M. K. El-Naggar and A. M. Rabie, "Moisture Regain and Dyeability of Poly(Acrylic Acid)- and Poly(Styrene)-Carbamoylethylated Cotton Graft Copolymers Induced by Gamma Radiation", Journal of Applied Polymer Science, 31, 1 (1986) 249-272

275. A. Hebeish, A. H. Zahran, A. M. Rabie and A. M. K. El-Naggar, "Modification of Partially Carboxymethylated Cotton Via Crafting with Acrylic Acid and Styrene Using Gamma Radiation", Journal of Applied Polymer Science, 32, 8 (1986) 6237-6257

276. N. A. Ibrahim, S. S. Aggour and A. Hebeish, "Improved Dyeing with Redox Systems: Part III: Dyeing Cotton and Viscose with Direct Dyes", American Dyestuff Reporter, 75, 4 (1986) 13-14, 16

277. N. A. Ibrahim, A. Bayazeed, R. Refai and A. Hebeish, "Studies of Some Basic Aspects in Easy Care Cotton Finishing: Part IX: Semicarbazide Hydrochloride - a New Catalyst for Easy Care Finishing", American Dyestuff Reporter, 75, 5 (1986) 13 - 25

278. N. A. Ibrahim, M. H. El-Rafie and A. Hebeish, "Combined Dyeing and Easy-Care Finishing of Cotton and Carbamoylethylated Cotton Fabrics", American Dyestuff Reporter, 75, 1 (1986) 38-42

279. N. A. Ibrahim, R. Refai and A. Hebeish, "Studies of Some Basic Aspects in Easy Care Cotton Finishing: Part XI: Improved Performance with Modified Magnesium Chloride Catalysts", American Dyestuff Reporter, 75, 7 (1986) 25-28, 30, 32

280. F. M. Tera, M. N. Micheal and A. Hebeish, "Study of the Spectrum Fading Curves of Disperse Dye on Cellulose Diacetate and Polyamide Films", Polymer Degradation and Stability, 16, 2 (1986) 163-167

281. A. Waly, A. M. Hassanien, A. Bendak and A. Hebeish, "Polyester/Cotton Blend Jig-Dyed with Only One-Dye Class Via Polymerization with Glycidyl Methacrylate", American Dyestuff Reporter, 75, 3 (1986) 15, 19-20, 41

282. A. Bayazeed and A. Hebeish, "Copolymers of Cotton and Cotton Blends by Grafting with Polymethacrylic Acid, as the Basis of a System of Combined Dyeing and Finishing", Tinctoria, 84, 1 (1987) 47 - 52

283. A. Bayazeed, A. Higazy and A. Hebeish, "Synthesis and Applications of Reactive Carbohydrates Part I: Behaviour of Carboxymethyl Starch before and after Acid Hydrolysis toward Grafting with Acrylamide", Starch - Stärke, 39, 8 (1987) 288-291

284. E. A. El-Alfy, F. Mahmoud, A. M. R. Ibrahim and A. Hebeish, "Synthesis and Application of Some New Azo Dyes: Part IV: Dyes

174

Prepared by Coupling of N-(M-Dihydroxyphenyl)-P-Toluenesulphonamide with Diazotized Amines", (1987)

285. E. A. El-Alfy, F. Mahmoud, A. M. R. Ibrahim and A. Hebeish, "Synthesis and Application of Some New Azo Dyes: Part V: Dyes Prepared by Coupling of N-(O-Hydroxyphenyl)-P-Chlorobenzene Sulphonamide with Diazotized Amines", Tinctoria, 84, 5 (1987) 59 - 66

286. A. Hebeish, E. A. El-Alfy and M. Mardini, "Combined Dyeing and Finishing of Diethylaminoethyl Cotton Fabric", American Dyestuff Reporter, 76, 10 (1987) 42-45, 47

287. A. Hebeish, E. A. El-Alfy and M. H. A. Mardini, "Factors Affecting Dyeability of Crosslinked Cottons", American Dyestuff Reporter, 76, 7 (1987) 33-34, 36

288. A. Hebeish, M. H. El-Rafie, E. A. El-Alfy, S. T. El-Sheltawi and F. F. El-Sisy, "Chemical Desizing and Development of One Stage Process for Desizing and Scouring of Starch Sized Cotton", Cellulose Chemistry and Technology, 21, 4 (1987) 401 - 411

289. A. Hebeish, M. H. El-Rafie and F. El-Sisy, "Combined Desizing Scouring and Bleaching of Starch Sized Cotton Fabric", Cellulose Chemistry and Technology, 23, 4 (1987) 683

290. A. Hebeish, M. H. El-Rafie, E. M. Khalil and S. A. Abdel-Hafiz, "Effect of Degradative Treatment on Cotton Graft Copolymers: Part III: Oxidation of Poly (Methacrylic Acid)/ Cotton Graft Copolymers by Sodium Hypochlorite", Acta Polymerica, 38, 3 (1987) 611

291. A. Hebeish, M. H. El-Rafie, E. M. Khalil and S. A. Abdel-Hafiz, "Effect of Degradative Treatment on Cotton Graft Copolymers: Part VI: Behavior of Poly (Methacrylic Acid) Cotton Graft Copolymers Towards Acid Treatment", Cellulose Chemistry and Technology, 21, 1 (1987) 47

292. A. Hebeish, N. A. Ibrahim, A. Bayazeed and R. Refai, "Studies of Some Basic Aspects in Easy Care Cotton Finishing: Part X: Structural Changes in Cotton Catalysed by Magnesium Chloride", Tinctoria, 84, 11 (1987) 30 - 35

293. A. Higazy, A. Bayazeed and A. Hebeish, "Synthesis and Applications of Reactive Carbohydrates Part II: Graft Polymerization of Starch and Hydrolyzed Starches with Acrylamide", Starch - Stärke, 39, 9 (1987) 319-322

294. M. I. Khalil, A. Bayazeed, S. Farag and A. Hebeish, "Chemical Modification of Starch Via Reaction with Acrylamide", Starch - Stärke, 39, 9 (1987) 311-318

175

295. F. M. Tera, M. N. Michael and A. Hebeish, "Spectrophotometric Study of the Photo-Degradation of Disperse Dyes on Cellulose Diacetate and Polyamide Films", Polymer Degradation and Stability, 17, 1 (1987) 13-19

296. A. Waly, N. Y. Abou-Zeid, A. Higazy and A. Hebeish, "Properties of Blend Fabrics from Polyester and Chemically-Modified Linen", Tinctoria, 84, 1 (1987) 67 - 72

297. M. H. Abo-Shosha, M. K. El-Kashouti and A. A. Hebeish, "Simultaneous Curing Transfer Printing of All Cotton and 50/50 Polyester/Cotton Fabrics Using Melamine Formaldehyde and Some Catalyst", Cellulose Chemistry and Technology, 22, (1988)

298. F. El-Sisi, S. a. A. El-Hafiz and A. Hebeish, "Synthesis and Applications of Reactive Carbohydrates: Part III: Preparation and Methylolation of Polyacrylamide Carboxymethyl Cellulose Graft Copolymers", Die Angewandte Makromolekulare Chemie, 156, 1 (1988) 79 - 84

299. F. El-Sisi, R. R. El-Sayed, S. A. Abdel Hafiz and A. Hebeish, "Improving Polyester/Cotton Blend Dyeability Via Thiocarbonation of the Cotton", American Dyestuff Reporter, 77, 11 (1988) 41

300. A. Hebeish, S. A. Abdel-Hafiz and F. El-Sisi, "Synthesis and Applications of Reactive Carbohydrates: Part IV: Reactive Finishes Based on Cmc and Oxidized Cmc Copolymers", Journal of Applied Polymer Science, 36, 1 (1988) 191-203

301. A. Hebeish, N. Y. Abou-Zeid, A. Waly and A. Higazy, "Chemical Modification of Flax Cellulose Via Etherification, Esterification and Crosslinking Reactions", Cellulose Chemistry and Technology, 22, (1988) 591 - 596

302. A. Hebeish, A. Bayazeed, E. A. El-Alfy and M. I. Khalil, "Synthesis and Properties of Polyacrylamide-Starch Graft Copolymers", Starch - Stärke, 40, 6 (1988) 223-229

303. A. Hebeish, A. Bayazeed and A. Higazy, "Grafting of Flax/Polyester Blend with Acrylamide Using Ferrous Cellulose Thiocarbonate/Persulphate Redox System", Acta Polymerica, 39, 9 (1988) 495 - 501

304. A. Hebeish, E. A. El-Alfy and A. Bayazeed, "Synthesis of Vinyl Polymer-Starch Composites to Serve as Size Base Materials", Starch - Stärke, 40, 5 (1988) 191-196

305. A. Hebeish, F. El-Sisi and S. a. A. Hafiz, "A Novel Method for Vinyl Grafting onto Cotton Fabric Using Ceric-Cellulose Thiocarbonate Redox System", Die Angewandte Makromolekulare Chemie, 157, 1 (1988) 153-163

176

306. A. Hebeish and A. Higazy, "Preparing Diethylaminoethyl Flax/Polyester Fabric with Improved Dyeability", American Dyestuff Reporter, 77, 2 (1988) 34, 37-44

307. A. Hebeish and A. Higazy, "Development of a Simple Technique for Preparation of Diethylaminoethyl Flax-Polyester Fabric with Improved Dyeability", American Dyestuff Reporter, 39, 9 (1988) 495-502

308. A. Hebeish and M. I. Khalil, "Characterization of the Reaction Products for Starch and Acrylonitrile", Starch - Stärke, 40, 3 (1988) 104-107

309. A. Hebeish and M. I. Khalil, "Chemical Factors Affecting Preparation of Carboxymethyl Starch", Starch - Stärke, 40, 4 (1988) 147-150

310. A. Hebeish, S. Shakra and W. Sabry, "Effect of Easy-Care Finishing Catalysts on the Light Fading of Printed Polyester/Cotton Blends", Kolorisztikal Ertesito, 1-2 (1988) 12-19

311. A. Higazy and A. Hebeish, "Thiocarbonate Built-in Catalyst for Dyeing Flax/Polyester Blend with Reactive Dyes", American Dyestuff Reporter, 77, 6 (1988) 26-28, 30

312. R. Refai, S. a. A. Hafiz, F. El-Sisi and A. Hebeish, "Synthesis and Application of Reactive Carbohydrates: Part V: Appropriate Conditions for Application of Reactive Cmc Finishes to Cotton Fabric", American Dyestuff Reporter, 77, 9 (1988) 72

313. A. Bayazeed, M. R. Elzairy and A. Hebeish, "Synthesis and Application of New Thickerners Part I: Preparation of Poly (Acrylic Acid)-Starch Graft Copolymer", Starch - Stärke, 41, 6 (1989) 233-236

314. A. Bayazeed, A. Higazy and A. Hebeish, "Synthesis and Application of Reactive Carbohydrates: Part VI: Application of Reactive Carbohydrates Derived from Starch and Hydrolysed Starches to Cotton Fabric", Starch - Stärke, 41, 5 (1989) 187-192

