WHAT IS POLYMER DEGRADATION ?

We all have noticed the plastic bucket left for long run in the sun and rain
loses its lusture and strength.
This deterioration in properties is due to a phenomenon called " polymer
degradation", which is characterized by an uncontrolled change in the
molecular weight or constitution of the polymer.[1]
Conventionally , the term 'degradation' is taken to mean a reduction in the
molecular weight of the polymer .
In day to day life , plastic articles have to face mechanical stresses , solar
radiations , atmospheric oxygen , moisture etc and this can degrade the
polymer .






Sample of Polycarbonate degraded [2]






[3]

Excellent properties of plastics made it irresistible component and part of
any industry or household products. Their production is increasing at high
rate , that calls the need to recycle them and degrade them to protect the
environment . Some polymers degrade easily by simple micro-organisms but
some take decades and centuries to degrade and persists in the environment
thus polluting the environment like Polethylene.





Polyethylene

Polyethylene (abbreviated PE) or polythene (IUPACname polyethene or
poly(methylene)) is the most common plastic. The annual production is
approximately 80 million metric tons.[4]Its primary use is within packaging
plastic bag,plastic films, containers including bottles etc.). Many kinds of
polyethylene are known, but they almost always have the chemical
formula(C
2
H
4
)
n
H
2
. Thus PE is usually a mixture of similar organic
compounds that differ in terms of the value of n.
ABS 4%
PC 2%
PP 25%


SPI Film & Bag May 2011
Global Plastics Consumption 2010
HDPE
17%
LLDPE
11%
LDPE
10%
PP
25%
PS
6%
ABS
4%
PVC
18%
PET
7%
PC
2%
2010 World Polymer Demand = 190 Million Metric Tons
[5]


Polyethylene is the most common and major polymer produce all over the
world owing to its different uses and its good properties. But Polyethylene is
the matter of concern.


Environmental issues of Polyethylene


One of the main problems of polyethelyne is that without special treatment it
is not biodegradable, and thus accumulates. In Japan getting rid of plastics in
an environmentally friendly way was the major problem discussed until the
Fukushima Disaster in 2011.
It was listed as a $90 billion market for solutions. Since 2008 Japan has
rapidly increased the recycling of plastics, but still has a large rate of plastic
wrapping which goes to waste.[6]]
During the 1980s and 1990s it was shown that many endangered marine
species including birds that live in the marine environment are at extra
hazard, with thousands of cases of suffocation from swallowing plastic bags
or plastic content.[7]
In May 2008, Daniel Burd, a 16-year-old Canadian, won the Canada-wide
Science Fair in Ottawa after discovering that Pseudomonas fluorescens, with
the help of Sphingomonas, can degrade over 40% of the weight of plastic
bags in less than three months.[8]
In 2009 it was discovered by a resident of Hawaii upon returning from a ship
race that degraded plastics are a major cause for marine life destruction,
being mixed in with plankton, comparable in size and weight but in much
larger numbers.[9]
In 2010 a Japanese researcher Akinori Ito released the prototype of a
machine which creates oil from Polyethylene using a small, self-contained
vapor distillation process.[10]


Why Polyethylene degradation is difficult ?

It is widely accepted that the resistance of polyethylene to biodegradation
stems from its high molecular weight, its three-dimensional structure and its
hydrophobic nature, all of which interfere with its availability to micro-
organisms," the researchers stated. Nevertheless, the researchers said several
studies have demonstrated partial biodegradation of polyethylene [11]
The researchers goal was to select a polyethylene-degrading micro-
organism and study the factors affecting its biodegrading activity.
Some efforts has been made to degrade the polyethylene using different
micro-organisms and pre-treatment of PE to facilitate degradation of
PE as discussed in next sections .

















1 . BIODEGRADATION OF POLYETHYLENE

INTRO-
The wide range of applications of polymers from sophisticated articles to
disposable things implies their importance and significance in our day to day
life . Thus enormous production of these polymers lead to accumulation in
the environment since they are not easily degraded by micro-organisms they
have become serious problems for both flora and fauna .

As reported by American Plastic Association, percentage distribution of
HDPE ( high density polyethylene ) , LLDPE and LDPE are 17.4 & , 12! %
and 8.2 % respectively in terms of sale and use in the year 2004 in US,
Canada and Mexico . [12]
Non-degradable plastics accumulate in the environment at a rate of 25
million tones per year . [13]

As polymer usage is unavoidable, ways have to be found to

1. Enhance the bio-degradability of the polymers by blending them with bio-
degradable natural polymers like starch or cellulose .

2. Mixing with pro-oxidants so that they are easily degraded

3. Isolate and improve micro-organisms that can efficiently degrade these
polymers










Overview of Bio-degradation of Polymers

A general overview of biodegradable polymers over a period of time is
schematically represented in Fig.1




Fig.1


Polymeric materials released into the environment can undergo physical ,
chemical , and biological degradation or combination of all these due to the
presence of moisture , air , temperature , light , high-energy radiation or
microorganisms . The rate of chemical and physical degradation are higher
when compared to biodegradation. Also physical and chemical degradation
facilitates microbial degradation and complete mineralization of the polymer
happen due to bio-degradation , which is the final step .





Environmental
polymer degrdation
Chemical
degradation
Oxidation
Hydrolysis
Physical /Physico-
chemical
degrdation
Thermal
degradation
Photo-degradation
Mechanical
Degradation
Bio-degradtion







1.1 Mechanism of Biodegradation




1. Attachment of micro-organisms to the surface of the polymer

2. Growth of micro-organisms utilizing the polymer as the carbon source



3. Primary degradation of the polymer

4. Ultimate Degradation



Fig .Degradation of plastic mechanism [24]




Micro-organisms can attach to the surface of the polymer if the surface is
hydrophilic . Since Polyethylene have only CH2 groups the surface is
hydrophobic. Initial physical or chemical degradation leads to the insertion
of hydrophilic groups on the polymer surface making it more hydrophilic , it
also helps in decreasing the surface energy . Once the organism gets attached
to the surface , it starts growing by utilizing the polymer as carbon source .
In the primary degradation , the main chain cleaves leading to the formation
of low-molecular weight fragments (oligomers) , dimers or monomers . The
degradation is due to extra cellular enzymes secreted by the organisms .
These low molecular weight compounds are further utilized by microbes as
carbon and energy sources . Small oligomers may also diffuse into the
organisms and get assimilated . The ultimate products of degradation are
C02 , H2O and biomass under aerobic conditions . Anaerobic conditions
may also degrade these polymers under anoxic conditions . The primary
products are C02 , H20, and CH4 and biomass under methanogenic
condition or H2S , CO2 , AND H2O under sulfidogenic conditions .
The environmental conditions decide the group of micro-organisms and the
degradative pathway involved . Ultimate degradation of recalcitrant
synthetic polymers may take several 100 years .



1.2 Factors Affecting Bio-degradability

Bio-degradability of the polymer is essentially determined by the following
important physical and chemical characteristics :-

1. Availability of functional groups that increases hydrophilicity
2. Size , molecular weight and density of the polymer

3. Amount of crystalline and amorphous regions

4. Structural complexity such as linearity or presence of branching in the
polymer

5. Presence of easily breakable bonds such as ester or amide bonds as
against carbon-carbon bonds .

6. Molecular composition (blend )

7. Nature and physical form of the polymer such as whether it is in form of
films , pellets , powder or fibers.

1.3 Some research papers on the biodegradability of polyethylene

Title of Paper Polymer Organism
Mechanical behavior of
biodegradable
polyolefins [14]
HDPE/BLENDS SOIL
MICRORGANISMS
DSC FTIR
Characterization of
biodegradation of
polyethylene [15]
polyethylene A.niger
Colonization , biofilm
formation and
biodegradation of
polyethylene [16]
LDPE blends Rhodococus rubber
Synergetic effect of UV
light soil burial
treatment of
LDPE /starch blends Soil microorganisms
biodegradation of
polyethylene [17]
Bio-degradation of
thermally oxidized low
density polyethylene
[18]
LDPE Soil microorganisms
Degradation product
pattern and morphology
as means to differentiate
abiotic and biotic aged
degradable polyethylene
[19]
LDPE/starch Arthobacter
parrafineus
Acquired
biodegradability of
polyethylene containing
pro-oxidant additives
[20]
LDPE/HDPE
BLENDS
R.rhodochrous and
Nocardia asteroids
Biodegradation of
polyethylene by
thermophillic bacterium
Brevibacillus
borstelensis
[21]
LDPE/HDPE blends Brevibacillus
borstelensis
Electrical thermal
analysis to assess
biodegradation of
LDPE/Starch


Bacteria Baccilus
clostridium and Fungi
mucor , pencilium
polyethylene
[22]

Surface Changes
brought about by corona
discharge treatment of
polyethylene film and
effect on subsequent
microbial colonization
[23]
LDPE FUNGUS






Inference from the above studies

In general , poly-olefins are inert materials not susceptible to microbial
attack because of the following reasons :-

1. Hydrophobic backbones consisting of long carbon chains that give high
resistivity against hydrolysis .

2. Addition of anti-oxidants and stabilizers during their manufacture which
keeps poly-olefins resistant to atmospheric oxidation .

