Mechanistic Implications of Plastic Degradation PDF

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Polymer Degradation and Stability 93 (2008) 561e584

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Review article
Mechanistic implications of plastic degradation

Baljit Singh*, Nisha Sharma
Department of Chemistry, Himachal Pradesh University, Shimla 171 005, India
Received 21 June 2007; received in revised form 6 November 2007; accepted 13 November 2007
Available online 19 November 2007
Abstract
Plastics have become an indispensable ingredient of human life. Their enormous use is a matter of great environmental and economic
concern, which has motivated the researchers and the technologists to induce different degrees of degradations in the plastic. These degradations
can be induced in a better way if their mechanistic implications are properly understood. A better understanding of the mechanism for these
degradations is also advocated in order to facilitate the proper use of the alternative waste disposal strategies. In view of the facts concerning
the plastic degradation, in this review article, we have discussed various types of polymeric degradations along with their mechanisms, which
include photo-oxidative degradation, thermal degradation, ozone-induced degradation, mechanochemical degradation, catalytic degradation and
biodegradation. This article also discusses the different methods used to study these degradations and the factors that affect these degradations.
2007 Elsevier Ltd. All rights reserved.
Keywords: Photo-oxidative degradation; Thermal degradation; Ozone-induced degradation; Mechanochemical degradation; Catalytic degradation and
biodegradation
1. Introduction
Plastics due to their versatility become the essential ingredients to provide a quality to life. These are now rival metals
in breadth of use and in severity of applications because of
their flexibility, toughness, excellent barrier and physical
properties and ease of fabrication [1e5]. The accumulation
of plastics in the environment is a matter of great concern
leading to long-term environment, economic and waste
management problems. Degradation of waste plastics through
various means becomes one of the alternatives to deal with
such problems [6,7]. A wide variety of synthetic polymers
absorb solar ultraviolet (UV) radiation and undergo photolytic,
photo-oxidative, and thermo-oxidative reactions that result in
the degradation of these materials [8,9]. The propensity of
plastic products to undergo solar UV radiation induced degradation/ozone-induced degradation has been increased by
addition of some additives in these polymers [10,11]. Besides
these degradations, biodegradation offers another most
* Corresponding author. Tel.: 91 0177 2830944; fax: 91 0177 2830775.
E-mail address: baljitsinghhpu@yahoo.com (B. Singh).
0141-3910/$ - see front matter 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.polymdegradstab.2007.11.008
efficient and attractive route to environmental waste management. The mechanisms involved in the biodegradation are
complex due to the interaction of different oxidative processes
which are caused by the oxygen present in the air either by the
microorganisms or by the combination of the two [12].
On the other hand, sometime the product needs stability
instead of degradation. Therefore, depending upon the product applications plastic needs controlled stability. In order
to increase the outdoor uses of plastics, the development
and production of polymers with increased weathering resistance is required similarly for the use in high temperature
applications, polymers need thermal stability [13e15]. To
control the stability, understanding of the mechanism is the
primary requisite. Keeping in view the facts for the plastic
degradation, in this review article, we have mainly discussed
the various types of polymeric degradations (photo-oxidative
degradation, thermal degradation, ozone-induced degradation,
mechanochemical degradation, catalytic degradation and biodegradation) and mechanism followed by these degradations.
We have also discussed the various methods used to study
these degradations and various factors which affect these
degradations.
562
B. Singh, N. Sharma / Polymer Degradation and Stability 93 (2008) 561e584
2. Types of plastics
Plastics can be synthesized via the polymerization (polyaddition or polycondensation) of small molecules and are in general
classified into two groups i.e. thermoplastics and thermoset
plastics [16]. Thermoplastics are linear chain macromolecules
where the atoms and molecules are joined end-to-end into a series of long, sole carbon chains. The bi-functionality necessary
to form a linear macromolecule from vinyl monomers can be
achieved by opening the double bond and reaction proceeds by
a free radical mechanism. Such type of polymerization is known
as addition polymerization, polyethylene and polypropylene are
the examples [17e19]. On the other hand, thermoset plastics are
formed by step-growth polymerization under suitable conditions
allowing bi-functional molecules to condense inter-molecularly
with the liberation of small by-products such as H2O, HCl, etc. at
each reaction step [18]. In this class, the monomers undergo
some chemical changes (condensation) on heating and convert
themselves into an infusible mass irreversibly [20,21].
3. Types of plastic degradation
Changes in polymer properties due to chemical, physical or
biological reactions resulting in bond scissions and subsequent
chemical transformations are categorized as polymer degradation [22]. Degradation reflects changes in material properties
such as mechanical, optical or electrical characteristics in crazing, cracking, erosion, discoloration and phase separation [23].
Depending upon the nature of the causing agents, polymer degradations have been classified as photo-oxidative degradation, thermal degradation, ozone-induced degradation, mechanochemical
degradation, catalytic degradation and biodegradation [24].
3.1. Photo-oxidative degradation
Photo-oxidative degradation is the process of decomposition
of the material by the action of light, which is considered as one
of the primary sources of damage exerted upon polymeric substrates at ambient conditions. Most of the synthetic polymers
are susceptible to degradation initiated by UV and visible light.
Normally the near-UV radiations (290e400 nm) in the sunlight
determine the lifetime of polymeric materials in outdoor
applications [25e27]. Polymer degradation occurs mainly in
the ether parts of the soft-segments, where photo-irradiation
generates ester, aldehyde, formate and propyl end groups
[28]. UV radiations have sufficient energy to cleave CeC
bond [29]. The most damaging UV wavelength for a specific
plastic depends on the bonds present and the maximum degradation therefore occurs at different wavelengths for different
types of plastics, e.g. it is around 300 nm for polyethylene
(PE) and around 370 nm for polypropylene (PP). Photodegradation changes the physical and optical properties of the plastic.
The most damaging effects are the visual effect (yellowing), the
loss of mechanical properties of the polymers, the changes in
molecular weight and the molecular weight distribution for
the same [30e40]. PE and PP films when exposed to solar
UV radiation readily lose their extensibility, mechanical
integrity and strength along with decrease in their average molecular weight [33e37]. Mechanical integrity of polystyrene
(PS) is diminished through extensive chain scission during photodegradation [38,39]. Another important study carried out on
light-induced damage to PS plastics compounded with flame
retardant additives has reduced the risk of fire when the plastics
have been used as building construction materials [40].
At any given temperature and moisture content, the rate of
weathering increases with an increase in UV flux. Tensile
stressing of stabilized types of PP in thermo-oxidative and
photo-oxidative environment has accelerated embrittlement of
the polymers [31]. In one study, tensile stress has been applied
at constant load (in the range of 0e6.86 MN/m2) to observe the
behavior of stabilized and unstabilized types of isotactic PP in
the course of thermo-oxidative aging at 80e130 C, photooxidative aging at 45 C and relative humidity of 65%. From
kinetic evaluation of the temperature-dependence of weight
changes of unstabilized PP during thermo-oxidative aging, it
has been found that the weight losses of unstressed and
tension-stressed specimens have obeyed the kinetic equations
for a reaction of the first order [32]. Along with stress, introduction of carbonyl group on polymeric backbone has also accelerated photochemical degradation. PS undergoes photochemical
ring-opening reactions, which leads to backbone cleavage by
subsequent Norrish Type II reactivity [41,42].
3.1.1. Mechanism of photodegradation
The mechanisms of the degradation and oxidation reactions
are determined by the extraneous groups and/or impurities in
the polymer, which absorb light quanta and form excited states.
Initially short-lived singlet state is transformed to long-lived
triplet state [43]. Excited triplet states may cleave the polymer
chains and form radical pairs (Norrish Type I reaction) or form
pairs of saturated and unsaturated chain ends by hydrogen
transfer (Norrish Type II reaction) [44]. The polymer radicals
thus formed may add molecular oxygen (in triplet ground state)
to peroxy radicals, which abstract hydrogen and form hydroperoxide groups, which absorb UV light or become excited by
energy transfer, the weak OeO bonds break and pairs of alkoxy
and hydroxyl radicals are formed which may react in various
ways, e.g. by hydrogen abstraction, chain scission, rearrangement, etc. and accelerate photodegradation [45]. Double bonds
may add excited oxygen molecules in singlet state. In this
reaction, the double bond is shifted to an adjacent CeC bond
and a hydroperoxide group is formed. Some synthetic polymers, e.g. aromatic polyesters and polyamides, have inherent
absorption of UV light, causing excitation, radical formation,
oxygen addition, splitting off small molecules, chain scission,
etc. Some of these polymers are auto-stabilized towards photodegradation by formation of an oxidized surface layer with high
absorption of near UV and visible light of short wavelengths,
preventing further penetration of light into deeper layers [46].
In photo-oxidative degradation, mechanism involves autooxidation cycle comprising various steps shown in Scheme 1.
3.1.1.1. Initiation. The absorption of UV light that has sufficient energy to break the chemical bonds in the main polymer
Initiation
.
R
.
*
Z
.
R
RiOOH
Z
Z*
RiOO
RiOO
Ri
O2
hv
Initiator
563
+ Z
Scheme 3.
Propagation
ROO
O2
ROO
ROOH
Termination
.
.
R
ROO
ROOR
Scheme 1.
chain leads to the initiation of mechanism responsible for

polymer degradation. It involves a radical chain mechanism
for the formation of initial radical. Different initiation steps
under varied conditions have been undertaken in different
polymers.
3.1.1.1.1. Direct UV initiated photolysis of CeC and CeH
bond. Bond dissociation energy of CeC bond (375 kJ/mol)
and CeH bond (420 kJ/mol) is equivalent to UV radiation
of 320 nm and 290 nm. Thus, direct photolysis of CeC and
CeH bond is possible and the radical formed in these
reactions become a source of initiation radicals as shown in
Scheme 2 [47].
3.1.1.1.2. Photosensitized cleavage. Photosensitizers are
highly photosensitive, readily get excited on exposure to light
and are generally employed to bring about effective homolysis
of the polymeric chains, which otherwise do not undergo
sufficient photo-excitation at the frequency of light available
to the system (Scheme 3) [45,48].
3.1.1.1.3. Catalyst residues as source of generation of
radicals. Some metal salts and oxidation products of such
residues when added to the polymers act as catalysts to generate
initiation radicals (Scheme 4) [48]. Many commercial polymers
contain metallic compounds as impurities or deliberately incorporated additives. The bulk of the latter types are pigments,
whereas the former include polymerization catalyst residues
or debris from processing equipment. Polymerization catalysts
such as transition metals (Ti) may remain in polyolefins at
uv
.H
H
C
2e100 ppm, depending on workup and catalyst efficiency.