315. M. H. El Rafie, F. F. El Sisi, S. A. Abdel Hafiz and A. Hebeish, "Novel Bleaching Formulations for Loomstate Cotton Fabric", American Dyestuff Reporter, 78, 1 (1989) 43-47, 49

316. M. H. El-Rafie, E. M. Khalil, M. K. Zahran and A. Hebeish, "Grafting of Cotton Fabric with Vinyl Monomers Using Cellulose Thiocarbonate/Potassium Bromate Redox System", Cellulose Chemistry and Technology, 23, 6 (1989) 683-692

317. F. El-Sisy, S. A. Abdel-Hafiz, M. H. El-Rafie and A. Hebeish, "Cellulose Thiocarbonate/Hydrogen Peroxide Redox System Induced Grafting of Methacrylic Acid onto Cotton Fabric", Cellulose Chemistry and Technology, 23, 3 (1989) 247-254

177

318. A. Hebeish, I. Abd El-Thalouth, R. Refai and A. Ragheb, "Synthesis and Characterization of Hypochlorite Oxidized Starches", Starch - Stärke, 41, 8 (1989) 293 - 298

319. A. Hebeish, K. Haggag, M. Abou Shousha and N. A. Ibrahim, "Polymerization of Carboxyl Group Containing Monomers with Chemical Initiators: Part I: Polymerization of Acrylic Acid", Acta Polymerica, 40, 12 (1989) 719-723

320. A. Higazy, A. Bayazeed and A. Hebeish, "Grafting of N-Methylolacrylamide onto Flax/Polyester Fabric Using Ferrous Cellulose Thiocarbonate/H2o2 Redox System", Die Angewandte Makromolekulare Chemie, 169, 1 (1989) 101-117

321. A. Ragheb, K. Haggag, R. El-Zairy, I. Abd El-Thalouth and A. Hebeish, "Cotton Printing with Carbamoylethyl Starch in Vat Dye Pastes", American Dyestuff Reporter, 78, 8 (1989) 27-37

322. I. Abd El-Thalouth, A. Ragheb, R. Refai and A. Hebeish, "Behaviour of Oxidized Starches Towards Cyanoethylation", Starch - Stärke, 42, 1 (1990) 18-23

323. S. A. Abdel Hafiz, F. El-Sisy and A. Hebeish, "Reactive Dyes Fixed on Cotton by Cellulose Thiocarbonate Catalyst", American Dyestuff Reporter, 79, 1 (1990) 43-46

324. F. El Sisi, S. A. Abdel Hafiz, M. H. El-Rafie and A. Hebeish, "Starch Size in Loomstate Cotton Fabric Accelerates Grafting of Methacrylic Acid Induced by Kmno4/Citric Acid System", Acta Polymerica, 41, 6 (1990) 324-328

325. F. F. El Sisi, S. a. A. Hafiz, M. H. El Rafie and A. Hebeish, "Development of a One-Step Process for Desizing/Scouring/Bleaching Cotton-Based Textiles", American Dyestuff Reporter, 79, 10 (1990) 39-40, 41

326. M. H. El-Rafie, S. A. Abdel Hafiz, F. F. El-Sisi, M. Helmy and A. Hebeish, "A Fast Desizing/Scouring/Bleaching System for Cotton-Based Textiles", American Dyestuff Reporter, 79, 12 (1990) 49-51

327. A. Hebeish and A. Higazy, "Synthesis and Application of Reactive Carbohydrates: Part VII: Acrylamidomethyl Starches as Reactive Finishes for Cotton", American Dyestuff Reporter, 79, 2 (1990) 43-48

328. A. Hebeish, E. M. Khalil, M. H. El-Rafie and M. K. Zahran, "Cellulose Thiocarbonate-Cr(VI) System Induced Graft Copolymerization of Vinyl Monomers onto Cotton Fabric", Cellulose Chemistry and Technology, 24, 2 (1990) 183-192

329. A. Hebeish, M. I. Khalil and A. Hashem, "Carboxymethylation of Starch and Oxidized Starches", Starch - Stärke, 42, 5 (1990) 185-191

178

330. N. A. Ibrahim, K. Haggag, M. A. Shoushda and A. Hebeish, "Polymerization of Carboxyl Group Containing Monomers with Chemical Initiators: Part II: Polymerization of Methacrylic Acid", Acta Polymerica, 41, 1 (1990) 59-63

331. E. M. Khalil, M. H. El-Rafie, M. R. Zahran and A. Hebeish, "Graft Copolymerization of Methacrylic Acid and Other Vinyl Monomers onto Cotton Fabric Using the Cellulose Thiocarbonate-Kmno4-Citric Acid System", Cellulose Chemistry and Technology, 24, 1 (1990) 65-76

332. M. I. Khalil, A. Hashem and A. Hebeish, "Carboxymethylation of Maize Starch", Starch - Stärke, 42, 2 (1990) 60-63

333. M. I. Khalil, K. M. Mostafa and A. Hebeish, "Synthesis of Poly(Methacrylic Acid-)Starch Graft Copolymers Using Mn-IV-Acid System", Starch - Stärke, 42, 3 (1990) 107-111

334. A. Ragheb, R. Refai, I. Abd El-Thalouth and A. Hebeish, "The Combined Effect of Oxidation and Carbamoyl- Ethylation on the Rheological Properties of Maize and Rice Starches", Starch - Stärke, 42, 11 (1990) 420 - 426

335. A. Waly, R. Rafai, M. H. El-Rafie and A. Hebeish, "Novel Method for Preparing Aminized Cotton Fabric with Improved Dyeability", American Dyestuff Reporter, 79, 7 (1990) 34-36, 39

336. N. Y. Abou-Zeid, A. Higazy and A. Hebeish, "Reductive Scouring of Linen Fabrics - a Key to Rapid Bleaching", Melliand Textilberichte, 72, 5 (1991) 362-365

337. A. Hafiz, F. El-Sisi, M. H. El-Rafie, M. Helmy and A. Hebeish, "Sodium Chloride/Potassium Chromate Cooxidant Induced Concurrent Desizing, Scouring and Bleaching of Cotton and Cotton/Polyester Blend Fabrics", American Dyestuff Reporter, 80, 3 (1991)

338. A. Hebeish, M. R. El-Zairy, M. H. El-Rafie, A. Higazy and F. El-Sisy, "Poly(Acrylic Acid) Starch Composite as a Substitute for Sodium Alginate in Printing Cotton Fabrics with Reactive Dyes", Starch - Stärke, 43, 3 (1991) 98-102

339. A. Hebeish, K. Haggag, A. El-Kashouti, A. El-Halwagi and I. Abd El-Thalouth, "Behavior of Cellulose and Hydrolyzed Celluloses toward Carboxymethylation", American Dyestuff Reporter, 80, 5 (1991) 53-54, 56

340. A. Hebeish and R. Rafai, "Synthesis and Application of Reactive Carbohydrates: Part VIII: Carboxymethyl Cellulose Containing Pendant Double Bonds", American Dyestuff Reporter, 80, 6 (1991) 37-44

179

341. A. Hebeish, R. Refai, A. Ragheb and I. Abd El-Thalouth, "Factors Affecting the Technological Properties of Starch Carbamate.", Starch - Stärke, 43, 7 (1991) 273

342. M. I. Khalil, S. Farag and A. Hebeish, "Preparation and Characterization of Cation Exchange Starches Containing Carboxyl Groups", Starch - Stärke, 43, 7 (1991) 254-261

343. M. I. Khalil, A. Waly, S. Farag and A. Hebeish, "Preparation and Characterization of Anion-Exchange Starches", Starch - Stärke, 43, 9 (1991) 349-355

344. M. I. Khalil, A. Waly, S. Farag and A. Hebeish, "Preparation of Cation-Exchange Starches Containing Phosphoric Acid Groups", Journal of Applied Polymer Science, 43, 12 (1991) 2303-2309

345. A. Ragheb, I. Abd El-Thalouth, H. El-Sayad and A. Hebeish, "Preparation and Characterization of Carboxymethylcellulose from Jute Wastes", Indian Journal of Fibre and Textile Research, 16 (1991) 263

346. F. M. Tera, A. Hebeish, N. A. Ibrahim and M. N. Michael, "Photofading Charachtaristics of Dyed-Easy Care Finished Cotton Cellulosic Substrate", Paper Presented at the 'Cellulose 91 Conferance', Louisiana, USA, December.(1991), 255-260

347. I. Abd El-Thalouth, A. Ragheb, H. El-Sayad and A. Hebeish, "Utilizing Cmc Derived from Jute Waste Fibres as a Printing Thickener", American Dyestuff Reporter, 81, 2 (1992) 25-33

348. M. H. El-Rafie, A. Higazy and A. Hebeish, "Bleaching of Linen Fabrics Using a Hydrogen Peroxide/Urea System", American Dyestuff Reporter, 81, 3 (1992) 48-55,67

349. F. El-Sisi, M. H. El-Rafie and A. Hebeish, "Urea- Activated Hydrogen Peroxide Induced Combined Desizing, Scouring and Bleaching of Loomstatc Cotton Fabric", American Dyestuff Reporter, 81, 6 (1992) 34

350. A. Hebeish, I. Abd El-Thalouth and M. K. El-Kashouti, "Agricultural Wastes as Base Materials for the Synthesis of Carboxymethyl Cellulose", Cellulose Chemistry and Technology, 26, (1992) 277 - 283

351. A. Hebeish, A. El-Halwagi, K. Haggag, M. A. El-Kashouti and I. Abd El-Thalouth, "Technological Properties of Carboxymethyl Celluloses Derived from Flax Shaves", American Dyestuff Reporter, 81, 3 (1992) 56-58

352. A. Hebeish, A. M. El-Naggar, F. El-Sisi, S. Abdel-Hafiz and K. El-Salmwi, "Improving the Sizeability of Starch Using Gamma Radiation", Polymer Degradation and Stability, 36, 3 (1992) 249-252

180

353. A. Hebeish, M. H. El-Rafie, A. Higazy and M. A. Ramadan, "Poly(Acrylic Acid)-Starch Composites. A Key for Improving Sizeability and Desizeability of Starch from Cotton Textiles", Starch - Stärke, 44, 3 (1992) 101-107

354. A. Hebeish, F. El-Sisy, S. A. Abdel-Hafiz, A. A. Abd El-Rahman and M. H. El-Rafie, "Oxidation of Maize and Rice Starches Using Sodium Chlorite Along with Formaldehyde", Starch - Stärke, 44, 10 (1992) 388-393

355. A. Hebeish and A. Higazy, "Graft Polymerization of Methacrylic Acid onto Flax/Cotton Blend Fabrics Using Kmno4 with Reductants", American Dyestuff Reporter, 81, 9 (1992) 64-72

