biodegradability and mechanical properties of poly(vinyl alcohol)-based blend plastics prepared...
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ORIGINAL PAPER
Biodegradability and Mechanical Properties of Poly(vinylalcohol)-Based Blend Plastics Prepared Through ExtrusionMethod
Martina Kopcilova • Jitka Hubackova • Jan Ruzicka •
Marie Dvorackova • Marketa Julinova • Marek Koutny •
Miroslava Tomalova • Pavol Alexy • Peter Bugaj • Jaroslav Filip
Published online: 2 August 2012
� Springer Science+Business Media, LLC 2012
Abstract Plastic blend materials consisting of poly(vinyl
alcohol), glycerol and xanthan or gellan were prepared
through laboratory extrusion. Their base mechanical
properties were compared with the properties of poly(vinyl
alcohol) foil and their biodegradability in soil, compost and
both activated and anaerobic sludge were assessed. In
samples with lower polysaccharide content (10–21 %w/w)
the tensile strength of 15–20 MPa was found; the elonga-
tion at break of all blends was relatively close to the
parameter of poly(vinyl alcohol) foil. The biodegradability
levels of the blends tested corresponded to the content of
natural components, and the mineralization of the samples
with the highest carbohydrate proportion (42 %) reached
50–78 %, depending on the type of the environment.
Complete biodegradation of all samples occurred in acti-
vated sludge.
Keywords Poly(vinyl alcohol) � Xanthan � Gellan �Biodegradation
Introduction
One alternative for reducing the quantity of plastic waste is
to develop and manufacture new types or blends of
degradable polymers, which under different environmental
conditions are subject to the action of microorganisms,
light, oxygen, temperature and other factors. Biodegradable
plastics are the most important group of such polymers and
their decomposition by bacteria or fungi has been the
subject of intense research.
The group of biodegradable plastics used for manufac-
turing packaging and other materials includes poly(vinyl
alcohol) (PVA); however, it proves to be almost non-
degradable in some environments (for example, under
certain anaerobic conditions [1] or in soils and compost
[2]), either due to the absence of suitable microorganisms
or unfavourable environmental conditions. For instance,
the latter has been shown in a study by Chiellini et al., who
demonstrated the adsorption of PVA onto clay particles,
resulting in a substantial inhibition of biodegradation [3].
For these reasons, efforts should be in place to reduce
the proportion of PVA in plastics for certain applications.
One possibility is to prepare blends containing biopolymers
derived from renewable sources, such as proteins (colla-
gen), polyesters (poly-b-hydroxybutyric acid) and particu-
larly polysaccharides (starch, cellulose). The properties,
applications and biodegradability of such materials have
been explored in several studies [4–7]. Bacterial polysac-
charides, within biodegradable plastics, have not yet been
studied because of the high costs involved. Nonetheless,
they allow for various alternatives of application due to
their different structure and properties compared to plant
polysaccharides. Bacterial polysaccharides are very diverse
in structure and application; in addition, some of them
are now produced commercially in large volumes, with
M. Kopcilova � J. Hubackova � J. Ruzicka (&) �M. Dvorackova � M. Julinova � M. Koutny � M. Tomalova �J. Filip
Department of Environmental Engineering,
Faculty of Technology, Tomas Bata University in Zlın,
TGM Square 275, 762 72 Zlın, Czech Republic
e-mail: [email protected]
J. Ruzicka � M. Julinova � M. Koutny
Centre of Polymer Systems, TGM Sqr. 5555,
760 01 Zlın, Czech Republic
P. Alexy � P. Bugaj
Department of Plastics and Rubber, Institute of Polymer
Materials, Slovak University of Technology, Radlinskeho 9,
812 37 Bratislava 1, Slovak Republic
123
J Polym Environ (2013) 21:88–94
DOI 10.1007/s10924-012-0520-8
xanthan and gellan being the most industrially applied—in
food, pharmaceuticals and cosmetics—whilst xanthan is
also utilized in some technical spheres.
In fact, blending PVA with xanthan or gellan was used
in several studies aimed to a preparation and utilization of
films, hydrogels or microspheres for certain medical
applications. In these cases solvent evaporation method or
emulsion cross-linking method were applied for obtaining
biodegradable polymer matrices for controlled drug deliv-
ery [8–11]. Nevertheless, these preparation methods are not
a way for the production of biodegradable plastics intended
for various technical applications; moreover, materials
biodegradation in different environmental spheres was not
tested in any above mentioned study.