3. High molecular weight ( from 10,000 to 40,000 )

4. High packing density



The decreasing order of susceptibility of polymers to degradation
in soil is mixed with municipal refuse was PE >>>LDPE >>>HDPE
as revealed by analyzing the weight loss of samples , C02 evolution ,
changes in tensile strength , changes in FTIR and bacterial activity in
the soil .

Outdoor soil burial tests were done on the samples of HDPE
blends with different biodegradable additives . DSC analysis of these
polymers with different additives after a year showed no changed in
melting temperature and fraction of crystalline region.
Therefore , it was concluded that the biodegradation begins at the
amorphous region rather than at the crystalline region.
Biodegraded HDPE blends are more brittle in nature compared to
non-degraded.

Fungi that include A.niger , Pencillium funiculosum , Fusarium
redolens and A.vesicolor , and soil microorganisms are reported to
degrade PE. DSC,FTIR and other mechanical and physical techniques
were used to monitor the nature of biodegradation. Thermal ,
UV,photo and corona treated PE has been found to degrade faster than
the untreated polymer .

Photo-oxidation is the triggering step in oxidative degradation of
polyethylene . UV radiation leads to radical formation , followed by
absorption of oxygen resulting in end products with carbonyl groups
.Ultimately , photo-oxidation leads to the formation of molecular
weight fragments and thus increases the hydrophilicity of the polymer.
Later , the two carbon acetyl CoA , enters the TCA cycle and gets
completely converted into carbon dioxide and water.


Cell homogenates from P.putida and Bacillus brevis were found
to degrade PE films by oxidative degradation resulting in the
formation of terminal hydroxyl , ketone and ester group . The
presence of alcohol dehydrogenase was confirmed indirectly in the
degradation reaction by inhibition studies .


The known lignin degrading bacteria S.virdosporos T7A ,
S.badius 252 and S.setonni 75vi2 and the fungus Phanerochaete
chrysosporium were used to assess their ability to degrade
biodegradable polyethylene .

Reduction in poly-dispersity and tensile strength were observed
in biodegradable PE with bacterial treatment not with fungus . A.niger
was reported to degrade commercially available PE.

DSC analysis showed reduction in amorphous region of polymer.
Biodegradation of LDPE was enhanced with Tween 80 in the
presence of P.aeuroginosa. This study explains the role of nonionic
surfactant in biofilm formation , prerequisite for biodegradation
process.

The bacteria , Arthobacter parrafineus was found to degrade
LDPE in 3 years by utilizing carboxylic acid formed during thermal
oxidation. The utilization was through B-oxidation mechanism that
yields the degradation products like acetyl CoA and propionyl CoA.

Corona discharge treatment was found to be more effective
towards colonization of micro-organisms on food packaging grade
LDPE films with little effect on the mechanical properties as
compared to UV degradation . This suggest that corona discharge
treatment is effecting the hydrophobicity of the surface of polymer
and not penetrating it . A reduction in hydrophobicity of LDPE from
92 % to 66.6% was noted.

Thermal treatment of LDPE ( pro-oxidant additive ) in aerobic
condition showed substantial polymer fragmentation with loss of
mechanical properties in period of 18months with further treatment
with soil microorganisms. Temperature is the crucial factor in
determining the rate of thermo-oxidation whereas the effect of
concentration of oxygen on the rate of thermo-oxidation is
insignificant.

Thermally stimulated current of PE films were exposed to various
aging conditions in soil were reported . After aging , new peaks were
detached on spectra . FTIR results show formation of functional
groups. Reduction in melting point through DSC analysis . The
degree of biological damage of films was function of starch content
in composites. The predominant microbial taxa in composites were
Bacillus, Micrococcus , Penicillum ,and Mucor .

Rhodococcus rubber C208 was isolated from the surface of PE in
polyethylene waste burial site by two step culture-enrichment
protocol.Weight loss of 8% of photo-oxidised PE was observed in
four weeks . This is higher than the rates already reported. The
analysis of extra-cellular polysaccharides in the biofilm of C208 was
2.5 folds higher than protein , suggesting its tole in biofilm
formation .

Cell surface hydrophobicity of R.ruber was studied and addition of
mineral oil enhanced the degradation of PE films by about 50% after
four weeks of incubation .

Brevibacillus borstelensis , a thermophillic bacterium , was found
to degrade polyethylene better than R.rubber , although the biofilm
forming capacity of the former was not found to be as good as on of
latter. Still it was able to show considerable reduction in mass and
molecular weight by 11-30% respectively for UV irradiated
polyethylene.

LDPE and HDPE films after photoxidation and thermal oxidation
were incubated with R.rhodochrous and Nocardia asteroids. ATP (
adenosine triphosphate) assay was done to see metabolic activities of
the cell in culture and those adhered to the surface of polymer. After
9months NMR analysis of this sample revealed the presence of
ethanol and formate , which are end products of PE oxidation . This
evidence support the initial fast growth of micro-organisms observed
by ATP analysis.


1.4 Conclusion

Pre-treated polymers degrade more easily than untreated ones . Most of the
examples deal with fungi and bacterial based degradation .
Also, degradation is more facile with starch and cellulose blended polymers.
Cell surface hydrophobicity and addition of surfactants showed an important
role in biofilm formation, which is pre-requisite for biodegradation .
Degradation leads to decrease in molecular weight , tensile strength and
viscosity , formation of new functional groups such as carbonyl etc.

Following approaches can be adopted to enhance the bio-degradation of PE
:-

1. Modify the polymer for microbial utility by i) addition of natural polymer
like starch and pro-oxidants ii) Modification of polymers by protein
hydrolysates and iii) Pretreatment of polymer

2. Modify the microbes to utilize the polymer by i) Modifying the medium
composition and thus enhancing the utilization of polymer ii) genetically
modify the micro-organisms to utilize the polymers.

Both these strategies require the understanding of mechanism of microbial
degradation of these polymers.
















2 .Thermal Degradation

PE can be and is processed practically with all thermoplastic processing
technologies including extrusion, injection molding, blow molding,
rotational molding, etc., but the largest amount of products are prepared by
extrusion. The polymer is subjected to the effect of heat, shear and oxygen in
all thermoplastic processing technologies. As an effect of these factors
chemical reactions take place in the processing machine with a number of
consequences. Although polyethylene is a simple polymer with an
apparently well defined structure, its molecular structure often contains
irregularities. The actual structure of PE depends on the polymerization
technology used for its production. Polymerization under high pressure with
radical initiation results in low density polyethylene with a large number of
branches, while catalytic processes usually yield linear chains with more
regular structures. However, even the catalyst used for the production
changes chain structure, chromium catalyst used in the Phillips process
create a double bond at the end of each chain, while the concentration of
unsaturations is at least an order of magnitude smaller in Ziegler type
polymers. Double bonds and other chain irregularities are potential reaction
sites on which chemical reactions take place during processing. These
reactions modify the chain structure of the polymer and also the properties
of the final product.
The thermal degradation of linear polyethylene in oxygen-free environment
starts with random scission of the polymer chains followed by random
intermolecular hydrogen abstraction and subsequent -scission.
RR R

+

R
According to Holstrm and Srvik [25] the thermal degradation of
polyethylene is a radical process, and it starts with the scission of CC bonds
in allylic position




