Polymer Degradation and Stability 91 (2006) 2282e2291

www.elsevier.com/locate/polydegstab

The effect of UV-irradiation on composting of polyethylene

modified by cellulose
Halina Kaczmarek*, Dagmara O1dak
Nicolaus Copernicus University, Faculty of Chemistry, Gagarin 7, 87-100 Torun, Poland
Received 15 February 2006; received in revised form 20 April 2006; accepted 23 April 2006
Available online 12 June 2006

Abstract

LDPE and its blend with cellulose, obtained by extrusion, were UV-irradiated with different doses or biodegraded in soil up to 1 year. Simul-
taneously, the same samples were 1 year biodegraded after 20 h UV pre-irradiation in the same conditions. The course of photo- and biodegra-
dation was monitored by estimation of average molecular weights and polydispersity, gel amount, changes of PE crystallinity and mechanical
properties. Moreover, the biodegradation degree was calculated on the basis of carbon dioxide evolved and surface morphological changes
were observed by SEM. It was found that biodegradation of PE cellulose is hampered by intermolecular crosslinking of both components.
Although, the rate of decomposition of PE cellulose blends is low it is enough for disintegration of such materials in the natural environment.
2006 Elsevier Ltd. All rights reserved.

Keywords: PE; PE cellulose compositions; Photodegradation; Biodegradation

1. Introduction factors influencing the polymer reactivity was found. For

Many ideas have been proposed for controlling plastics life-
time and acceleration of their decomposition for the purpose
of waste reduction [1e10]. The blending of stable synthetic
polymers with biopolymers, and the chemical or physical
modification of polymeric composites are examples of solu-
tions used for inducing degradability.
There are a numerous publications devoted to biodegrada-
tion of PE starch blends [11e20], however, not so many works
concern another potentially degradable composition: PE with
cellulose. Cellulose is a most abundant polysaccharide. It is
a component of wood or natural vegetable fibres (cotton,
flax, hemp, jute, ramie, sisal, etc).
It has been suggested that preliminary UV modification of
such polyolefin/natural polymer blends can lead to enhance-
ment of their biodegradability. Synergetic effect of some
* Corresponding author.
E-mail address: halina@chem.uni.torun.pl (H. Kaczmarek).
example, UV-irradiation or heat treatment seems to be a simple
method leading to the formation of functional groups in hydro-
phobic polymer chains making them sensitive to further
microbial attack [21e23].
However, there are still a lot of controversial communica-
tions on the behavior of degradable composites during storage
and the action of environmental factors during waste disposal.
For example, the observed trends in changes of crystallinity
degree in polymers during photo- and biodegradation are con-
tradictory [21,24]. It was found that photodegradation of PE/
starch leads to increase of crystallinity but biodegradation
causes the drop of order in the same sample. In the case of
PP/starch blends the opposite situation occurred e an increase
of crystallinity was observed during biodegradation, contrary
to photodegradation.
Recently, the theoretical consideration and modeling of
decomposition were explored [25e28]. Such works are very
useful and allow us to predict lifetime of polymeric compos-
ites and final effect of biodegradation but, in our opinion, all
theoretical models should be verified experimentally.

0141-3910/$ - see front matter 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.polymdegradstab.2006.04.024
 H. Kaczmarek, D. O1dak / Polymer Degradation and Stability 91 (2006) 2282e2291
The aim of this work is to check the susceptibility of PE/
cellulose blends (not containing any specially introduced
pro-degradant or pro-oxidants) to microorganism action in
the natural environment. The course of polymer biodegrada-
tion during soil burial testing was monitored using comple-
mentary experimental techniques (GPC, estimation of gel
amount, DSC, measurements of CO2 evolved, tensile tests
and SEM). For inducing oxidative degradation, the samples
were submitted to short-wavelength ultraviolet irradiation be-
fore placing in soil.
The conception of UV modification of PE/cellulose blends
for altering their biodegradability was used in this work. Our
previous results obtained by spectrophotometric methods
(FTIR-ATR and Raman) indicate that biodegradation process,
although accelerated, is not very efficient in case of PE sam-
ples containing 5e30% cellulose [29]. Probably, the prepara-
tion method and thermal history of the specimen also have
great influence on the degradation. The present article is a con-
tinuation of the mentioned work.
2. Experimental part
2.1. Materials
The following materials, commercially available, were
used:

low density polyethylene (LDPE) supplied by Petrochemia
P1ock, Poland;

cellulose powder (SigmaeAldrich);