356. R. Refai, S. A. Abdel-Hafiz and A. Hebeish, "Easy -Care Finishing of Cotton Using Glyoxal Plus Hydrolyzed Starches", American Dyestuff Reporter, 4, 1 (1992) 42 - 47

357. E. A. El-Alfy, S. H. Samaha, A. Hebeish and F. M. Tera, "Synthesis of Starch Carbamate", Paper Presented at the '2nd Arab International Conference on Advances in Material Science and Engineering (Polymeric Materials)', Cairo & Fayoum. Egypt, 6-9 Sept.(1993),

358. M. H. El-Rafie, M. K. Zahran and A. Hebeish, "Cellulose Thiocarbonate-Ferric Nitrate Redox System Induced Graft Copolymerization of Vinyl Monomers on to Cotton Fabric", Polymer Degradation and Stability, 42, 3 (1993) 223-230

359. A. Hebeish, M. H. El-Rafie and M. K. Zahran, "Pentavalent Vanadium Ion–Cellulose Thiocarbonate Redox-System Induced Grafting of Methyl Methacrylate and Other Vinyl Monomers onto Cotton Fabric", Journal of Applied Polymer Science, 50, 12 (1993) 2099-2104

360. A. Hebeish, F. El-Sisi, M. K. El-Bisi and M. H. El-Rafie, "Bleaching of Loomstate Cotton Fabric Using a Sodium Chlorite/ Formaldehyde System", American Dyestuff Reporter, 82, 7 (1993) 31-34

361. M. I. Khalil, K. M. Mostafa and A. Hebeish, "Graft Polymerization of Acrylamide onto Maize Starch Using Potassium Persulfate as Initiator", Die Angewandte Makromolekulare Chemie, 213, 1 (1993) 43-54

362. A. Ragheb, I. Abd El-Thalouth, H. El-Sayad and A. Hebeish, "Preparation of Carboxymethyl Cellulose from Kenaf Fibers for Textile Printing Pastes", American Dyestuff Reporter, 82, 2 (1993) 20-25

363. F. A. Abdel-Mohdy, A. Waly, A. Higazy and A. Hebeish, "Synthesis and Application of Reactive Perfluoroheptyl

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Methacrylate - Acrylamide Copolymers: Synthesis and Application", Pigment and Resin Technology, 23, 2 (1994) 10 - 14

364. A. T. El-Aref, N. Zamzam and A. Hebeish, "Chemical Finishing of Cotton: Part I: Preparation of Easy Care Cotton Fabric with Improved Strength", Cellulose Chemistry and Technology, 28, 2 (1994) 143 - 148

365. M. H. El-Rafie, S. A. Abdel-Hafiz, S. M. Hassan and A. Hebeish, "Grafting of Methacrylic Acid to Loomstate Viscose Fabric Using Kmno4/Nahso3 System", Polymers and Polymer Composites, 2, 2 (1994) 99-104

366. M. H. El-Rafie, F. El-Sisi, M. K. El-Bisi and A. Hebeish, "Accelerated Bleaching of Loomstate Cotton Fabric with Sodium Chlorite/Sodium Thiosulphate", American Dyestuff Reporter, 83, 8 (1994) 42-45

367. A. Hebeish, A. T. El-Aref, M. H. Abo-Shosha and N. Zamzam, "Chemical Finishing of Cotton: Part II: Combiend Easy Care Flam Retardance Finishing of Cotton", Cellulose Chemistry and Technology, 28, 2 (1994) 299 - 306

368. A. Hebeish, A. T. El-Aref, A. Higazy and N. Zamzam, "Chemical Finishing of Cotton: Part III: Multifinishing of Cotton Fabric in a Single Stage Process", Cellulose Chemistry and Technology, 28, 2 (1994) 315 - 321

369. A. Hebeish, A. El-Kashouti M, I. Abd El-Thalouth, K. Haggag and A. El-Halwagi, "Carboxymethylation of Cotton Linters before and after Oxidation", Cellulose chemistry and technology, 28, 4 (1994) 409-418

370. A. Hebeish, M. H. El-Rafie, F. El-Sisi, S. Abdel Hafiz and A. A. Abd El-Rahman, "Oxidation of Maize and Rice Starches Using Potassium Permanganate with Various Reductants", Polymer Degradation and Stability, 43, 3 (1994) 363-371

371. A. Hebeish, M. H. El-Rafie, A. Higazy and N. Y. Abou-Zeid, "Rapid Bleaching of Linen Fabric", Cellulose Chemistry and Technology, 28, (1994) 563 - 572

372. A. Hebeish, F. El-Sisi, A. El-Halwagy, M. El-Kashouti and H. Omar, "Agricultural Wastes as a Base for Synthesis of Vinyl Polymer-Cellulose Composites", Polymers and Polymer Composites, 2, 6 (1994) 377-385

373. A. Hebeish, A. Ragheb, R. Refaie, M. A. Saad and I. Abd El-Thalouth, "Technological Evaluation on Nitrogen Containing Starch Derivaties as Sizing Agents", Starch - Stärke, 46, 3 (1994) 109 - 113

182

374. A. Hebeish, A. Waly, A. T. El-Aref, F. A. Abdel-Mohdy and N. E. Zamzam, "Behaviour of Chemically Modified Cottons Towards Flame-Retardancy Finishing", Polymer Degradation and Stability, 43, 3 (1994) 447-459

375. A. Hebeish, A. Waly, A. Higazy and F. A. Abdel-Mohdy, "Technological Evaluation of Starch Bearing Aromatic Amino Groups as Cationic Exchanger", Starch - Stärke, 46, 2 (1994) 63 - 67

376. M. I. Khalil, S. Farag, K. M. Mostafa and A. Hebeish, "Some Studies on Starch Carbamate", Starch - Stärke, 46, 8 (1994) 312-316

377. A. Waly, F. A. Abdel-Mohdy, A. Higazy and A. Hebeish, "Synthesis and Properties of Starch Phosphate Monoesters", Starch - Stärke, 46, 2 (1994) 59-63

378. A. Waly, A. T. El-Aref, F. A. Abdel-Mohdy, N. E. Zamzam and A. Hebeish, "Synthesis and Application of Phosphorylated Glucose in Flame Retardancy Finishing", Polymers and Polymer Composites, 2, 1 (1994) 27-34

379. S. A. Abdel-Hafiz, M. H. El-Rafie, S. M. Hassan and A. Hebeish, "Grafting of Methacrylic Acid to Loomastate Viscose Fabric Using Kmno4/Naclo2 System", Journal of Applied Polymer Science, 55, 7 (1995) 997-1005

380. M. H. Abo Shosha, N. A. Ibrahim, H. M. Fahmy and A. Hebeish, "Utilizing Water Soluble Size Additives in Easy-Care Finishing", American Dyestuff Reporter, 84, 7 (1995) 44-46

381. M. H. El-Rafie, M. K. Zahran, K. F. El-Tahlawy and A. Hebeish, "A Comparative Study of the Polymerization of Acrylic Acid with Native and Hydrolyzed Maize Starches Using a Potassium Bromate-Thiourea Dioxide Redox Initiation System", Polymer Degradation and Stability, 47, 1 (1995) 73-85

382. F. El-Sisi, S. A. El-Hafiz, A. R. Saleh and A. Hebeish, "Oxidation of Starch Bearing Nitrogen Containing Moities with Ammonium Persulphate", Egyptian Journal of Applied Science and Technology, 10, 1 (1995) 12 - 18

383. M. M. Hashem, E. Bach, W. Kesting, A. A. Hebeish and E. Schollmeyer, "Synthesis of Chemically Bonded Poly(Vinyl Alcohol)-Starch Composite", Die Angewandte Makromolekulare Chemie, 230, 1 (1995) 189-204

384. A. Hebeish, M. A. El-Kashouti, M. R. El-Zairy, K. Haggag, I. Abd El-Thalouth and F. Kantoush, "Rheological Properties of Thickened Printing Pastes", American Dyestuff Reporter, 84, 2 (1995) 28-34

183

385. A. Hebeish, M. H. El-Rafie, A. Higazy and M. A. Ramadan, "Preparation and Characterization of Water Soluble Poly(Aa-)-Starch Composite", Al-Azhar Bulltien of Science, 6, 1 (1995) 789

386. A. Hebeish, K. Haggag, M. A. El-Kashouti, M. R. El-Zairy, A. Ragheb, I. Abd El-Thalouth and F. Kantouch, "Printing Cotton Fabrics with Reactive Dyes Using Cmc", American Dyestuff Reporter, 84, 8 (1995) 60-67

387. A. Higazy, M. H. El-Rafie, M. A. Ramadan and A. Hebeish, "Partial Replacement of Kerosene Oil by Poly (Acrylic) Starch Composite in Pigment Printing", Pigment and Resin Technology, 24, 5 (1995) 8 - 12

388. M. I. Khalil, A. Hashem and A. Hebeish, "Preparation and Characterization of Starch Acetate", Starch - Stärke, 47, 10 (1995) 394-398

389. A. Waly, M. K. Zahran, M. R. El-Zairy, M. Rashad and A. Hebeish, "Textile Improvement of Cellulosic Fibres and Blends", Tinctoria, 92, 9 (1995) 35-46

390. S. A. Abdel-Hafiz, M. H. El Rafie, S. M. Hassan and A. Hebeish, "Grafting of Methacrylic Acid to Loomstate Viscose Fabric Using a Potassium Permanganate/Potassium Chlorate System", Polymers and Polymer Composites, 4, 8 (1996) 577-582

391. S. A. Abdel-Hafiz, F. F. El-Sisi, M. Helmy and A. Hebeish, "Concurrent Grafting and Dyeing of Cotton with a Acrylamide/Potassium Permanganate/Citric Acid System", Journal of the Society of Dyers and Colourists, 112, 5-6 (1996) 162-166

392. S. A. Abdel-Hafiz, F. F. El-Sisi, M. Helmy and A. Hebeish, "A System for Polymerising Acrylonitrile onto Loomstate Cotton Fabric Using Potassium Permanganate/Citric Acid", Journal of the Society of Dyers and Colourists, 112, 2 (1996) 57-61

393. A. Bayazeed, M. H. El-Rafie, K. F. El-Tahlawy, A. Hebeish and M. K. Zahran, "Polyacrylic Acid Hydrolyzed Starch as Recoverable Sizing Agent", Melliand Textilberichte, 77, 5 (1996) 294-298

394. M. M. Hashem, W. Kesting, A. A. Hebeish, N. Y. Abou-Zeid and E. Schollmeyer, "Characterization and Application of Poly(Vinyl Alcohol)/Starch Composite as a Sizing Agent", Die Angewandte Makromolekulare Chemie, 241, (1996) 149-163

395. A. Hebeish, N. Y. Abou-Zeid, A. Higazy and M. M. Hashem, "Grafting of Preformed Polymers: Part I: Grafting of Hydrolyzed Starch onto Poly(Vinyl Alcohol)", Egyptian Journal of Applied Science and Technology, 11, 3 (1996) 115 - 121