The primary radicals formed in the initiation reaction participate in the
following further reactions under thermal conditions:
depolymerization through -scission,
intramolecular hydrogen transfer,
intermolecular hydrogen transfer. Decomposition reactions follow the
intramolecular and intermolecular hydrogen transfer in the thermal
degradation of polyethylene. -scission of the radicals results in the
formation of small molecular fragments, further alkyl radicals and
vinyl groups:

Some
of the primary radicals are expected to isomerize by intramolecular
hydrogen abstraction (back-biting) and to form secondary radicals, which
are more stable. Intramolecular hydrogen transfer can occur from the fourth
or fifth carbon atom to the first one :
In
the case of 5 1 hydrogen transfer the reaction can proceed inside the
polymer chain:
Hydrogen transfer can occur also in intermolecular reactions:
where R, R and R are alkyl groups; R is hydrogen or alkyl group
The intermolecular hydrogen abstraction can be followed by -scission. The
reactions of secondary radicals lead to the formation of vinyl groups, while
those of tertiary radicals result in the formation of vinylidene and vinylene
groups:
Holstrm and Srvik considered the intermolecular hydrogen abstraction
followed by -scission the most important propagation reactions in the
degradation of polyethylene. These reactions result in a significant decrease
of the average molecular mass and yield volatile products. On the basis of
activation and bond dissociation energies Kuroki et al. [26] claimed that
back-biting reactions and intermolecular radical-transfer reactions are much
more likely to occur than depolymerization reactions.
Intermolecular hydrogen abstraction followed by isomerization of a vinyl
group results in the formation of vinylene group:


Recombination and disproportionation are the most important termination
reactions of thermal degradation.


Holstrm and Srvik observed that the tendency to disproportionation
increases with increasing temperature. From the trans-vinylene group/long
chain branches content ratio of high density polyethylene Kuroki et al.
concluded that the probability of the recombination termination reaction
between primary and secondary macro radicals is 2-5 times larger than that
of the disproportionation reaction. Although both types of termination
reactions have zero activation energy, termination reactions are diffusion
controlled in practice and the rate constant depends on the rate of diffusion
of macro radicals in the media. If either of the radicals diffuses outside the
field of reaction created by the surrounding polymer segments (cage),
propagation (depolymerization, intra- and intermolecular radical transfer)
and termination reactions take place, leading to the formation of volatiles
and a decrease in molecular mass. Thus both the molecular mass increase
and the degradation reactions become dependent on the rate of diffusion, in
relation to the viscosity of the media, of the two radicals outside the cage.

















2.1 Thermo-oxidative degradation
The oxidation of hydrocarbons is a free radical-initiated autocatalytic chain
reaction. The reaction is slow at the start and accelerates with increasing
concentration of the resulting hydroperoxides. The process can be regarded
as proceeding in three distinct steps: chain initiation, chain propagation, and
chain termination.
Chain initiation:

Chain propagation:

Chain branching:

Chain termination:

Many schemes were proposed for the initiation step, but the origin of the
primary alkyl radical R

is still controversial. It can be formed as an effect of
heat, shear, catalyst residues, radical initiators, and/or impurities in the
monomer. The alkyl radicals react with molecular oxygen practically
without activation energy forming peroxy radicals. The rate constant for the
reaction of most alkyl radicals with oxygen is of the order of 10
7
-10
9
mol
-
1
s
-1
.
The peroxy radicals form hydroperoxides upon abstraction of hydrogen from
the polymer chain, which requires the breaking of a C-H bond, i.e. needs
activation energy. Therefore this is the rate-determining step in autoxidation.
The rate of the abstraction reaction decreases in the following order:
hydrogen in -position to a C=C double bond (allyl) > benzyl hydrogen and
tertiary hydrogen > secondary hydro- gen > primary hydrogen. Primary and
secondary peroxy radicals are more reactive in hydrogen abstraction than the
analogous tertiary radicals, and the most reactive are acylperoxy radicals.
The peroxy radicals oxidize olefins ina way in which the oxidation of double
bond is considered the most important reaction by Brill and Barone.


Hydroperoxides decompose fast to reactive oxy and hydroxyl radicals. The
rate of decomposition increases with rising temperature. Metal ions and
ultraviolet radiation catalyze hydroperoxide decomposition. The reactions
with metal ions are described by reactions :

Oxy and hydroxyl radicals formed in the decomposition of hydroperoxides
are far more reactive than peroxy radicals, and lead to the branching of the
reaction chain, i.e. auto-acceleration of the degradation process. -scission
of oxy macro-radicals yields carbonyl groups and other free alkyl radicals.
Chain termination occurs by recombination or disproportionation of radicals.
At high oxygen concentrations and moderate temperatures chain termination
proceeds by the recombination of peroxy radicals. If the concentration of R

radicals is much higher than that of peroxy radicals (characteristic for poly-
ethylene processing), chain termination is caused by recombination with
other available radicals. The disproportionation of alkyl radicals leads to the
formation of an unsaturated group but does not result in a decrease of
molecular mass. The chain termination processes do not stop the thermo-
oxidative reactions. The reaction products formed in the recombination
reaction of peroxy radicals participate in further reactions. Norrish-II type
breakdown of ketones results in the formation of vinyl and hydroxyl groups
under irradiation:
The melt processing of polyethylene takes place in oxygen poor
environment under shear. The high mechanical forces lead to C-C chain
scission resulting in macro- radicals. The oxygen dissolved in the polymer
reacts with the alkyl radicals forming peroxy radicals, subsequently
hydroperoxides and new alkyl radicals. These hydro- peroxides decompose
rapidly to the corresponding alkoxy and hydroxyl radicals. The latter can
form inactive products (ROH and H
2
O) and further alkyl radicals through
hydrogen abstraction, while -scission leads to the scission of the
macromolecule. The number of weak sites in the polymer chain, the type
and amount of catalyst residues, as well as the processing conditions affect
significantly the rate and direction of reactions. At high concentrations of
unsaturated groups (Phillips type polyethylene) crosslinking reactions
predominate during processing, while at low unsaturated group contents
(Ziegler-type and metallocene polyethylenes) the direction of the reactions
depends both on the number of vinyl groups and the processing conditions.
Transition metal impurities, including catalyst residues, accelerate the
decomposition of hydroperoxides leading to detrimental effects.

2.2 Effects of thermal degradation
The chemical reactions involved in thermal degradation lead to physical and
optical property changes relative to the initially specified properties.
Thermal degradation generally involves changes to the molecular weight
(and molecular weight distribution) of the polymer and typical property
changes include:
Reduced ductility and embrittlement
Chalking
Color changes
Cracking
General reduction in most other desirable physical properties
The dominant mechanism of degradation and the degree of resistance to
degradation depends on the application and the polymer concerned. The
results are the same for most polymer families and significant property
degradation can occur when thermal degradation does occur.

2.3 Protecting Plastics with Stabilizers
Plastics can be protected from thermal degradation by incorporating
stabilizers into them. Stabilizers are used to keep the polymer chains and the
original molecular structure intact and therefore properties such as strength,
stiffness and toughness can be retained over a longer period.
Stabilizers can work in a variety of ways but in most cases they work by
interrupting the thermal degradation cycle to slow down or prevent the cycle
from completing. Some stabilizers work by mopping up the available free
radicals (radical scavengers). In this case the stabilizer reacts rapidly with
the available free radicals to produce another much less active free radical
and thus slow the process down.

2.4 Protecting plastics with radical scavenger stabilizers
A second group of stabilizers work by reacting with the hydroperoxide
(ROOH) to produce inactive and stable products such as ROH and break the
cycle at the hydroperoxide propagation step.
Other groups of stabilizers exist for specific materials and applications and
there are many different chemical families of stabilizers.
In most cases a given plastic will incorporate a mix of stabilizers that are
designed to work as a system to give the desired properties for the
application. This mix will be designed specifically for the polymer being
used and the requirements of the application. The mixture will also be
designed to be applied at a specific concentration over dosing stabilizers
can in fact be detrimental to the plastic and the effect of the stabilizer.