These residues have been implicated in both photo- and thermal
stability problems. For example, TiO2 is a well-known photosensitizer for polyamide and polyolefin degradation and
absorbs at 480 nm. Photosensitization involves the formation
of highly reactive species including atomic oxygen, OH,
OOH and O2. The primary process involves the promotion of
the Ti electron to the conduction band of the semiconductor
to form an electron-positive hole pair. The relative proportions
of the reactive species depend on the presence of water. No
TiO2 sensitization will be observed unless both oxygen and
water are present [29].
3.1.1.1.4. Incorporation of carbonyl groups. Carbonyl
groups formed by mild oxidation of polymer during synthesis
or processing act as chromophores and become source of the
initiation radicals. Carbonyl chromophore absorbs near-UV
radiations and subsequently forms radicals following Norrish
Type I, Norrish Type II and H-atom abstraction processes
(Scheme 5) [49].
3.1.1.1.5. Introduction of peroxides or site of unsaturation.
The peroxides or C]C sites become source of initiation
radicals as shown in Scheme 6 [45]. The near UV component
of sunlight (280e390 nm) is energetic enough to cleave CeC
bond and Ceheteroatom bonds provided that light of the appropriate wavelength is absorbed. Chain oxidation occurs in
most of the polymers because of the labile OeO bond present
in the macrohydroperoxide eCeOOH, the macroalkoxyl and
hydroxyl radicals thus formed may abstract hydrogen from
the surrounding polymer matrix to generate alcohol, water
and new macroalkyl radicals which can then take part in
many cycles of the chain-initiation reactions. In the case of
unsaturated polymers, light generated singlet oxygen 1O2
reacts with an unsaturated site by way of an ene reaction
and starts chain oxidation (Scheme 6) [29].
3.1.1.1.6. Reactions of singlet and triplet stage. Reaction of
a ketone in a triplet-excited state with ground state oxygen is
another potential initiation reaction (Scheme 7). In these reactions, UV light is absorbed by carbonyl or other chromophoric
groups and the energy of the excited groups is transferred to
oxygen molecules. The resulting excited oxygen species react
uv
C
Scheme 2.
hv
TiCl4
hv
TiO2
TiO2
TiCl3
O2 , RH
Scheme 4.
Cl
TiO2
HOO
564
O
O
H2
C
CH 2
C
C
H2
CH 2
CH 2
C
C
H2
H2
C
Type I
CH 2
C
H2
H2
C
Type II
C
C
H2
CH 2
CH 2
CH 2
CH 3
OH
RH
Scheme 5.
with vinyl or other unsaturated groups forming hydroperoxide

which then initiate free radical reaction mechanism [43].
3.1.1.2. Propagation reaction. The propagating reactions of
auto-oxidation cycle are common to all carbon backbone
polymers. These reactions lead to generation of hydroperoxide
species (Scheme 8) and are not directly led to backbone cleavage but are the key intermediates to further reactions as shown
in Scheme 1. Hydroperoxide species generated in propagating
step lead to backbone degradation through cleavage of
hydroperoxide OeO bond followed by b-scission (Scheme 9).
Polymer backbone cleavage occurs through Norrish Type I
and II reactions of chromophores (carbonyl) following bscission route, which is a prevailing route for photo-oxidative
degradation. In semi-crystalline polymers, this scission occurs
in the amorphous domains. The scission process generates two
chain ends that are free to restructure, and can often lead to
increase in crystallinity as oxidative degradation proceeds
[29,41]. PS undergoes photo-oxidative bulk degradation via
a free radical mechanism (Schemes 10 and 11). Oxidative
process involves two steps: (1) formation of hydroperoxide
and (2) decomposition of these hydroperoxides. Such oxidative reactions are initiated when hydrogen is removed through
a photoreaction. The free radical formed on polystyrene reacts
with oxygen to form peroxy radical, which can abstract a proton from some other labile positions, thereby forming
hydroperoxides and a new radical site. The newly formed hydroperoxide group is subjected to decomposition and resulting
ultimately in chain cleavage into ketones and olefins [46].
Macroalkyl radicals may combine to give a crosslinked,

branched or disproportionated product. Peroxyl radicals eventually terminate by reaction with other radicals to give dialkyl
peroxides, carbonyl species or alcohols [29,30].
3.1.2. Methods for photodegradation
3.1.2.1. Natural weathering method. Outdoor exposure can be
performed on samples mounted on testing racks, oriented under standard conditions to expose the material to the full
radiation spectrum besides the temperature and humidity of
that location [23]. In order to observe the aging of the material,
it is characterized with respect to mechanical properties (elongation at break, tensile properties or impact strength) and visible characteristics, such as crack formation, chalking, and
changes in color [5]. The alterations in the polymeric materials
on exposure can be characterized with FTIR spectroscopy and
ultra violet/visible (UV/vis) spectroscopy [50,51].
3.1.2.2. Artificial weathering method/laboratory test. Pure
laboratory testing involves using environmental chambers
and artificial light sources to approximately replicate outdoor
conditions but with a greatly reduced test time under highly
controlled conditions. Laboratory testing can quickly assess
the relative stability of plastics but has the major disadvantage
that the quicker the test lower is the correlation to real behavior in the field [52]. Lundin et al. [53] have studied accelerated
weathering of fiber-filled PE composites.
3.2. Thermal degradation
3.1.1.3. Termination reactions. The termination of photodegradation is achieved by mopping up the free radicals to
create inert products. This occurs naturally by combining
free radicals or assisted by using stabilizers in the plastic.
O
OH
Under normal conditions, photochemical and thermal

degradations are similar and are classified as oxidative degradation. The main difference between the two is the sequence
O
C
OH
O
C
H
CH
CH2 CH2
O2
HC
Scheme 6.
OH
CH CH CH 2
Radical formation
via above eq.

3
O2
hv
O2
RCH
O2
hydroxyacids, aldehyde acids, etc. are also identified in small

quantities [65].
O
1
565
RCH2CH
CH2
RCH
CHCH2OOH
Radical Reactions
CHCH2OOH
Scheme 7.
of initiation steps leading to auto-oxidation cycle. Other

difference includes that thermal reactions occur throughout
the bulk of the polymer sample, whereas photochemical
reactions occur only on the surface [41]. Thermal degradation
of polymers occurs through random and chain degradation
(depolymerization reaction) initiated by thermal and UV light
[54]. The depolymerization reaction in thermal degradation
need not be initiated at terminal end of the macromolecule,
instead, imperfections in the chain structure (initiator fragment
or a peroxide or ether link) form a weak link from where
depolymerization starts. A large number of addition polymers
depolymerize at elevated temperature [55], for example,
polymethylmethacrylate (PMMA) has been converted almost
quantitatively back to the monomer and PE has been decomposed into longer olefinic fragments and actually producing
little monomer. Thermal degradation above 200 C leads to
chain scission and largely depends on impurities like unsaturation sites, head-to-head units, etc. [56]. Polyolefins are known
to be sensitive to thermal oxidation, due to the impurities
generated during their manufacture at high temperatures
[57]. Drago et al. [58] have studied thermally stimulated
oxidative degradation of high impact PS with nitric acid.
Mechanism of oxidation and nitration depends upon temperature and leads to the molecular and chemical heterogeneity
and also lowering in mechanical properties of the polymer.
PS thermally gets degraded into organic compounds such as
phenol, quinine, naphthalene and diphenylamine at the experimental temperature of 350e450 C [59e62]. Complex
reactions occurring in thermal degradation of polymers depend
on various factors like heating rate, pressure, reaction medium,
and reactor geometry. Polymers have high viscosity, which
complicates the process by impeding heat and mass transfer
[63,64]. Thermo-oxidative degradation of polyesters yields
a variety of products such as formaldehyde, acetaldehyde,
formic acid, acetic acid, CO2 and H2O. In addition to these
compounds, various other compounds like hydroxyaldehydes,
CH3
C
3.2.1. Mechanism of thermal degradation

The mechanism of thermal degradation of polymers is an
interesting subject, not only from fundamentals of polymer reactions point of view but also in understanding heat-resisting
characteristics, polymer processes such as extrusion or injection molding, and the effective utilization of plastic wastes.
The thermal degradation of polymers consists of two distinct
reactions, which occur simultaneously in the reactor. One is
a random scission of links, causing a molecular weight reduction of the raw polymer, and the other is a chain-end scission
of CeC bonds, generating volatile products. The chain-end
scission takes place at the gaseliquid interface in the working
reactor [66]. The type and composition of the pyrolysis
products give useful information about mechanism of thermal
degradation [67,68]. Thermal dehydrochlorination of poly(vinyl chloride) (PVC) begins with internal allylic chloride and
tertiary chloride structural defects formed during polymerization. During thermal degradation, ordinary monomer units are
converted into internal allylic chloride defects by a mechanism
that may include the abstraction of hydrogen by triplet cation
diradicals derived from polyene intermediates. Cyclization
reactions seem likely to contribute to the termination of
polyene growth [69]. Thermal degradation of the polymers
follows either chain end degradation (also known as unzipping
route) (Eqs. (1 and 2)) or random degradation route (Eq. (3))
as shown below:

Mn /Mn1
M

/Mn2
M
Mn1
Mn /Mx My
The chain end degradation starts from the end of the chain and
successively releases the monomer units. This type of degradation route is also known as depolymerization reaction, which
involves successive release of monomer units from the chain
ends. Such reactions are the opposite of the propagation step
in addition polymerization and occur through free radical
mechanism. In this type of degradation, molecular weight of
the polymer decreases slowly and large quantity of the
monomer is liberated simultaneously. For example, poly amethylestyrene synthesized through anionic mechanism upon
heating from 70 C to 60 C undergoes degradation from
the chain end carrying the active carbanion in such a manner
C
CH2
CH3
CH3
CH3
CH2
C(O)OCH3
C(O)OCH3
Scheme 8.
566
O
OH H
hv
OH
Scheme 9.
that at 60 C, the entire polymer gets converted into the

monomer [20]. The major degradation products for fluorinated
polyacrylate are monomer, dimer, saturated diester, trimer, and
corresponding methacrylate along with remarkable amounts of
alcohol [67,68]. In general, chain-end degradation occurs
when the backbone bonds are weaker than the bonds of the
side groups and only with polymer molecules, carrying active
chain ends with a free radical, cation, anion, etc. In general, asubstituted vinyl polymers degrade mostly through the process
of depolymerization. PMMA, poly a-methyl styrene, PP,
polytetrafluoroethylene and poly a-methyl acrylonitrile, on
pyrolysis, have been converted to their respective monomers
almost quantitatively. The unzipping process involves a free
radical path [70e72].
Random degradation occurs at any random point along the
polymer chain. This is reverse to polycondensation process
where the polymer degrades to lower molecular weight fragments but practically no monomer is liberated. For random
degradation to occur, the polymer chain does not require
necessarily to carry any active site [20]. Polyesters undergo
hydrolytic degradation resulting in chain scission. PE also undergoes random degradation through migration of a hydrogen
atom from one carbon to another thus generating two fragments [72]. In general, vinyl polymers such as polystyrene,
poly(acrylonitrile), etc. are degraded by the random chain
scission process. The monomer yield from such polymers is
usually low, and the pyrolyzed fragments are ordinarily larger
than corresponding monomer unit [71]. For example, poly(ethylene terephthalate) follows random thermal degradation route
(Scheme 12); the initial step resulting in scissions leads to
carboxyl and vinyl groups [46]. In general, initiation reaction
occurs by random chain scission or chain end initiation. This
step is followed by de-propagation step forming monomer.
+H
H
CH2
CH2
H
CH2
CH2
hv
O
O
H
C
CH2
CH2
O2
Scheme 10.
H
CH2
CH2
Termination takes place through radical coupling and radical

disproportionation (Scheme 13) [73].
Rodryguez-Vazquez et al. [74] while investigating thermal
degradation of LDPE at 400 C observed that intra-molecular
hydrogen abstraction followed by b-scission is a major
degradation route [15]. Radical termination occurred by combination and disproportionation. PS on thermal degradation
yields 42% monomer as volatile product in dispropagation
reaction (Scheme 14) [18]. Thermal degradation of saturated
polymers such as PS follows a hydroperoxide mechanism
[20]. Thermal oxidation of PP at 120e280 C results in
multiple oxidative chain scission and around 40 volatile compounds are identified by GC/MS technique. Backbone scission
route shown by polyolefins is b-scission of the macroalkoxyl
radicals [29].
3.2.2. Methods for thermal degradation
3.2.2.1. Batch reactor method. The thermal degradation of
waste plastic can be carried out in a glass reactor under
atmospheric pressure with definite weight of sample that is
loaded into bottom of the reactor for thermal degradation.
The purging of the reactor with nitrogen gas at a flow rate
of 10 mL/min at 120 C for 60 min is required to remove
the physically adsorbed water from the plastic sample. After
stopping the nitrogen flow, the reactor temperature is increased
to the degradation temperature (430 C) at a heating rate of
3 C min1 and the waste plastic bed temperature is taken as
the temperature of the degradation. The gaseous products
can be condensed (using a cold-water condenser) to liquid
products and trapped in a measuring jar. The quantitative analysis of the liquid products can be performed by using a gas
chromatograph equipped with a flame ionization detector,
atomic emission detector, an ion chromatograph and mass
selective detector. The solid residue can be identified by
FTIR spectrometer [75].
3.2.2.2. Thermogravimetric analysis. Thermogravimetric
analysis (TGA) can be used for the investigation of oxidative
and thermal degradation of the polymers [76]. The rate of degradation in TGA (da/dt) is defined as the rate of change of the
degree of conversion. The degree of degradation or conversion
can be calculated in terms of mass as shown below:
a W0 W=W0 WN
where W0, W and WN are the initial weight, the actual weight
at each point of the curve, and the final weight measured at the
end of the degradation process, respectively [77]. In TGA
+ OH
H
CH2
567
CH2
CH2
CH2
H2C
CH2
Scheme 11.
instrument, sample is submitted to constant heating rate from

room temperature to 600 C under the nitrogen flow. The
reaction products can be analyzed by gas chromatography
[78e84].
3.2.2.3. Pyrolysis GC/MS method. In this method, volatile
pyrolysis products at different temperatures can be identified
with the help of GC/MS [73]. The pyrolyser is based on a technique in which a small deactivated stainless steel cup loaded
with a sample is dropped into a small sized vertical furnace
by gravitational free-fall with push button mechanism. This

system is designed to provide precise temperature control.
Once the system starts, the sample controller stops sampling
after 0.5 min and the pyrolysis gases from the samples directly
pass into GC/MS analysis system [85].
3.3. Ozone-induced degradation
Atmospheric ozone usually causes the degradation of
polymers under conditions that may be considered as normal;
O
C
CH2
CH2
O
C
CH O
OH + CH2
O
C
OH
+ CH
CH
O
C
CH
CH2
O HC
CH2
+ CO2
O
C
OH
CH2
CH
CH3
CH
O
C
CH
+ CH3 C
Scheme 12.
CH3 + CO
568
Initiation
(R)n
(R)n
(R)n-1
Propagation
(R)n
+ R
Termination
R
+ RO
ROR
+ ROO
ROOR
RO
+ RO
ROOR
RO
+ ROO
ROR
ROO
+ ROO
+ O2
ROOR
+ O2
Scheme 13.
when other oxidative aging processes are very slow and the
polymer retains its properties for a rather longer time
[86e88]. The presence of ozone in the air, even in very small
concentrations, markedly accelerates the aging of polymeric
materials [89]. This process in saturated polymers is accompanied by the intensive formation of oxygen-containing
compounds, by a change in the molecular weight and by
impairment of the mechanical and electrical properties of
the specimens [5]. Exposure of polymers to ozone results in
the rapid and consistent formation of a variety of carbonyl
and unsaturated carbonyl products based on aliphatic esters,
ketones, and lactones as well as aromatic carbonyl associated
with the styrene phase. This follows by a more gradual formation of ether, hydroxyl and terminal vinyl groups with time
and concentration [90]. These reactions of ozone with
polymers occur with main chains containing C]C bonds,
aromatic rings or saturated hydrocarbon links. The reaction
proceeds through unstable intermediates such as the bipolar
ion or peroxy radicals, which can isomerize or degrade, cause
decomposition of macromolecules [91]. Under the influence of
external load, the rate of ozone oxidation and hydrogen atom
abstraction from the polymer chain increases. This is due to

the change in hybridization of the reaction centre from the
state sp3 to the state sp2 [92e95]. In poly(vinyl alcohol)
(PVAL) the chain scission is based on the ozone oxidation
of the alcoholic groups of PVAL with formation of ketone
groups which in turn are the source of a ketoeenol tautomerism which leads to random chain scission by further ozone
attack. PVAL forms a strong hydrogen-bond complex with
ozone for which the interaction energy is of the order of
47.3 kJ/mol and it is slowly degraded by ozone. The analysis
with FTIR spectra indicates that the final product is a PVAL
oligomer with numerous ketone groups along the main
oligomer backbone and with carboxylic end groups [96].
PS is slowly attacked by ozone as compared to unsaturated
polymers. The relative yield of products identified from this
attack is 35% peroxide, 18% ketone and 47% acid. These
products are similar to those expected from free radical chain
oxidation processes. Ozen et al. [97] have studied the effect on
structural and mechanical properties of packaging films by
ozone exposure and have reported that ozone treatment has affected the PE and polyamide films differently. It is responsible
for formation of oxygen-containing functional groups,
degradation of polymeric chains in PE films and increase in
the eCeNe stretching in polyamide. Clough and Gillen
[98] have observed that the ozone generated by the action of
the ionizing radiation in the air present in the atmosphere
surrounding the samples affect the surface of the polymer
[98]. This observation has been made during gamma-radiation
degradation studies of poly(butadiene-co-styrene) [SBR
rubber] and poly(butadiene-co-acrylonitrile) [Buna-n rubber]
in the presence of air. The oxides of nitrogen, sulfur, and
ozone promote UV-induced oxidative damage of common
plastics, particularly in rubber products [11]. Ozone mainly
affects vulcanized rubbers with unsaturation in the main polymer chain and causes cracking in stretched form in rubber
[17]. Exposure to ozone gas causes change in the mechanical
properties of linear LDPE, oriented PP and biaxially oriented
nylon [99]. Gatenholm et al. [100] have studied the effect of
ozone on the microporous structure of PP. Exposure of isotactic PP to ozone results in surface oxidation which further
increases when a microporous membrane has large surface
area [100].
OOH
CH2 CH
CH2 CH
CH2
CH
CH2
CH
CH2 CH
O2200 C
CH2 CH
CH2
CH2 CH
O
CH2 CH
O
CH2 CH
CH2 CH
CH2
CH2 CH
CH2
CH2
Scheme 14.
CHO
CH2
CH
CH2
HO
CH2 CH
3.3.1. Mechanism of ozone-induced degradation

Ozone normally attacks the unsaturation in unsaturated
polymers and this reaction generally occurs in three principal
steps (Schemes 15 and 16). The first step is a cycloaddition of
ozone to the olefin double bond to form ozoneeolefin adduct
referred to as the primary ozonide which is an unstable
species because it contains two very weak OeO bonds. The
second step in the ozonolysis mechanism is the decomposition
of the primary ozonide to carbonyl compounds and a carbonyl
oxide. The carbonyl oxide is considered to be the key intermediate in the C]C bond ozonolysis mechanism. The third step
in the ozonolysis mechanism is the fate of the carbonyl oxide,
which depends on its source, as well as on its environment.
The carbonyl oxide flips over with the nucleophilic oxyanion
attacking the carbon atom of the carbonyl group [101e104].
The ozonization of conjugated polymers (polyacetylene,
polyphenylacetylene) has showed that the conjugated double
bonds of the polyenes react more slowly with ozone than the
isolated double bonds of the diene rubbers [86e88].
This is due to the reason that the rubber molecule breaks into
radicals, and oxygen as radical scavenger readily reacts with
them, leading to permanent chain breakage, whereas nitrogen
is not a radical scavenger and thereby led to radical recombination [18]. The degradation of high molecular weight PS
occurs under the turbulent flow and the drag reduction efficiency decreases with time due to the mechanical degradation
of the polymer molecules [106,107]. In one study mechanical
degradation of polymers during their mechanical mixing of binary mixtures of cis-polyisoprene with stereo-regular poly(butadiene), and with butadieneemethylstyrene or butyl rubbers
leads to considerable changes in the molecular characteristics
of the components [108]. The mechano-degradation of polymers in melts occurs in terms of free radical processes. In
this processing, there is a decrease in the width of the molecular weight distribution function, a quantitative correlation
between ruptures and crosslinks on the one hand and change
in double bond concentration on the other and an increase in
long-chain branching due to the reaction of chain-side radicals
[109e111]. The mechanochemical degradation of PMMA in
the presence of nitroxides acting as chain terminating agents
creates macro-radicals, which are used in free radical polymerization reactions [112]. Mechanochemical dechlorination of
PVC with various oxide powders, i.e. CaO, Fe2O3, SiO2 and
Al2O3, in air reduces the molecular weight of PVC [113].
3.3.2. Method for ozone degradation