aminosilane (SigmaeAldrich) e H2Ne(CH2)3Si(OCH3)3
as compatibiliser.
2.2. Sample preparation
PE blends containing 2% compatibiliser and 5e30% cellu-
lose were obtained by extrusion using a single screw Plasticor-
der PLV-151 (Brabender) with a sheet die at 170  C.
Non-transparent tapes with thickness of 0.5e0.6 mm were
obtained. Dumbbell specimens (according to tensile test stan-
dards) were cut from the tapes.
2.3. Photodegradation
All specimens were UV-irradiated (two-sided) under the
same conditions (room temperature, air atmosphere) using
a low-pressure mercury vapor lamp TUV 30 W (Philips,
Netherlands), emitting l 253.7 nm radiation. Incident light
intensity, measured by radiometer IL 1400A (International
Light, USA), was 3.5 mW/cm2. Time of irradiation was 20,
40, 50, 60, 80 and 100 h.
2.4. Biodegradation
Biodegradation experiment was carried out as a soil burial
test under laboratory conditions. The sample was placed in
2283
forest soil. Soil humidity and pH were checked systematically
and kept constant. Besides virgin blends, samples previously
UV-irradiated (20 h) were simultaneously biodegraded under
the same conditions. The chemical and microbiological soil
analyses were done according to prescription [30].
Time of soil burial test was 2, 4, 6, and 12 months. In some
cases the experiment was prolonged to 18 months. After each
biodegradation period, the samples were taken from the soil,
carefully washed with distilled water, dried in a vacuum
oven and analyzed.
The biodegradation degree was evaluated by separate test on
the basis of conversion of organic carbon in the sample to car-
bon dioxide [31e33]. Flasks of 2 L volume, filled by wet soil
(inoculum) and the samples were joined to a closed line, where
CO2-free air was pumped through a pressure controller.
For air purification from CO2, it flowed through flasks contain-
ing NaOH and Ba(OH)2 solutions. Air flow was constant. To
avoid excessive water evaporation, the air was humidified by bub-
bling through water. Two control bottles, containing only soil and
soil with Hg2Cl2 (for sterilization) were placed in parallel.
CO2 produced during biodegradation was trapped in
Ba(OH)2 solution, where BaCO3 was precipitated. The solu-
tion before and after CO2 absorption (everyday) was titrated
by HCl (c 0.05 mol/dm3) with phenolphthalein.
Biodegradation degree (B%) was calculated on the basis of
CO2 (mCO2) evolved during composting:
mCO2 sample  mCO2 soil
B  100% 1
ThCO2
where ThCO2 is the theoretical CO2 amount calculated from
the equation:
44
ThCO2 Mt Ci  g 2
12
where Mt e sample mass in reactor; 44 and 12 e molar mass
of CO2 and C, respectively.
2.5. Analysis of degraded samples
Number and weight average molecular weights (M n ; M w )
of PE were determined by Gel Permeation Chromatography
using a Waters 150-C chromatograph with differential refrac-
tometer detector, at a flow rate of 0.8 ml/min through Mixed-A
(2000e40 000 000) and Mixed-B (500e10 000 000) columns
with 1,2,4-trichlorobenzene as eluent at 142  C. Eluent con-
tained Santanox-R (0.25 g/dm3) as stabilizer. Twenty one PE
standards with 1320e18 000 000 molecular weight range
were used for calibration. Each dissolved sample (250 ml)
was injected twice.
Molecular weight distribution (polydispersity, P) and
average number of chain scission per macromolecule (S )
were calculated according to the formulae:
Mw
P 3
Mn
2284 H. Kaczmarek, D. O1dak / Polymer Degradation and Stability 91 (2006) 2282e2291

