radiation modification of synthetic polymers - hacettepe of synthetic fibers and textiles, ......
TRANSCRIPT
Radiation Modification of Synthetic PolymersLecturer : Assoc. Prof. Dr. Murat Şen
Hacettepe University Department of Chemistry,Polymer Chemistry Division, 06532, Beytepe, Ankara, TURKIYE
1
APPLICATIONS OF RADIATION PROCESSING
Topic: Radiation Modification of Synthetic Polymers
Human Health Materials Environment
2
Topic: Radiation Modification of Synthetic Polymers3
Cross-linkingHigh voltage, low power flame retardant cables of TV sets
High temperature and solvent resistance pipesHeat shrinkable products, films, tubing tape etc.Radiation vulcanization of natural rubber latex
DegradationProduction of teflon sprays from tetraflouroethylene
High quality printing inks from PTFEReclamation of rubber
Preparation of oligosaccharides
CuringCoating on the different substrates (wood, paper, plastic)
Foil lamination, printing inksMagnetic media (magnetic tapes, and floppy disks)
Graft polymerizationGrafting of synthetic fibers and textiles, polymer based biocompatible artificial organs
Superpermaable membranes for battery separators, Diagnostic systems
Topic: Radiation Modification of Synthetic Polymers [1,2]
Major Processes For the Radiation Modification of Synthetic Polymers
4
Radiation cross-linking improves thermal, mechanical, chemical properties
Free from chemicalsRapid processEnergy saving
Value addition to productsCross-linked insulation in cables/wires, LDPE O-rings for harsh conditions e.g. temperature (locomotives, automobiles)
Topic: Radiation Modification of Synthetic Polymers5
Crosslinking of Pipes
Topic: Radiation Modification of Synthetic Polymers6
SiO
SiO
Si OSi
(CH2)3O
O
O C C CH2
CH3O
(CH2)3 O C C CH2
O CH3
O
HO
(CH2)3OCCH2CCH3
O
(CH2)3OCCH2CCH3
O OH
SiO2 nanoparticle:
mechanical properties viscoelastic properties
polysiloxane shell: S2
radiation curing solubility in acrylates
OH
OHOH
OH HO
Si
O
O
Si
OSi
O O
Si
OH
O
(CH2)3
(CH2)3 O C C CH2OOH
O
O CH3
Si
O C C CH2
CH3O
(CH2)3 O C C CH2
CH3O
CH3O
CH2CCO(CH2)3
O
CH3OCH2CCO(CH2)3
Topic: Radiation Modification of Synthetic Polymers7
Applications: Microstructuredpolyacrylate surfaces
Three steps of the replication process
11
2 2
33
UV/EB irradiation
Topic: Radiation Modification of Synthetic Polymers8
Radiation cross-linked heat shrinkable tubes
Topic: Radiation Modification of Synthetic Polymers [3]
Thin-walled plastic tubing andplastic films are cross-linked to obtain the so-called “memory” effect from the cross-linked network. Radiation cross-linking fixes or stabilizes the original dimensions of the tubing or films.
When the material is heated abovethe temperature where the unirradiatedmaterial would melt, it becomes elastic and can be expanded to at least twice its original dimension.
When cooled, it maintains the expanded dimension but retains the “memory” of İts original dimension.
When heated again, it contracts to the original dimension.
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Topic: Radiation Modification of Synthetic Polymers [3]10
Topic: Radiation Modification of Synthetic Polymers [4-5]
EB crosslinking tires
Another significant industry to be affected by EB crosslinking is tire manufacturing. Here, EB equipment is primarily used to only partially
crosslink tire components to improve their "green strength" or dimensional stability, prior to assembly and conventional thermal
vulcanization. This EB pre-cure essentially allows the uncured rubber-based polymer to deform uniformly under stress, without sagging or non-uniform thinning. The benefits can include fewer off-spec tires,
the ability to use higher percentages of synthetic rubber, and an overall savings in the amount of rubber required.
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Topic: Radiation Modification of Synthetic Polymers
Research involving both the University of Maryland and DAMILIC Corporation scientists has resulted in the invention of a new formulation for the
manufacture of Styrene-Butadiene Rubber (SBR) products.