3.3.2.1. Ozone exposure test. Sample of the polymer can be
exposed in a HAMPDEN (model 2000-AM ozone cabinet)
at 40 C in atmospheres of 50, 100 and 200 ppht (parts per
hundred thousand) of ozone in air. Before exposure to ozone
atmosphere the specimens are subjected to a deformation of
20% under stress and maintained this way for 72 h in the
absence of light. Those samples that in general terms exhibit
any crack formation, minimal or even superficial, during the
ozone attack assay are termed non-ozone resistant samples
and those which do not exhibit any crack formation are termed
ozone resistant samples. The samples can be analyzed with
FTIR to study the formation of new functional moieties in the
sample [90].
3.4.1. Mechanism of mechanochemical degradation

When excessive stress is applied, the molecular chain
breaks and produces a pair of free radicals, which can take
part in subsequent reactions. In the presence of oxygen, the
first reaction results in the formation of peroxy radicals. The
most important application of this type of reaction is the mastication of natural rubber to make it processable. Mechanically
generated radicals are believed to result from the cleavage of
the main backbone segments of polymer chains in the stressed
amorphous regions connecting crystallites [114]. High intensity ultrasounds can induce mechanochemical degradation in
polymeric materials. Polymer in such a case is subjected to
very high vibrations, which are only mechanical forces. As
ultrasonic waves pass through the solution, the localized shear
gradient produces tear off molecules leading to chain scission
and decrease in molecular weight [20]. The relevant mechanism for the observed phenomena has been explained by the
interaction of ultrasound and component molecules. In a liquid,
upon irradiation of ultrasound, molecules have been exposed
to alternate compression and expansion modes, by which bubbles are formed and eventually collapsed. On the molecular
level, this implies a rapid motion of solvent molecules to
3.4. Mechanochemical degradation

Mechanochemical degradation of polymers involves the
degradation of polymer under mechanical stress and by strong
ultrasonic irradiations [105]. Breakdown of molecular chains
under shear or mechanical force is often aided by a chemical
reaction and is known as mechanochemical degradation. For
example, mastication of rubber can lead to chain breakage
and development of plasticity under shear. In the atmosphere
of nitrogen at ordinary temperature mastication of rubber
does not change the plasticity and molecular weight appreciably, but in the presence of oxygen, degradation occurs rapidly.
O3
C
OO+ O
O
C
569
O-
Scheme 15.
O
C
+C
OC
570
CH3
CH2
CH3
CH2
CH3
CH
CH2
CH2
O3
CH2
CH
O
CH2
CH
CH2
CH3
CH
CH2
H2O Hydrolysis
CH 3
CH2
CH
CH3
CH2
CH2
CH
CH2
H2O2
Scheme 16.
which the macromolecules embedded in the solvent cannot be

adjusted. Thus, friction is generated which causes strain and
eventually bond rupture in the macromolecules [115]. In the
absence of oxygen, various carbon radicals have been generated from polyolefins, PMMA, etc. At low temperature, the
radicals from main-chain scission have been detected; upon
warming, these attack the polymer matrix and lead to further
scission reactions through radical-rearrangement reactions
(Scheme 17) [29].
In the presence of oxygen above 113 C, quantitative
conversion of macroalkyl to peroxy radicals occurs. Thus
mechanical work generates the primary radicals and the oxidation can form the usual oxidation products. In the melt, it is
difficult to separate the degradative effect of heat and mechanical work [29]. Gel permeation chromatographic (GPC)
studies of the degradation of LDPE and HDPE under high
shear conditions have indicated that most of the changes in
molecular weight distribution and long-chain branching have
occurred from thermal or thermo-oxidative degradation. On
the other hand, the orientation of solid PP under high shear
conditions (high draw rates and relatively low temperatures)

has produced oxidation products directly as a result of the
shear process [116]. Ultrasound is responsible for the breakage
of macromolecular CeC bonds and termination reactions of
mechano-radicals occur as disproportionation and combination reactions which suppress in the presence of radical
scavengers [112].
3.4.2. Method for mechanochemical degradation

In mechanochemical degradation polymer is subjected to
mechanical stresses through high speed stirring or milling.
Agitation, grinding or extrusions are the methods of mechanochemical degradation. The basic phenomenon involved is
subjecting the polymer to very powerful shearing force that
will break the molecule. Mechanical degradation reduces the
average molecular weight of the polymer [117]. Electronspin spectroscopy has graphically demonstrated that stretching, grinding, milling and shearing process has produced
free radicals because of main chain fracture [29].
CH 3
CH 3
mill
CH2
OCH 3
CH 3
CH3
PMMA attack
C
OCH 3
77C
C
O
CH2
CH 2
CH2
CH 3
CH 3
OCH 3
OCH3
CH 3
CH 3
CH 3
-scission
CH2
H
OCH 3
C
O
CH2
CH2
OCH 3
OCH 3
Scheme 17.
OCH 3
OCH 3
3.5. Catalytic degradation

Catalytic transformation of waste polymers into hydrocarbons with higher commercial value is a field of great interest.
Polyolefins are thermally or catalytically degraded into gases
and oils. The interest has been directed towards polyolefins
(PE, PP, PS) which constitute an important part of industrial
and domestic waste. The addition of a catalyst not only
improves the quality of products obtained from pyrolysis of
plastic wastes, lower the temperature of decomposition, but
also enable a given selectivity to a certain product to be
achieved. Solid acid catalysts, such as zeolites, favor hydrogen
transfer reactions due to the presence of many acid sites. The
access of molecules to catalyst reactive sites is limited to
the pore size as well as the growth of end products inside
the pores. Therefore, zeolite catalysts may produce molecular
sieving and shape selectivity [118]. Garforth et al. [119] have
investigated catalytic degradation of polyolefins using TGA as
a potential method for screening catalysts and have found that
the presence of catalyst led to the decrease in the apparent
activation energy. For polymer degradation, different types
of catalysts have been reported in the literature which
include PteCo and PteMo supported over SiO2 [120], zeolite
catalysts and non-zeolite catalysts [121], transition metal
catalysts (Cr, Ni, Mo, Co, Fe) on the support (Al2O3, SiO2)
[122], zeolite [123] and zirconium hydride [124].
3.5.1. Mechanism of catalytic degradation
Sekine and Fujimoto [125] have proposed a free radical
mechanism for the catalytic degradation of PP using Fe/
activated carbon catalyst. The various steps in catalytic degradation are shown in Scheme 18. In initiation step, random
breakage of the CeC bond of the main chain occurs with
Initiation
R1
R2
R1
R2
Propagation
R3
R1
R2
C2
R2
R4
R4
Termination
R5
R6
R5
R7
R8
R7
R6
R8
Catalysts
Fe/ Activated charcoal +H2
R9
R9
R10
R10
R11
R11
Scheme 18.
571
heat to produce hydrocarbon radicals. In propagation, the hydrocarbon radical decomposes to produce lower hydrocarbons
such as propylene, followed by b-scission and abstraction of H
radicals from other hydrocarbons to produce a new hydrocarbon radical. Disproportionation or recombination of two radicals is termination reaction. During catalytic degradation with
Fe/activated charcoal (AC) in a H2 atmosphere, hydrogenation
of hydrocarbon radical (olefin) and the abstraction of the H
radical from hydrocarbon or hydrocarbon radical generate
radicals, enhancing degradation rate. In a reaction temperature
lower than 400 C or a reaction time shorter than 1.0 h, many
macromolecular hydrocarbon radicals exist in the reactor, and
recombination occurs readily because these radicals cannot
move fast. However, with Fe/AC in a H2 atmosphere, these
radicals are hydrogenated and therefore recombination may
be suppressed. Consequently, it seems as if the decomposition
of the solid product is promoted, including low polymers
whose molecular diameter is larger than the pore size of the
catalysts. Wall et al. [126] have studied the catalytic degradation of waste plastics and have found that when these polymers
have been heated above 380 C, they undergo depolymerization and degradation by a free radical chain reaction.
3.5.2. Methods for catalytic degradation
3.5.2.1. Batch autoclave method. The thermal and catalytic
degradation of plastic sample can be performed in a batch
autoclave. Definite weight of polymer sample and definite
weight of catalyst are charged into the reactor. After purging
the inner air of the reactor with a reaction gas (H2 or Ar),
more reaction gas is added to 4.0 MPa and heated to the reaction temperature while being agitated at 70 times/min. At the
end of the reaction, the heaters are removed and the reactor is
cooled to ambient temperature in air. The gaseous products
can be analyzed through gas chromatography and liquid products can be separated from solid products by suction filtration
with an aspirator. The boiling-point distribution of the liquid
products is obtained by simulated distillation. The residue
from the suction filtration is then washed with toluene, dried
in air, and weighed as a solid product. This solid product
includes both unreacted product (low polymer) and excessive
cracked product (coke precursor or coke). However, the latter
is produced on the surface of the catalyst and could not be
separated from the former when the reaction temperature is
low or the reaction time is short [127]. PP has been pyrolyzed
over various catalysts using a laboratory fluidized-bed reactor
operating isothermally at ambient pressure using zeolite
catalysts [121]. Solid phase microextraction has also been
used to analyze the products evolved in the thermal degradation of PP [59].
3.6. Biodegradation
H
H
Biodegradation is a biochemical transformation of compounds in mineralization by microorganisms. Mineralization

of organic compounds yields carbon dioxide and water under
aerobic conditions, and methane and carbon dioxide under
572
anaerobic conditions. Abiotic hydrolysis, photo-oxidation and