The given mechanisms can be substantiated using a report (33) aimed at
studying the thermal and UV degradation of HDPE, LLDPE and
metallocene grade materials, by means of the CL technique, and TGA in
terms of determination of the frequency factor and the activation energy for
the overall photooxidation process. For this purpose, their analysis was
based on the kinetic analysis method developed by Park et al. [34], which
allows calculation of A0 and Ea, and to predict the degradation of
polyolefins at any time.
The chain branching was expressed by the CH3 content determined by FTIR
as the ratio A/d, where A is the absorption at 1378cm
1
corresponding to the
deformation band of CH3 groups (CH3), and d the sample thickness. It was
seen to increase in the following order: HDPE < m-PE < LLDPE. The
results obtained indicate a clear relationship between activation energy and
the chain branching of the polymers, Ea decreases as the chain branching
increases. Such behavior can be explained by the mechanism described
previously.
An analysis of the three polymers before and after thermal ageing at 90

C
was undertaken using FTIR. In general, the metallocene polymer exhibited
the lowest initial concentration of oxidised products associated with a low
oxidation level during the manufacturing process. Hydroperoxide
concentration for m-PE was seen to gradually increase up to 144h of ageing,
whereas, for HDPE which gave the highest initial hydroperoxide values, and
LLDPE, an autocatalytic oxidation process was observed. HDPE was the
most unstable polymer, followed by LLDPE and m-PE.
A similar order for the stability of the polyethylenes was found through the
measurement of carbonyl index growth (see figure). Carbonyl index gives a
measure of the amount of oxidized products in the system i.e. it tells us
about the hydrophilicity. It is the ration between absorption intensities of
C=O and CH
2 .


Figure: Carbonyl index (1720 cm
1
) vs. oven ageing time at 90

C for
films of HDPE, LLDPE and m-PE polymers (d (= 290 10
4
cm) is the
film thickness.

The m-PE and LLDPE samples showed an initial autoretarding effect,
whereas, HDPE film exhibited a shorter induction period and the highest
carbonyl levels up to 144 h heating.
As already described, different vinyl types are generated in the thermal
degradation of polymers. The analysis of the initial concentration and
evolution of those species in HDPE, LLDPE and m-PE after thermal ageing,
was undertaken using second order derivative UV analysis.
In general, HDPE exhibited the higher initial concentration of vinyl groups
compared to LLDPE and m-PE. HDPE had a very strong band at 199 nm
(not present in LLDPE and m-PE), assigned to less substituted vinyl. m-PE
showed a band at 205 nm corresponding to disubstituted vinyl, and was not
present in HDPE and LLDPE. The three polymers have a band at 194 nm
assigned to monosubstituted vinyli- dene groups, HDPE showed the highest
absorbance of this band and a greater increase of those species with ageing
time. From the results obtained, the order established for the oxidation
susceptibility is as follow: HDPE > LLDPE > m-PE in accordance with
carbonyl index results.
CL spectra of the initial polyethylenes films were measured at 170

C (see
figure).

Figure: CL spectra under nitrogen of HDPE, LLDPE and m-PE polymers at
170

C.
The CL in polymers is due to the light emission that accompanies the
thermal decomposition of the thermooxidative degradation products
(hydroperoxides), which are formed during processing or service life of the
material under ambient conditions. By means of the CL technique, it is
possible to determine the degree of oxidation, and even to predict the long
term stability of the polymer.
The metallocene polymer exhibited the lowest CL intensity, at 170

C, for
initial sample which corresponds to the lowest concentration of oxidized
products as determined by FTIR.
For the three polyethylenes, the intensity of CL of the fresh and aged
samples were measured from 25 to 250

C. The intensity of CL of the aged

samples is very much higher than that of the initial polymers, due to the
decomposition of the hydroperoxides generated during the thermal
degradation. LLDPE and m-PE show a gradual increase of the intensity of
CL with ageing time, whereas, for HDPE an autocatalytic oxidation process
was observed; and the emission was detected at lower temperature than
LLDPE and m-PE, which showed an inhibition period. This result would
indicate that HDPE is more susceptible to oxidation, followed by LLDPE
and m-PE, in agreement with the above commented results.




Taking the attention to the report on Polyethylene degradation: effect of
polymerization catalyst, by Karmele Sanchez, Norman Allen, and Chris
Liauw. They used several PE resinse.g., high-density PE (HDPE), using a
Phillips (Ph) metal-oxide catalyst, and linear low-density PE (LLDPE),
based on Ziegler-Natta (ZN) and metallocene catalyst technology to acquire
insights into the effect of different polymerization catalyst systems on
degradation-product formation during melt processing. They used color
measurement, IR spectroscopy, hydroperoxide determination, and melt-
flow-rate measurements to monitor degradation as a function of the number
of passes though a twin-screw extruder.
Relative to a range of additive-free PEs , they recorded unusually good
thermo-oxidative stability during melt processing for PEs produced by
means of the metallocene route, especially medium- density PE. This
relatively high stability is probably due to low levels of nocuous metal-
catalyst residues, as well as very low vinyl-unsaturation content. The
relatively high melt stability of the metallocene PEs was manifested as a
weak tendency to chain extend/crosslink and the lowest recorded rate of
carbonyl-group formation (see Figure).



Transmission Fourier-transform IR spectra illustrating the carbonyl region
of
(a) metallocene medium-density polyethylene (PE),
(b) metallocene linear low-density PE (LLDPE),
(c) Ziegler-Natta LLDPE, and
(d) Phillips high-density PE.
The absorbance was normalized to the internal standard at 2018cm
-1
.
Upper group: Pass 0 samples. Lower group: Pass 5 samples.

In contrast, Ph-HDPE had a strong tendency to chain extend/crosslink and
oxidize because of the abundant vinyl groups in this polymer. Vinyl groups
are the origin of chain extension/crosslinking by addition of macro-radicals
(see Figure ).

Normalized vinyl-group absorbanceAbs908/Abs2019 versus the number
of extruder passes for m-MDPE (squares), m-LLDPE (circles), ZN-LLDPE
(triangles), and Ph-HDPE (stars).
The relative ease of melt oxidation of Ph-HDPE led to high hydroperoxide
production levels, despite the presence of chromium catalyst residues that
are believed to decompose hydroperoxides into free radicals. This results in
acceleration of the auto-oxidation process. On the other hand, it was
observed that significantly reduced hydroperoxide production within the
metallocene and ZN PEs. This was entirely consistent with the carbonyl-
index trends, since these PEs generally featured less carbonyl growth during
multipass extrusion.
They recorded an increase in yellowness index with increased number of
extruder passes for all PEs examined (see Figure ).

Yellow index versus the number of extruder passes for m-MDPE (squares),
m-LLDPE (circles), ZN-LLDPE (triangles), and Ph-HDPE (stars).

The increase was most and least significant for, respectively, ZN-LLDPE
and metallocene LLDPE and Ph-HDPE. Previous work

indicates that the
increased color development in ZN-LLDPE may be caused by chelation of
the titanium catalyst residues. In the other polymers, discoloration may be
attributed to extensive formation of conjugated systems consisting of
transvinylidene unsaturation and carbonyl groups.
What next is needed to be examined is the effect of catalyst type on melt-
stabilization performance of single antioxidants, antioxidant combinations,
melt- processing oxidation-product chemiluminescence, and the largely
neglected area of the effect of stabilizer type on the production of low-
molar-mass (volatile) oxidation products.

Another report (35) on the effect of pro-oxidant on the lifetime of polymer
by non-isothermal thermo- gravimetry has been investigated. The
incorporation of these additives is expected to decrease the lifetime of
polyethylene in general. This study is concerned with the degradation
behaviour of a series of formulations containing cobalt stearate in the
concentration range (0.05 0.2% w/w) using non-isothermal
thermogravimetric analysis in two different atmospheres: nitrogen and air.
The kinetic parameters have been calculated which have been subsequently
employed to predict the effect of cobalt stearate on the lifetime of LDPE. Air
oven aging studies have also been performed at two different temperatures
(70C and 100C) to demonstrate practically the pro-oxidant activity of
cobalt stearate on LDPE.