The new rubber has improved wear resistance, hot tear strength, ozone resistance, crack initiation, and crack growth characteristics. DAMILIC Corporation has secured rights to this technology through a patent and formation of the subsidiary DAMILIC Rubber Co., owned jointly with the
University of Maryland.
With the University of Maryland's improved formulation, the sulfur is reducedor eliminated, and an additional crosslinking agent is added. Curing is
accomplished in a two step process, with the second step consisting of a radiation cure.
The resulting product exhibits an improvement in ozone resistance - with more than 12,000 times the resistance of conventionally cured formulations. This
special radiation curable formula survived for two months in an ozone chamber (at elevated ozone concentrations) at the National Institute of
Standards and Technology. Standard sulfur/heat cured SBR samples failed within 3 hours under the same conditions.
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Testing results in general have demonstrated that radiation curing of rubber offers a new technology to the rubber industry for the manufacture of materials
with properties unattainable by traditional chemical curing techniques.
Topic: Radiation Modification of Synthetic Polymers
Mechanical Properties Sulfur Cured SBR EB Cured SBR Tensile Strength 3300 psi 3390 psi200% Modulus 650 psi 655 psiHot Tear 130 lb/in 182 lb/in Elongation at Break 515% 610% Crack Initiation 20,000 cycles >200,000 cycles Crack Growth 25 mil/min 9.4 mil/min
Mechanical Characteristics of E-Beam v. Sulfur Cured Rubber
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Wear-resistant ultra high molecular weight polyethylene for hip jointUltra high molecular weight polyethylene (UHMWPE) has mechanical and chemical propertieshighly suitable for orthopaedic implants. Radiation crosslinking process was used to increase wear resistance of acetabular cup in artificial hip joint The effect of e-beam irradiation on the structure and mechanical properties of UHMWPE specimen was irradiated at 140 oC and room temperature with different dosages of electron beam. Following irradiation at room temperature, the UHMWPE were thermally treated at 110, 130, 145 oCeliminate all the remaining free radicals.The polymer pin on a metal plate type-testing apparatus was used to test the wear property.
The irradiation of electron-beam in molten state resulted in the best wear resistant property of UHMWPE. UHMWPE having the enhanced crosslinking after irradiation will be used to extend the life time of artificial joints.
Topic: Radiation Modification of Synthetic Polymers [1,2]14
Hydrogel burn/wound dressings by radiation synthesis cum sterilization
Sterile coverCooling effectRegulates O2 supplyHealing progress fastLess scar formation
INGREDIENTSPoly Vinyl Alcohol, PVPNatural Polysaccharide like AgarDistilled Water
AdvantagesCross linking + sterilization in one stepBio-compatible materialsCost effective
Topic: Radiation Modification of Synthetic Polymers [6-8]15
Topic: Radiation Modification of Synthetic Polymers
RADIATION STERILIZATION
• Medical products/ devices
• Packing materials• Labware• Raw materials• Some cosmetics and
pharmaceutical goods• Tissues• Midwifery kits• IAEA-UNDP support to• several countries.
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PVP/EGDMA HYDROGELS
HYDROGELSTopic: Radiation Modification of Synthetic Polymers17
POLY(N-VINYL-2-PYRROLIDONE)AND
POLY(VINYL ALCOHOL) BASED HYDROGEL DRESSINGS
Poland: The Technical University of Lodz. KIK-gel® and AQUA-gel®
Brazil: Instituto de Pesquisas Energeticas e Nucleares (IPEN). Biogel®
Japan: Takasaki Radiation Chemistry Research Establishment (JAERI)
Egypt: The National Center for Radiation Research and Technology (NCRRT)
India: Bhabha Atomic Research Center (BARC)
Turkey: Hacettepe University, Chemistry Department (HU)
Topic: Radiation Modification of Synthetic Polymers18
Aqua-gel Wound Dressing
Topic: Radiation Modification of Synthetic Polymers19
Board of Radiation and Isotope Technology, Department of Atomic Energy, Government of India
Topic: Radiation Modification of Synthetic Polymers20
A commercial wound dressing (Aqua-gel®)
Topic: Radiation Modification of Synthetic Polymers21
Some applications of “DermoGel-A” such as on arm and hand
Topic: Radiation Modification of Synthetic Polymers [9]22
Topic: Radiation Modification of Synthetic Polymers [10-11]
When polymers such as polyethylene and ethylene-vinyl acetate copolymers (EVA) are filled with conductive fillers such as carbon black, conductive composite materials are formed.