physical disintegration of polymers may enhance biodegradation of polymers by increasing their surface area for microbial
colonization or by reducing molecular weight [128]. Biodegradation has been defined in various ways by different investigators. It is defined as change in surface properties or loss of
mechanical strength [129], assimilation by microorganisms
[130], degradation by enzymes [131], backbone chain
breakage and subsequent reduction in the average molecular
weight of the polymers [132,133]. Degradation can occur by
any of the above mechanisms alone or in combination with
one another. According to ASTM standard D-5488-94d
biodegradation is defined as process which is capable of
decomposition of materials into carbon dioxide, methane,
water, inorganic compounds, or biomass in which the predominant mechanism is the enzymatic action of microorganisms,
that can be measured by standard tests, in a specified period
of time, reflecting available disposal conditions. Biodegradability is also defined as the propensity of a material to get
breakdown into its constituent molecules by natural processes
(often microbial digestion). The metabolites released by
degradation are also expected to be non-toxic to the environment and redistributed through the carbon, nitrogen and sulfur
cycles. Biological degradation is chemical in nature but the
source of the attacking chemicals is from microorganisms.
These chemicals are of catalytic nature e.g. enzymes. The
susceptibility of the polymers to microbial attack generally
depends on enzyme availability, availability of a site in the
polymers for enzyme attack, enzyme specificity for that
polymer and the presence of coenzyme if required [134].
Biodegradation can occur at different structural levels, i.e.
molecular, macromolecular, microscopic and macroscopic depending upon the mechanism [135]. It has been argued that the
phenomenon of degradation in vivo might not be equated with
the term biodegradation, since biodegradation implies the
active participation of biological entities such as enzymes or
organisms in the degradation process [136]. It is, however,
difficult to identify the involvement and the role of biological
species in in vivo degradation. Both hydrolytic and enzymatic
processes may contribute to the degradation to different extent
during the different stages of the degradation process. Degradation may begin by hydrolysis, but as the polymer breaks and
surface area and accessibility increases, enzymatic degradation may dominate. Thereby biodegradation includes all types
of degradation occurring in vivo whether the degradation is
due to hydrolysis or metabolic processes. Therefore, biodegradation is also defined as the conversion of materials into less
complex intermediates or end products by solubilization,
simple hydrolysis or the action of biologically formed entities
such as enzymes and other products of the organism. Polymer
molecules may, but not necessarily breakdown to produce
fragments in this process, but the integrity of the material
decreases in this type of process [137].
3.6.1. Mechanism of biodegradation
Biodegradation of polymers occurs through four different
mechanisms: solubilization, charge formation followed by
dissolution, hydrolysis and enzyme-catalyzed degradation

[138,139].
3.6.1.1. Solubilization. The hydration of polymers depends on
the hydrophilicity of the polymer. The hydration results from
disruption of secondary and tertiary structure stabilized by
van der Waals forces and hydrogen bonds. During and after
hydration, the polymer chains may become water soluble
and/or the polymer backbone may be cleaved by chemical
or enzyme-catalyzed hydrolysis to result in the loss of polymer
strength [140]. For crosslinked polymers, the polymer strength
may be reduced by cleavage of either of the polymer
backbone, crosslinker or pendent chains. In non-swellable
polymer systems, the reduction in the polymer molecular
weight may lead to the loss of coherence between polymer
chains [141]. Barkay et al. [142] have studied biodegradation
of polyaromatic hydrocarbons using a bio-surfactant which
have enhanced the solubility and biodegradation of hydrophobic hydrocarbons.
3.6.1.2. Ionization. Some polymers are initially water
insoluble but become solubilized by ionization or protonation
of a pendent group. Polyacids become soluble at high pH and
become hydrophilic [143]. Cellulose acetate phthalate
becomes water soluble at a pH > 6, while poly(vinyl acetate
phthalate) and hydroxyl propyl methyl cellulose phthalate
are ionized at a lower pH [144].
3.6.1.3. Hydrolysis. Water insoluble polymers containing
pendent anhydride or ester groups may be solubilized if anhydride or esters hydrolyze to form ionized acids on the polymer
chain. For example, poly(methacrylate) and poly(methyl
methacrylate) which are esters derived from poly(acrylic
acid) and poly(methacrylic acid), respectively, are not water
soluble but become water soluble upon hydrolysis of the
pendent esters, and subsequent ionization of the carboxylic
group [145]. Chain length of ester group and degree of substitution exert the effect on anaerobic biodegradation [146].
Hydrolysis of the polymer backbone is most desirable since
it produces low molecular weight by-products. Natural polymers undergo degradation by hydrolysis whereas synthetic
polymers are water insoluble. They tend to be more crystalline
and this property account for their water-insolubility [147].
For hydrolysis to occur, the polymer has to contain hydrolytically unstable bonds, which should be reasonably hydrophilic
for the access of water. Biodegradable polymers include esters
and ester derivative polymers [148e151]. Polyesters are
degraded mainly by simple hydrolysis. The first stage of the
degradation process involves non-enzymatic, random hydrolytic ester cleavage and its duration is determined by the initial
molecular weight of the polymer as well as its chemical
structure [152,153].
3.6.1.4. Enzyme-catalyzed hydrolysis. Enzymes function as
catalysts for a specific reaction or a series of reactions, such
as oxidation, reduction, hydrolysis, esterification, synthesis
and molecular inter-conversions [154]. Hydrophobic polymers
with no hydrolyzable bonds such as PE, PP, PMMA and PS are

expected to be the most stable [21]. Wool et al. [155] have
studied degradation of PEestarch composites enzyme diffusion, which results in the back-diffusion of small molecules
to the surface for further assimilation by microorganisms
[155]. The enzymatic degradation of certain natural polymers
follows the unzipping or chain-end degradation mechanism.
For example, b-amylase degrades starch to maltose, beginning
with the chain ends [20]. Chattopadhyay and Madras [156]
have studied the lipase catalyzed degradation of poly(vinylacetate) (PVAc) and observed that the ester bonds in the side
chains are broken specifically to yield oligomers with acid
and alcohol groups. There are many side branches in PVAc because chain transfer to the methyl groups in the acetate groups
of PVAc takes place frequently during the polymerization of
vinyl acetate. Enzymatic degradation of poly(3-caprolactone)
has been successfully carried out in supercritical carbon
dioxide (scCO2). Candida antarctica lipase has smoothly
catalyzed the hydrolytic degradation in scCO2 to give
oligo(3-caprolactone) [157].
3.6.1.5. Microbial degradations. Microbial degradation
results from the action of naturally occurring microorganisms
such as bacteria, fungi, algae, etc. The product so formed is
not visible and need not be screened after composting [158].
The production of biodegradable plastics that get decomposed
completely in nature have received remarkable attention globally as they are totally ecofriendly and helpful in waste landfill
management. Addition of natural polymers to thermoplastics
having long-term potential is one of the approaches to enhance
biodegradability [159]. To prepare biodegradable plastic
involves adding special additives to the synthetic polyolefins,
which make it susceptible to microbial degradation, and these
additives also disconnect the continuity of CeC chain of
polyolefin. Few additives having hydrophilic groups make
plastic hydrophilic and susceptible for photo- and chemical
degradation. Modification of backbone through copolymerization and through anchoring monosaccharide with polyolefin or
blending with nutrients and biodegradable fillers makes the
plastic degradable [160e163]. These micronutrients help the
growth of specific microorganisms thus inducing biodegradability and through incorporation of polar functional groups
which can serve as point of microbial attack [164,165].
Generally, polyolefin constitutes a non-biodegradable class
of plastic and in order to make it degradable, research has been
carried out on biological degradation of PE. Biodegradation of
PE occurs through two mechanisms: hydro-biodegradation
and oxo-biodegradation [166]. These two mechanisms work
successfully on the modified PE (by additive starch) making
the material hydrophilic. The starch present in the composite
has been catalyzed by amylase enzyme. Chiellini et al. [167]
have reported the oxidative degradation of PE film containing
pro-oxidant additives. Some strains of the bacteria such as
Pseudomonas aeruginosa, Pseudomonas fluorescens and fungi
Penicillium simplicissimum have been reported as the most
commonly used organisms for the plastic degradation
[168,169]. Sielicki et al. [170] have studied the microbial
573
degradation of [b-14C] PS and 1,3-diphenylbutane in soil

and liquid enrichment cultures, and it has been determined
by 14CO2 evolution from applied [14C] PS. Metabolism of
1,3-diphenylbutane appeared to involve the attack by a monooxygenease to form 2-phenyl-4-hydroxyphenylbutane
followed by a further oxidation and subsequent fission of the
benzene ring to yield 4-phenylvaleric acid and an unidentified
5-carbon fragment via the classic meta-fission pathway. The
basal salt medium (water containing trace elements) triggered
auto-oxidation of the pro-oxidant through decomposition of
trace hydroperoxides, which in synergistic combination with
biodegradation of the starch, eventually initiated autooxidation of the LDPE matrix [171]. Hadad et al. [172] have
isolated thermophilic bacterium strain of Brevibacillus borstelensis for the degradation of LDPE and have studied the effect
of UV photo-oxidation on the extent of biodegradation of PE
which has enhanced the extent of biodegradation. Gilmore
et al. [173] have carried out degradation study of six types
of plastics and plastic blends in municipal wastewater. Samples consist of 6% starch in PP, 12% starch in linear LDPE,
30% polycaprolactone in LDPE, and poly(-hydroxybutyrateco-hydroxyvalerate) (PHB/V), a microbially produced
polyester in activated sludge of 5 months and found no sign
of degradation of blended samples except PHB/V, which has
showed a considerable loss of mass and a significant loss of
tensile strength in municipal wastewater. Biodegradable polymers can be synthesized by the modification of natural polymers by blending and fermentation [174e180]. NakajimaKambe et al. [181] have isolated, purified and characterized
polyurethane (PU) degrading enzymes from Comamonas
acidovorans [182,183]. These enzymes are cell-associated
membrane bound PU-esterase and an extracellular PU-esterase. The membrane bound enzyme provides cell mediated
access to the hydrophobic polyurethane and extracellular
enzyme stick on surface.
3.6.2. Methods for biodegradation
The most important factor in determination of biodegradation is the proper selection of test procedure based on the nature
of plastic and the climatic conditions of the study environment
[184]. There are wide varieties of methods currently available
for measuring the biodegradability of polymeric materials
[185]. Several test methods to assess the potential biodegradability of plastics have been developed by International
Standard Organization (ISO) [186] and American Society for
Testing and Materials (ASTM) [187]. Biodegradation can be
characterized with loss of weight, change in tensile strength,
change in dimensions, change in chemical and physical properties, carbon dioxide production, bacterial activity in soil and
change in molecular weight distribution [188,189].
3.6.2.1. Soil burial method. Soil burial method is one of the
frequently used methods for the determination of biodegradability of plastic [185,190]. In this method, biodegradation
test is performed under natural conditions or laboratory conditions. Sample with definite weight and dimension is buried in
specific depth in the soil for different time intervals. After
574
a specified time, sample is taken out of soil, thoroughly rinsed

