journal of bioremediation & biodegradation open access...polymers especially plastics are...

1713 Cm-1 hv

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roupJ Bioremed Biodegrad

ISSN:2155-6199 JBRBD, an open access journal

Journal of Bioremediation & Biodegradation - Open AccessResearch Article

OPEN ACCESS Freely available online

doi:10.4172/2155-6199.1000108

Volume 1• Issue 2•1000108

A New Synthesis of Nickel 12-Hydroxy Oleate Formulation to Improve Polyolefi n’s DegradationAnniyyappa Umapathi Santhoskumar, Komaragounder Palanivelu*, Shailendra Kumar Sharma and Sanjay Kumar Nayak

Department of Plastic Technology, Central Institute of Plastic Engineering and Technology, Guindy, Chennai-600032, India

*Corresponding author: K.Palanivelu, Department of Plastics Engineering

& Technology, TVK Industrial Estate, Guindy, Chennai – 600 032, India,Tel: +919677123881, +914422254708; Fax: +914422251707; E-mail:

[email protected], [email protected]

Received August 31, 2010; Accepted October 20, 2010; Published October 23, 2010

Citation: Santhoskumar AU, Palanivelu K, Sharma SK, Nayak SK (2010) A

New Synthesis of Nickel 12-Hydroxy Oleate Formulation to Improve Polyolefi n’s Degradation. J Bioremed Biodegrad 1:108. doi:10.4172/2155-6199.1000108

Copyright: © 2010 Santhoskumar AU, et al. This is an open-access article

distributed under the terms of the Creative Commons Attribution License, which

permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.

Abstract

A new additive Nickel (Ni) 12-hydroxyoleate was successfully synthesized and their performance on the photodegraded low density polyethylene and polypropylene fi lms were subjected to biodegradation in the presence of the microbes such as Aspergillus niger and Pencillium funculosum isolated from a dump. Fragments occur progressively in the biodegradation of the photodegradaded fi lms. Moreover, the biodegradation test results reveal that 19% and 23% respectively of the material degradation at the end of 45 days. This Ni 12-hydroxyloleate blended with LDPE and PP fi lms has been exposed to abiotic and biotic environments. The abiotic degradable of the fi lms were UV irradiated for periods of maximum within 96 hours of LDPE and 72 hours of PP in different percentage before being mixed with water and organic fraction municipal solid compost were examined by infrared spectroscopy. The carbonyl peak increased with time in the abiotic environment and the oxidative degradation. In the presence of a biotic environment however, this peak decreased. At the same time there was an increase in double bonds which was related to weight loss. This mechanism is compared, on the one hand, with abiotic photo-oxidation, Norrish type I degradation and on the other with biotic polyolefi n’s degradation to produce double bond formation fi nd out peak in FTIR. So it is proxidante and bioactive

LDPE and PP-Ni 12-hydroxyloleate degradable simply. The SEM micrograph confi rms the presence of the deterioration

of fi lm increases with increase of percentage additive due to the presence of microbial exposure.

Keywords: Biodegradation; Biotic environment; Abioticenvironment; Low-density polyethylene; Polypropylene; Nickel 12-hydroxy oleate

Introduction

The solution of plastic ecological problem lies in the development of photodegradable and biodegradable polymer with controlled lifetime. The additives like Ketones, quinones and peroxides are initiators of photo-degradation reactions [1-11].

Polyolefin’s is relatively inert due to its hydrophobic chain and high molecular weight. So degradability offers a complimentary strategy to deal with this waste problem. One of the simplest ways of modifying the existing polymer is to accelerate the degradation process already taking place. Different approaches to develop photo degradable polyolefin have been adopted, including both co-polymerization with ketene or CO groups and addition of photo initiating metal complexes such as transition metal 12-hydroxy oleate as shown in Figure 1 and its reaction Figure 2. Photo-oxidation leads to an increase in the low molecular weight fraction by chain scission, thereby facilitating biodegradation. It also leads to an increase in the surface area through embrittlement. In addition, the formation of carbonyl groups on the surface increases its hydrophilicity. Consequently, the possibility of further degradation induces a significant enhancement towards mineralization of plastic material.

Figure 1: New class of generally structure of transition metal 12 hydroxyl

oleate.

Figure 2: Photo oxidation of polyethylene the oxidation of photo activator Ni2+ to Ni3+ (high radiation) and carbonyl group norrish type 1 reaction high quantum yield than Norrish type II reaction. We have well known infra red

spectral region 1713-1.