184

396. A. Hebeish, N. Y. Abou-Zeid, A. Higazy and M. M. Hashem, "Grafting of Preformed Polymers: Part II: Characterization and Application of PVA-Starch Composite", Egyptian Journal of Applied Science and Technology, 11, 3 (1996) 122 - 133

397. A. Hebeish, M. H. El-Rafie, A. Higazy and M. A. Ramadan, "Synthesis, Characterization and Properties of Polyacrylamide-Starch Composites", Starch - Stärke, 48, 5 (1996) 175-179

398. A. Hebeish, N. A. Ibrahim, M. H. Abo Shosha and H. M. Fahmy, "Rheological Behavior of Some Polymeric Sizing Agents Alone and in Admixtures", Polymer - Plastics Technology and Engineering, 35, 4 (1996) 517-543

399. A. Hebeish, R. Refai, M. K. Zahran and A. A. Ali, "Easy-Care Properties of Simultaneously Grafted and Crosslinked Cotton Fabrics", Journal of Applied Polymer Science, 60, 12 (1996) 2165-2176

400. A. Hebeish, M. K. Zahran, M. H. El-Rafie and K. F. El-Tahlawy, "Preparation and Characterisation of Poly (Acrylic Acid) Starch Polyblends", Polymers and Polymer Composites, 4, 2 (1996) 129-141

401. A. Higazy, M. M. Hashem, N. Y. Abou Zeid and A. Hebeish, "The Effect of Non-Cellulosic Constituents on the Behaviour of Flax Towards Sodium Chlorite, Urea and Dyes", Journal of the Society of Dyers and Colourists, 112, 10 (1996) 281-286

402. A. Higazy, M. M. Hashem, N. Y. Abou-Zeid and A. Hebeish, "Rendering Flax Fibre Dyeable with Basic Dyes Via Partial Carboxymethylation", Journal of the Society of Dyers and Colourists, 112, 11 (1996) 329-332

403. A. Waly, F. A. Abdel-Mohdy, A. Higazy, A. S. Aly and A. Hebeish, "Decolorizing Wastewater Containing Acid or Reactive Dyes Using Starch, Melamine Resin Containing Tertiary Amino Groups", Al-Azhar Bulltien of Science, 7, 1 (1996) 1 - 10

404. A. Waly, A. Hebeish, M. K. Zahran, M. R. El-Zairy and M. Rashad, "Cellulose Thiocarbonate-Potassium Bromate Redox System-Initiated Graft Copolymerisation of Acrylic Esters on to Cotton Fabric", Polymers and Polymer Composites, 4, 1 (1996) 53-60

405. S. A. Abdel-Hafiz, F. F. El-Sisi, M. Helmy and A. Hebeish, "Simultaneous Grafting and Dyeing of Loomstate Cotton Fabric Using Potassium Permanganate Citric Acid Methacrylic Acid Dye System", Pigment and Resin Technology, 26, 4 (1997) 235-242

406. M. M. Hashem, W. Kesting, N. Y. Abou-Zeid, A. Hebeish and E. Schollmeyer, "Recovery of Sizes Based on Poly(Vinyl Alcohol)-

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Starch Graft Copolymer Using the Ultrafiltration Technique", Paper Presented at the '4th International Conference on Frontiers of Polymers and Advanced Materials ', Cairo, Egypt, 4 - 9 January.(1997),

407. A. Hebeish, A. Bayazeed, A. Higazy, M. H. El-Rafie and M. A. Ramadan, "Recovery of Sizes Based on Poly (Aa)-Starch Composite Using the Ultrafiltration Technique", Egyptian Journal of Textile Polymer Science and Technology, 1, 1 (1997) 50 - 58

408. A. Hebeish, M. H. El-Rafie, A. Higazy and M. A. Ramadan, "Poly (Aa-)-Starch Composite as Substitute for Sodium Alginate in Printing Cotton Fabrics with Reactive Dyes", Egyptian Journal of Textile Polymer Science and Technology, 1, 1 (1997) 1 - 9

409. A. Hebeish, A. A. Ragheb and H. S. El-Sayad, "Using Composites as a Base in Printing Paste", American Dyestuff Reporter, 86, 2 (1997) 18-25

410. A. Hebeish, A. A. Ragheb, K. Haggag and A. A. Abdel-Rahman, "Utilization of Modified Moghat Mucilage as Thickener in Printing Polyester with Disperse Dyes", Paper Presented at the 'AATCC International Conference and Exhibiton', Atlanta, Georgia, USA, Oct.(1997),

411. A. Hebeish, A. A. Ragheb, K. Haggag and A. a. A. El-Rahman, "Oxidation of Moghat Mucilage with Sodium Chlorite", Polymer Degradation and Stability, 58, 1–2 (1997) 33-40

412. A. Hebeish, A. Waly, F. A. Abdel-Mohdy and A. S. Aly, "Preparation of Starch Ethers Using the Dry Process: Carbamoylethyl and Cyanoethyl Starches and Their Copolymeric Products with Acrylamide/Acrylonitrile Mixture", Pigment and Resin Technology, 26, 2 (1997) 88-96

413. A. Hebeish, A. Waly, F. A. Abdel-Mohdy and A. S. Aly, "Synthesis and Characterization of Cellulose Ion Exchangers: Part I: Polymerization of Glycidyl Methacrylate, Dimethylaminoethyl Methacrylate, and Acrylic Acid with Cotton Cellulose Using Thiocarbonate-H2o2 Redox System", Journal of Applied Polymer Science, 66, 6 (1997) 1029-1037

414. A. Hebeish, A. Waly, M. H. El-Rafie and M. A. El-Sheikh, "Synthesis and Characterization of New Polymeric Materials Based on Water Soluble Starch Composites", Paper Presented at the '213th National Meeting', San Francisco, CA, USA.(1997), 213, 32-Cell

415. N. A. Ibrahim, M. H. Abo Shosha, H. M. Fahmy and A. Hebeish, "Effect of Size Formulation on Sizability and Desizability of Some

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Soluble Sizes", Polymer - Plastics Technology and Engineering, 36, 1 (1997) 105-121

416. A. A. Ragheb, A. A. Abdel Rahman and A. Hebeish, "Carbamoylethylation of Moghat Mucilage", Die Angewandte Makromolekulare Chemie, 251, 1 (1997) 23-35

417. A. A. Ragheb, H. S. El-Sayiad and A. Hebeish, "Preparation and Characterization of Carboxymethyl Starch (Cms) Products and Their Utilization in Textile Printing", Starch - Stärke, 49, 6 (1997) 238-245

418. A. Waly, M. H. El-Rafie, A. S. Aly and A. Hebeish, "Preparation of Spherical Cellulosic Beads", Egyptian Journal of Applied Science and Technology, 1, 2 (1997) 141

419. A. Waly, M. H. El-Rafie, A. S. Aly and A. Hebeish, "Cellulosic Ion – Exchangers Bearing Aromatic Amino and Sulphonic Groups", Egyptian Journal of Applied Science and Technology, 1, 2 (1997) 119

420. A. Waly, M. H. El-Rafie, A. S. Aly and A. Hebeish, "Synthesis of Various Ionic Exchangers Using Cellulosic Copolymers in the from of Beads", Paper Presented at the '4th Arab International Conference of Polymer Science and Technolgy', Egypt, Sep. 27-30 (1997),

421. F. A. Abdel-Mohdy, A. Waly and A. Hebeish, "Etherification of Starch by Dry Process, Part II: Synthesis and Evaluation of Diethylamino Hydroxy Propyl Starch-G-Poly (Aam)", Journal of the Textile Association, 59, (1998) 199 - 203

422. F. A. Abdel-Mohdy, A. Waly, M. S. Ibrahim and A. Hebeish, "Synthesis of Poly(Vinyl Acetate) - Chitin Graft Copolymers as a Base for Chitosan-Poly(Vinyl Alcohol) Ion Exchangers", Polymers and Polymer Composites, 6, 3 (1998) 147-154

423. A. Bayazeed, S. Farag, S. Shaarawy and A. Hebeish, "Chemical Modification of Starch Via Etherification with Methyl Methacrylate", Starch - Stärke, 50, 2-3 (1998) 89-93

424. M. K. Beliakova and A. Hebeish, "Novel Approach for Preparation of Antibacterial Cotton Fabrics", American Dyestuff Reporter, 87, 3 (1998) 46-49

425. F. F. El-Sisi, S. A. Abdel-Hafiz, A. R. Saleh and A. Hebeish, "Behaviour of Starch Bearing Nitrogen-Containing Moieties Towards Acid Degradation", Polymer Degradation and Stability, 62, 2 (1998) 201-210

426. A. Hebeish, "Natural Thickeners for Textile Printing", Paper Presented at the 'International Conference in Recent Advances in

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Wet Processing of Textiles', BTRA, Bombay, India, 1 - 3 February.(1998),

427. A. Hebeish, M. K. Beliakova and A. Bayazeed, "Improved Synthesis of Poly(Maa)–Starch Graft Copolymers", Journal of Applied Polymer Science, 68, 10 (1998) 1709-1715

428. A. Hebeish and Z. H. El-Hilw, "Preparation of Deae Cotton-G-Poly(Methacrylic Acid) for Use as Ion Exchanger", Journal of Applied Polymer Science, 67, 4 (1998) 739-745

429. A. Hebeish, M. I. Khalil, S. Farag and A. Waly, "Reaction Mechanism Involved in Starch –Urea – Acid System, a Key for Preparing Water Soluble Starch", Egyptian Journal of Textile Polymer Science and Technology, 2, (1998) 81 - 105

430. A. Waly, F. A. Abdel-Mohdy, A. S. Aly and A. Hebeish, "Synthesis and Characterization of Cellulose Ion Exchangers: Part II: Pilot Scale and Utilization in Dye Heavy Metal Removal", Journal of Applied Polymer Science, 68, 13 (1998) 2151-2157

431. A. Waly, F. A. Abdel-Mohdy and A. Hebeish, "Chemical Modification of Starch-Poly (Vinyl Acetate) Materials", Polymers and Polymer Composites, 6, 3 (1998) 161-170

432. Z. H. El-Hilw and A. Hebeish, "Dependence of the Dyeability of Modified Cotton on the Substituents and the Nature of the Dye", Journal of the Society of Dyers and Colourists, 115, 7-8 (1999) 218-223

433. M. M. Hashem, A. Higazy and A. Hebeish, "Synthesis and Characterization of a Dextrin-Polyacrylamide Hybrid Size for Cotton", Polymers and Polymer Composites, 7, 7 (1999) 481-490

434. A. Hebeish, M. K. El-Bisi and M. H. El-Rafie, "Preparation and Characterization of Poly (Acrylamide)/Starch Composite Using Alkali Pretreated Maize Starch", Paper Presented at the '5th Arab International Conference of Polymer Science and Technolgy', Luxor- Aswan, Egypt, Sep.18-22.(1999),