with distilled water following immersion in distilled water and
after that dried at 50 C for 24 h in a vacuum oven. Sample is
allowed to equilibrate to ambient temperature and humidity
for at least 24 h before measurement. In one study starche
plastic films buried in a forest soil have developed rapid
colonization (15 days later) by fungal hyphae and showed
degradation of the starch granules on the films [191].
3.6.2.2. Pure culture method. In pure culture method, specific
bacteria and fungi can be applied for degradation of polymers.
In laboratory conditions, isolated microorganism strain has
been allowed for sufficient growth in different nutrient media
[160,172,188]. In pure culture method, pre-weighed disinfected films are aseptically added to sterilized culture medium
and films in culture medium are incubated with shaking for
24 h before inoculation to ensure asepsis. Culture medium is
inoculated with spores from a specific microorganism and is
incubated with shaking at 125 rpm for 4 weeks at optimal
growth temperature for the selected microorganism. Four
replicates are prepared for each different pretreated film. The
sample is weighed after washing with 70% ethanol and drying
at 45 C until equilibrated. Each of the different films is then
compared with the corresponding uncultured material
[192,193]. The presence of microbes can be confirmed by
using a microscope [194].
3.6.2.3. Compost method. In this method, the definite weight
of the dry plastic is subjected to the mixture of definite amount
of mature compost and then incubated at 58 C with maintained moisture content at 65%. Biodegradation is measured
based on the amount of material carbon converted to gaseous
carbon dioxide [195]. Nature of compost affects the degree of
degradation [196e198]. Unexpected trends have been reported
for the biodegradation of plastics in the compost stored at
20 C, 4 C and 20 C for different periods. Viable cells in
the compost stored at 20 C is expected to be fewer than
those in the compost stored at 4 C and 20 C, because
microbes may be under stress or even be killed due to the formation of ice crystals at the subzero temperature. Mesophilic
bacteria and mesophilic actinomycetes [the mesophilic microorganism live at medium temperatures (20e45 C)] are fewer
in number in the compost stored at 20 C than in the compost
stored at the other two lower temperatures contrary to
expectation. In contrast, both thermophilic bacteria and thermophilic actinomycetes [thermophilic microorganism thrive
above 45 C and some live at or even above the boiling point
of water] are fewest in the compost stored at 20 C as
expected, indicating that thermophilic microbes are more susceptible to stress in the freezing conditions than the mesophilic
ones. Activity of the extracellular enzymes plausibly excreted
by the microbes in the compost decreased as a result of the
storage [196]. Shape of the plastic sample [185] and additives
in the compost [199] effect the plastic degradation in the
compost.
Vermiculite, a clay mineral, can be activated and used as
a solid matrix in place of mature compost. The composting
test method based on activated vermiculite is a comprehensive

system for the assessment of the environmental impact of
biodegradable plastics. Activated vermiculite affects neither
the biodegradation rate nor the final biodegradation level.
On the other hand, possible metabolic intermediates and polymeric residues left after biodegradation can be recovered more
easily from activated vermiculite than from mature compost,
a very complex organic matter. Therefore, at end of the test
it has been possible to determine the carbon balance that is
by taking into account both the evolved CO2 and a polymeric
residue extracted from vermiculite [200].
3.6.2.4. An aerobic degradation in the presence of sewage
sludge. Because of enriched environment of sewage sludge,
the microbes present are more diverse in composition than
other disposed methods encountered [140]. In laboratory
conditions, samples have been inoculated with sewage
microbes. Gaseous CO2 and CH4 are monitored by headspace
analysis using GC/MS [201].
4. Factors affecting polymer degradation
Degradation is defined as a process which leads to a deterioration of any physical property of a polymer [17]. In general,
the degradation process affects the thermal stability, mechanical properties, crystallinity and lamellar thickness distribution
and begins in the amorphous/crystalline interface [56]. Degradations of plastic affected by various factors are given below:
4.1. Chemical composition
Chemical composition of the polymers plays a very important role in their degradation. Presence of only long carbon
chains in the thermoplastic polyolefins makes these polymers
non-susceptible to degradation by microorganisms. By the
incorporation of the heterogroups such as oxygen in polymer
chain makes polymers labile for thermal degradation and
biodegradation [20]. Presence of heteroatom in the polymer
chain affects the strength of neighboring CeH bonds of the
polymer and promotes carbanion formation in the presence
of bases. Linear saturated polyolefins are resistant to oxidative
degradation. Presence of unsaturation in the polymer chain
makes them susceptible to oxidation, for example natural rubber is more susceptible to degradation than PE [3]. Amorphous
regions in the polymer have been reported to be more labile to
thermal oxidation as compared to crystalline areas because of
their high permeability to molecular oxygen [17]. Oxidation
rates depend on the reactivity of the peroxy radicals formed
and on the dissociation energies of available carbonehydrogen
bonds in the polymer substrate. A polymer with no hydrogen
at all or with unreactive methyl and phenyl groups shows
resistance to oxidation [17].
4.2. Molecular weight
Increase in molecular weight of the plastic decreases the
rate of plastic degradation [202]. It has been reported that
some microorganisms utilize polyolefins with low molecular

weight faster as compared to high molecular weight polyolefins [203,204]. Linear polyolefins with molecular weight lower
than 620 support microbial growth [205]. It is easy to form the
ozone adduct in low molecular weight olefins which rearranges to ozonide and during this operation, if the polymer
chain is under tension during reaction, the broken chain ends
separate out before rearrangement to ozonide occurs [17].
4.3. Hydrophobic character
Petrochemical-based plastic materials are not easily
degraded in the environment because of their hydrophobic
character and three-dimensional structure [203]. Hydrophobicity of PE interferes with the formation of a microbial bio-film,
thus decreases the extent of biodegradation [172].
4.4. Size of the molecules
Size of the molecules in the polymers affects their
mechanical degradation, thermal degradation and biodegradation. These degradations increase as the size of the molecule
decreases [20].
4.5. Introduction of functionality
Introduction of carbonyl groups in polyolefins makes these
polymers susceptible to photodegradation. As the number of
chromophores increases the rate of photodegradation increases
due to the more sites, which are available to absorb more
photons and to initiate the reaction for degradation. The
carbonyl chromophore absorbs near-UV radiation and form
radicals by the Norrish Type I, II and H-abstraction processes
for photochemical degradation. Chromophores other than
carbonyl group pC]O such as metalemetal bond if incorporated in polymer backbone induce photodegradability. In such
a case, metalemetal bond cleaves homolytically on irradiation
[206]. Polyolefins undergo slow sulfonation and oxidative
degradation by reagents based on concentrated sulfuric acid.
In chromic acid, sulfonation results in more rapid oxidative
degradation of PP with a slower attack on PE. Relative rates
of attack on CeH sites are 4600:75:1 for tertiary:secondary:
primary (Scheme 19) [207].
To observe the effect of hydrophilic moieties on the
degradations of the polymers, Singh and Sharma [208] have
carried out biodegradation study of pure PS and grafted PS
CH2
C
H
that is [PS-g-poly(AAc)], [PS-g-starch] and [PS-g-poly(AAc)co-starch] films by soil burial method. It has been observed
that 37% degradation has occurred in PS when modified
with starch after 160 days and no degradation has been seen
in the case of PS grafted with poly(AAc). This is because
starch is a natural hydrophilic polymer and has more susceptibility for bacterial and fungal degradations in soil as ambient
environment available for their growth. This is possible due to
scissoring caused by the microorganism in some chains at the
site of grafting and polymer chains may get breakdown and
decrease the number of carbon atom in the chains [208]. It
has also been observed by Wool and co-workers that the following exposure to soil test conditions, micrographs of thin
films clearly showed the colonization of microorganisms
within channels of the matrix that has been initially occupied
by starch [155]. Apart from weight loss, change in color of the
starch modified PS films has also been observed. FTIR spectra
have shown that with passage of time, the soil microorganisms
have consumed starch portion of the grafted product [208].
4.6. Additives
Non-polymeric impurities (such as residues of polymerization catalysts, transformation products of additives), fillers or
pigments affect the resistance to degradation. Yang et al.
[209] have reported that the thermal stability slightly decreases and the ash content increases when the ligno-cellulosic
filler loading increases in the sample. The dispersion and interfacial adhesion between the ligno-cellulosic filler and thermoplastic polymer are the important factors affecting the thermal
stability of the composite system [209]. Metals act as good
pro-oxidants in polyolefins making polymer susceptible for
thermo-oxidative degradation. For example, manganese (Mn)
is a suitable metal participating in metal combination for
pro-oxidant activity. Upon activation by heat in the presence
of oxygen, pro-oxidants have produced free radicals on the
polyethylene chain which have undergone oxidation and
have changed the physical properties of the polymers [4]. In
addition, the pro-oxidant catalyzes the reaction of chain scission in the polymer, producing low molecular mass oxidation
products, such as eCOOH, eOH, C]O group containing
products [210]. Traces of transition metals have accelerated
thermal oxidative processes of polyolefins by inducing hydroperoxide decomposition [21]. For example, TiO2 delustrant
has made the polyamides susceptible for heat- and lightinduced oxidation [29]. Oxidation of plastic (polyolefin) is
chromic acid
CH2
80-100C
CH2
575
CH2
H2O
CH2
CH2
CH2
CH2
OH
Cr
C
(OH)3
H
Scheme 19.
C
OH
576
influenced by the amount of pro-oxidant additives, chemical