Citation: Santhoskumar AU, Palanivelu K, Sharma SK, Nayak SK (2010) A New Synthesis of Nickel 12-Hydroxy Oleate Formulation to Improve Polyolefi n’s Degradation. J Bioremed Biodegrad 1:108. doi:10.4172/2155-6199.1000108

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ISSN:2155-6199 JBRBD, an open access journal Volume 1• Issue 2•1000108

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The photodegraded films to evaluate biodegradation using microorganisms such as Aspergillus niger and Pencillium funculosum are involved in the degradation of both natural and synthetic plastics. As shown in Figure 3. The biodegradation of plastics proceeds actively under various organic fraction solid compost or municipal solid waste conditions according to their properties, because the microorganisms responsible for the degradation differ from each other and they have their own optimal growth conditions in the organic fraction of solid compost. Polymers especially plastics are potential substrates for heterotrophic microorganisms. Biodegradation is governed by different factors that include polymer characteristics, type of organism, and nature of pretreatment. The polymer characteristics such as its mobility, tacticity, crystalline, molecular weight, the type of functional groups and substituent’s present in its structure, and plasticizers or additives added to the polymer all play an important role in its degradation. During degradation the polymer is first converted to its monomers, and then these monomers are mineralized.

Nickel 12-hydroxyloleate within the polyolefin such as Polyolefin’s this additive most polymers are too large to pass through cellular membranes, so they must first be depolymerized to smaller monomers before they can be absorbed and biodegraded within microbial cells than to the virgin Polyolefin’s. The initial breakdown of a polymer can result from a variety of physical and biological forces physical forces, such as heating or cooling, freezing or thawing, or wetting or drying, can cause mechanical damage such as the cracking of polymeric materials. The growth of many living (fungi) can also cause small-scale swelling and bursting, as the fungi penetrate the polymer solids.

High molecular weights result in a sharp decrease in solubility making them unfavorable for microbial attack because bacteria require the substrate to be assimilated through the cellular membrane and then further degraded by cellular enzymes. At least two categories of enzymes are actively involved in biological degradation of polymers: extracellular and intracellular depolymerases during degradation, exoenzymes from microorganisms break down complex polymers yielding smaller molecules of short chains, g., oligomers, dimers, and monomers, that are smaller enough to pass the semi-permeable outer bacterial membranes, [13] and then to be utilized as carbon and energy sources. The process is called depolymerization. When the end products are CO

2, H

2O, or CH

4, the degradation is called

mineralization. It is important to note that biodeterioration and degradation of polymer substrate can rarely reach 100% and the reason is that a small portion of the polymer will be incorporated into microbial biomass, humus and other natural products dominant groups of microorganisms and the derivative pathways associated with polymer degradation are often determined by the environmental conditions. When O

2 is available, aerobic microorganisms are mostly

responsible for destruction of complex materials, with microbial

biomass, CO2, and H

2O as the final products.

Experimental

Materials and methods

Ammonium Nickel (II) sulphate hexahydrate, sodium hydroxide,

Ricinoleic acid were used without further purification. General

purpose film grade LDPE 24FSO40 and PP H034SG has been used

to prepare films. Milli Q ultrapure water was used throughout the

course of this work. Ba(OH)2 and hydrochloric acid SQ qualigens in

Fisher Scientific.

Synthesis and preparation of Nickel 12-hydroxyl oleate

1 mole of NaOH is mixed with 1000 ml of ethanol in a volumetric

flask to get 1N NaOH solution. The required amount of NaOH

solution is prepared in a volumetric flask. 720 ml of 1N NaOH and

80 ml of fatty acid are taken in a round –bottmed flask and refluxed

for one hour. Porcelain pieces are put inside the round-bottomed

flask to avoid spitting out of solution. Condensed is attached and

continuous supply of water is provided during reflux. Cotton plug is

kept on the neck of the condenser to avoid evaporation. 100 ml of

15 N HCl is mixed in 1400 ml of distilled water in beaker to get 1N

HCl.1 mole of NaOH was dissolved in 1000 ml of distilled water to get

one mole aqueous NaOH solution. 60 g of the collected mixture was

dissolved in 200 ml of 1mole aqueous NaOH solution and as a result a

single phase solution of sodium salt is got. 46 g of (Nickel ammonium

sulphate) FAS is dissolved in required amount of water to get one

mole of FAS solution. One mole of FAS solution was mixed with water

several times till a pure water layer is separated. Then the remaining

mixture is washer with a small amount of ethanol and taken in a there

resulting mixture is called the Ni 12-hydroxyl oleate.

Blending and film preparation of LDPE

LDPE was blended with synthesized Ni 12-hydroxyl oleate additive

in varies percentage 1%,3% and 5% by using Torque Rheometer,

blending was carried out at a temperature range of 130-190°C and

at a screw speed of 75 rpm. Subsequently, the pellets are dried in a

dehumidifier at 70°C for two hours to remove moisture. The film was

prepared by using film die for all the three percentage of additive.