435. A. Hebeish, A. Waly and A. M. Abou-Okeil, "Flame Retardant Cotton", Fire and Materials, 23, 3 (1999) 117-123

436. A. Hebeish, A. Waly, M. H. El-Rafie, S. Shalaby and K. F. El-Tahlawy, "Polymerization of Hydroxyethyl Acrylate with Chitosan", Egyptian Journal of Textile Polymer Science and Technology, 3, 1 (1999) 1 - 23

437. M. H. Mohamed, A. M. Seyam, O. Ozkurt, W. Logan, A. Hebeish and N. Y. Abou-Zeid, "Environmentally Friendly Sizing Agents for Cotton Warps", Paper Presented at the 'Cotton Incorporated, 12th EFS System Research Forum', Raleigh, NC, USA, 4-5, November.(1999),

188

438. M. Hashem and A. Hebeish, "Synthesis of Reactive Polymers and Their Applications to Cotton Fabrics as Permanent Size", Molecular Crystals and Liquid Crystals Science and Technology, Section A: Molecular Crystals and Liquid Crystals, 353, (2000) 109-126

439. A. Hebeish, A. Bayazeed, Z. H. El-Hilw and S. Shaarawy, "Etherification of Starch with Butyl Acrylate", Mansoura Engineering Journal, 25, (2000) 2

440. A. Hebeish, A. Bayazeed, S. Farag, Z. H. El-Hilw and S. Shaarawy, "Optimization of Grafting of Butyl Acrylate onto Starch and Rheological Properties of Resultant Copolymers before and after Saponification", Paper Presented at the '3rd International Engineering Conference', El-Mansoura, Egypt, 11-13 April.(2000),

441. A. Hebeish, A. Bayazeed, S. Farag and S. Shaarawy, "Chemical Susceptibility of Starch Macromolecules Bearing Methyl Methacrylate Moieties", Egyptian Journal of Textile Polymer Science and Technology, 4, (2000) 63 - 73

442. A. Hebeish, S. Farag, S. Shaarawy and A. Bayazeed, "The Grafting Copolymerization of Methyl Methacrylate onto Starch", Egyptian Journal of Textile Polymer Science and Technology, 4, 1 (2000) 1 - 17

443. A. Hebeish, "Textile Industry of Egypt within Global Scene", Texsci 2000, (2001) 37-39

444. A. Hebeish and Z. H. El-Hilw, "Chemical Finishing of Cotton Using Reactive Cyclodextrin", Coloration Technology, 117, 2 (2001) 104-110

445. A. Hebeish and Z. H. El-Hilw, "Flame Retrdancy-Grafting-Anticrease Multifinishing in One Stage Process", Journal Fire and Materials, 113, (2001) 220 - 300

446. A. Hebeish, M. El-Hussami, M. Hashem and R. Mahfoze, "Fixing Reactive Dyes: Improvement by Post-Treatment with Non-Polluting Compounds, Enhancement of the Reactive Dye Fixation Via Aftertreatment of the Dyed Fabric with Environment Friendly Compounds", Tinctoria, 98, 9 (2001) 44 - 51

447. A. Hebeish, M. El-Hussami, M. M. Hashem and R. Mahfouze, "Enhancement of the Reactive Dye Fixation Via Aftertreatment of the Dyed Fabric with Environment Friendly Compounds", Tinctoria, 98, 9 (2001) 44 - 51

448. A. Hebeish, M. Hashem and A. Higazy, "A New Method for Preventing Catalytic Degradation of Cotton Cellulose by Ferrous

189

or Ferric Ions During Bleaching with Hydrogen Peroxide", Macromolecular Chemistry and Physics, 202, 6 (2001) 949-955

449. A. Hebeish, A. Waly, K. F. El-Tahlawy and S. M. El-Rafie, "Chitosan Hydrochloride for Concurrent Catalysis of Resin Finishing and Imparting Cationic Properties of the Finished Cotton Fabric", Paper Presented at the '6th Arab International Conference on Polymer Science and Technology', Ismaielia - Sharm El-Sheikh, Egypt, Sep. 1-5.(2001), 6, 527 - 546

450. Z. H. El-Hilw and A. Hebeish, "Improving the Durable Press Performance of Citric Acid Finished Cotton Fabrics Using Reactive Cyclodextrin", Egyptian Journal of Textile Polymer Science and Technology, 6, (2002) 91 - 111

451. S. M. El-Rafie, K. F. El-Tahlawy, M. A. Gaffar and A. Hebeish, "Synthesis and Application of Cyclodextrin/Poly(Acrylic Acid) Graft Copolymer", Egyptian Journal of Applied Science and Technology, 17, 8 (2002)

452. M. Hashem, M. El-Bisi and A. Hebeish, "Innovative Scouring for Cotton-Based Textiles", Engineering in Life Sciences, 2, 1 (2002) 23-28

453. A. Hebeish and H. O. B. El-Dine, "Rheological Properties of Polyacrylic Graft Cmc Polymer", Egyptian Journal of Textile Polymer Science and Technology, 6, (2002)

454. A. Hebeish, F. El-Sisi, A. Ragheb, M. A. El-Kashouti and H. O. B. El-Din, "Synthesis and Properties of Poly (Vinyl)-Cmc Composites", Egyptian Journal of Textile Polymer Science and Technology, 6, (2002) 35

455. M. I. Khalil, S. Farag, A. A. Aly and A. Hebeish, "Some Studies on Starch-Urea-Acid Reaction Mechanism", Carbohydrate Polymers, 48, 3 (2002) 255-261

456. A. M. Seyam, M. H. Mohamed, T. Hamilton, N. Y. Abou-Zeid, A. Waly and A. Hebeish, "Synthesis, Characterization and Application of Environmentally Friendly Sizes for Cotton Warps", Paper Presented at the '82th World Conference', Cairo, Egypt, March.(2002),

457. F. A. Abdel-Mohdy and A. Hebeish, "Durable Flame Retardancy Finishing of Cotton through Polymerization of N and P-Containing Vinyl Monomers", Paper Presented at the '7th Arab International Conferencc on Polymer Science & Technology and 3rd Arab Conference on Materials Science', Cairo-Hurghada, Egypt, October 5-9.(2003), 3, 275 - 286

458. M. Hashem, M. El Bisi and A. Hebeish, "Catalytic Activation of Peracetic Acid Using Chitosan-Metal Complex for Low-

190

Temperature Bleaching of Cotton Fabric", Indian Journal of Fibre and Textile Research, 28, 4 (2003) 444-449

459. A. Hebeish, A. S. Aly, M. El-Hossami and A. B. Moustafa, "Wet Processes of Cotton Fabrics Using Different Enzymes", Paper Presented at the '7th Arab International Conference of Polymer Science and Technolgy', Cairo-Hurghada, Egypt, October 5 - 9.(2003), 271

460. H. H. Sharawy, M. H. El-Rafie and A. Hebeish, "Electro-Catalytic Degradation of Acid Azo Dyes in Textile Waste Water by Rh/Ti Modified Electrode", TESCE, (2003) 86-105

461. F. A. Abdel-Mohdy, A. S. Aly, A. Hashem, M. El-Bendary and A. Hebeish, "Antimicrobial and Wrinkle Resistance Finishing for Cotton Using Polycarboxylic Acids", Journal of the Textile Association, 65, 1 (2004) 25-30

462. A. S. Aly, A. B. Moustafa and A. Hebeish, "Bio-Technological Treatment of Cellulosic Textiles", Journal of Cleaner Production, 12, 7 (2004) 697-705

463. A. Hashem, A. A. Aly, A. S. Aly and A. Hebeish, "Derivation of Quaternized Products from Cotton Stalks and Palm Tree Particles", Journal of the Textile Association, 65, 1 (2004) 35-39

464. A. Hashem, A. A. Aly, A. S. Aly and A. Hebeish, "The Removal of Acid Dyes from Aqueous Solutions Using Derivations of Quaternised Products from Particles of Cotton and Palm Stems", Tinctoria, 101, 8 (2004) 24-30

465. A. Hebeish, A. Bayazeed and S. Shaarawy, "Synthesis and Application of Novel Sizes Based on Starch Containing Butylacrylate Moities: Part I: Grafting of Starch Bua Ether with Poly(Bua)", Egyptian Journal of Textile Polymer Science and Technology, 8, 2 (2004) 17 - 22

466. A. Hebeish, A. Bayazeed and S. Shaarawy, "Synthesis and Application of Novel Sizes Based on Starch Containing Butylacrylate Moities: Part II: Etherification of Starch-G-Poly(Bua) Using Bua", Egyptian Journal of Textile Polymer Science and Technology, 8, 2 (2004) 23 - 29

467. A. Hebeish, R. Rafei and A. Elshafei, "The Cross-Linking of Chitosan with Glutaraldehyde for the Removal of Dyes and Heavy Metal Ions from Aqueous Solution "La Reticolazione Del Chitosano Con Aldeide Glutarica Per La Rimozione Di Coloranti E Ioni Di Metalli Pesanti Da Soluzione Acquose"", Tinctoria, 101, 4 (2004) 28-34

468. A. Hebeish, R. Refaie and A. El-Shafei, "Crosslinking of Chitosan with Glutaraldehyde for Removal of Dyes and Heavy Metal Ions

191

from Aqueous Solutions", Egyptian Journal of Chemistry, 47, Special Issue (M.Kamel) (2004) 65 - 79

469. A. Hebeish, A. Waly and A. Abou-Okeil, "Augmentation of Cotton Fabric Resilience Via Treatment with Diammonium Salt of Ethylenediamine Tetraacetic Acid", Paper Presented at the '1st

International Conference of Textile Research Division, NRC; Textile Processing: State of the Art & Future Developments', Cairo, Egypt, March 2 - 4.(2004), 1,

470. A. Hebeish, A. Waly, A. Higazy and A. El-Shafei, "Carboxymethylation of Chitosan", Paper Presented at the '1st

International Conference of Textile Research Division, NRC; Textile Processing: State of the Art & Future Developments', Cairo, Egypt, March 2 - 4.(2004),

471. A. Hebeish, A. Waly, A. Higazy and A. El-Shafei, "Hydrolytic and Oxidatative Degradation of Chitosan", Egyptian Journal of Chemistry, 47, Special Issue (M.Kamel) (2004) 101-122

472. A. A. Hebeish, S. Z. Mousa, M. A. Saad and R. F. Abdel-Aziz, "Evaluation of Some Flame Proofing Materials & Improving Their Functional through Design ", Paper Presented at the 'Textile Processing: State of the Art & Future Developments'', Cairo ,Egypt.(2004),

473. M. H. Abo-Shosha, N. A. Ibrahim, H. M. Fahmy and A. Hebeish, "Polyethylene Glycol/Toluene Diisocyanate/Dodecanol Adducts as Softeners for Cotton Fabric", Paper Presented at the '2nd

International Conference of Textile Research Division, NRC; Textile Processing: State of the Art & Future Developments', Cairo, Egypt, 11-13 April (2005),