M n0 3.1. Gel content

S 1 4
Mn
Table 1 shows the results of estimation of insoluble gel in
PE and PE containing 30% cellulose. In pure PE there is no
In formula (4), M n0 and M n are the number average molecular gel before degradation, in contrast to PE cellulose sample,
weights of PE before degradation and after degradation, in which about 8% is formed resulting from thermal process-
respectively. ing. It can be also caused by entanglement of macro-chains
Gel content (%) was estimated by sample extraction in during sample preparation.
a Soxhlet apparatus using p-xylene as a solvent (at boiling Exposure to UV leads to an increase of crosslinked polymer
temperature 139.1  C) during 13 h. The separated gel was content. In pure PE, efficient photo-crosslinking was observed
dried at 80  C and weighed. The result is an average of three after 20 h UV action. After longer irradiation, the changes are
measurements. negligible (only few %). PE composting does not cause addi-
Temperature and heat of phase transitions were measured tional crosslinking; also in pre-irradiated and composted PE,
using a Perkin Elmer, Diamond DSC under nitrogen flow the gel amount is only about 3% lower than in 20 h UV-
with heating and cooling rates of 10  C/min and 20  C/min, irradiated PE. It means, that some intermolecular bonds were
respectively. The apparatus was calibrated with an indium broken during biodegradation. Probably, the most sensitive
standard. for microbial attack are peroxide type crosslinks.
The crystallinity of PE (Xc) was calculated from the In PE 30% cellulose some acceleration of photo-cross-
relation: linking in first step of exposure (20 h) was found comparing
to PE alone, whereas the long-term irradiation (50e100 h)
leads to some drop of gel amount. During composting of
this sample, gel is also formed (above 14%). Composting of
DH
Xc  100% 5 pre-irradiated blend somewhat reduces its crosslinking
DHt (41.7% gel) comparing to the effect observed in UV-irradiated
(49.3% after 20 h UV) sample.
where DH is enthalpy measured and DHt is the enthalpy of In the last row in Table 1 are gel values obtained after sub-
completely crystalline PE (DHt 291.3 J/g [34]). traction of gel amount formed during processing from total gel
Tensile tests were performed at room temperature on a mod- content. This way, one can approximately extract photo-
ernized INSTRON 1026. The dumbbell specimens were crosslinking and bio-crosslinking process from thermal gel
stretched at an extension rate of 10 mm/min. The stressestrain formation. It is clearly seen from Table 1, that photo-crosslink-
curves were recorded. The values of stress at break and per- ing is the dominant process in PE but gel is not formed in com-
centage elongation at break were calculated as average of posted PE. In PE cellulose, besides photo-crosslinking, also
a minimum of six measurements. bio-crosslinking occurs.
The surface morphology of gold covered samples was
observed using Scanning Electron Microscopy LEO 1430 3.2. Molecular weights and its distribution
VP at an accelerating voltage of 27e28 kV.
The changes of average molecular weights (M n , M w ), num-
ber of chain scission (S ) and polydispersity (P) in PE and in
3. Results PE cellulose blend during photodegradation are presented
in Table 2. They concern only PE because cellulose is insolu-
UV-irradiation of PE and PE cellulose samples was ble in trichlorobenzene (GPC eluent) and was separated from
applied to check if their biodegradability can be enhanced. the analyzed soil.
Time of 20 h for UV exposure (corresponding to dose It was found that continuous degradation takes place in
252 J/cm2) was chosen. During photooxidative degradation both PE samples, which is confirmed by the decrease of M n
at this time, the decrease of molecular weight and formation
Table 1
of functional groups, sensitive to microorganisms action Gel fraction in PE and PE 30% cellulose samples after UV-irradiation (time
were expected. Although the concentration of photooxidation in hours: 0e100), after biodegradation in soil during 1 year and after 1 year in
product in polymers is usually a function of exposure time, soil followed by 20 h UV exposure
longer irradiation is disadvantageous because it can lead to Sample Gel amount (%)
high amount of photo-crosslinked gel. Thus, a compromise 0h 20 h 50 h 60 h 80 h 100 h 1 Year 20 h
time of UV-irradiation was selected. 1 Year
Generally, very small amounts of cellulose (5e15%) in PE PE 0.0 33.0 48.7 52.8 57.3 61.2 0.8 29.8
composite do not change its degradability. The difference in PE 30% cel 7.9 49.3 56.2 55.6 59.8 68.1 14.3 41.7
properties of PE 30% cellulose blend with respect to PE PE 30% cela 0.0 41.4 48.3 47.7 51.9 60.2 6.4 33.8
alone was found, thus, mainly results for these samples are dis- a
Gel amount calculated after subtraction of insoluble part formed during
cussed below. processing (7.9%) from total gel content.
 H. Kaczmarek, D. O1dak / Polymer Degradation and Stability 91 (2006) 2282e2291 2285

Table 2
Number and weight average molecular weights (M n ; M w ), polydispersity (P
M w =M n ) and number of chain scission (S M n0 =Mn  1) in PE alone and in
PE in blend with 30% cellulose exposed to UV
Sample Time of Mn Mw P S
irrdiation
(h)
PE 0 23 200 133 400 5.74 e
20 12 400 71 700 5.76 0.87
100 4500 10 700 2.35 4.16
PE in 0 18 700 119 300 6.38 e
cellulose 20 10 600 52 900 5.00 0.76
blend 100 5500 15 400 2.79 2.40