The three percentages of additives. The wall thickness of the film

was kept at 50 microns by controlling the speed of the nip rollers

and output rate.

Blending and film preparation of PP

The Ni 12-hydroxyl oleate was melt blended with PP at three

different formulations 1, 2 & 3% respectively in Torque Rheometer.

Blending was carried out at temperature range of 210,200, 190,180

and 150°C (From die to hopper) and a screw speed of 100 rpm.

Subsequently, the pellets are dried in a dehumidifier at 70°C for two

hours to remove moisture. The pellets produced were subsequently

dried and subjected to film cast process to produce films of 50

microns thickness.

Polyethylene and Polypropylene was blended with the

synthesized Ni 12-hydroxyoleate additive containing double bond

acting as plasticizing effect, hydroxyl group as compatibilizer, long

alkyl group and pendent group for compatibility during processing

and metal and carbonyl group for combined effect of photo activator

by UV radiation in polyethylene and polypropylene films. This

biological activity of transition metal 12-hydroxyoleate containing

functional group as multifunctional active. This may represented as

multifunctional active additive (MFA) as shown in Figure 1.

Figure 3: Generally affected polyolefi n’s by microorganism.


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The above Nickel (Ni) 12-hydroxy oleate was successfully synthesized and their performance on the photodegradation of (QUV Accelerated weathering tester model QUV/spray with solar eye irradiative control) low density polyethylene and polypropylene films were subjected to biodegradation in the presence of the microbes such as Aspergillus niger and Pencillium funculosum isolated from a dump. The above mentioned film ASTM D 5338-98 test method determine the degree and rate of aerobic biodegradation of plastic materials on exposure to a controlled- composting environment under laboratory conditions. This test method is designed to yield reproducible and repeatable test results under controlled conditions that resemble composting conditions. The test substances are exposed to inoculums that are derived from compost from municipal solid waste. The aerobic composting takes place in an environment where temperature, aeration and humidity are closely monitored and controlled.

Elemental analysis

The carbon content of the each test sample determined by elemental analysis by using Carlo Erbal model 1106 elemental analysis.

Biodegradation of polyolefin’s evaluated from the blank and sample vessels based on ASTM 5338-98 compost biodegradation

The method used for the determination of the biodegradability

of the polyolefin’s was based on the International Standard (ASTM

5338-98) that measures the evolved CO2 amount from both the

blank vessel without a sample and the sample vessel including a

10 g polyolefin’s sample, 600 g mature solid compost The newly

developed biodegradation measurement system using the compost

biodegradation apparatus with the absorption columns is shown

in Figure 4. This evaluation system for the biodegradation uses

the CO2 trap system with CO

2 absorption columns. This compost

biodegradation mechanism is as follows. First, room air is passed

into the carbon dioxide trap to remove the CO2 in the air. This air

is moisturized and passed into the reaction vessel controlled at

58±2°C. The air with the produced CO2 from the biodegradation

of the samples and respiration of the microorganisms in the solid

compost is passed into the Ba(OH) 2

aqueous solution to remove

the produced BaCO3 from the compost to obtain an accurate carbon

dioxide using a titration method [14].

Biodegradability has always been considered an important

attribute for chemicals, but until recently it was rarely quantitatively

incorporated into safety assessments. Concern about environmental

quality and advances in models for predicting environmental

concentrations have significantly increased a demand for reliable

biodegradation data. Therefore, various laboratory test methods for

investigating and monitoring biodegradation processes have been

developed and standardized. Most efforts have been concentrated

on biodegradation tests in the aerobic aquatic environment.

Conventional CO2 evolution test

The principle of the widely used CO2 evolution test (ASTM 5338-

98) was the determination of the ultimate biodegradability of organic compounds by aerobic microorganisms, using a static aqueous test system and the evolution of CO

2 as the analytical parameter. A

1.50-liter test mixture was prepared in 2-liter vessels containing an

inorganic medium and the organic compound as the sole source of carbon at a concentration of 10 to 40 mg of organic carbon liter−1.

Usually organic fraction solid compost, obtained from a wastewater

treatment plant or from another source in the environment, was used

as mixed inoculums. The vessels were aerated with 1 to 2 bubbles of

CO2-free air per sec (50 ml min−1) and incubated at 58 ± 2°C for usually

minimum 45 days. The bigamous CO2 formed during the microbial

degradation was trapped in two external adjacent vessels (volume,

1500 ml) containing an aqueous Barium hydroxide Ba(OH)2 solution

(0.25 N). Samples were taken at regular intervals to determine the

amount of dissolved inorganic carbon (DIC) and to calculate the

amount of CO2 produced with titrated Hydrochloric acid this evolved

CO2 was compared with the calculated theoretical amount (ThCO

2),

and the degree of biodegradation was expressed as a percentage.