474. A. S. Aly, H. H. Sokker, A. Hashem and A. Hebeish, "Preparation of Cellulosic Membrane Containing Pyrolidone Moiety Via Radiation Induced Grafting and Its Application in Wastewater Treatment", American Journal of Applied Polymer Science, 2, 2 (2005) 508 - 513

475. A. Elshafei, R. Refaei and A. Hebeish, "How to Improve the Easy Care Finishing of Cotton Fabric "Come Migliorare Il Finissaggio Easy Care Del Tessuto in Cotone"", Tinctoria, 102, 11 (2005) 23-30

476. A. El-Shafei, R. Refaie and A. Hebeish, "Improving Non Formaldehyde Easy Care Finishing of Cotton Using Glyoxal - Chitosan Combination", Tinctoria, 102, 11 (2005)

477. A. El-Shafei, S. Shaarawy and A. Hebeish, "Graft Copolymerization of Chitosan with Butyl Acrylate and Application

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of the Copolymers to Cotton Fabric", Polymer - Plastic Technology and Engineering, 44, (2005) 1523 - 1535

478. A. Hashem, E. S. Abdel-Halim, K. F. El-Tahlawy and A. Hebeish, "Enhancement of the Adsorption of Co+2 and Ni+2 Ions onto Peanut Hulls through Esterification Using Citric Acid", Adsorption Science and Technology, 23, 5 (2005) 367-380

479. A. Hashem, M. A. Afifi, E. A. El-Alfy and A. Hebeish, "Synthesis, Characterization and Saponification of Poly (an)-Starch Composites and Properties of Their Hydrogels", American Journal of Applied Polymer Science, 2, 3 (2005) 614 - 621

480. M. Hashem, R. Refaie and A. Hebeish, "Crosslinking of Partially Carboxymethylated Cotton Fabric Via Cationization", Journal of Cleaner Production, 13, 9 (2005) 947-954

481. A. Hebeish, M. H. Abo-Shosha and Z. H. El-Hilw, "Easy Care Cotton Containing Cyclodextrin Moieteis as Substrate for Perfume Deposition", Paper Presented at the '2nd International Conference of Textile Research Division, NRC; Textile Processing: State of the Art & Future Developments', Cairo, Egypt, 11-13 April (2005), 599-603

482. A. Hebeish, M. M. El-Molla, Z. H. El-Hilw and H. S. El-Sayad, "Wet Transfer Printing of Cationised and Aminated Cotton Fabrics", Tinctoria, 102, 5 (2005) 15-24

483. A. Hebeish, A. a. A. El-Rahman, Z. El-Hilw and M. Hashem, "Cationized Starch Derived from Pre-Oxidized Starch for Textile Sizing and Printing", Starch - Stärke, 57, 12 (2005) 616-623

484. A. Hebeish, A. El-Shafei and M. El-Bisi, "Synthesis and Characterization of Poly(Acrylic Acid) and Poly(Glycidyl Methacrylate) Chitosan Graft Copolymers and Their Application to Cotton Fabric", Polymer - Plastics Technology and Engineering, 44, 3 (2005) 427-445

485. A. Hebeish, A. Waly and A. Abou-Okeil, "Antimycotic Agent for Cotton Fabrics: Low-Molecular-Weight Chitosan", Tinctoria, 102, 4 (2005) 33-40

486. A. Hebeish, A. Waly and A. Abou-Okeil, "Mono and Diammonium Citrate as Finishing Agents for Improving Resilience of Cotton Fabrics", Tinctoria, 102, 7 (2005) 19-30

487. A. Hebeish, A. Waly and A. Abou-Okeil, "Preparation and Application of Low Molecular Weight Chitosan as Antifungus Agent for Cotton Fabric", Tinctoria, 102, 5 (2005)

488. R. Refaie, M. Hashem and A. Hebeish, "Inducing Durable Press Performance to Ionically Crosslinked Cotton Fabric", Research Journal of Textile and Apparel, 9, 2 (2005) 47 – 63

193

489. S. H. Samaha, H. E. Nasr and A. Hebeish, "Synthesis and Characterization of Starch-Poly(Vinyl Acetate) Graft Copolymers and Their Saponified Form", Journal of Polymer Research, 12, 5 (2005) 343-353

490. N. F. Ali, S. Shakra and A. Hebeish, "Dyeing Cotton with Vat Dyes Using Iron (II) Salt", Paper Presented at the '3rd International Conference of Textile Research Division, NRC; Textile Processing: State of the Art & Future Developments', Cairo, Egypt, April 2-4.(2006), 1, 44-46

491. A. Elshafei, R. Refaei and A. Hebeish, "Improving Non Formaldehyde Easy Care Finishing of Cotton Using Glyoxal - Chitosan Combination", Egyptian Journal of Chemistry, 49, 6 (2006) 731-743

492. A. Hashem, A. A. Aly, A. S. Aly and A. Hebeish, "Quaternization of Cotton Stalks and Palm Tree Particles for Removal of Acid Dye from Aqueous Solutions", Polymer - Plastics Technology and Engineering, 45, 3 (2006) 389-394

493. A. Hebeish, M. M. El-Molla, Z. H. El-Hilw and H. S. El-Sayad, "Susceptibility of Cationized and Aminized Cotton Fabrics before and after Crosslinking Towards Wet Transfer Printing", Indian Journal of Fibre and Textile Research, 31, 2 (2006) 320-329

494. A. Hebeish, H. M. Fahmy, M. H. Abo-Shosha and N. A. Ibrahim, "Preparation of a Chemical Polyblend Sizing Agent Via Polymerization of Acrylic Acid with Polyvinyl Alcohol", Polymer - Plastics Technology and Engineering, 45, 3 (2006) 309-315

495. A. Hebeish, M. Hashem, A. A. Abd El-Rahman and Z. H. El-Hilw, "Improving Easy Care Non-Formaldehyde Finishing Performance Using Polycarboxylic Acids Via Pre-Cationization of Cotton Fabric", Journal of Applied Polymer Science, 100, 4 (2006) 2697 - 2704

496. A. Hebeish, M. M. Hashem, M. El-Hosamy and S. Abbas, "Cationization of Linen Fabric: Studying the Process Parameters", Research Journal of Textile and Apparel, 10, 1 (2006) 73 - 88

497. A. Hebeish, M. M. Hashem, M. El-Hosamy and S. Abbas, "No-Salt Dyeing Behaviour of Cationized Linen Fabric", Research Journal of Textile and Apparel, 10, 2 (2006) 43 - 57

498. A. Hebeish, A. Higazy and A. El-Shafei, "New Sizing Agents and Flocculants Derived from Chitosan", Starch - Stärke, 58, 8 (2006) 401 - 410

499. A. Hebeish, A. Higazy, A. El-Shafei and S. Sharaf, "Investigation into Reactions of Starch with Monochlorotriazinyl- ß - Cyclodextrin and Application of Their Products in Textile Sizing",

194

Polymer - Plastics Technology and Engineering, 45, (2006) 1163 - 1173

500. A. Hebeish, A. Ragheb, E. Allam and J. I. A. El-Thalouth, "Innovative Printing Paste from Tara Seeds and Other Plant Seeds", Egyptian patent, 530. (2006)

501. A. A. Hebeish, A. Ragheb, S. H. Nassar, E. E. Allam and J. I. Abd El-Thalouth, "Technological Evaluation of Reactive Cyclodextrin in Cotton Printing with Reactive and Natural Dyes", Journal of Applied Polymer Science, 102, 1 (2006) 338-347

502. A. A. Hebeish, A. A. Ragheb, S. H. Nassar, E. E. Allam and J. I. Abd El-Thalouth, "Polymerization Products of Acrylic Acid with Gleditsia Triacanthos Gum as Thickeners for Reactive Printing", Journal of Applied Polymer Science, 101, 2 (2006) 931-943

503. N. A. Ibrahim, A. Hebeish, H. M. Fahmy and M. H. Abo-Shosha, "Synthesis, Characterization, and Application of Poly(Acrylamide)/ Poly(Vinyl Alcohol) Polyblends", Polymer - Plastics Technology and Engineering, 45, 3 (2006) 341-350

504. M. A. Ramadan, A. Higazy and A. Hebeish, "Optimization of Bleaching of Partially Carboxymethylated Linen Fabric for Subsequent Dyeing", Egyptian Journal of Textile Polymer Science and Technology, 10, 2 (2006) 87-100

505. A. Abou-Okeil, A. El-Shafei and A. Hebeish, "Chitosan Phosphate Induced Better Thermal Characterization to Cotton Fabric", Journal of Applied Polymer Science, 103, (2007) 2021 - 2026

506. A. S. Aly, A. B. E. Mostafa, M. A. Ramadan and A. Hebeish, "Innovative Dual Antimicrobial & Anticrease Finishing of Cotton Fabric", Polymer - Plastics Technology and Engineering, 46, 7 (2007) 703-707

507. K. F. El-Tahlawy, E. Abdelhaleem, S. M. Hudson and A. Hebeish, "Acylation of Iminochitosan: Its Effect on Blending with Cellulose Acetate", Journal of Applied Polymer Science, 104, 2 (2007) 727-734

508. K. F. El-Tahlawy, S. M. Hudson and A. A. Hebeish, "Spinnability of Chitosan Butyrate/Cellulose Acetate for Obtaining a Blend Fiber", Journal of Applied Polymer Science, 105, 5 (2007) 2801-2805

509. A. Hebeish and N. A. Ibrahim, "The Impact of Fronteir Sciences on Textile Industry", Colourage Annual, 54, 4 (2007) 41 - 69

510. A. A. Hebeish, A. A. Ragheb, S. H. Nassar, E. E. Allam and J. I. A. El-Thalouth, "Involvement of Cyanoethylation of Cotton in Printing for Better Performance O Fabric Prints", Paper Presented at the '4th International Conference of Textile Research Division,

195

NRC; Textile Processing: State of the Art & Future Developments', Cairo, Egypt, April 15-17.(2007), 254-263

511. A. Higazy, M. A. Ramadan and A. Hebeish, "Novel Application of Partial Carboxymethylation in the Wet Processing of Linen Fabric", Journal of Applied Polymer Science, 104, 2 (2007) 996-1001

512. A. S. Aly, A. S. Montaser and A. A. Hebeish, "Preparation of Hydrogels Based on Chitosan/Pva Blends and Its Application in Drug Delivery System", Paper Presented at the '5th International Conference of Textile Research Division, NRC; Textile Processing: State of the Art & Future Developments', Cairo, Egypt', Cairo, Egypt, April 6 - 8.(2008),

513. A. Hebeish, A. S. Ali, E. Drage and M. H. El-Rafie, "Innovative Starch- Based Size Formulation for Industrial Application", Egyptian Journal of Textile Polymer Science and Technology, 12, 1 (2008) 77 - 90

514. A. Hebeish, A. A. Aly, A. M. El-Shafei and S. Zaghloul, "Innovative Starch Derivatives as Textile Auxiliaries for Application in Sizing, Finishing and Flocculation", Starch - Stärke, 60, 2 (2008) 97-109