and M w . Simultaneously, the polydispersity (P) decreases,

which indicates that polymer in the soil fraction becomes
more uniform. The number of chain scissions per macromole-
cule is significant after longer irradiation time (>50 h). Some-
what higher changes of all molecular parameters are recorded
for pure PE than for PE blend exposed to UV, which suggests
that cellulose slightly retards PE photodegradation. It is neces-
sary to mention that starting molecular weights (before degra-
dation) in PE (M n 23 200 and M w 133 400) are somewhat
higher than those for undegraded PE in the blend (M n
18 700 and M w 119 300). It can be understood, if one recalls
that formation of insoluble gel resulting from intermolecular
thermal crosslinking takes place during blend processing.
In this process, the longest chains were incorporated into
the gel and thus, the molecular weight of the remaining
soluble part was lower. It is interesting to know that PE is
completely soluble before degradation, although it was formed
in the same conditions as PE cellulose blend. It is simple
evidence that cellulose participates in intermolecular cross-
linking with PE. Fig. 1. DSC curves for: PE sample UV-irradiated during 0e100 h (a);
The influence of composting on molecular weights, S and P PE 30% cellulose before degradation, after 20 h UV-irradiation and after
in both PE samples is very low (Table 3). This is an expected combined degradation: 20 h UV 1 year biodegradation in soil (b).
effect because PE is classified as non-biodegradable as long as
its initial molecular weight is high [5]. Somewhat more
efficient biodegradation was found in samples preliminarily 3.3. Crystallinity
UV-irradiated, however, the cellulose effect seems to be insig-
nificant. The number of chain scissions per macromolecule is DSC measurements were used for estimation of tempera-
still lower than 1. The drop of polydispersity in composted tures characterising the melting (Tm) and crystallization (Tc)
samples is lower than in photodegraded ones. as well as enthalpy of fusion (DHm) of PE (Fig. 1). Crystallin-
ity of PE and its changes during photo- and biodegradation
Table 3
were calculated on the basis of DHm. The initial crystallization
Number and weight average molecular weights, polydispersity and number of of PE samples obtained by extrusion is much lower than that
chain scission in PE alone and in PE in blend with cellulose before degradation of the original PE powder (about 45%). It means that during
and after 1 year in soil processing at high temperature, crystals were melted and did
Sample Treatment Mn Mw P S not re-built after fast specimen cooling.
PE e 23 200 133 400 5.74 e The melting endotherm of pure PE exhibits a maximum at
1 Year 20 300 129 100 6.34 0.14 107.5  C. UV-irradiation shifts this maximum to lower temper-
comp. atures and changes the shape of the DSC curve (Fig. 1a). The
20 h UV 1 12 000 68 700 5.74 0.93 broadening of the DSC curves after UV exposure can be caused
year comp.
PE in e 18 700 119 300 6.38 e
by alteration of crystallites size and their distribution [21].
cellulose 1 year 16 700 112 200 6.70 0.20 UV-irradiation leads to decrease of DHm and Xc in this PE
blend comp. sample (Table 4). Formation of functional groups (such as
20 h UV 1 10 200 46 800 4.59 0.83 hydroxyls, ketones, branching) during photooxidative degra-
year comp. dation usually disturbs macro-chain order and loses compact
2286 H. Kaczmarek, D. O1dak / Polymer Degradation and Stability 91 (2006) 2282e2291

Table 4 a
Crystallization and melting temperature (Tc, Tm), heat of fusion (Hm) and crys- 12
tallinity degree (Xc) in UV-irradiated PE and PE 30% cellulose obtained
from DSC measurements 10

Stress at break [MPa]

Sample Time of Tc (  C) Ttm (  C) DHm (J/g) Xc (%)
8
irradiation (h)
PE 0 94.4 107.5 67.7 23.21 6
20 93.9 106.4 64.6 22.17
50 93.4 103.9 62.0 21.25 4
100 93.8 102.4 60.0 20.58
PE in 0 94.0 105.5 54.6 18.74 2
cellulose 20 94.2 105.8 52.3 17.97
blend 50 94.8 106.4 52.7 18.09 0
100 93.9 105.1 52.7 18.07 0 10 20 30 40 50 60 70 80
Irradiation time [h]
5% cel 10% cel 15% cel 30% cel PE
polymeric structure. There is no influence of composting on
crystallinity degree (Xc) in pure PE (Table 5). b
Cellulose addition to PE leads to very small shift of Tm and 350
Tc. Simultaneously, DHm somewhat decreases in PE 30%

Elongation at break [%]