TG/DTG traces for the thermal decomposition in nitrogen atmosphere at
different heating rates a) 3C/min, b) 5C/min, c) 7C/min

As is evident from the figure, all the samples exhibit single step
decomposition in nitrogen atmosphere over a relatively short temperature
range. In inert atmosphere, random scission has been reported to be the
primary pathway for degradation in polyethylene. However, this is also
accompanied by polymer branching. From the figures, it can be concluded
that both, scission as well as branching, occur simultaneously resulting in a
single mass loss step. The degradation temperature was found to increase
with increase in the heating rate, which corresponds to the time temperature
superposition principle. A shorter time is required for the sample to reach a
given temperature at a faster heating rate. The onset temperature of
degradation (Tonset), temperature of maximum loss (Tmax), end
temperature of degradation (Tend), temperature corresponding to 5% loss
(T5l) and 50% loss (T50l) have been calculated from the DTG curves
(3C/min) and are presented in Table1. It was observed that Tonset shifts to
lower temperatures with increase in the concentration of cobalt stearate,
which also results in larger difference of Tonset and Tend. This also
indicates that the degradation require relatively longer time periods.
In air atmosphere, a slight increase in the weight due to heating till 160
200C, and this has been attributed to the formation of polymeric oxides(see
figure). Contrary to the behavior in nitrogen atmosphere, the degradation
temperature was not found to increase with increase in the heating rate in air.
Table 2 reports the temperature at which 5% and 50% mass loss occurs as
T5l and T50l respectively.

TG/DTG traces for the thermal decomposition in air atmosphere at different
heating rates a) 3C/min, b) 5C/min, c) 7C/min

Table1


Table 2
On comparing Table 1 and 2, we observe that the degradation occurs at
much lower temperatures in air than in nitrogen atmosphere. Addition of
cobalt stearate to polyethylene leads to further lowering of these
characteristic temperatures, which indicate its pro-oxidative nature.











3. Photo-degradation

The phenomenon of 'weathering' of polymeric materials is usually caused by
a complex series of chemical reactions initiated by the absorption of ultra-
violet light which ultimately result in the deterioration of the physical
properties of the polymer.[37]
All polyethylene (PE) is susceptible to degradation upon long-term exposure to sunlight.
This degradation is brought about by physical changes, which occur in the polyethylene
as a result of exposure to the ultraviolet (UV) portion of sunlight.
UV light contains shorter wavelengths than visible light. The shorter the wavelength, the
more energy it contains and thus, the more damage it does.
Most commercial organic polymers undergo chemical reaction upon
irradiation with ultraviolet light, because they possess chromophoric groups
(as regular constituents or as impurities) capable of absorbing UV light.
Carbonyl groups play a prominent role among these chromophoric groups
[23]. Therefore, the photochemistry of ketone polymers was selected to
demonstrate how light-induced chemical reactions proceed. Here we take
into consideration the Norrish reaction I and II.

We emphasis on photo-oxidation/degradation of polythene by following
ways:
Accelerating the weathering conditions artificially.
Photo-catalytic degradation using doped or un-doped TiO2
nanoparticles.

Depending on the use of the particular polymer, as well as its identity, some
mechanisms may be prominent, while others might not act at all. The
degradation of LDPE films used as covering material is governed mainly by
thermal, radiation, mechanical and chemical mechanisms.






3.1 The Details and Mechanisms

Poly-olefins rapidly lose most of their mechanical properties after severe
processing or periods of thermal and light exposure. Low molecular weight
hydrocarbon analogues are generally resistant to oxidation at ambient
temperatures, but surprisingly the degree of degradation is unexpectedly
high[2]. Degradation is a complicated non-linear time-dependent process
which affects directly, or indirectly, several properties of the material related
to its functional characteristics. In its final stage of degradation, a material
does not meet its functional requirements and is easily prone to mechanical
failure. As a practical rule, the useful life of a material is considered to be
reached when its initial mechanical strength is reduced by 50% (Henninger
& Pedrazetti, 1988). There are several factors to monitor and criteria to
determine the degree of degradation (Randy & Rabek, 1983).[40]
Poly-olefins should, in theory, be impervious to photo-degradation like pure
aliphatic hydrocarbons, which do not absorb the UV radiation present in
sunlight. It is generally assumed that impurities, or chromophores, which
absorb UV light, initiate the photo-oxidation of commercial poly-
olefins.[39]



Also, relatively little chemical change is required to generate major changes
in physical properties. The elongation at break (expressed as a %) appears to
be a more sensitive &index' of degradation than the tensile strength, the
stress at yield or the modulus of elasticity. Actually, the material becomes
more brittle with degradation and so it cannot retain its initial elongation at
break.
This is especially important when the final product is exposed to weathering
in outdoor applications, where degradation is initiated by the near-ultraviolet
(UV) component of sunlight and oxygen. UV light alters the physical
characteristics of polyethylene (PE).It does this by breaking the carbon and hydrogen
bonds, creating free radicals which, in turn, break the PE into shorter
molecules and thus, a more brittle polymer. Effectively, UV light creates a higher
melt index polyethylene, especially on the exposed surface area. This shows up as a
reduction in break elongation and impact properties, typical of higher melt index PE.
The subsequent attachment of oxygen to these broken sites leads to further accelerated
degradation and the formation of oxidized species such as carbonyl and car-boxyl
structures, which are often used as analytical indicators of UV degradation.[41]



Coming to the mechanism of photo-oxidative degradation, the starting
reaction is always bond scission in polymer chain or in some other molecule
initiating degradation. This clarifies the fact that degradation follows a free
radical mechanism initiated by scission of chromophores and other additive
molecules. Subsequent reactions include crosslinking and the formation of
double bonds. Polyethylene undergoes chain scission, branching and
crosslinking, which occur as competitive reactions, whereas polypropylene
undergoes chain scission predominantly, as shown below.[39]


Oxidation without UV involvement is much slower than photo-oxidation.
After long exposure to UV light of short wavelength (254 nm) in a vacuum
or in a nitrogen atmosphere, chain scission and hydrogen abstraction occur.
Also
Cross-linking and evolution of hydrogen are observed. [38]

The photo-oxidation happens mostly by the Norrish process I or II.


The Norrish reaction in organic chemistry describes the photochemical
reactions taking place with ketones and aldehydes. The Norrish type I
reaction is the photochemical cleavage or homolysis of aldehydes and
ketones into two free radical intermediates. The carbonyl group accepts a
photon and is excited to a photochemical singlet state. Through intersystem
crossing the triplet state can be obtained. On cleavage of the -carbon
carbon bond from either state, two radical fragments are obtained. A Norrish
type II reaction is the photochemical intra-molecular abstraction of a -
hydrogen (which is a hydrogen atom three carbon positions removed from
the carbonyl group) by the excited carbonyl compound to produce a 1,4-
biradical as a primary photoproduct (IUPAC definition). [41]
Copolymerization of ethylene monomer with small amount of carbon
monoxide forms an ethylene-carbon monoxide copolymer, known to
degrade on sunlight exposure by Norrish type I and II reactions. Both cases
are equivalently dangerous to the durability of the polymer. If the polymer
degrades according to Norrish I mechanism, two free radicals are formed
simultaneously. When the Norrish II mechanism controls degradation, two
molecules capable of absorbing sunlight are formed.[39]
High-density PE and low-density PE contain unsaturations. The presence of
these unsaturations (vinylidene groups) leads to formation of allylic
hydroperoxides during the thermooxidative processes, and this becomes the
major mechanism of initiation as shown in the figure below. [39]


This structure can be further converted by heat, UV, or other radicals to free
radicals and/or to structures containing UV-absorbing groups (e.g.,
carbonyl). Unsaturations then usually predominantly lead to chain scission
reactions, but crosslink formation also occurs as shown in the next figure.