Titration method of CO2 determined test

The degradation of chemical compounds in the titration CO2

evolution was based on the same principle as the conventional CO2

evolution test. Test vessels were cylindrical bottles with a 2-liter volume containing the same mixture of inorganic (Barium hydroxide) medium, organic test substance, and mixed inoculums in a liquid volume of 1.5 liter. Incubation, aeration with CO

2-free air, and

agitation of the test mixture, blank, and control vessels were also comparable. The exhaust gas from the vessels was passed through a glass chamber (volume, 1500 ml) that was immersed in the test mixture and filled with 50 ml of a 0.25 N aqueous Ba(OH)

2 solution

titrated with HCl after the end point remain Barium Hydroxide calculated and subtracting the blank values, biodegradation was calculated and expressed as a percentage of the CO

2. There was a

linear correlation between the amounts of carbon dioxide liberated. This correlation was determined for each volume and concentration of absorption solution used.

Oxygen a llowed complete oxidative biodegradation of the test compound. The concentration of inoculums was 30 mg of dry matter of Solid compost, and the concentration of the test compound was 100 mg of substance liter−1, or 50 to 100 mg liter−1 of theoretical

Figure 4: Biodegradation Instrument.


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oxygen demand (ThOD). The test duration was minimum 45 days, and the tests were performed at an incubation temperature of 58±2°C [14].

ASTMD-5338: Test procedure

The amount of CO2 produced pass through the Ba(OH)

2 Solution

and is precipitated as Ba CO3

Ba(OH)2 +CO

2 → BaCO

3+H

2O

Determine the CO2 by titrating the remaining Ba(OH)2 with 0.05n HCI

Ba(OH)2 +2HCI → Ba CI

2+2H

2O

%gaseus C yield =

1.1* ml HCL *12 *100

44 * y

Y=mg carbon charged to flask

Biodegradation Calculation

%biodegradation =g g

i

Mean C (test) Mean C (test)

C

Where; C

g= amount of gaseous carbon produced g, and

Ci= amount of carbon in test compound in the sample,g.

Scanning electron eicroscopic analysis (SEM)

The scanning electron microscope analysis of fractured surface of

LDPE and PP- Ni 12-hydroxyloleate films were carried out using CARL ZESIS Model; EVO MA 15 scanning electron microscope. The surface of the samples was coated with conductive heavy metal such as gold / palladium.

Fourier transform infrared spectrophotometer (FTIR)

The structural changes in LDPE and PP films in the presence of Ni 12-hydroxyl oleate after effect of UV exposure eight and three days respectively and then after microbial exposure for 45 days were studied by Nicolet 6000 (USA) Fourier Transform Infrared Spectrometer (FTIR) with the wave number range of 400-4000 cm-1. The degradation of the film was monitored with an IR instrument the films were cold drawn to make it possible to obtain transmission spectra. Samples to be analyzed by IR were cut out from the films and washed with distilled water to remove traces of organic fraction solid compost etc. In the IR spectra, special interest was focused on the following absorption peaks 1636 cm-1 double bonds (-C==C-) in this additive.

Thermal properties

Differential scanning calorimeter (DSC) analysis: Melting behavior of 12 hydroxyl oleate blended samples (LDPE and PP) after effect of UV exposure eight and three days respectively and then after microbial exposure were studied for 45 days by employing Perkin Elmer (USA) differential scanning calorimeter. Sample 2 mg weight were scanned from 45 to 200°C at the heating rate of 10°C/min to detect the melting characteristics of the sample before and after exposure to biotic environment. The percentage of crystallinity of 12 hydroxyl oleate blended LDPE and PP films were calculated as follows.

% of Crytallinity = (Hm-H

c)/ Hco

Where Hm- Enthalpy of melting (J/g)

Hc- Enthalpy of Crystallization (J/g)

HC

o-Enthalpy of 100 % crystalline polymer (277.3 J/g)

Thermo gravimetric analyses: Thermal degradation of LDPE and PP, Ni 12-hydroxyl oleate blended samples the effect of UV exposure five days and three day respectively and then after biotic environment films for 45 days were analyzed by Perkin Elmer (USA), at the heating rate of 10°C/min from 50 to700°C.

Results and Discussion

Elemental analysis

C, H, N elemental analysis reported in table below and then pure Nickel 12-hydroxy oleate. Nickel percentage 6.37% as shown in

Table 1. It has Carbon, Hydrogen and Nitrogen analysis only. Carbon values of cellulose dependent carbon and hydrogen analysis only

independent of the oxygen in molecular structure. So it has carbon content 84% by the elemental analysis.