These materials can be cross-linked by radiation to obtain a useful property called the “PTC effect”.
The PTC effect refers to the sudden drastic increase of electric resistivity of the material upon reaching a certain temperature when the material is heated .
The resistivity can increase by many orders of magnitude.. This property can be employed to make self-limiting heating cables, resettable microfuses, etc.
Upon reaching the critical temperature, the electric circuit would be broken, and the material would stop heating itself
Positive TemperatureCoefficient (PTC) Effect
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The unirradiated scrap is too tough, doughy and slippery to grind, but the irradiated material can be ground readily
PTFE has a high G(S) and can be readily degraded to lower molecular weight by radiation
The dose requirements can be very high, in the range of 500to 1000 kGy, although doses as low as 50 kGy are also used for some specific applications[
When polymers such as PTFE are irradiated in air, the oxygen and moisture in the air cause oxidation in addition to degradation.
The polar functional groups such as the carboxylic acid groups on PTFE can helpimprove the compatibility of PTFE with other polymers.
Topic: Radiation Modification of Synthetic Polymers [12-13]
Production of teflon spreys and powder from tetraflouroethylene
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“Micropowders” made from polytetrafluoroethylene (PTFE) are used in a wide range of products to enhance their lubricating properties or produce plastic parts with a smoother feel, such as computer keys.
These fine micro powders are made from virgin or recycled PTFE that has first been treated with electron beam or gamma to make it easier
to grind into these fine powders
Topic: Radiation Modification of Synthetic Polymers
PTFE LUBRICANTS
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Radiation-Induced Graft Polymerization Modification Routes Leading to Chelating and Coordinating Polymers
Topic: Radiation Modification of Synthetic Polymers26
Topic: Radiation Modification of Synthetic Polymers [14]27
The preparation of nonwoven fabric containing surface grafted chains with two
amidoxime groups per one monomeric unit requires the three steps;
(1) grafting of an epoxy-group containing monomer, glycidyl methacrylate GMA,
by pre-irradiation grafting technique,
(2) functionalization of epoxy ring with 3,3’-iminodipropionitrile, and
(3) amidoximation reaction of CN groups on the grafted chains.
Schematic preparation of polymeric fabric adsorbent containing twoamidoxime groups per repeating unit of grafted chains
Polyethylene/Polypropylene
nonwoven fabric HO N
CH2CH2CN
CH2CH2CN
Polyethylene/Polypropylene
GMA HN(CH2CH2CN)2 NH2OH
HO NCH2CH2C
CH2CH2C
NH2
NH2
NOH
NOH
Polyethylene/Polypropylene
Amidoxime groupcontainingnonwoven fabric
electron beam
Polyethylene/Polypropylene
O
GMA graftednonwoven fabric
GMA
electron beam
n onwovenfabric
GM A graffedno nwoven fabric
Amid oxim e-group-co ntainingn on woven fabric
Polyethylene/Polypropylene
O
H N(C H2CH 2C N)2
HO
NH 2O H
HO N
NH 2
CH 2CH 2C NO H
CH 2CH 2C NO H
NH 2
NCH 2C H 2CN
CH 2C H 2CN
Polyethylene/Polyprop ylen e
Polyethylene/Polypropylene
Polyethylene/Polyprop ylen e
Topic: Radiation Modification of Synthetic Polymers [15]28
Total Dose: 200 kGy
(Voltage of 2 MeV,
Current of 1 mA)
Topic: Radiation Modification of Synthetic Polymers [16-17]29
Characterization by SEM
SEM photographs of a) trunk non-woven fabric, b) 150 % GMA grafted non-woven fabric, at two different
magnifications (1500X and 500X)
a
b
Trunk polymer
11.6 μm
150 %, GMA grafted fabrics
27.4 μm
Topic: Radiation Modification of Synthetic Polymers [16-17]30
Recently prepared fluorine-based polymer electrolyte membranes by Japanese researchers with an ion-exchange capacity being three times larger than that of
the conventional films based on the methods of radiation cross-linking and grafting. These membranes are chemically stable and show restricted swelling
properties in liquid alcohol because of their cross-linking structures. The investigation on the suitability for use in solid polymer type fuel cells, especially a direct methanol fuel cell, is now in progress for developing basic techniques
to reduce the size and weight of the fuel cells.