300
cellulose blend compared to pure undegraded PE. It suggests
that cellulose impedes PE order. 250
In case of UV-irradiated blend, both temperatures: Tm and 200
Tc are practically unchanged and the heat of fusion decreases 150
slightly after just 20 h exposure (Table 4). It is due to small
100
drop of crystallinity degree, caused by photooxidative degra-
50
dation. Blend composting also does not visibly change the
crystallinity of PE even in the case of samples pre-exposed 0
0 10 20 30 40 50 60 70 80
to UV (Table 5). The small increase in Xc can be caused by Irradiation time [h]
consumption of amorphous part of polymer by microorgan-
5% cel 10% cel 15% cel 30% cel PE
isms; however, these changes (<1%) are in the experimental
error limits. Fig. 2. Stress at break (a) and elongation at break (b) of UV-irradiated PE
samples.
It should be added that crystallinity of cellulose cannot be
studied by DSC because it decomposes before melting. We
can only mention that originally highly crystalline cellulose
(about 95%) is much more disordered after moulding with Even the addition of 2% compatibiliser does not improve their
PE, where its crystallization degree is 59% (which was miscibility enough.
checked by X-ray diffraction). In pure PE irradiated up to 80 h, there are practically no
changes in stress at break values. In PE blends containing
cellulose, an increase of s was found just after 20 h UV-
3.4. Mechanical properties
irradiation but longer exposure does not cause further distinct
changes. The reason is efficient photo-crosslinking e gel
Stress at break (s) and ultimate elongation (3) of PE alone
amount in blends after 20 h UV-irradiation is significantly
are higher than those in PE cellulose blends, which is obvi-
higher than that in PE exposed at the same time.
ous because of components immiscibility (Fig. 2(a) and (b)).
Ultimate elongation is approximately constant up to 40 h
Table 5
exposure and then it decreases in all samples but the highest
Crystallization and melting temperature (Tc, Tm), heat of fusion (Hm) and crys- drop was observed in PE without cellulose. This effect is
tallinity degree (Xc) in biodegraded, in soil PE and PE 30% cellulose ob- caused by efficient chain scission accompanying crosslinking.
tained from DSC measurements Moreover, after longer irradiation, the crosslinking density
Sample Treatment Tc (  C) Tm (  C) DHm (J/g) Xc (%) increases and samples become very brittle.
PE 0 94.4 107.5 67.7 23.21 The stress at break of PE composted in soil through 1 year
1 year comp. 94.3 107.3 66.6 22.87 slightly increases, whereas in blends with cellulose the s
20 h UV 93.8 107.0 65.1 22.35 values increase significantly just after 6 months biodegrada-
1 year comp. tion. Prolongation of composting time (>1 year) leads to con-
PE in 0 94.0 105.5 54.6 18.74
cellulose 3 Months comp. 94.2 105.5 56.9 19.55
siderable s decrease in all samples, which is evidence of their
blend 6 Months comp. 94.3 105.7 53.0 18.20 bio-decomposition (Fig. 3a).
1 Year comp. 93.8 105.5 56.9 19.53 A similar trend, with the initial increase followed by the de-
20 h UV 94.0 105.5 52.7 18.08 crease, was observed in elongation of composted samples
1 year comp. (Fig. 3b). Only for PE, the 3 maximum appears earlier e after
 H. Kaczmarek, D. O1dak / Polymer Degradation and Stability 91 (2006) 2282e2291 2287

a a
16
14

Stress at break [MPa]

14
12
Stress at break [MPa]

12
10 10
8 8
6
6
4
4
2
2 0
0 2 4 6 8 10 12
0
0 2 4 6 8 10 12 14 16 18 Composting time [months]
Composting time [months] PE 5% cel 10% cel 15% cel 30% cel
5% cel 10% cel 15% cel 30% cel PE
b
b 200
120

Elongation at break [%]

Elongation at break [%]

150
100

80 100

60
50
40
0
20 0 2 4 6 8 10 12
Composting time [months]
0
0 2 4 6 8 10 12 14 16 18 5% cel 10% cel 15% cel 30% cel PE
Composting time [months]
Fig. 4. Stress at break (a) and elongation at break (b) of UV-irradiated and
5% cel 10% cel 15% cel 30% cel
biodegraded PE samples.
Fig. 3. Stress at break (a) and elongation at break (b) of biodegraded PE
samples.
(Fig. 5). It is not surprising that B is low in PE but is also neg-
6 months. Contrary to s, the 3 value changes much more in PE ligible in PE containing 30% cellulose. In this PE blend only
than in blends during composting. about 1/6 of cellulose is consumed after 1 month composting.
The curve of s versus composting time for pre-irradiated Because of such unsatisfied results, we finally decided to
PE samples during composting exhibits a different shape check the course of biodegradation in blends with higher
(Fig. 4a). The maximum on this curve appears at 2 months. cellulose amount (PE/cellulose e 1:1). Also in this sample
The ultimate elongation shows lowering tendency in all 20 h the biodegradation degree does not exceeds 15% at the end
irradiated and composted samples. In pure PE, the drop is of experiment. Comparatively, pure cellulose is degraded
highest at 4 months. at that time to above 60%. Very small efficiency of biodegra-
The changes of mechanical properties show that compli- dation in PE containing 30% or even 50% cellulose is
cated processes compete in UV-irradiated and/or composted
PE samples. The cellulose addition alters PE mechanical
strength during degradation. 60
Biodegradation degree [%]