Biodegradation of the LDPE and PP with Ni 12-hydroxyl oleate

Figure 5 and Figure 6 shows Conditions of reaction mixtures: Organ of compost; livestock excrement, municipal and Vegetable waste used the method used for the determination of the biodegradability

of the polyolefin’s was based on the International Standard (ASTM 5338-98) that measures the evolved CO

2 amount from both the blank

vessel without a sample and the sample vessel including a 10g LDPE and PP, Ni 12-hydroxyl oleate samples. According to the experimental 2.9 ASTM 5338 test procedure. Polyethylene and polypropylene the

percentage of biodegradation 19% and 23% respectively.

Reaction temperature : 58±2°C

Dry solid (%) : 52%Volatile solid (%) : 19%Air flow rate : 100 ml/minTest duration (day) : 45 day

Sample Cellulose 1% PP 3 %PP 5%PP Compost

Carbon 84.47 86.35 85.76 85.33 14.26

Hydrogen 14.76 14.77 14.34 14.08 1.76

Nitrogen 0.11 .06 0.11 0. 2 1.54

(a)

(b)

Sample Cellulose

(%)

1% LDPE

(%)

3% LDPE

(%)

5%LDPE

(%)

Compost

(%)

Carbon 84.47 86.22 84.36 85.36 13.32

Hydrogen 14.96 14.86 13.89 14.67 1.83

Nitrogen 0.11 .06 .11 .16 1.50

Table 1: Elemental analysis percentage of carbon, hydrogen, Nitrogen for LDPE

and PP –Ni 12 hydroxyl oleate.

Figure 5: Biodegradation curve for the photodegradable product of PP 1%, 3% and 5%.


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Reference material : CelluloseVolume of reaction vessel : 2000mlMoisture percentage in compost : 28 %

Figure 8 shows the virgin LDPE samples to be analyzed by IR were cut out from the films. In the IR spectra, special interest was focused on the following absorption peak: 729 cm-1, rocking vibration (-CH

2-); 1376 anti symmetric deformation(-CH

3-); 1470 cm-1 symmetric

deformation (–CH2-); 1604 cm-1, Symmetric deformation (–CH

3-);

2913 anti symmetric deformation (–CH-); 2847 symmetric stretching (–CH

3-).

Figure 10 shows the virgin PP samples to be analyzed by IR were cut out from the films. In the IR spectra, special interest was focused on the following absorption peak: 973 cm-1, rocking vibration (-CH

2-); 997 cm-1, rocking vibration (-CH

2-); 1167 cm-1 anti symmetric

deformation (-CH3-); 1454 cm-1 symmetric deformation (–CH

2-);

1167 cm-1, Symmetric deformation (–CH3-); 1167 anti symmetric

deformation (–CH-); 2929 symmetric stretching (–CH3-).

Figure 6: Biodegradation curve for the photodegradable product of LDPE

1%,3% and 5%.

Figure 7: Characteristic peak in FTIR for Ni 12 hydroxyl oleate.

Figure 8: Characterization peak in FTIR for virgin pure LDPE.

S.No.

Absorption bands (cm-1) and their peak assignments

LDPE (Low density Polyethylene)

1. 729 -CH2 Rocking Vibration

2. 1376 -CH3 anti symmetric deformation

3. 1470 -CH2 symmetric deformation



6. 2847 -CH3 symmetric stretching

Table 3: Characterization peak in FTIR for LDPE.

Tables 4: Characterisatation peak in FTIR for LDPE- 1, 3, 5%Ni 12 hydroxy oleate after biodegradation -C=C- slightly increases 1636 cm -1.


LDPE (Low density Polyethylene) 1%,3%and 5%

Nickel 12 hydroxyl oleate comparable virgin LDPE

1. 720 -CH2

Rocking Vibration



4. 1636 - C=C- stretching form from -CH3 symmetric deformation


6. 2847 -CH3 symmetric stretching

7 2336 -CH3 symmetric deformation

8 1026 -C-O- Stretching Acid deformation

Fourier transform infrared spectrophotometer (FTIR)

Characterization of ferrous and nickel 12-hydroxy oleate: In

Table 2 and in Figure 7, the FTIR spectra of the Ni 12-hydroxyl oleate

exhibited absorbance at 1592 cm-1 due to asymmetric vibration

stretching of the carboxylic group coordinated to the metal ion. The

UV-Vis spectra of the oleate in ethanol show absorption maximum

290-305 nm as Ni 12-hydroxy oleate.