Development of Highly Conductive Ion-Exchange Membranes
Topic: Radiation Modification of Synthetic Polymers31
Topic: Radiation Modification of Synthetic Polymers32
Cured Monomer Grafted to Wood
+ Dimensional Stability: near-zero change+ Flexural Modulus: >40% tougher than control
Topic: Radiation Modification of Synthetic Polymers33
A REVIEW ON THE A REVIEW ON THE Polymer Recycling : Potential Application of Polymer Recycling : Potential Application of
Radiation TechnologyRadiation TechnologyG. G. BurilloBurillo, R. Clough, T. , R. Clough, T. CzvikovszkyCzvikovszky, O. , O. GGüüvenven, A. Le , A. Le MoelMoel,,
W. Liu, A. Singh, J. Yang, T. W. Liu, A. Singh, J. Yang, T. ZaharescuZaharescuinin
Radiation Physics and Chemistry 41Radiation Physics and Chemistry 41--51, 64, (2002)51, 64, (2002)
The status of radiation-assisted polymer recycling
Radiation reclamation of butyl rubber
Future prospects for using radiation in polymer recycling
Topic: Radiation Modification of Synthetic Polymers [18]34
WASTE RUBBER AND ENVIRONMENTWASTE RUBBER AND ENVIRONMENTParallel to the increase in the number of vehiclesin the whole world, waste tires are an important economical and ecological problem.
Scrap tyres have become a symbol of the global waste problem despite their accounting only for about 2 % of the total amount of waste
Large amount of rubbers are used as tires forAeroplanes, Trucks, Cars, Two wheelers, etc.
Topic: Radiation Modification of Synthetic Polymers35
WASTE RUBBER AND ENVIRONMENTWASTE RUBBER AND ENVIRONMENTEvery year :2Mtonnes of tyres are scrapped in EUROPE2.8 Mtonnes in the USA30.000 tonnes in China
APPROACHES
Two major approaches to solve this problem are recycle and reuse of used and waste rubber, and
reclaim of rubber raw materials
Topic: Radiation Modification of Synthetic Polymers36
RECLAIMING FROM RUBBER PRODUCTSRECLAIMING FROM RUBBER PRODUCTS
Reclaiming of scrap rubber is, therefore, the most desirable approach to solve the disposal problem
Many attempts have been made since 1910 for reclaiming of scrap rubber productsReclaiming process may be broadly classified intotwo groups
Physical reclaiming processChemical reclaiming processRADIATION RECLAMATION OF RUBBER
Topic: Radiation Modification of Synthetic Polymers37
Tire industry in China and waste Butyl rubber
With the development of car industry, the output of tire in China has been an annual growth of 5-10 % over the years, reaching up to 80,000,000 in 1999.
Accordingly, the demand of tire industry on butyl rubber is steadily, the estimated amount for the year 2000 amounting to 80,000 tons.
In 2000 February, china’s first production line of butyl rubber with an annual capacity of 30,000 tons.
In pace with the development of tire industry, the generation of waste butyl vulcanizates such as butyl inner tube, water tube and bladder multiplies.
Currently, around 30,000-40,000 tons of used butyl rubber vulcanizates are being generated annually, with approximately 7000 tons being collected.
It is estimated the above number will respectively reach up 80,000-120,000 tons by the year 2010.