Other photosensitive groups introduced during processing and use are:
(a) hydroperoxides and peroxides which are primary products of thermal
oxidation during processing, are extremely photochemically active and are
initiators of photo-reactions;
(b) carbonyl groups produced by thermal oxidation during processing and
storage and from photo-oxidation during use which are also well-known key
initiators of the Norish I and II type photo-reactions
(c) reactive forms of oxygen such as ozone (O3) which is present in the
atmosphere and singlet oxygen (1O2) which can be produced inside the
polymer by quenching of UV excited species by ground-state oxygen (3O2).
All these impurities lead to enhancement of photodegradation by either
absorbing energy of the UV spectrum, or by being initiators of photo-
oxidation reactions (in the case of carbonyl and hydroperoxide groups).[39]
Once these impurities are present in the LDPE films, the photo-degradation
proceeds, in two distinct parts:
(a) photo-oxidation of the outer layers which can come in direct contact with
the atmospheric oxygen, and proceeds rapidly mainly through radical chain
oxidation reactions, while
(b) the inner layers, which cannot under usual circumstances be reached by
the atmospheric oxygen, degrade more slowly through photo-reactions of
peroxy radicals or reaction of radical pairs. Usual products of these reactions
are carbonyl (C=O), hydroxyl (OH) and vinyl groups, while trans-vinylene
groups are produced in trace amounts.[39]
Factors influencing polyolefin photodegradation include molecular structure,
polymer morphology (degree of tacticity and crystallinity), internal
impurities, specimen thickness, temperature, irradiation intensity and other
climatic conditions. Since the additives' presence renders the polymers
apparently useless, addition of stabilisers becomes inevitable avoiding which
shall make the polymer material short lived. However, many stabilizers and
antioxidants are lost over time through sacrificial transformations,
evaporation, blooming or leaching. Consequently it is common practice to
add further stabilizers to aged polymer material, a process known as re-
stabilization [38]. Studies investigate mechanical, rheological behaviour of
poly-olefins, including blends, intended for outdoor use that had been
subjected to accelerated ageing by UV radiation for a variety of exposure
periods. Gloss and colour measurements are taken to observe any changes in
surface characteristics. Gel permeation chromatography (GPC) is employed
to observe any changes in chemical properties. Since in the laboratory, we
create accelerated weathering conditions, so, comparisons are made in
artificially degraded and naturally degraded samples of poly-olefins to
calculate the similarities and hence application of the accelerated weathering
conditions method. [38]

Now comes the catalytic photo-oxidation of polythene[42]. Titanium
dioxide (TiO2) is one of the most well-known efficient photocatalysts. The
capability of TiO2-based photocatalyst to degrade gaseous and aqueous
contamination makes it a good candidate for use in air clean up and water
purification. The most promising approach of activation of TiO2, in the
visible light region, is modification of its chemical structure to shift the
absorption spectrum to the visible light region. This type of modification
involves introduction of doping with metal and non-metal species. The
process of recycling polymers is expensive and time consuming; only a
small percentage of the plastic waste
is currently being recycled . Biodegradable plastics have shown considerable
promise in this context. However, the biodegradable plastics till now cannot
completely solve the problem due to their chemical stability and non-
affordable cost. More recently, photo degradation of plastics has also started
receiving attention. The composition of plastic and TiO2 nanoparticles
(NPs) has been proven to be a new and useful way to decompose solid
polymer in open air. Investigations on the photo degradation of polyvinyl
chloride (PVC), polystyrene (PS), and polythene (PE) have been carried out
. More specifically, a few recent reports describe the use of TiO2 and
goethite and so forth as the photo-catalyst for oxidative degradation of PE
with very encouraging. Currently we focus on solid phase photo-catalytic
degradation of polyethylene plastic with TiO2 as photo-catalyst and Fe, Ag
metals as dopants.[42]


3.2 Effect of morphology on photodegradation

Degradation of PE is influenced by a great extent of its crystallinity. It has
long been known that branched polyethylene oxidizes faster than linear
polyethylene, and it has been discovered that its oxidation rate is roughly
proportional to the amount of amorphous fraction present. This suggests that
the oxidation of semi-crystalline polyethylene is restricted to its amorphous
region. It was subsequently discovered that the crystalline region absorbs
practically no gas which implies that oxygen is simply not available in the
crystalline region. [39]
Based upon these facts, polyethylene of low crystallinity has a high rate of
carbonyl formation and a low concentration of radicals.
Crystallinity changes during the course of degradation. In the initial stages
of
photodegradation, chain scission prevails which reduces molecular weight.
Shorter chains are more mobile and are thus able to crystallize more readily.
Therefore, embrittlement of PE is controlled by two associated processes:
reduction of molecular weight and increased Crystallinity.
Characterization
Characterization of TiO2 Nanoparticles
X-Ray Diffraction Analysis:
Crystal size of the prepared photocatalyst was studied by powder XRD
technique. X-ray diffraction patterns were obtained on JEOL JDX-II X-ray
diffractometer using Cu-K radiation at an angle of 2 from
10 to 80. The crystallite size was determined fromthe X-ray diffraction
patterns, based on the Scherer equation.

where k is a shape factor = 0.9, is the radiation wavelength= 1.54051A,
is the Bragg angle, = full width of a diffraction line at one half of
maximum intensity in radian. [42]
SEM Study. SEM study of doped and undoped TiO2 NPs was conducted
with JEOL JSM-6460 scanning electron microscope to see the distribution
of metal on the surface of TiO2 in doped species.
EDS Analysis. Energy dispersive spectroscopic (EDS) analysis was
conducted with Oxford INCA X-sight 200 to perform the quantitative
analysis of the TiO2 both in doped and undoped conditions.[42]

3.3 Experimental



Conclusions
The photo degradation proceeds mainly by photo initiated oxidation
reactions.
Although photo oxidation mechanisms of poly-olefins are very similar, their
weather resistance is different. The photo degradation of poly-olefins is
strongly influenced by their morphology. Oxidation rate is roughly
proportional to the amount of amorphous fraction present, which suggests
that the oxidation of more crystalline polymer is slower than that of lower
crystallinity. The effect of polymorphism on the degradation is also
observed.
In summary, three major functional groups are accumulated during
degradation:
ketones, carboxylic acids, and vinyl groups. During photolysis, ketones and
vinyl groups increase linearly with time of exposure, whereas carboxylic
acids accumulate exponentially.
If polyethylene is exposed for long periods outdoors, it is degraded by the
concerted action of atmospheric oxygen and radiation at the UV end of the
solar spectrum. The degradation leads to a deterioration in impact resistance
and ultimate elongation, and possibly, to discoloration. Elongation of HDPE
especially is reduced to almost zero.


Method 1. The effects of accelerated weathering conditions as seen
experimentally can be bulleted in the following points:
The effect of UV exposure, whether in the field or in the artificial
environments, was not significant up to 1000 h as far as the
mechanical properties of the materials are concerned. Any surface
effects would not compromise the mechanical integrity of the
product. However, surface appearance may be an issue.
It is likely that the difference in results for field-aged and
artificially aged materials was due to variability in the source
materials. This was demonstrated by the molecular weight and
viscosity analysis.
The field-aged material had a higher overall molecular weight in
comparison with the new material. This increase could be due to
degradative crosslinking.
Method 2. The analysis of photocatalytic degradation using TiO2
nanoparticles highlights the following points:
Doping of TiO2 NPs by Liquid Impregnation method alters its
characteristics such as particle size and surface morphology.
The effect of mix doping is midway between that of the doping effect
by a single metal alone. This indicates that metal ratios can be
adjusted to get a desired impact for a particular requirement.
This idea was implied and verified in the photo degradation of PE
under UV and artificial light irradiation.
Photo degradation of PE-TiO2 films occurred at faster rate and was
more complete than the simple photo degradation of pure PE films
under UV and artificial light irradiation.
Overall degradation trend can be represented as
o PE-doped TiO2 > PE-undoped TiO2 > simple PE.
Catalytic trend among the doped TiO2 NPs under UV irradiation can
be represented as
o Fe/Ag mix doped TiO2 > Ag doped TiO2 = Fe doped TiO2.


It is an observation that development of this kind of composite polymer can
lead to an environmental friendly polythene product.












4 . POLYETHYLENE STARCH BLENDS

Although several microorganisms facilitate the biodegradation of
hydrocarbon , the biodegradation polyethylene is somewhat slow.
Studies show that biodegradation of polyethylene is extremely slow, the rate
of conversion was 2% per year . This suggest that the PE films could not be
degraded significantly . This is because the degradation mechanism for
linear hydrocarbon involves the oxidation of terminal methyl group to
carboxylic acid group and the degradation of resulting fatty acid by stepwise
B-oxidation ( two carbon at same time ). In high molar mass linear
polyethylene , there are only two methyl groups , which are not located in
the bulk of hydrophobic medium and there are not readily accessible to the
micro-organisms . On the other hand , if ester groups could be
introduced into backbone of polyethylene , it would become
biodegradable .