Figure 1 showing the new class of generally structure of Ni

12-hydroxy oleate used for a study of the IR spectra of biotically

degraded LDPE and PP. It was observed that the carbonyl index

decreased with prolonged incubation time after the effect of UV

exposure LDPE and PP- Ni 12-hydroxyl oleate for eight days and

three days respectively. In Figure 9 and 11(A,B and C) the explanation

for this is given by the mechanism in some IR spectra of biotically

degraded LDPE and PP a peak was noted corresponding to double


(Nickel 12 hydroxyl oleate)

1710 -C=O stretching

2853 -C-H out of plane bend

2922 -C-H stretching

1432 -C=C stretching

1377 -CH3 symmetric deformation

3350 -OH slightly broad peak

1592Asymmetric vibration oleate containing carboxyl group coordinated to the metal

Table 2: Characterization peak in FTIR for Ni 12hydroxy oleate.

Tables 5: Characterization peak in FTIR for PP.

S.No.Absorption bands (cm-1) and their peak assignments

PP (Polypropylene)






6. 2929 -CH2 anti symmetric stretching


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bond groups1636 cm -1 in the additive. In Figure 9 and Figure 11(D)

this peak was missing in abiotic (photo degradation) samples. In table

3-6 differentiate FTIR spectra for virgin LDPE and PP compared to

biotically degraded film from the photodegraded films.

The photodegraded films or Before biodegradation typical FTIR

spectra as shown in Figure 9 and Figure 11(D) the measurement of

carbonyl index 1714 cm-1, the conventional spectroscopic monitor of

polymer degradation were made by measuring the IR transmission

spectral of film after exposure for increasing lengths of time in QUV

accelerated weathering equipment fitted with UVA -340 tubes and

operated at 60°C the broad band radiation from the UVA-340 tubes

has been shown to emulate sunlight in the wavelength range below

360 nm. The development of carbonyl groups was monitored and

the carbonyl index, the absorbance at 1714 cm -1 was recorded. (As

the film used in this study were 50 thickness, the carbonyl index is

numerically equivalent to the absorbance).

Reference [15] is frequently made to Ni 12-hydroxy oleate

films degradation by microorganisms when LDPE and PP its

instability towards environmental factors are discussed. This

is fairly understandable since a Ni 12-hydroxyl oleate can be

classified as a very short-chain LDPE and PP, The length of typical

Ni 12-hydroxyloleate, being 10-20 carbons chains. Microorganisms

preferentially use linear carbon chain, whereas the corresponding

branched isomers are almost completely inert to biodegradation.

Figure 12 the mechanism for degradation of Ni 12-hydroxy oleate by

microorganisms responsible for the attack on Ni 12-hydroxy oleate

can be, for example, aspergillus niger and pencillium funculosum.

The polyethylene and polypropylene chain is oxidized to a

carboxylic acid and the resultant acid undergoes -oxidation which,

by reaction with coenzyme A, removes two carbon fragments from

the carboxylic molecule. The two carbon fragments, acetyl-SCoA,

enter the citric acid cycle, from which carbon dioxide and water are

released. From a Ni 12- hydroxyl oleate molecule with n carbons, a

total of n molecule of carbon dioxide evolved [16].

A proposed mechanism for the biodegradation of LDPE and PP

is given in Figure 13 it is thought that the alteration of LDPE and PP

molecule is initially the same in both the abiotic (phtodegradation)

and biotic samples. When carbonyl groups had been formed, the

abiotic sample evidently did not undergo Norrish type II degradation

as no double bond peak could be found in the IR spectra from

abiotically (photodegradation) degraded LDPE and PP Figure 9 and

Figure 11(D). According to the Figure 9 and Figure 11(D), the carbonyl

index increased with prolonged incubation in an abiotic atmosphere.

Alkenes formation had, however taken place, as was confirmed by the

presence of peaks at 1636 cm-1 in biologically affected films.

Thermal properties

Differential scanning colorimetry: The differential scanning calorimetry data pertaining to the melting point and degree of crystallinity of Ni 12-hydroxyl oleate blended LDPE and PP film after

the effect of UV exposure initiate the films and then after exposure biotic environment is presented in Table 7 and Table 8.

The virgin LDPE shows its melting point at 111.45°C. On the incorporation of Ni 12-hydroxyl oleate, the melting point is found

to change slightly due to the presence of additive containing double bond as plastizing effect in LDPE matrix. After the effect of UV exposure or the photodegraded films LDPE, Ni 12-hydroxyl oleate

samples exposed to biotic exposure for 45 days a marginal decrease in

the melting point from 109.68 to 103.76°C was observed. This could be due to the new double bond formation (new peak formation find out in FTIR) by biotic exposure the biodegraded film. So it has faster biodegradation of LDPE films in the presence of Ni 12-hydroxyloleate

Figure 9: Characterization peak in FTIR for LDPE 1, 3, 5% Ni 12 hydroxyl oleate after biodegradation -C=C- slightly increases 1636 cm -1.