Topic: Radiation Modification of Synthetic Polymers [19]
Radiation reclamation of butyl waste38
Topic: Radiation Modification of Synthetic Polymers [19]39
Topic: Radiation Modification of Synthetic Polymers [19]40
Topic: Radiation Modification of Synthetic Polymers [19]41
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RUBBER CONSUMPTION IN TURKEYRUBBER CONSUMPTION IN TURKEY
Yıl 1989 1990 1995 2000 2005 Consumption Rubber Increase Rate
NR 52 56 80 94 109 7.6
SBR 23 26 46 52 75 7.7
CBR 9 10 18 22 30 7.8
Others 11 12 21 24 34 7.5
Total 95 104 165 192 245 7.7Rubber
Carbon 43 48 82 102 135 7.4black
*Thousand tone*Thousand tone
Topic: Radiation Modification of Synthetic Polymers43
TYRE AND INNER TUBE PRODUCTION IN TYRE AND INNER TUBE PRODUCTION IN TURKEYTURKEY
* piece / year* piece / year
Company Tyre Inner tube
Bridgesa 4.070.000 1.765.000
Good Year 3.095.000 902.000
Pirelli 2.944.000 1.980.000
Petlas 1.225.000 450.000
Total 11.334.000 5.097.000
Topic: Radiation Modification of Synthetic Polymers44
ISOBUTYLENEISOBUTYLENE--ISOPRENE RUBBER (IIR)ISOPRENE RUBBER (IIR)
Isobutylene Isoprene
97 - 99.5 mole % isobutylene0.5 - 3.0 mole % isoprene
CH2 C
CH3
CH3
CH2 C
CH3
CH CH2
Topic: Radiation Modification of Synthetic Polymers45
Experimental StudiesExperimental Studies
Material :Material : Butyl RubberButyl Rubber
EXXON 165 IIR (0.8 % IP) (Ex165)EXXON 165 IIR (0.8 % IP) (Ex165)(M(Mw w = 320.000 = 320.000 MMnn = 112.000 = 112.000 MMvv = 286.000)= 286.000)
EXXON 268 IIR (1.7 % IP) (Ex268)EXXON 268 IIR (1.7 % IP) (Ex268)(M(Mw w = 456.000 = 456.000 MMnn = 167.500 = 167.500 MMvv = 334.000)= 334.000)
POSINTEZKAUT BK1675N (1.7 % IP) (POS)POSINTEZKAUT BK1675N (1.7 % IP) (POS)(M(Mw w = 447.000 = 447.000 MMnn = 200.000 = 200.000 MMvv = 340.000)= 340.000)
Topic: Radiation Modification of Synthetic Polymers [20]46
RADIATION PROCESSING OF INNER TUBESRADIATION PROCESSING OF INNER TUBES
INNER TUBESINNER TUBES
Cutting by knifeCutting by knife Irradiation Irradiation
LowLow DoseDose RateRate HighHigh DoseDose RateRate
Characterization Characterization
0.18 kGy/h 3 kGy/h
Topic: Radiation Modification of Synthetic Polymers [20]47
EFFECT OF DOSE RATE ON THE GEL FRACTIONEFFECT OF DOSE RATE ON THE GEL FRACTION
0 25 50 75 100 125 150 175 200 225 2500
102030405060708090
100
HDR LDR
Gel
Fra
ctio
n, %
Dose (kGy)
SOLSOL--GEL ANALYZES GEL ANALYZES
Topic: Radiation Modification of Synthetic Polymers [20]48
Experimental StudiesExperimental Studies
Irradiation ConditionsIrradiation ConditionsDose rate Dose rate
Air NAir N22 Air Air NN22
LowLow DoseDose RateRate HighHigh DoseDose RateRate(0.18 kGy/h) (3.0 kGy/h)
Topic: Radiation Modification of Synthetic Polymers [20]49