515. A. Hebeish, M. M. G. Fouda, I. A. Hamdy, S. M. El-Sawy and F. A. Abdel-Mohdy, "Preparation of Durable Insect Repellent Cotton Fabric: Limonene as Insecticide", Carbohydrate Polymers, 74, 2 (2008) 268-273

516. A. Hebeish, M. M. G. Fouda, I. A. Hamdy, S. M. El-Sawy and F. A. Abdel-Mohdy, "Preparation of Durable Insect Repellent Cotton Fabric, Treatment with Polymer Containing Permethrin", Paper Presented at the '5th International Conference of Textile Research Division, NRC; Textile Processing: State of the Art & Future Developments', Cairo, Egypt, April 6 - 8.(2008),

517. A. Hebeish, A. A. Ragheb, S. H. Nassar, E. Allam and J. I. A. El-Thalouth, "Carboxymethyl Tara Gum : A Novel Substitute for Sodium Alginate in Thickening Pastes of Reactive Printing of Cotton Textiles ", Paper Presented at the '5th International Conference of Textile Research Division, NRC; Textile Processing: State of the Art & Future Developments'.(2008), 5, 432-441

518. N. A. Ibrahim, M. H. Abo-Shosha, H. M. Fahmy, Z. M. El-Sayed and A. A. Hebeish, "Hybrids for Finishing Cotton Fabric with Durable Handle Performance", Journal of Materials Processing Technology, 200, 1-3 (2008) 385-389

519. F. A. Abdel-Mohdy, I. A. Hamdy, S. M. El-Sawy and A. Hebeish, "Role of Polymeric Binders in Treatment of Cotton Fabrics against

196

Mosquitoes", Egyptian Journal of Textile Polymer Science and Technology, 13, 1 (2009) 49 - 61

520. M. H. El-Rafie, M. A. Asem, T. I. Shaheen and A. Hebeish, "Investigation into the Bio-Synthesis of Silver Nanoparticles Using Fungi Secreted Enzymes and Proteins: Part I: Extracellular Synthesis of Nano-Sized Silver Particles Using Filtrate and Biomass of Four Fungal Strains with Special Reference to Aspergillus Fumgatus and Aspergillus Niger", Paper Presented at the '6th International Conference of Textile Research Division, NRC; Textile Processing: State of the Art & Future Developments', Cairo, Egypt, 5 - 7 April.(2009), 6, 115 - 127

521. M. M. G. Fouda, A. El-Shafei, S. Sharaf and A. Hebeish, "Microwave Curing for Producing Cotton Fabrics with Easy Care and Antibacterial Properties", Carbohydrate Polymers, 77, 3 (2009) 651-655

522. A. Hebeish, E. S. Abdel-Halim, I. A. Hamdy, S. M. El-Sawy, M. S. Ibrahim and F. A. Abdel-Mohdy, "Synthesis of Cotton Graft Copolymers Containing Glycidyl Methacrylate and Different Cyclodextrin Moieties Using Linear Beam Radiation", Research Journal of Textile and Apparel, 13, 3 (2009) 57 - 68

523. A. Hebeish, A. A. Aly, A. El-Shafei and S. Zaghloul, "Synthesis and Characterization of Cationized Starches for Application in Flocculation, Finishing and Sizing", Egyptian Journal of Chemistry, 52, 1 (2009) 73 - 89

524. A. Hebeish, A. El-Shafei and S. Shaarawy, "Synthesis and Characterization of Multifunctional Cotton Containing Cyclodextrin and Butylacrylate Moieties", Polymer - Plastics Technology and Engineering, 48, 8 (2009) 839-850

525. A. Hebeish, I. A. Hamdy, S. M. El-Sawy and F. A. Abdel-Mohdy, "Prallethrin Treatment-Induced Permanent Insect Repellence to Cotton Fabric", Egyptian Journal of Textile Polymer Science and Technology, 13, 1 (2009) 35 - 48

526. A. Hebeish, I. A. Hamdy, S. M. El-Sawy and F. A. Abdel-Mohdy, "Bioallethrin-Based Cotton Finishing to Impart Long-Lasting Toxic Activity against Mosquitoes", Research Journal of Textile and Apparel, 13, 1 (2009) 24-33

527. A. Hebeish, M. Hashem, N. Shaker, M. A. Ramadan, B. El-Sadek and M. Abdel-Hady, "New Development for Combined Bioscouring and Bleaching of Cotton-Based Fabrics", Carbohydrate Polymers, 78, 4 (2009) 961-972

528. A. Hebeish, M. Hashem, N. Shaker, M. A. Ramadan, B. El-Sadek and M. Abdel-Hady, "Effect of Post- and Pre-Crosslinking of

197

Cotton Fabrics on the Efficiency of Biofinishing with Cellulase Enzyme", Carbohydrate Polymers, 78, (2009) 953 - 960

529. A. A. Hebeish, N. A. Ibrahim, M. H. Abo-Shosha, Z. El-Sayed and H. M. Fahmy, "Hydrophilic Non Anionic Softening Materials for Textiles Containing Cellulose", Egy. Patent, 24334. 28 Jan., (2009)

530. F. A. Abd-Elmohdy, Z. El Sayed, S. Essam and A. Hebeish, "Controlling Chitosan Molecular Weight Via Bio-Chitosanolysis", Carbohydrate Polymers, 82, 3 (2010) 539-542

531. A. S. Aly, A. M. Abdel-Mohsen and A. Hebeish, "Innovative Multifinishing Using Chitosan-O-PEG Graft Copolymer/Citric Acid Aqueous System for Preparation of Medical Textiles", Journal of the Textile Institute, 101, 1 (2010) 76-90

532. M. H. El-Rafie, A. A. Mohamed, T. I. Shaheen and A. Hebeish, "Antimicrobial Effect of Silver Nanoparticles Produced by Fungal Process on Cotton Fabrics", Carbohydrate Polymers, 80, 3 (2010) 779-782

533. A. El-Shafei, S. Shaarawy and A. Hebeish, "Application of Reactive Cyclodextrin Poly Butyl Acrylate Preformed Polymers Containing Nano-Zno to Cotton Fabrics and Their Impact on Fabric Performance", Carbohydrate Polymers, 79, 4 (2010) 852-857

534. M. Gouda and A. Hebeish, "Preparation and Evaluation of Cuo/Chitosan Nanocomposite for Antibacterial Finishing Cotton Fabric", Journal of Industrial Textiles, 39, 3 (2010) 203-214

535. A. Hebeish, J. I. Abd El-Thalouth, M. A. Ramadan and M. Abdel-Hady, "Dependence of Reactive Prints of Cotton Fabrics on Type and Condition of the Scouring System", Journal of the Textile Institute, 101, 12 (2010) 1106-1111

536. A. Hebeish, M. H. El-Rafie, E. Drage and A. S. Aly, "Industerial Innovation for Cleaner Production of Sized Warp Yarns", Paper Presented at the '7th International Conference of Textile Research Division, NRC; "Current and Prospective Innovations in Chemistry & Technology of Textiles"', Cairo, Egypt.(2010), 7, 921-926

537. A. Hebeish, M. H. El-Rafie, A. A. Mohamed and T. I. Shaheen, "Investigation into Bio-Synthesis of Silver Nanoparticles Using Fungi Secreted Enzymes and Proteins, Part III: Factors Affecting the Bio Synthesis Using Biomas Filterate of Fusarium Solani (Co3)", Paper Presented at the '3rd International conference as biotechnology for the wellness industry & wellness industry exhibition', Malaysia, October 8-9.(2010), 3,

198

538. A. Hebeish, I. A. Hamdy, S. M. El-Sawy and F. A. Abdel-Mohdy, "Preparation of Durable Insect Repellent Cotton Fabric through Treatment with a Finishing Formulation Containing Cypermethrin", Journal of the Textile Institute, 101, 7 (2010) 627-634

539. A. Hebeish, A. Higazy, A. El-Shafei and S. Sharaf, "Synthesis of Carboxymethyl Cellulose (Cmc) and Starch - Based Hybrids and Their Applications in Flocculation and Sizing", Carbohydrate Polymers, 79, 1 (2010) 60 - 69

540. A. Hebeish, A. A. Ragheb, S. H. Nassar, E. Allam and J. I. A. El-Thalouth, "Tara Cum Carbamate : A New Thickening System for Cotton Printing Using Vat Dyes", Journal of American science, 6, 11 (2010) 623-631

541. A. A. Hebeish, M. A. El-Gamal, T. S. Said and R. a. M. Abd El-Hady, "Major Factors Affecting the Performance of Esd-Protective Fabrics", Journal of the Textile Institute, 101, 5 (2010) 389-398

542. A. A. Hebeish, M. H. El-Rafie, F. A. Abdel-Mohdy, E. S. Abdel-Halim and H. E. Emam, "Carboxymethyl Cellulose for Green Synthesis and Stabilization of Silver Nanoparticles", Carbohydrate Polymers, 82, 3 (2010) 933-941

543. M. A. Ramadan, S. Sharaf, M. M. Abdel-Hady and A. Hebeish, "A Novel Approach for Incorporation of Chitosan in Cotton for Improving Fabric Performance", Paper Presented at the '7th

International Conference of Textile Research Division, NRC; "Current and Prospective Innovations in Chemistry & Technology of Textiles"', Cairo, Egypt, October 10-12.(2010), 7,

544. A. M. Abdel-Mohsen, A. S. Aly, R. Hrdina, A. S. Montaser and A. Hebeish, "Biomedical Textiles through Multifunctioalization of Cotton Fabrics Using Innovative Methoxypolyethylene Glycol-N-Chitosan Graft Copolymer", Journal of Polymers and the Environment, (2011) 1-13

545. A. M. Abdel-Mohsen, A. S. Aly, R. Hrdina, A. S. Montaser and A. Hebeish, "Eco-Synthesis of PVA/Chitosan Hydrogels for Biomedical Application", Journal of Polymers and the Environment, 19, 4 (2011) 1005-1012

546. M. H. El-Rafie, M. E. El-Naggar, M. A. Ramadan, M. M. G. Fouda, S. S. Al-Deyab and A. Hebeish, "Environmental Synthesis of Silver Nanoparticles Using Hydroxypropyl Starch and Their Characterization", Carbohydrate Polymers, 86, 2 (2011) 630-635

547. A. Hebeish, F. A. Abdel-Mohdy, M. M. G. Fouda, Z. El-Sayed, S. Essam, G. H. Tammam and E. A. Drees, "Green Synthesis of Easy

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Care and Antimicrobial Cotton Fabrics", Carbohydrate Polymers, 86, 4 (2011) 1684-1691

548. A. Hebeish, M. E. El-Naggar, M. M. G. Fouda, M. A. Ramadan, S. S. Al-Deyab and M. H. El-Rafie, "Highly Effective Antibacterial Textiles Containing Green Synthesized Silver Nanoparticles", Carbohydrate Polymers, 86, 2 (2011) 936-940