Figure 10: Characterization peak in FTIR for virgin PP.

Figure 11: Comparison FTIR spectra of PP-Ni 12-hydroxyl oleate the effect of

UV exposure or before biodegradation and after biodegradation.


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additive. Corresponding H peak get broadening indicates the

formation of low molecular weight species due to biodegradation.

The percentage of crystalline decreases by increasing the additive

concentration. It was observed that the degree of crystallinity of

LDPE films with 5 % Ni 12-hydroxyl oleate decreases from 70 to

58% due to the new double bond formation and the bond strength decreases through hydrolytic as well as oxobiodegradation during the biotic exposure and also act as plasticizing effect. These results are in agreement with the FTIR biotic degradation mechanism.

Similarly, in PP films with Ni 12-hydroxyl oleate the melting point data shows that the melting decreases by about 7°C with increasing the concentration of the additive from 1% to 3%. Also, the percentage of crystallinity decreases from 98 to 64% for 45 days in biotic environmental exposure. These results indicate that the PP films degrade faster than LDPE as it was expected due to the presence of methyl substituent groups in polypropylene.

Thermo gravimetric analysis (TGA): The thermo gravimetric analysis of LDPE and PP with Ni 12-hydroxyl oleate additive is summarized in Table 9 and Table 10. The results shows that the initial decomposition temperature of LDPE and PP blending with Ni 12-hydroxyl oleate decreases significantly after the effect of UV exposure for eight and three days respectively or before biodegraded films. After the biotic exposure, films LDPE and PP - percentage of initial decomposition temperature 42% and 0.08% respectively. This

S.No.


PP (Polypropylene) with Nickel 12 hydroxy oleate

1%,2% and 3% comparable with virgin PP






6. 2951 -CH2 anti symmetric stretching

7 1636 --C=C- stretching form from -CH3 symmetric deformation

Tables 6: Characterization peak in FTIR for PP 1%, 2%, 3% Ni-12 hydroxyl oleate

after biodegradation -C=C- slightly increases 1636 cm -1.

Table 7: Effect of oleate on melting temperature of LDPE –Ni 12 hydroxyl oleate before and after biodegradation.

Sample Identifi cation Melting Temperature °C Degree of crystallinity

LDPE VIRGIN 111.45 100

LDPE 1 % D5BBD 109.68 70

LDPE1% D5 ABD 103.98 66

LDPE3 % D5 BBD 109.59 65

LDPE3% D5 ABD 103.89 62

LDPE5 % D5 BBD 109.46 62

LDPE5% D5 ABD 103.76 58

BBD= Before Biodegradation m, ABD = After Biodegradation,

Table 8: Effect of oleate on melting temperature of PP–Ni 12 hydroxy oleate before and after biodegradation.

Sample Identifi cation Melting Temperature °C Degree of crystallinity

PP VIRGIN 165.26 100

PP 1 % D1 BBD 164.98 98

PP 1 % D1 ABD 158.02 94

PP 2 % D1 BBD 164.68 80

PP 2 % D1 ABD 157.56 76

PP 3 % D1 BBD 164.55 68

PP 3 % D1 ABD 157.03 64

Table 9: Effect of oleate on thermal degradation of LDPE –Ni 12-hydroxyl oleate before and after biodegradation.

S.No. Sample ID Initial Decomposition Temperature (°C)

1 LDPE VIRGIN 330

2 LDPE 1 % D5 BBD 218

3 LDPE 1 % D5 ABD 203

4 LDPE 3 % D5 BBD 208

5 LDPE 3 % D5 ABD 195

6 LDPE 5 % D5 BBD 205

7 LDPE 5 % D5 ABD 192

Table 10: Effect of oleate on thermal degradation of PP- Ni 12-hydroxy oleate

before and after biodegradation.

S.No. Sample ID Initial decomposition Temperature (°C)

1. PP Virgin 449

2. PP-MFA-1 D5 BBD 428

3. PP-MFA-1 D5 ABD 424





Figure 13: Proposed mechanisms for the biodegradation of polyethylene.

Figure 12: Biotic Paraffi n Degradation Mechanism to H.G Schlagel [15].

Figure 14: Pure LDPE (a) and PP (b) Scanning electron micrograph.