EFFECT OF GAMMA RAYS ON THE VISCOSITY OF EFFECT OF GAMMA RAYS ON THE VISCOSITY OF EXXON 165 IIR (0.8 % IP)EXXON 165 IIR (0.8 % IP)
0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.20.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
0kGy 30kGy 60 kGy 90 kGy 120 kGy 150 kGy 210 kGyη s
p/c
Concentration (g/dL)
LOW DOSE RATE
0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.20.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6 0 kGy 25 kGy 50 kGy 100 kGy 145 kGy 200 kGy 250 kGyη s
p/c
Concentration (g/dL)
HIGH DOSE RATE
Atmosphere : AirAtmosphere : Air
Topic: Radiation Modification of Synthetic Polymers [20]50
EFFECT OF ATMOSPHERE ON THE LIMITING VISCOSITY EFFECT OF ATMOSPHERE ON THE LIMITING VISCOSITY NUMBERNUMBER
EXXON 165 IIR (0.8 % IP)EXXON 165 IIR (0.8 % IP)
0 50 100 150 2000,0
0,2
0,4
0,6
0,8
1,0
1,2 N2 Air
Lim
iting
visc
osity
num
ber [
η]
Dose (kGy)
Dose Rate: 0.18 Dose Rate: 0.18 kGy/hkGy/h
Topic: Radiation Modification of Synthetic Polymers [20]51
EFFECT OF ATMOSPHERE ON THE LIMITING VISCOSITY EFFECT OF ATMOSPHERE ON THE LIMITING VISCOSITY NUMBER EXXON 268 IIR (1.7 % IP)NUMBER EXXON 268 IIR (1.7 % IP)
Dose Rate: 0.18 Dose Rate: 0.18 kGy/hkGy/h
0 50 100 150 2000.0
0.2
0.4
0.6
0.8
1.0
1.2 N2 Air
Lim
iting
visc
osity
num
ber [
η]
Dose (kGy)
Topic: Radiation Modification of Synthetic Polymers [20]52
EFFECT OF ATMOSPHERE ON THE LIMITING VISCOSITY EFFECT OF ATMOSPHERE ON THE LIMITING VISCOSITY NUMBER OF EXXON 268 IIR (1.7 % IP)NUMBER OF EXXON 268 IIR (1.7 % IP)
Dose Rate: 3.0 Dose Rate: 3.0 kGy/hkGy/h
0 50 100 150 2000.0
0.2
0.4
0.6
0.8
1.0
1.2 N2 Air
Lim
iting
visc
osity
num
ber [
η]
Dose (kGy)
Topic: Radiation Modification of Synthetic Polymers [20]53
EFFECT OF ATMOSPHERE ON THE LIMITING VISCOSITY EFFECT OF ATMOSPHERE ON THE LIMITING VISCOSITY NUMBER OF POSINTEZKAUT BK1675N (1.7 % IP)NUMBER OF POSINTEZKAUT BK1675N (1.7 % IP)
Dose Rate: 3.0 Dose Rate: 3.0 kGy/hkGy/h
0 50 100 150 2000.0
0.2
0.4
0.6
0.8
1.0
1.2 N2 Air
Lim
iting
visc
osity
num
ber [
η]
Dose (kGy)
Topic: Radiation Modification of Synthetic Polymers [20]54
RUBBER TYPE AND CHANGES OF [RUBBER TYPE AND CHANGES OF [η η ] ]
0 50 100 150 200
0.2
0.4
0.6
0.8
1.0
1.2 Ex165 LDR Air Ex268 LDR Air POS LDR Air
Lim
iting
visc
osity
num
ber [
η]
Dose (kGy)0 50 100 150 200
0.2
0.4
0.6
0.8
1.0
1.2 Ex165 LDR N2 Ex268 LDR N2 POS LDR N2
Lim
iting
visc
osity
num
ber [
η]
Dose (kGy)
0 50 100 150 200
0.2
0.4
0.6
0.8
1.0
1.2 Ex165 HDR N2 Ex268 HDR N2 POS HDR N2
Lim
iting
vis
cosi
ty n
umbe
r [η]
Dose (kGy)0 50 100 150 200
0,2
0,4
0,6
0,8
1,0
1,2 Ex165 HDR Air Ex268 HDR Air POS HDR Air
Lim
iting
visc
osity
num
ber [
η]
Dose (kGy)
Topic: Radiation Modification of Synthetic Polymers [20]55
RUBBER TYPE AND % CHANGES OF [RUBBER TYPE AND % CHANGES OF [η η ] ]
0 50 100 150 2000
1020304050607080