50 cellulose
3.5. Evolution of carbon dioxide
40

The amount of CO2 evolved during sample composting 30

PE/30%cel
was used to reveal the biodegradation degree of modified PE.
20 PE/50%cel
According to the standard recommended for estimation of
plastics biodegradability by this method, the maximum time 10
of biodegradation is 1 month [32]. Longer time of composting PE
0
(>1 month) would be connected with exchange of soil in ex- 0 5 10 15 20 25 30
perimental flask and thus running the experiment again, which Composting time [days]
will cause other perturbations and errors. Fig. 5. Biodegradation degree (%) of cellulose, PE and it blends containing
The biodegradation degree (B) calculated on the basis 30% and 50% cellulose versus time (obtained from CO2 amount
of this measurement is very low in the studied samples measurements).
2288 H. Kaczmarek, D. O1dak / Polymer Degradation and Stability 91 (2006) 2282e2291
probably caused by sample morphology. Perhaps the cross-
linked surface hinders the access of microorga-
nisms water oxygen to sample inside and protects it
against biodegradation.
Fig. 6. SEM microphotographs of PE before degradation (a), after 100 h
UV-irradiation (b) and after 20 h UV-irradiation 1 year biodegradation (c).
3.6. Surface morphology
Scanning Electron Microscopy was used to check the
changes in surface morphology of studied samples during their
degradation.
Undegraded PE samples exhibit a rough surface with no nu-
merous defects. No separated domains, typical for immiscible
polymers, are seen at the surface of PE cellulose blend
(Fig. 6). The reason is rather absence of compatibiliser; the
blend sample seems to be coated by a PE layer, which protects
the polymer bulk. This fact allows us to understand the diffi-
culties in blend biodegradation and its very slow decomposi-
tion during composting.
Both degrading factors: UV-irradiation and composting
cause surface erosion e formation of cracks, crazes and holes
(Figs. 7 and 8). Surface roughness increases especially in PE
with cellulose. These defects are the results of consumption
of biopolymer by microbes. Moreover, during photodegrada-
tion, the partial removal of amorphous PE also leads to surface
development. Such surface destruction can facilitate the trans-
port of degrading factors to the polymer bulk and further
accelerate degradation occurring in the environment.
3.7. Chemical and microbiological soil analyses
The soil used in composting test was characterized by fol-
lowing parameters:

pH 4.60,

amount of organic carbon 1.70%,

amount of organic nitrogen 0.08%,

amount of organic phosphor 243 mg/kg,

ratio C/N 21.2.
Soil acidity is favourable for fungi growth.
Microbiological analysis concerned estimation of total
amount of bacteria and fungi. The colony-forming unit
(CFU) was around 4.73  105 and 9.73  105 per 1 g dry
soil for bacteria and fungi, respectively.
Such results are typical for forest soil, which is proper for
cellular microorganism (mainly fungi) growth. Thus, the soil
inoculum used in this study is rich enough for cellulose
biodegradation.
4. Discussion
The studies of PE decomposition in the environment are
important because this polymer is still a dominant material
for production of plastic, which is broadly applied in everyday
life. Most of PE products are not reused and not recycled, thus,
finally they are dumped on landfills, where they remain for
many years. The idea of replacement of pure polyolefins by
their blends with biopolymers is profitable from an ecological
point of view, because the biodegradable component is
consumed by microorganisms and the remaining matrix
undergoes dissipation and can be mixed with soil.
 H. Kaczmarek, D. O1dak / Polymer Degradation and Stability 91 (2006) 2282e2291
Fig. 7. SEM microphotographs of PE 30% cellulose before degradation (a),
after 100 h UV-irradiation (b) and after 1 year biodegradation (c).
2289
Fig. 8. Examples of enlarged surface defects formed in PE 30% cellulose
after 100 h photodegradation (a) and combined degradation (20 h UV 1
year biodegradation) (b).
Plastic decomposition processes in natural environment are
very complicated because many factors influence them. Also
the numerous ingredients in plastics can effect or mask the
final biodegradation.
The degradability of pure PE and cellulose is still doubtful,
there are many controversial opinions concerning the use of
blends based on renewable materials such as cellulose. We
decided to check if such polymer blend storied in forest soil
undergoes biological processes.
It is known why the long hydrocarbon chains are very resis-
tant to biodegradation e because there are no enzymes capable
of CeC bond scission. In addition, usually antioxidants and
stabilizers are added to commercial PE products. The neces-
sary conditions and mechanism of biodegradation of PE
were described [1,3,10,35e40]. The preliminary oxidation of
macro-chains is important for induction of biological reac-
tions. Formation of hydroperoxides resulting from chemical
peroxidation (abiotic oxidation) and further processes leading
to carboxylic and other carbonyl group generation facilitate
microorganisms attack. The formed oxidized chains undergo
splitting resulting from the action of various factors: tempera-
ture, water, electromagnetic radiation and chemical agents
present in surroundings.
2290 H. Kaczmarek, D. O1dak / Polymer Degradation and Stability 91 (2006) 2282e2291
Enzymes produced by living microorganisms are proteins,
which have to form active complex with macromolecules be-
fore their catalytic decomposition. The affinity of enzymes to
hydrophobic polymers can be improved for instance, by intro-
ducing the surfactants. Also the functional groups formed dur-
ing peroxidation increase PE hydrophilicity, allow for microbe
growth and contribute to reaction of enzymes with macromol-
ecules. These reactions and formation of enzymeepolymer
complex are difficult in case of steric hindrances.
The mechanism of cellulose biodegradation is known. The
main process is breaking of glycosidic bonds between rings
upon enzyme (cellulase) action. It leads to formation of cello-
biose and finally glucose, which undergoes oxidation or
fermentation.
Concluding, the biological decomposition of oxidized poly-
olefins is different from biodegradation of cellulose. In case of
cellulose the carbon is transformed to CO2 (second main prod-
uct is H2O), whereas the carbon from PE contributes to humus
and biomass.
It was reported that polymer biodegradation can be acceler-
ated by the incorporation of pro-degradants or pro-oxidants
[1,10,35e37]. These are inorganic or organic transition metal
compounds (mainly iron, cobalt, manganese salt; for example,
iron dialkyldithiocarbamate), which initiate or catalyse poly-
mer peroxidation. The metal cations lead to rapid buildup of
hydroperoxides and next, the secondary chain degradation pro-
cesses occur in polymer. In the presence of light, peroxides of
different types photolyse; in the absence of radiation, typical
chemical decomposition takes place. The pre-oxidized poly-
meric chains undergo simultaneous photolysis, hydrolysis and
biodegradation. The other active agent produced in the natural
environment in the presence of microorganisms is superoxide
radical ion (O2), which is readily reduced to hydrogen perox-


ide. The H2O2 reversibly react with iron ions (Fenton reactions)
increasing the content of hydroxyl radicals initiating radical
polymer decomposition. The presence of metallic compounds
and other pro-degradants in soil cannot be excluded.
The macromolecule scission, occurring as a result of oxida-
tive degradation, leads to the reduction of polymeric molar
weight and to an increase of concentration of functional groups
at the chain ends. Moreover, resulting of sample fragmentation,
surface area of polymer is developed, which increases the num-
ber of active sites. Such modified polyolefin becomes a nutrient
for microorganisms and bioassimilation process starts.
Pre-irradiation of samples leads to photooxidative degrada-
tion of the polymer [40,41]. As usually, the initiation of pho-
tolysis is attributed to impurities and chromophores formed
during polymerization, processing and storage. The secondary
photochemical processes in PE and cellulose are different be-
cause of differences in chemical structure of both polymers.
The main photoreactions in PE are random chain scission,
oxidation and crosslinking resulting of radical recombination.
Most of the oxidized groups formed are photosensitive, for ex-


ample, hydroperoxides undergo splitting into hydroxyl (HO )