Incorporation of starch into a polyolefin matrix was first proposed as an
effective means of accelerating the deterioration of plastics under biotic
environment exposure conditions .The inclusion of starch , a readily
available biodegradable polymer , into the synthetic polymer believed to
result in rapid enzymatic hydrolysis of starch under biotic exposure
conditions , leading to void-containing matrix , the reduced mechanical
integrity of the ensuing void -containing matrix leads to facile deterioration
and perhaps even promotes subsequent biodegradation of synthetic polymer
, due to increased surface area available for interaction with the
microorganisms. [43]



Physical incorporation of granular starch derivatives as functional additives
and fillers into poly-olefins during polymer processing example :extrusion
,injection molding or film blowing is well known and had been used for
many years . In the absence of additives , films made from starch or amylose
are brittle and sensitive to water .


A technique for blending gelatinized starch and poly( ethylene-co-acrylic
acid ) ( EAA ) to produce flexible blown films that contain high levels of
starch was introduced . Ammonia and 2% moisture were essential
ingredients for obtaining uniform films . The inclusion of polyethylene in
film formulation improved the economics and increased the UV stability and
rate of biodegradability of films . The films have potential applications as
agriculture mulches and packaging , especially where bio-degradation is
important.



The biodegradation of PE films containing ( by weight ) 40% gelatinized
cornstarch and 15% EAA was studied in variety of aqueous environments .
In the laboratory , some amylotic bacteria degraded starch in the film more
rapidly and to a greater extent than others during 60 day incubation . Loss of
starch was accompanied by a concomitant decrease in film tensile strength ,
facilitating the disintegration of film from mechanical stresses. Films
composed of PE-EAA and PE-EAA-starch were exposed to three fresh
water ecosystems for 90days . The surfaces of all 3 films were rapidly
coated by a complex biofilm containing bacteria , algae , fungi , protozoa
and diatoms . These data suggest that microbial starch degradation ,
mechanical disintegration , bio-disintegration are all factors that influence
the environmental fate of starch containing plastics .[44]


The effect of marine environment on un-stabilized PE-starch composites
,with or without a metal catalyst ( MC ) and auto-oxidants (AO) has been
studied . Starch tends to absorb water. For PE-starch composites containing
metal catalyst and anti-oxidants exposed under plain sea-water , there
appears to be practically no microbial activity as indicated by no surface
erosion and no change in tensile properties . However , the decrease in
molecular weight on the surface indicates ongoing chemical degradation due
to presence of MC and AO .[45]


The use of starch additives in PE and EAA has been applied commercially in
manufacture of bags. Compatibility problems are minimized by use of silane
coupling agents. In theory the polymers in contact with soil or water are
attacked by microbes which ingest the starch additives in the polymer
matrix. This leaves behind a porous sponge like structure with a high
interfacial area and a low structure integrity. Thus the starch component is
ingested first , followed by enzymatic attack on the polymer. This attack
consists of many consecutive enzymatic reactions . In each cycle of attack ,
one base unit , usually an acetic acid molecule , is split off . Thus the
average molecular weight tends to decrease relatively slowly .


During irradiation , the tensile strength decreased to almost the same extent
for all three materials - a mean value of 70% of the initial value was
obtained after irradiation . The elongation at break for pure LDPE decreased
during irradiation from 650 to 500% . After irradiation the decrease was
considerable - a mean value of 60% being recorded for the elongation at
break LDPE .[46]









5 CHARACTERISATION OF DEGRADED POLYTHENE
The level of polythene degradation can be determined by the various
methods as well as analytical techniques and the detail is given. At
topographical level, the Scanning Electron Microscopy (SEM) are being
used to see the level of scission and attachment of the microbes on the
surface of the polythene before and after the microbial attack [47]. The
microdestruction of the small samples is widely analyzed by an important
tool such as Fourier Transform Infrared spectroscopy (FT-IR), and due to
the recent up-gradation of this instrument the map of the identified
compounds on the surface of the sample can be documented via collection of
large number of FT-IR spectra [47]. To measure the physical changes of the
polythene after the microbial attack various parameters are usually used to
determine the weight loss, percentage of elongation and change in tensile
strength .The products from polythene degradation are also characterized
using various techniques such as Thin Layer Chromatography (TLC), High
Performance Liquid Chromatography (HPLC) and Gas Chromatography-
Mass Spectrometry (GC-MS).

5.1 OXIDATIVE DEGRADATION OF HDPE
It has long been known that PE materials are susceptible to oxidative
degradation in certain environments. Wholesale oxidative degradation of PE
leads to a reduction in the molecular weight of the polymer with a
consequent loss of mechanical properties .Oxidized PE material eventually
can become so degraded that it will respond to an applied stress in a very
brittle fashion with an elongation to break of only a few percent - as opposed
to PE material in its normal form where the elongation to break can be from
600 1000%. The steps that are normally taken to prevent oxidative
degradation from occurring in PE materials include adding various chemical
stabilizers, antioxidants (AO's) of various types, to the PE resin.
Generally carbon black is added at 2 3 weight percent to protect the
material against oxidative degradation from exposure to UV radiation,
processing stabilizers (antioxidants to prevent oxidation during pipe
extrusion at 350o 400oF) and other antioxidants intended to provide
protection against oxidation caused by long-term exposure to water
containing dissolved air (oxygen) and other oxidative agents such as water
disinfectants.


5.2 FOURIER TRANSFORM INFRARED SPECTROSCOPY (FTIR)
Micro-FTIR spectroscopy and ATR-FTIR spectroscopy are utilized to
measure the degree of oxidation on the PE film samples. Oxidation of PE
results in the formation of carbonyl groups onto the PE molecules. These
groups have characteristic infrared absorption frequencies. Among these
groups, the strongest absorption peak is observed at about 1710 to 1720 cm-
1. Weaker peaks are seen at about 1735 and 1775 cm-1. The stabilizer
compounded into the PE has a carbonyl group with a characteristic infrared
absorption peak at 1740 cm-1. When oxidation occurs, a ketone carbonyl
peak near 1710 cm-1 to 1720 cm-1 is formed, which progressively increases
in intensity as the degree of polymer oxidation increases.
The carbonyl index (C.I.) is defined as the ratio of this carbonyl absorbance
to that of a polymer absorption band at 1465 cm-1. The use of this ratio
compensates for any differences in sample thickness and serves as an
internal standard.
ATR-FTIR is used to measure the C.I. right at the inner surface of the
sample.
The sample is clamped against the diamond crystal and then analyzed. The
depth of penetration for this method is very small, on the order of 5 microns,
yielding another infrared spectra measurement of oxidation at the inner
surface of the sample.
In past experience in characterizing oxidation of polyolefins, C.I. values less
than 0.02 were not considered as significantly oxidized.[48]






OXIDATIVE INDUCTION TIME (OIT)

This test is a relative measure of the amount of antioxidant still remaining in
the film after extrusion and service. OIT was measured at both the inner
surface and at the interior core of each pipe sample.
Most of the samples tested exhibited very low OIT values at the inner
surface, which correlates well with the FTIR and bend back test results. It is
not uncommon for the inner surface OIT value to be low in polyolefin films
that has been exposed to an oxidizing environment for an extended period.
[48]







5.3 CHARACTERIZATION OF POLYMERS USING TGA
Thermogravimetric analysis (TGA) is one of the members of the family of
thermal analysis techniques use to characterize a wide variety of materials.
TGA provides complimentary and supplementary characterization
information to the most commonly used thermal technique, DSC. TGA
measures the amount and rate (velocity) of change in the mass of a sample
as a function of temperature or time in a controlled atmosphere. The
measurements are used primarily to determine the thermal and/or oxidative
stabilities of materials as well as their compositional properties. The
technique can analyze materials that exhibit either mass loss or gain due to
decomposition, oxidation or loss of volatiles (such as moisture). It is
especially useful for the study of polymeric materials, including
thermoplastics, thermosets, elastomers, composites, films, fibers, coatings
and paints. TGA measurements provide valuable information that can be
used to select materials for certain end-use applications, predict product
performance and improve product quality. The technique is particularly
useful for the following types of measurements:
Compositional analysis of multi-component materials or blends
Thermal stabilities
Oxidative stabilities
Estimation of product lifetimes
Decomposition kinetics
Effects of reactive atmospheres on materials
Filler content of materials
Moisture and volatiles content