Ex165 LDR Air Ex268 LDR Air POS LDR Air
% C
hang
es [η
]
Dose (kGy)0 50 100 150 200
01020304050607080
Ex165 LDR N2 Ex268 LDR N2 POS LDR N2
% C
hang
es [η
]
Dose (kGy)
0 50 100 150 2000
102030405060708090
Ex165 HDR N2 Ex268 HDR N2 POS HDR N2
% C
hang
es [η
]
Dose (kGy)0 50 100 150 200
0102030405060708090
Ex165 HDR Air Ex268 HDR Air POS HDR Air
% C
hang
es [η
]
Dose (kGy)
Topic: Radiation Modification of Synthetic Polymers [20]56
Gel Permeation Chromatograms of IIRGel Permeation Chromatograms of IIRDose Rate: 0.18 kGy/h Atmosphere : Air
20 25 30 35 40 45
0 kGy 21 kGy 31 kGy 62 kGy 94 kGy 125 kGy 157 kGy 220 kGy
Retention volume (ml)
BK1675N
20 25 30 35 40 45
0 kGy 21 kGy 31 kGy 62 kGy 125 kGY 157 kGY 220 kGy
Retention volume (ml)
Ex 268
Topic: Radiation Modification of Synthetic Polymers [20]57
Effect of Dose on Molecular WeightEffect of Dose on Molecular Weight Ex268Ex268
0 50 100 150 200 2500
100000
200000
300000
400000
500000
LDR Air Mw Mn
Mol
. Wei
ght
Dose (kGy)0 50 100 150 200
0
100000
200000
300000
400000
500000
HDR Air Mw Mn
Mol
. Wei
ght
Dose (kGy)
0 50 100 150 200 2500
100000
200000
300000
400000
500000
LDR N2 Mw Mn
Mol
. Wei
ght
Dose (kGy)0 50 100 150 200 250
0
100000
200000
300000
400000
500000
HDR N2 Mw Mn
Mol
. Wei
ght
Dose (kGy)
Topic: Radiation Modification of Synthetic Polymers [20]58
G(s) and G(x) valuesG(s) and G(x) values
0 50 100 150 200 250 3000
10
2030
4050
6070
80
90100
Mw Mn
1/M
ol. W
eigh
t x 1
0
Dose (kGy)
LDR
Air N2G(s) G(x) G(s)/G(x) G(s) G(x) G(s)/G(x)
Ex268 4.2 0.2 18.2 1.9 0.3 5.5
BK1675N 3.8 0.3 12.5 2.9 0.4 7.2HDR
Ex268 5.4 0.5 10.3 7.7 1.1 7.1BK1675N 2.5 0.1 24.7 6.4 1.1 5.9
1/Mw=1/Mwo +[G(s)/2-2G(x)]D/100NA
1/Mn=1/Mno +[G(s)-G(x)]D/100NA
6
Topic: Radiation Modification of Synthetic Polymers [20]59
CHEMICAL STRUCTURE OF GAMMA CHEMICAL STRUCTURE OF GAMMA IRRADIATED BUTYL RUBBERIRRADIATED BUTYL RUBBER
LOW DOSE RATE (N2) EXXON 165 BUTYL RUBBER (0.8 % IP)EXXON 165 BUTYL RUBBER (0.8 % IP)
0 kGy30 kGy
60 kGy
95 kGy
158 kGy
220 kGy
250 kGy
Topic: Radiation Modification of Synthetic Polymers [20]60
CHEMICAL STRUCTURE OF GAMMA CHEMICAL STRUCTURE OF GAMMA IRRADIATED BUTYL RUBBERIRRADIATED BUTYL RUBBER
HIGH DOSE RATE (N2) EXXON 165 BUTYL RUBBER (0.8 % IP)EXXON 165 BUTYL RUBBER (0.8 % IP)
0 kGy
25 kGy
50 kGy
100 kGy
145 kGy
200 kGy
250 kGy
Topic: Radiation Modification of Synthetic Polymers [20]61
Application of Biodegradable PolymerSince melt viscosity of aliphatic polyester Poly(epsilon-caprolactone) was
enhanced by induction of branch structure during irradiation at lower dose in the range of 20 to 50 kGy, the foam and film can be produced with high speed in
industry. Application on packaging film, garbage bag and foam are expected to be develop as a friendly product for environment.