structure, morphology of plastic sample and the surface area
[211]. Chain-breaking (hindered phenol) antioxidants inhibit
the oxo-biodegradation of the polyolefins under thermooxidative conditions during service [212]. Photo-stabilizers
decrease the chances of photodegradation of plastic materials.
Effective light absorbers such as benzotriazoles, benzophenones, and phenyl esters, as well as hindered amine light stabilizers are presently used in plastic formulations intended for
outdoor use (usually at a 0.05e2.0 wt.% level) [213]. Many
transition metal ions are effective accelerators for peroxidation
and hence for the biodegradation of the hydrocarbon polymers. Since the sequence of reactions shown in Scheme 20
leads to the rapid buildup of hydroperoxides in the polymer,
peroxidation cannot be controlled by chain-breaking antioxidants such as the hindered phenols since the latter are rapidly
destroyed by hydroxyl and peroxyl radicals (Scheme 20) [212].
As the antioxidants and the stabilizers make polyolefins resistant to degradation, the use of pro-oxidant additives can
therefore make them oxo-biodegradable by making polymer
hydrophilic and also catalyze breakdown of high molecular
weight polyolefin to lower molecular weight product [213].
Susceptibility towards biodegradation of polyolefins enhances
by blending with starch or other polyesters and biodegradation
depends upon the type of polymer and the blend composition
[214]. Along with this filler, pro-oxidants accelerate the
process of biodegradation. Averous and co-workers [215]
have studied the effect of ligno-cellulosic fractions from wheat
straw as natural fillers in composites of a polyolefin (a copolymer of PE and PP) and a biodegradable polyester [poly(butylenes adipate-co-terephthalate)] [216,217]. It has been
observed from the study that amount of natural composites affects the degradation of the composites. In another case grafting of the wheat starch had affected the tensile strength of the
composites [218].
4.7. Chemical bonding
Linkage affects the degree of degradation in plastic. In
thermoplastic, head-to-head addition of monomer units and
tail-to-tail addition of monomer units during addition polymerization create weak points which make the plastic susceptible
for degradation. Head-to-head linkage in PMMA enhances
Iron Catalysed Peroxidation

of Hydrocarbon Polymers
Fe2+
POOH
Fe3+
+ PO + OH
Fe3+
+ POOH
Fe2+
+ POO
POO
PO
+
+
PH
PH
+ P
POOH
POH
Scheme 20.
thermal degradation of the polymer [219]. Branching in polymer chain increases thermal degradation [3,20]. Crosslinking
decreases the rate of photodegradation by locking the polymer
structure and preventing lamellar unfolding because these
actions prevent the separation of photo-produced radicals and
favor the radicaleradical combination [41].
4.8. Methods of synthesis
Methods of synthesis show the noteworthy effect on the
stability of the polymers [220]. For example, anionic polymerized PS showed more photo-stability than free radically
formed polymer due to the presence of peroxide residue in
the latter, which is labile for photodegradation [221]. PP
synthesized by bulk polymerization and by ZieglereNatta
catalyst is more susceptible towards photodegradation as
compared to copolymerized PP [222].
4.9. Effect of substituents
Substituents effect the degradation processes in many
polymers containing labile a-hydrogen in the repeating units
and modify the reaction course profoundly even if the mainchain scission reactions prevail. For ethylene and 1-substituted
ethylene, chain-end scission reactions are predominant,
producing either little or up to 50% monomer as volatiles. In
1,1-Disubstituted ethylene, repeated units apparently favored
100% monomer yield, whereas chlorine as substituents did not
favor chain end degradation route [18]. Thermal stability of
a polymer decreases as the number of substituents on polymer
backbone increases. Phenyl group in styrene unit of PS makes
CeC backbone labile for thermal degradation. Based on the
same fact PE shows more thermal stability as compared to
PP and polyisobutylene. The effect of substituent groups on
the stability of the backbone CeC bond is apparent from the
comparison of the bond dissociation energies for CeC bond
(in kcal/mol), CH3eCH3 88, CH3CH2CH3 85, (CH3)3
CCH3 80 and C6H5CH2CH3 70. In PVC, the presence of
allylic positioned chlorine atom favored dehydrochlorination
of the polymeric chain as double bond activated the release
of chlorine radical as shown in Scheme 21.
The elimination of the first molecule of HCl and consequent formation of a double bond on PVC chain subsequently
activates the neighboring chlorine atom which has assumed
the nature of an allylic chlorine, causing elimination of
another HCl molecule, with the process continuing to repeat
CH2
CHCl
CH2
CH2
CHCl
CH2
CH2
CHCl
CH
CH
CHCl
CHCl
+ H+
CH
CH
CHCl
+ Cl
O 2 / PH
POOH
O2 / PH
POOH
CH
Scheme 21.
CH
CHCl
+ HCl
577
temperature and high humidity enhance hydrolytic degradation of the polymers. Temperature of the material and the
presence of moisture show a considerable synergistic effect
on the photodegradation of the polymeric materials [11].
Moisture promotes the light-induced degradation due to the
fact that under high humidity soluble photo-stabilizers might
leach out of the plastic matrix, reducing the effectiveness of
the light stabilizer and leading to degradation. The presence
of high humidity, particularly at the higher temperatures tends
to increase the photo-damage in polymers such as thermoplastic polyester elastomers [39]. Even a small increase in solar
UV level dramatically accelerates the deterioration processes
in plastics at high temperature [224]. It is the synergistic effect
of high temperature and solar UV radiation that is responsible
for the rapid degradation of the polyethylene films under these
conditions [224]. Weathering is a degradation process and as
such is temperature dependent, i.e. it will occur more rapidly
at higher temperatures. The general rule is that for every 10 C
increase in temperature the reaction rate will double. Tropical
areas therefore suffer not only from an increase in UV
exposure but also faster reaction rates because of the increased
temperatures. Humidity also affects the degradation processes;
most weathering processes are considerably slower in hot dry
climates than in hot wet climates [30].
Oxygen affects the mechanochemical degradation of rubber
at ambient temperature. For instance, degradation has been
found to be almost absent when rubber is masticated in an atmosphere of nitrogen. However, when the process has been
repeated in the presence of a small amount of oxygen or air,
degradation has been observed very quick and significant.
This is because during degradation free radicals are produced
at the end of the scissor fragments of the chain. In nitrogen,
however, the primary radicals formed under shear immediately
recombine to give no effective chain breakage. Oxygen due to
its radical scavenger nature readily reacts with the free radicals
formed at the fragmented ends of the polymer molecule and
renders the chain break permanent [65]. Thermal dehydrochlorination of PVC in the presence of oxygen occurs faster than
the inert atmosphere [213]. During processing, carbon radicals
are formed from chain scission because of strong shear forces.
These radicals then react with oxygen to form peroxy radicals,
and finally, hydroperoxides [225].
itself finally producing a conjugated polyene structure by an

autocatalytic effect [18,29]. Contrary to this, all substituents
not always reduce thermal stability of the polymeric systems.
For example, the presence of electronegative groups as
fluorine in teflon increases the thermal stability of the polymer
due to high dissociation energy (108 kcal/mol) of CeF bond
[3,20]. Aromatic groups in a polymeric backbone increase
the thermal stability.
4.10. Effect of stress
Stress has significant effect on polymer degradation.
Tensile stress increases the rate of photodegradation whereas
compressive stress retards the photodegradation rate. Stress
changes the quantum yields of the reactions that lead to
bond photolysis, the efficiency of radical recombination following homolysis, and changes the rate of the radical trapping
reaction (Scheme 22) [41,220].
The polymer morphology is one of the key factors to
interpret the effect of stress on degradation rates. Higher stress
causes significant morphological changes, including the
straightening of the polymer chains in the amorphous regions.
When stretched bonds are cleaved by light, the probability of
radical recombination decreases as compared to non-stressed
polymer because entropic relaxation of the chain drives the
radicals apart and prevents their efficient recombination because of their increased separation [41]. Stress induces a chain
orientation that is more favorable for degradation, apparently
due to chain conformation that becomes more susceptible to
hydrogen abstraction [223]. Stress also effects the thermooxidative degradation [32]. Degradation of stressed specimens
occurred with considerably higher rate as compared to the
unstressed state and is marked by a decrease in apparent
activation energy as well as by an increased rate of crack
development. The cracks developed in the direction perpendicular to the tensile stress and have the shape of hollow funnels
widening outward. An accelerated embrittlement of the polymer occurred due to the tensile stressing of stabilized types of
PP in thermo-oxidative and photo-oxidative environments,
manifested particularly by a marked decrease of elongation
at break [32].
4.11. Environmental conditions
5. Plastic materials: future perspectives,

challenges and other issues
Biodegradation of polymer depends upon environmental

conditions such as moisture, temperature, oxygen, and suitable
population of microorganisms [4]. In warm climates when the
relative humidity exceeds above 70%, the rate of polymer
degradation by the microorganisms increases [17]. High
Various types of plastics may be of use in packages,

biomedical products, electronic components, non-returnable
goods, construction materials, etc. However, an important
homolysis
M
k recombination
Scheme 22.
X = trap
2
578
aspect of these materials for a sustainable society is to predict

their lifespan. How a material affects its environment is always
important [226,227]. Sustainability, industrial ecology, ecoefficiency, and green chemistry are the new principles that
are guiding the development of the next generation of plastic
products and processes. Ecofriendly, biodegradable polymers
are the major breakthrough in plastic and polymer industries.
Bio-based economy is challenging to agriculture, forestry,
academic, society, and industry to develop and commercialize
agricultural based new materials. A grand challenge facing
government, industry, and academia in the relationship of
our technological society to the environment is reinventing
the use of materials. To address this challenge, collaboration
from an interdisciplinary group of stakeholders will be necessary. An emerging approach to this grand challenge seeks to
embed the diverse set of environmental perspectives and interests in the everyday practice of the people most responsible for
using and creating new materials chemists [212,228e230].
5.1. Sustainable polymers
Polymer material has brought not only tremendous wealth
for human being, but also unfortunately the serious environmental problems. We must solve these problems through
sustainable development which can be carried out in two
ways: (1) recycling the waste plastic and (2) developing environmental friendly polymer materials [231]. The term
sustainable is often assumed to be synonymous with renewable. Sustainable polymers also have to be industrially
acceptable and biodegradable. The ideal biopolymer is of
renewable biological origin and biodegradable at the end of
its life. Biopolymers include polysaccharides such as cellulose
and starch, carbohydrate polymers produced by bacteria and
fungi, protein polymer derived from soy protein and animal
protein based biopolymers such as wool, silk, gelatin, and
collagen. On the other hand, polylactic acid (PLA), PVA,
and poly(butylenes succinate) (PBS) are examples of polymers
that have synthetic origin but are also biodegradable. The
extremely high price of petroleum and the growing environmental problems are some of the driving forces in looking
towards renewable source based plastics to meet the
challenges [212,232,233].
5.2. Plastic recycling
Recycling is an expanding area of the chemical industry in
general, plastic recycling and waste management in particular
being closely examined in academia, commercial organizations and governmental institutions. Finding suitable solutions
can lead to the recycling of potentially hazardous materials on
the one hand and production of acceptable commercial products with little or no outlay in raw materials on the other.
The recycling of post-consumer plastics is of increasing
importance as land filling and incineration becomes more
expensive and environmentally risky. In addition to reducing
the amount of plastic waste requiring disposal, recycling plastic can have several other advantages such as conservation of
non-renewable fossil fuels, reducing energy consumption,