(a) (b)

(a) (b)

(a) (b)

(a) (b)

(a) (b)

(a) (b)

(a) (b)


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could be due to the new double bond formation and the bond strength

decreases through hydrolytic and oxobiodegradation during the

biotic exposure in ASTM D 5338. Decrease in initial decomposition

temperature was observed with higher additive concentration than

lower additive. This result does not confirm the biodegradability but

initial decomposition temperature changes slightly after the effect

biotic exposure films.

Scanning electron micrograph

A comparative compilation of scanning electron micrographs of

two samples (LDPE and PP with Ni 12-hydroxyl oleate) at magnification

of 500 to 2000. Figure 14 as is apparent from the surface of non

degraded LDPE and PP is smooth, without fractured and free from

defects. After the UV exposure both the sample compacted film

leads to rapid disintegration of the surface for 15 and 45 days Figure

15-17(a, b) show typical pattern of microbial growth on the top

surface of the sample. Erosion of the surface can be observed but

interestingly, although microorganism grows fissure resulting from

fracture propagation, none grow within the fracture suggesting

that the most of the low molecular weight nutrient migrate to the

surface from the (oxidized) layer of the polymer. It can be seen that

the surface agglomerates were formed which could be due to the

biodegradation involving deterioration of molecular chains. More

surface agglomerations could be seen in the case of LDPE and PP, Ni

12-hydroxyl oleate indicating the faster rates of biodegradation. Also,

the brittleness of the surface increases with increasing the exposure

time and percentage of additive concentration. These results are

in agreement with the FTIR mechanism as shown in Figure 12 and

Figure 13.

Figure 18 shows the surface developed more crack and groove

due to for 45 day biotic exposure for 3% Ni 12-hydroxyl oleate with

LDPE and PP blend higher than 15 day biotic exposure.

Figure 19 shows the surface developed some crack and narrow

grooves for 15 days by biotic exposure 3% Ni 12-hydroxyl oleate with

LDPE and PP blends.

Figure 20 shows that the damage is much more pronounced in

the sample containing Ni 12-hydroxy oleate with LDPE and PP blends

after the biotic exposure for 45 days.

Conclusion

The rate of the new additive Nickel(Ni) 12-hydroxyoleate

was successfully synthesized and their performance on the

photodegraded low density polyethylene and polypropylene films

were subjected to biodegradation of LDPE and PP film is very high

at higher concentration of Ni 12-hydroxyl oleate. The LDPE and

Figure 18: 45 days LDPE-Ni 12 hydroxyl oleate 3% (a) and 45 Days PP-Ni 12

hydroxyl oleate 2 % (b) biotically affected fi lm in SEM.

Figure 16: 45 days LDPE-Ni 12 hydroxyl oleate 1%(a) and 45 Days PP-Ni 12 hydroxyl oleate 1%(b) biotically affected fi lm in SEM.

Figure 15: 15 days LDPE-Ni 12 hydroxyl oleate 1% (a) and 15 Days PP-Ni 12

hydroxyl oleate 1% (b) biotically affected fi lm in SEM.

Figure 17: 15 days LDPE-Ni 12 hydroxyl oleate 3% (a) and 15 Days PP-Ni 12 hydroxyl oleate 2%(b) biotically affected fi lm in SEM.

Figure 19: 15 days LDPE-Ni 12 hydroxyl oleate 5 % (a) and 15 days PP-Ni12 hydroxyl oleate 3 % (b) biotically affected fi lm in SEM.

Figure 20: 45 days LDPE-Ni 12 hydroxyl oleate 5 % (a) and 45 days PP-Ni 12

hydroxyl oleate 5% (b) biotically affected fi lm in SEM.


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PP film containing 5% Ni 12-hydroxyl oleate has shown slightly

changes degradation in thermal properties and reduction in degree

of crystallinity on biotic exposure. After the biotic exposure in the

FTIR analysis shows that a peak at around 1636 cm-1 corresponding

to double bond group of transition metal 12 hydroxyl oleate

was observed for LDPE and PP films with upto 5% and 3% additive

respectively. The scanning electron micrographs of fractured surface

of films after the biotic exposure show the brittle mode of fracture.

The biotically degraded product when subject to biodegradation has

results in 19% of LDPE and 23 % of PP biodegradation in 45 days. So,

Ni 12-hydroxyl oleate is used as an effective biodegradable additive

for LDPE and PP films.

Acknowledgements

The research was funded through The Department of Science and Technology

sponsored CSIR project on “Technology development of biodegradable additive

performance evaluation of biodegradation with various plastic” under grant number

DST/TSG/WP/2006/58. We acknowledge discussions with our collaborators

Dr. Rajeeve Sharma, Government of India, Ministry of Science &Technology,

Technology Bhavan, New Delhi.

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