Topic: Radiation Modification of Synthetic Polymers62
Biodegradability of Crosslinked Polymer
Biodegradability of crosslinked PCL was evaluated by soil burial test. It was found that crosslinking structure was almost not affected by biodegradability test.
Topic: Radiation Modification of Synthetic Polymers63
Radiation Crosslinking of Aliphatic PolyesterPoly(epsilon-caprolactone), PCL was irradiated at solid, molten and super cooled states to improve its heat stability. Among three phases, irradiation at super cooled state gave the highest gel fraction and it heat stability was durable even at 373K.
Topic: Radiation Modification of Synthetic Polymers64
Nano-Fabrication of Organic Thin Films Using Ion- and Electron-Beams
In contrast to photo- or electron beam lithography, single heavy ion particles deposit a local concentration of radiation energy (single particle events) along the ion-path
through the materials. This induces nanoscopic damage sufficient for the ion-path to be susceptible to development in an etchant, resulting in the formation of through-holes with an aspect ratio (the ratio between a film thickness and a hole diameter)
greater than 1000
Topic: Radiation Modification of Synthetic Polymers65
The ion track membrane can be converted into high performance separation membranes and nano-scale bio-reactors by the chemical modification of pore surfaces and immobilizing enzymes and cells in it. These membranes can be also converted to nanoscopic electronic devices such as conductive films, field emitters, and magnetic field sensors through hybridization with inorganic materials such as conducting metals and semiconducting alloys.
Topic: Radiation Modification of Synthetic Polymers66
Topic: Radiation Modification of Synthetic Polymers67
Topic: Radiation Modification of Synthetic Polymers68
Topic: Radiation Modification of Synthetic Polymers69
Cross-linking
Grafting
Blending
Environmental Applications
Biomaterials
Composite and Adhesives
Natural Polymers
Emulsion Polymers
Some of the potential new areas of industrial applications for the near future
Topic: Radiation Modification of Synthetic Polymers70
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2) M. R. Cleland, L. A. Parks and S. Cheng, Applications For Radiation Processing of Materials, ANNUAL TECHNICAL CONFERENCE OF THE SOCIETY OF PLASTICENGINEERING (ANTEC), 2003.
3) Ota, S., Current Status of Irradiated Heat-Shrinkable Tubing in Japan, Radiation Physics and Chemistry, Vol. 18, Nos. 1-2, pp. 81-87, 1981.
4) Hunt, J. D. and Alliger, G., Rubber – Application of Radiation to Tire Manufacture, Radiation Physics and Chemistry, Vol. 14, Nos.1-2, pp. 39-53, 1979.
5) Bradley, R., Radiation Technology Handbook, Marcel Dekker, Inc. New York, 1984.6) Ikada, Y., Mita, T., Horil, F., Sakurada, I. and Hatada, M., Preparation of Hydrogels
by Radiation Technique, Radiation Physics and Chemistry, Vol. 9, Nos. 4-6, pp. 633-645, 1977.
7) J. M. Rosiak and F. Yoshii Hydrogels and their medical applications, Nucl.Instr. and Meth., B, 151 (1-4), 56-64 (1999)
8) J.M. Rosiak and P. Ulański, Synthesis of hydrogels by irradiation of polymers in aqueous solution, Radiat. Phys. Chem., 55(2), 139-151 (1999).
9) M. Şen and E. N. Avcı “Radiation Synthesis of Poly(vinyl pyrrolidone)-Kappa Carrageenan hydrogels and Their use wound dressing applications, I : Preliminary Laboratory Tests” Journal of Biomedical Materials Research: A, 74A, 187-196, (2005). Laboratory Tests” Journal of Biomedical Materials Research: A, 74A, 187-196, (2005).
Topic: Radiation Modification of Synthetic Polymers
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Topic: Radiation Modification of Synthetic Polymers72