and alkoxyl radicals (RO ); carbonyl groups of different type
undergo Norrish I and II reactions. The photochemical degra-
dation of cellulose is connected with few reactions: main chain
scission (i.e. breaking of the glycosidic bonds), dehydrogena-
tion, dehydroxylation and dehydroxymethylation, which
induce the changes of supramolecular structure and physico-
mechanical properties.
The mechanism of photo- and biodegradation of PE
cellulose blend can be considered on the basis of processes
occurring in both polymers because of their immiscibility. How-
ever, the cross-reactions between active degradation products
(molecules in excited states, free radicals, intermediates) from
both polymers are also possible, mainly at the boundary area.
We found that bio-decomposition of PE cellulose is not
so fast but processes once initiated, systematically occur.
Long-time biodegradation is not harmful for environment be-
cause concentration of degraded product evolved is low. More-
over, in case of PE and cellulose, these decomposition
products are not toxic and are inert, thus, they can be gradually
assimilated by surroundings [38,39].
Our results showed that two main competitive reactions:
random chain scission and crosslinking occur during UV-
irradiation of PE samples (see changes of molecular weights).
The chain scission is more efficient in pure PE than in PE
cellulose blend. During composting, this process is insignificant
in both type of samples (PE alone and PE cellulose) but in
case of combined degradation, the efficiency of degradation is
somewhat higher but it is still not fast enough for classification
of material studied as biodegradable. It is confirmed by the mea-
surement of CO2 evolved.
Tensile tests showed that biodegradation of our samples leads
to deterioration of mechanical properties after longer compost-
ing time (>1 year). It is caused by the decrease of molar mass,
sample embrittlement and in consequence chain fragmentation.
However, the sample pre-irradiation does not cause the expected
accelerating effect. The preparation of PE cellulose blends
needs high temperature because both polymers are insoluble in
most conventional organic solvents at room temperature, thus
casting method is excluded. Applied temperature (170  C) dur-
ing extrusion leads to significant destruction of supramolecular
structure of polymers and the drop of component crystallinity.
However, as was mentioned, the accompanying effect is
formation of crosslinked gel and chain entanglements in com-
position. These facts have opposite effect on degradation e
destruction of crystallites and increase of amorphous phase fa-
cilitates degradation, whereas crosslinking can hamper it. In
our case, both factors compete and influence the final, rela-
tively low degradation degree.
The observed changes of sample crystallinity during all
types of degradation are also very low in samples studied.
The method of sample preparation and its thermal history
has an important influence on its properties and aging pro-
cesses. Moreover, the conditions of degradation test effect the
degradation course. In laboratory, conditions are kept constant,
while in outdoor biodegradation they are changeable. Specially
variations of pH and temperature can be more or less suitable
for microbes growth and lead to unexpected results.
Our experiments does not confirm enthusiastic reports con-
cluding that modification of synthetic polymers by natural
polysaccharides leads to obtain easily biodegradable materials.
 H. Kaczmarek, D. O1dak / Polymer Degradation and Stability 91 (2006) 2282e2291
The synergistic effect of both degrading agents: UV-radiations
and microbes action were not found in presented studies.
It should be pointed out, that the durability of
PE cellulose blends depends on the resistance of surface
layer. When this protecting layer is destroyed, the degrading
factors have free access to interior of composites and further
environmental aging can be much faster and efficient. Such
prediction can be done on the base of observation of surface
morphology in degraded samples by SEM. It is also confirmed
by the drop of mechanical properties after long-time storage of
samples in soil.
We know that PVC cellulose blends are produced and we
can expect that such used materials are dumped in landfills.
Therefore, it is important to know what happens with such
waste and to predict of their lifetime.
5. Conclusions
The fast, controlled biodegradation of polyolefin-based ma-
terials needs the incorporation of special additives inducing
their oxidation and chain scission. However, their presence
in degraded material is not completely inert for living organ-
isms. It is possible to avoid their addition to polymeric blend
containing natural biodegradable polymer such as cellulose.
On the base of presented results, we can conclude that
PE cellulose blends (not containing other accelerating and
stabilizing additives) prepared by extrusion moulding are not
very susceptible to biodegradation. In such blends even cellu-
lose consumption by microorganisms is impeded. The influ-
ence of pre-irradiation on biological decomposition is also
negligible. The results described in this work confirm our ear-
lier conclusions based on spectrophotometric measurements
[29]. The reason for relative resistance of blends studied is
their partial crosslinking, which impedes the penetration of
water carrying enzymes. However, the observed non-efficient
decomposition effects do not exclude the biodegradability of
PE cellulose blends in the natural environments, where other
active ingredients exist.
The presence of PE in landfill is a fact, thus it is better to
replace at least some part of PE-based products by its blends
with cellulose, undergoing slow but systematic disintegration,
which has no harmful impact on environment.
Acknowledgements
We wish to thank Professor Hanna Dahm and co-workers
from the Department of Microbiology (Institute of General
and Molecular Biology, Nicolaus Copernicus University,
Torun, Poland) for microbiological soil analysis.
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