reducing carbon dioxide emissions, and many others [234].
A fairly new utilization of plastic waste is conversion of
post-consumer plastic waste into oil by two methods that is direct liquefaction and pyrolysis followed by hydroprocessing of
the pyrolysis liquids [235]. Post-consumer waste plastics can
be used in cement-based composite. Also, mechanochemical
treatment can be used to develop composite plastic materials
from post-consumer plastic waste [236]. Recycling plastic
usually involves processes such as melting, shredding or
granulation of waste plastics. An option with great potential
is feedstock recycling, which includes a variety of processes
like pyrolysis, catalytic conversion, depolymerization and gasification, designed to transform plastic waste into hydrocarbon
products for use in the preparation of recycled polymers,
refined chemicals or fuels. Despite not being used extensively,
feedstock recycling is attracting increasing scientific and
commercial attention as an alternative with the potential to
absorb very large amounts of plastic wastes. The application
of catalysts is giving feedstock recycling a new impulse that
is expected to put this technology at the forefront of plastic
management [237e239].
5.3. Biodegradable plastics: as an alternative
to the existing petrochemical-based polymers
Advanced technology in petrochemical polymers has
brought many benefits to mankind. Synthetic- and petroleum-based polymers are extremely stable and are commonly
used in agriculture, food packaging, fast-food restaurants, and
on military and commercial ships. However, their attractive
stability is counterbalanced by two problems: polymers
contribute to the demand for expensive imported oil and their
great resistance to biodegradation. Petroleum reserves will be
exhausted in less than a century. It is therefore necessary to
find another raw material for the fuel area, but also for plastic
industry. The shortage and high cost of fossil resources require
that alternative resources and processes must take over in the
near future. Biodegradable polymers are now being considered
as an alternative to the existing petrochemical-based polymers
[175,240].
New applications based on synthetic polyester-based biodegradable polymers have been commercialized, especially in
the packaging industry, paper coating and garbage bags. These
polyesters are made using modified polyethylene polymerization processes and as blends. A second class of biodegradable
polyesters includes polylactic acid (PLA) and thermoplastic
starch-based polymers. These polyesters environmentally
degrade into water and carbon dioxide when exposed to microorganisms and water in composting piles. A third type of
biodegradable plastics includes aliphatic co-polyesters such
as polyhydroxyalkanoates or PHAs produced by bacteria.
Potato, corn and wheat starch are renewable raw materials
for starch-based plastics [241]. Fully biodegradable synthetic
polymers are commercially available since 1990. Among these
biopolymers, PLA was extensively studied in medical
implants, suture, and drug delivery systems since 1980s due
to its biodegradability. PLA has been attractive for disposable

and biodegradable plastic substitutes due to its better mechanical properties. However, PLA is still more expensive than
conventional plastics. Also, the degradation rate is still slow
as compared to the waste accumulation rate. The newly
developed plastics from this research could provide possible
solutions to the problem. Also, the plastics from this proposed
research could be used as biomedical and pesticide slowreleasing carrying matrix. The industrial-scale production of
PLA from lactic acid generated by fermentation now provides
a renewable resources-based polyester as a commodity plastic
for the first time [242e246].
Starch may offer a substitute for petroleum-based plastics.
Starch is a renewable, degradable carbohydrate biopolymer
that can be purified from various sources by environmentally
sound processes. It is a relatively low-cost polymer available
from agricultural surplus with potential thermoplasticity.
However, it needs water for processing and the water content
of the product influences its stability. Another widely available
carbohydrate material is cellulose, which is biodegradable, but
cannot be thermally processed, because it decomposes before
melting. Chemical modifications can improve thermoplasticity
but decreases biodegradability. While numerous attempts have
been made using starch and a few other carbohydrates as
components in various formulations for biodegradable plastics,
generally the major technical problem is the need to strike
a balance between stability and moldability. Water content
and molecular weight are two keys to this balance. The final
products should be biodegradable after fulfilling the requirements of their use, however, they must be stable during the application. The stability requires a low water content and
resistance to water. On the other hand, most agricultural
polymers use water as a plasticizer during molding. High
molecular weight provides better stability and physical
strength but decreases the moldability [2,240,241,247,248].
Synthetic hydrophobic biodegradable polymers are available
since 1990. However, these synthetic polymers are usually
more expensive than petroleum polymers and also have
a slow degradability. Blending starch with these degradable
synthetic polymers has recently become the focus of
researchers [2,56]. This will increase the cost and decrease
the mechanical strength properties of the blends. Potato,
corn and wheat starch are renewable raw materials for
starch-based plastics [161e163,249].
5.4. Biodegradable plastics: limitations and
obstacles for use
While a number of alternatives have emerged, one of the
main limitations for synthetic biodegradable polymers such
as polyesters and starch-based blends is higher cost compared
to synthetic polymers. Another serious obstacle is a lack of
suitable infrastructure for sorting, recycling and composting
solid wastes. Development of process technology for completely biodegradable polymers is generally costly. Either
the cost of monomers is prohibitive for its commercialization
or the polymerization technology is not yet competitive with
579
the conventional processes. Further research and development

efforts are necessary to make the biodegradable polymers cost
effective. Another drawback in the development of completely
biodegradable polymers is the limited availability of monomers. Processability, performance limitations, cost, and rate
of degradation present formidable obstacles to widespread
adoption. Bio-based polymers such as cellulose and starch
are not so conducive to mechanical recycling, and they also
have a lower calorific value on incineration [228,176,211,
250e252].
5.5. Future directions
Any decision to use a degradable polymer should be based
on a good understanding of where and how the product will
degrade, recognize and minimize life cycle environmental
impacts (not just end of life), and deliver real commercial
benefit [228,252].
6. Conclusion
It is concluded from the foregone discussion that
understanding about the mechanism can go a long way in
helping the researchers and the technologists to induce the
different types of degradation in the plastic. These degradations can further be enhanced by the addition of the additives
in the plastic and by understanding the various factors responsible for these degradations. It is also concluded from this
discussion that plastic degradation could be enhanced by its
modification with natural polymers and this acquaintance
can further be exploited for environmental waste management.
Acknowledgement
This article is prepared from the literature collected for the
project sponsored by the Ministry of Environment and Forest.
The authors wish to thank the Ministry of Environment and
Forest, Government of India, for providing the financial
assistance for the project.
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Polymer Degradation and Stability 93 (2008) 561e584

Mechanistic implications of plastic degradation

B. Singh, N. Sharma / Polymer Degradation and Stability 93 (2008) 561e584

B. Singh, N. Sharma / Polymer Degradation and Stability 93 (2008) 561e584

chain leads to the initiation of mechanism responsible for

2e100 ppm, depending on workup and catalyst efficiency.

B. Singh, N. Sharma / Polymer Degradation and Stability 93 (2008) 561e584

with vinyl or other unsaturated groups forming hydroperoxide

Macroalkyl radicals may combine to give a crosslinked,

Under normal conditions, photochemical and thermal

B. Singh, N. Sharma / Polymer Degradation and Stability 93 (2008) 561e584

hydroxyacids, aldehyde acids, etc. are also identified in small

of initiation steps leading to auto-oxidation cycle. Other

3.2.1. Mechanism of thermal degradation

B. Singh, N. Sharma / Polymer Degradation and Stability 93 (2008) 561e584

that at 60 C, the entire polymer gets converted into the

Termination takes place through radical coupling and radical

B. Singh, N. Sharma / Polymer Degradation and Stability 93 (2008) 561e584

instrument, sample is submitted to constant heating rate from

by gravitational free-fall with push button mechanism. This

B. Singh, N. Sharma / Polymer Degradation and Stability 93 (2008) 561e584

abstraction from the polymer chain increases. This is due to

B. Singh, N. Sharma / Polymer Degradation and Stability 93 (2008) 561e584

3.3.1. Mechanism of ozone-induced degradation

3.3.2. Method for ozone degradation

3.4.1. Mechanism of mechanochemical degradation

3.4. Mechanochemical degradation

B. Singh, N. Sharma / Polymer Degradation and Stability 93 (2008) 561e584

which the macromolecules embedded in the solvent cannot be

conditions (high draw rates and relatively low temperatures)

3.4.2. Method for mechanochemical degradation

B. Singh, N. Sharma / Polymer Degradation and Stability 93 (2008) 561e584

3.5. Catalytic degradation

Biodegradation is a biochemical transformation of compounds in mineralization by microorganisms. Mineralization

B. Singh, N. Sharma / Polymer Degradation and Stability 93 (2008) 561e584

anaerobic conditions. Abiotic hydrolysis, photo-oxidation and

dissolution, hydrolysis and enzyme-catalyzed degradation

B. Singh, N. Sharma / Polymer Degradation and Stability 93 (2008) 561e584

with no hydrolyzable bonds such as PE, PP, PMMA and PS are

degradation of [b-14C] PS and 1,3-diphenylbutane in soil

B. Singh, N. Sharma / Polymer Degradation and Stability 93 (2008) 561e584

a specified time, sample is taken out of soil, thoroughly rinsed

test method based on activated vermiculite is a comprehensive

B. Singh, N. Sharma / Polymer Degradation and Stability 93 (2008) 561e584

some microorganisms utilize polyolefins with low molecular

B. Singh, N. Sharma / Polymer Degradation and Stability 93 (2008) 561e584

influenced by the amount of pro-oxidant additives, chemical

Iron Catalysed Peroxidation

B. Singh, N. Sharma / Polymer Degradation and Stability 93 (2008) 561e584

itself finally producing a conjugated polyene structure by an

5. Plastic materials: future perspectives,

Biodegradation of polymer depends upon environmental

Various types of plastics may be of use in packages,

B. Singh, N. Sharma / Polymer Degradation and Stability 93 (2008) 561e584

aspect of these materials for a sustainable society is to predict

non-renewable fossil fuels, reducing energy consumption,

B. Singh, N. Sharma / Polymer Degradation and Stability 93 (2008) 561e584

to its biodegradability. PLA has been attractive for disposable

the conventional processes. Further research and development

B. Singh, N. Sharma / Polymer Degradation and Stability 93 (2008) 561e584

[6] Karaduman A. Pyrolysis of polystyrene plastic wastes with some