549. A. Hebeish, A. El-Shafei, S. Sharaf and S. Zaghloul, "Novel Precursors for Green Synthesis and Application of Silver Nanoparticles in the Realm of Cotton Finishing", Carbohydrate Polymers, 84, 1 (2011) 605-613

550. A. Hebeish, M. M. Kamel, M. El-Hossamy, H. M. Helmy and N. S. El-Hawary, "Enzymatic Α- Amylase Treatment - Reactive Dyeing - Easy Care Finishing in Wet-Wet Consecutive Sequence for Production of High Performance Cotton Textile", Paper Presented at the '1st SMARTEX-Egypt (World Textiles Conference)', Kafrelsheikh University, Egypt.(2011),

551. A. Hebeish, A. A. Ragheb, S. H. Nassar, E. E. Allam and J. I. A. El-Thalouth, "Eco-Friendly Technology for Textile Printing Using Innovative Self Printing Paste", Egyptian Journal of Chemistry, 54, 6 (2011) 663-678

552. A. Hebeish, M. A. Ramadan, E. Abdel-Halim and A. Abou-Okeil, "An Effective Adsorbent Based on Sawdust for Removal of Direct Dye from Aqueous Solutions", Clean Technologies and Environmental Policy, 13, (2011) 713 - 718

553. A. Hebeish, M. A. Ramadan, M. E. El-Naggar and M. H. El-Rafie, "Rendering Cotton Fabrics Antibacterial Using Silver Nanoparticles–Based Finishing Formulation", Research Journal of Textile and Apparel, 15, 2 (2011) 114 - 120

554. A. Hebeish, S. Sharaf and M. M. Abd El-Hady, "Ultrasound Aided Kmno4-Acid Systems for Bleaching Linen Fabric", Carbohydrate Polymers, 83, 3 (2011) 1370-1376

555. M. H. El-Rafie, T. I. Shaheen, A. A. Mohamed and A. Hebeish, "Bio-Synthesis and Applications of Silver Nanoparticles onto Cotton Fabrics", Carbohydrate Polymers, 90, 2 (2012) 915-920

556. A. Hebeish, M. Hashem, M. A. Ramadan, B. Sadek and M. Abdel-Hady, "Bioscouring Aided by Edta and Β-Cyclodextrin for Purification of Loomstate Cotton and Blend Fabrics", Research Journal of Textile and Apparel, 16, 3 (2012) 127 - 138

557. A. Hebeish, M. Hashem, N. Shaker, M. A. Ramadan, B. El-Sadek and M. Abdel-Hady, "Cellulase Enzyme in Biofinishing of Cotton Based Fabrics: Effect of Process Parameters", Research Journal of Textile and Apparel, 16, 3 (2012) 57 - 65

200

558. A. Hebeish, S. Sharaf, R. Refaie and A. El-Shafei, "Multi Finishing Cotton Fabric Using Microwave Technique", Research Journal of Textile and Apparel, (2012)

559. A. A. Hebeish, N. F. Ali and J. I. Abd El-Thalouth, "Green Strategy for Development of Antimicrobial Printed Textile Fabrics", Research Journal of Textile and Apperal, 16, 1 (2012) 77-85

560. M. A. Ramadan, W. M. Raslan, E. M. El-Khatib and A. Hebeish, "Rendering of Cellulose Acetate Fabrics Self-Cleaning through Treatment with Tio2 Nano Particles", Materials Sciences and Applications, 3, 872-879 (2012)

561. M. Hashem, S. Sharaf, M. M. Abd El-Hady and A. Hebeish, "Synthesis and Characterization of Novel Carboxymethylcellulose Hydrogels and Carboxymethylcellulolse-Hydrogel-Zno-Nanocomposites", Carbohydrate Polymers, 95, 1 (2013) 421-427

562. A. Hebeish, M. H. El-Rafie, M. A. El-Sheikh and M. E. El-Naggar, "Ultra-Fine Characteristics of Starch Nanoparticles Prepared Using Native Starch with and without Surfactant", Journal of Inorganic and Organometallic Polymers and Materials, (2013) 1-10

563. A. Hebeish, M. H. El-Rafie, M. A. El-Sheikh and M. E. El-Naggar, "Nanostructural Features of Silver Nanoparticles Powder Synthesized through Concurrent Formation of the Nanosized Particles of Both Starch and Silver", Journal of Nanotechnology, 2013, (2013) 1-10

564. A. Hebeish, M. H. El-Rafie, M. A. Ramadan and M. E. El-Naggar, "Investigation into the Synthesis and Characterization of Silver Nanoparticles", Research Journal of Textile and Apparel, 17, 3 (2013) 83-97

565. A. Hebeish, S. Farag, S. Sharaf, A. M. Rabie and T. I. Shaheen, "Modulation of the Nanostructural Characteristics of Cellulose Nanowhiskers Via Sulfuric Acid Concentration", Egyptian Journal of Chemistry, 56, 3 (2013)

566. A. Hebeish, M. Hashem, M. M. Abd El-Hady and S. Sharaf, "Development of Cmc Hydrogels Loaded with Silver Nano-Particles for Medical Applications", Carbohydrate Polymers, 92, 1 (2013) 407-413

567. A. Hebeish, M. M. Kamel, H. M. Helmy and N. S. El-Hawary, "Science-Based Options for Application of Cellulase Biotreatment and Reactive Dyeing to Cotton Fabrics", Life science Journal, 10, 4 (2013) 3281-3289

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568. A. Hebeish, A. R. Mousa, M. A. Ramadan and A. Saleh, "New Route for Novel Polycarboxylic Starch Hybrid", Materials Sciences and Applications, 4, 11 (2013) 695-703

569. A. Hebeish, M. F. Shaaban and K. A. Ahmed, "Chitosan Induced Bactericidal Properties and Improved Printability to Cotton Fabrics", Journal of Applied Sciences Research, 9, 3 (2013) 1754-1758

570. A. Hebeish, S. Sharaf and A. Farouk, "Utilization of Chitosan Nanoparticles as a Green Finish in Multifunctionalization of Cotton Textile", International Journal of Biological Macromolecules, 60, 0 (2013) 10-17

571. A. A. Hebeish, M. M. Abd El-Hady and A. M. Youssef, "Tio2

Nanowire and Tio2 Nanowire Doped Ag-Pvp Nanocomposite for Antimicrobial and Self-Cleaning Cotton Textile", Carbohydrate Polymers, 91, 2 (2013) 549-559

572. M. A. Ramadan, W. M. Raslan, M. M. Abdel-Hady and A. Hebeish, "Novel Method for Fast Bleaching of Cellulose Acetate Fabric by Using H2o2 Aided by Ultrasonic Waves", Research Journal of Textile and Apparel, 17, 4 (2013) 40-48

573. M. A. Ramadan, S. Sharaf, M. M. Abdel-Hady and A. Hebeish, "A Novel Approach to Incorporation of Chitosan in Cotton for Improving Fabric Performance (P.64)", Research Journal of Textile and Apparel, 17, 4 (2013) 64-71

574. S. Sharaf, A. Higazy and A. Hebeish, "Propolis Induced Antibacterial Activity and Other Technical Properties of Cotton Textiles", International Journal of Biological Macromolecules, 59, 0 (2013) 408-416

575. J. Wiener, M. A. Ramadan, R. Gomaa, R. Abbassi and A. Hebeish, "Preparation and Characterization of Conductive Cellulosic Fabric by Polymerization of Pyrrole", Materials Sciences and Applications, 4, 10 (2013) 649-655

576. A. A. Almetwally, H. M. F. Idrees and A. A. Hebeish, "Predicting the Tensile Properties of Cotton/Spandex Core-Spun Yarns Using Artificial Neural Network and Linear Regression Models", Journal of the Textile Institute, (2014)

577. M. Gouda, A. A. Hebeish and A. I. Aljafari, "Synthesis and Characterization of Novel Drug Delivery System Based on Cellulose Acetate Electrospun Nanofiber Mats", Journal of Industrial Textiles, 43, 3 (2014) 319-329

578. A. Hebeish, M. H. El-Rafie, M. A. El-Sheikh, A. A. Seleem and M. E. El-Naggar, "Antimicrobial Wound Dressing and Anti-

202

Inflammatory Efficacy of Silver Nanoparticles", International Journal of Biological Macromolecules, 65 (2014) 509-515

579. A. Hebeish, M. H. El-Rafie, A. M. Rabie, M. A. El-Sheikh and M. E. El-Naggar, "Ultra-Microstructural Features of Perborate Oxidized Starch", Journal of Applied Polymer Science, 131, 8 (2014)

580. A. Hebeish, S. M. El-Sawy, M.Ragaei, I. A. Hamdy, M. K. El-Bisi and F. A. Abdel-Mohdy, "New Textiles of Biocidal Activity by Introduce Insecticide in Cotton-Poly (GMA) Copolymer Containing B-Cyclodextrin", Carbohydrate Polymers, 99, (2014) 208-217

581. A. Hebeish, A. El-Shafei, S. Sharaf and S. Zaghloul, "In Situ Formation of Silver Nanoparticles for Multifunctional Cotton Containing Cyclodextrin", Carbohydrate Polymers, 103, 1 (2014) 442-447

582. A. Hebeish, S. Farag, S. Sharaf and T. I. Shaheen, "Thermal Responsive Hydrogels Based on Semi Interpenetrating Network of Poly(Nipam) and Cellulose Nanowhiskers", Carbohydrate Polymers, 102, (2014) 159-166

583. A. Hebeish, F. A. Nassar, I. A. Hamdy, S. M. El-Sawy and F. A. Abdel-Mohdy, "Innovative Approach for Bed Bug Control by Inclusion of Permethrin in Poly (GMA)-Cotton Graft Copolymers Containing Cyclodextrins", in"Research Journal of Textile and Apparel", (Accepted for Publication 2012)

584. A. Hebeish, A. A. Aly and S. Farag, "Synthesis and Evaluation of New Environment-Friendly Starch Hydroxypropyl Phosphate as Flocculant", in"Egyptian Journal Chemistry", (Accepted for publication 2013)

585. A. Hebeish, M. H. El-Rafie, M. A. El-Sheikh, A. A. Seleem and M. E. El-Naggar, "More Insight on Characterization of Nanosized Particles of Silver Powder and Their Application in Anti-Inflammatory Efficacy", in"Egyptian Journal of Chemistry", (Accepted for publication 2013)

586. A. Hebeish, M. M. Kamel, H. M. Helmy and N. S. El-Hawary, "Innovative Technology for Multifunctionalization of Cotton Fabric through Cellulase Biotreatment, Reactive Dyeing and Easy Care Finishing", in"Egyptian Journal of chemistry", (Accepted for publication 2013)

587. M. K. El-Bisi, H. M. El-Rafie, M. H. El-Rafie and A. Hebeish, "Honey Bee for Eco-Friendly Green Synthesis of Silver Nanoparticles and Application to Cotton Textile", Egyptian Journal of Chemistry, (sent for Publication 2013)

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