TGA decomposition information can be used to predict the useful product
lifetimes of some polymeric materials, such as the coatings for electrical or
telecommunication cables. The sample is heated at three or more different
heating rates. The use of the different heating changes the time scale of the
decomposition event. The faster the applied heating rate, the higher the
given decomposition temperature becomes. This approach establishes a link
between time and temperature for the polymer decomposition and this
information can be used to model the decomposition kinetics. Shown in
graph 1 are the TGA results generated on a sample of polyethylene at
heating rates ranging from 1 to 40 C/min. As the heating rate is increased,
the onset of decomposition is moved to higher temperatures. The kinetics
analysis provided by the software provides valuable predictive information
on polymeric materials, including lifetime estimations. Displayed in graph 2
are the isoconversion curves, which presents the time to achieve a particular
level of conversion as a function of temperature. These are particularly
useful for product lifetime assessments. If the desired level of critical
conversion is known, then the time to achieve this critical level at a
particular operating or end use temperature can be predicted.[49]




























REFERENCES:-

1) VR Gowariker , Polymer science , (2010) , 263 pg
2) http://en.wikipedia.org/wiki/Polymer
3)http://www.polymernotes.org/resources/coventry8.htm
4) Piringer & Baner 2008, p. 32.
5)http://spi.files.cms-
plus.com/about/fbf/H%20Rappaport%20SPI%20Film%20%26%20Bag%20
05%2011.pdf
6)Prideaux, Eric (3 November 2007). "Plastic incineration rise draws ire"
7)Presentation on plastic pollution to marine life at the University of
Floridawebsite.
8) "CanadaWorld WCI student isolates microbe that lunches on plastic
bags". The Record.com.
9) Drowning in Plastic A Daily Telegraph article from 2009 about the
discovery of the plastic particles from degrading plastics and Polyethylene.
10)Plastic into biodiesel machine (at smartplanet.com website)
11) http://www.plasticstoday.com/blogs/Degradation-of-polyethylene-
0618201201

12) Zheng Y & Yanful E K , A review of plastic degradation , Crit Rev
Biotechnol , 25(2005) 243-250
13) Pometto A L & Lee B , Process of biodegradation of high molecular
weight of Polyethylene by aerobic lignolytic mirco-organisms , US Pat
5145779 8 08sept,1992
14) Jakubowicz I , Evaluation of degradability of biodegradable PE ,
Polymer Degradation Stability ,80(2003) 39-43

15) Raghavan D & Torma E A , DSC and FTIR characterization of PE ,
Polymer Engineering Science ,32(1992) 438-442

16) Gilan I , Hadar Y & Sivan A , Colonisation and biofilm formation and
biodegradation of PE by strain of Rhodococcus rubber , Appl Microbial
Biotechnol 65 (2004) 97-104

17) Abd El-Rehim H A, Hegazy E A , Ali A M & Rabie A M , Synergistic
effect of combining UV-sunlight soil burial treatment on the biodegradation
rate of LDPE/STARCH blends , J Photochem Photobio A: Chem 163(2004)
547-556
18) Weiland M , Daro A & David C , Biodegradation of thermally oxdized
PE , Polymer Degradation Stability ,48(1995) 275-289
19) Alberston A-C , Barenstedt C , Karlsson S & Linberg T , Degradation
product pattern and morphology changes as means to differentiate
abiotically and biotically aged degradable PE , Polymer ,36 (1995) 3075-
3083)
20) Koutny M , Lemaire J & Delort A-M , Biodegradation of PE films with
pro-oxidants additives , Chemasphere 64(2006) 189-198

21) Hadad D , Geresh S & Sivan A , biodegradation of PE by the
thermophilic bacterium Brevibacillus borstelensis , Journal Application
Microbial , 98 (2005) 1093-1100

22) Pinchuk L S , Makarevich A V , Vlasova G M , Kravtsov G A &
Shapovalov V A , Electrical-thermal analysis to assess biodegradation of
polymer composites , Int BIodeterior Biodegrad ,54(2004) 13-18

23) Matsunaga M & Whitney J P , Surface changes brought about by corona
discharge treatment of PE film and the effect on subsequent microbial
colonization . Polymer Degradation Stability ,70(2000) 325-332

24)http://www.sciencedirect.com/science/article/pii/S1359511306002200

References
25).Holmstrm A, Srvik EM. Thermal degradation of polyethylene in a
nitrogen atmosphere of low oxygen content. II. Structural changes occurring
in low- density polyethylene at an oxygen content less than 0.0005%. J Appl
Polym Sci 1974;18:761-78.
26).Kuroki T, Sawaguchi T, Niikuni S, Ikemura T. Mechanism for long-
chain branching 1982;15:1460-4.
27) Howard JA, Schwalm WJ, Ingold KU. Absolute rate constans for
hydrocarbon autoxidation. VII. Reactivities of peroxy radicals toward
hydrocarbons and hydroperoxides. Adv Chem Ser 1968;75:6-23.
28)Howard JA, Ingold KU, Symonds MS. Absolute rate constants for
hydrocarbon oxidation. VIII. The reactions of cumylperoxy radicals. Can J
Chem 1968;46: 1017-22.
29)Zaikov GE, Howard JA, Ingold KU. Absolute rate constants for
hydrocarbon autoxidation. XIII. Aldehydes: photo-oxidation, co-oxidation,
and inhibition. Can J Chem 1969;47:3017-29.
30)Brill WF, Barone BJ. The liquid phase oxidation of the lower olefins. J
Org Chem 1964;29:140-3.
31) Zweifel H. Stabilization of Polymeric Materials. Berlin: Springer, 1998.
32)Chirinos-Padrn AJ, Hernndez PH, Chvez E, Allen NS, Vasiliou C,
DePoor- tere M. Influences of unsaturation and metal impurities on the
oxidative degrada- tion of high density polyethylene. Eur Polym J
1987;23:935-40.
33)Piiroja EK, Lippmaa HV. Low-temperature oxidation of unstabilized
low-density polyethylene. Acta Polymerica 1985;36:196-9.
34)Photooxidative and thermal degradation of polyethylenes:
interrelationship by chemiluminescence, thermal gravimetric analysis and
FTIR dataT. Corrales
a,
, F. Catalina
a
, C. Peinado
a
, N.S. Allen
b
, E.
Fontan
c

35)J.W. Park, S.Ch. Oh, H.P. Lee, H.T. Kim, K.O. Yoo, Polym. Degrad.
Stab. 67 (2000) 535540.
36)Thermal degradation studies of LDPE containing cobalt stearate as pro-
oxidant P. K. Roy
1
, P. Surekha
1
, C. Rajagopal
1
, V. Choudhary
2*

37)FUNDAMENTAL PROCESSES IN THE UV DEGRADATION AND
STABILIZATION OF POLYMERS , J. E. GUILLET
38)J. Attwood et al. / Polymer Degradation and Stability 91 (2006)
3407e3415
39)http://dspace.k.utb.cz/bitstream/handle/10563/1469/va%C5%A1ek_2006
_bp.pdf?sequence=1
40)http://www.scribd.com/doc/49336970/UV-Effect-on-PE
41)Wikipedia
42)Hindawi Publishing Corporation , Journal of Nanomaterials, Volume
2011, Article ID 461930, 8 pages doi:10.1155/2011/461930
43)Baum , B. and Deanin , R.D. ,Polymer Plastic Technology Eng. (1999)
,21
44)Gorzynaska , J. , Int. Biodet. Bull ,(1998) , 10
45)Otey , F.H., Westhoff , R.P and Mehltretter ,CL , Starke , (2004),24
46)Gage,P, Tappi J. ,(1990),73
47) A Review on Biodegradation of Polythene: The Microbial Approach
Manisha K Sangale, Mohd Shahnawaz and Avinash B Ade, J Bioremed
Biodeg, Department of Botany, University of Pune, Maharashtra, India

48) oxidative degradation of high density polyethylene pipes from exposure
to drinking water disinfectants, ESI file no. 29261A
49) W.J. Sichina, Characterization of Polymers Using TGA