Generally, during polymers mixing the possibility of
mutual interaction between individual blend components
exists and thus the potential to influence the biodegradability
of the resultant material as well. In the case of PVA and
gellan, interaction was detected by Sudhamani et al. [12],
who studied the mechanical properties of several blends of
these two polymers. DSC thermogram data of PVA ? gel-
lan foils, prepared through the casting method, showed that
their glass transition temperature and melt isotherm shifted
towards a higher temperature with increasing proportion of
PVA; therefore, it was concluded that molecular interac-
tions between PVA and gellan had occurred [12].
For these reasons, the target of this study has been to
prepare, identify the base mechanical properties and test
the biodegradability of polymer blends of PVA ? gellan
and PVA ? xanthan, as prepared through plasticization of
basic ingredients with subsequent extrusion under indus-
trial conditions (i.e. temperatures). The results of the bio-
degradability of these blends under anaerobic conditions
have been published by Hrncirik yet and compared to PVA
blends containing starches [13]. This paper presents the
complete results of microbial degradability in various
environmental conditions and the base mechanical prop-
erties of the plastics, and contrasts these with the properties
of pure PVA or PVA foil. In addition to these, FTIR
spectra of all base component and the final blends were
measured and discussed.
Experimental
Chemicals
Poly(vinyl alcohol), PVA (Mowiol 5–88, Kuraray): total
carbon content 50.8 %, viscosity 5.5 ± 0.5 mPa s, degree
of hydrolysis 88 %
Gellan (Gellan gum, Fluka): total carbon content
31.3 %, CODCr 1,355.9 mg g-1
Xanthan (Xanthan gum, Fluka): total carbon content
31.3 %, CODCr 905.6 mg g-1
Glycerol (H.C.I. Comp.): total carbon content 39.1 %
Polymer Blends
The preparation of samples and the evaluation of their
mechanical properties were performed by the Department
of Plastics and Rubber, Institute of Polymer Materials at
the Slovak University of Technology in Bratislava. All the
polymer blends were prepared in two steps. Firstly, mix-
tures of both PVA ? glycerol and polysaccharide ?
glycerol were made ready, exposed at 130 �C for 15–45
min and cooled. Afterwards, plasticized PVA was mixed
with plasticized polysaccharide and the blend was treated
on a twin-screw Labtech extruder under the thermal pro-
file of 120–130–140–150–160–170–180–190–160–150 �C
(feed hopper-extrusion head). The screw diameter of
16 mm, L/D ratio of 40 and extruder speed of 300 rpm
were further parameters. The compositions of all final
polymer blends are given in Table 1.
Mechanical Properties of Polymer Blends
In order to measure mechanical properties, dumb-bell
shaped specimens were prepared from all the blends. Tests
for determining tensile strength and elongation at break
were performed on a 5 kN Metrotest according to the norm
ISO 527, using a crosshead speed of 1 mm min-1 to the
extent of deformation of 0–3 % and -50 mm min-1 at the
deformation [3 %, all at 25 �C [14].
Table 1 Composition of final
polymer blendsComponent Polymer blend
PVA/G10 PVA/G21 PVA/G42 PVA/X10 PVA/X21 PVA/X42
Glycerol [%] 14.7 17.4 25.2 14.7 17.4 25.2
Gellan [%] 10.5 21 42 – – –
Xanthan [%] – – – 10.5 21 42
PVA [%] 74.8 61.6 32.8 74.8 61.6 32.8
J Polym Environ (2013) 21:88–94 89
123
Determining Biodegradability in Anaerobic Mesophilic
Sludge
Preparation of inoculum: Anaerobic sludge from a local
wastewater treatment plant was centrifuged (5,0009g,
20 �C, 10 min), washed by nitrogen-bubbled water and,
following repeated centrifugation, suspended in mineral
medium [15] to reach 3–4 g L-1 of dry mass.
Testing: Evaluations were performed according to the
ISO 11734 [15], on the basis of the amounts of CH4 and
CO2 produced during the tests. Portions of 100 ml of
resuspended anaerobic sludge were placed in 250 ml vol-
ume flasks, thoroughly bubbled with nitrogen and then
20 mg of sample was added into each flask, excluding
blanks. After repeated nitrogen bubbling, all the flasks
were sealed with caps equipped with a gas-tight sampling
valve. Incubation was performed at 35 �C and the gas
phase of each flask was sampled several times per week.
CH4 and CO2 concentrations were determined by gas
chromatography (CHROM 5 equipped with a PORAPAK
Q column and TCD detector, with Helium as a carrier gas,
Tsample = 100 �C, Tt = 50 �C, Tdet = 100 �C). At the end
of each test, a concentration of inorganic carbon (IC) was
determined in liquid phase using an automatic TOC ana-
lyzer (Shimadzu 5000A). All the tests were conducted in
triplicate.
The final level of sample biodegradation was evaluated
by the relation of the amount of carbon released in the form
of both gas products (CH4 and CO2) and liquid compounds
(IC), corrected by a blank, to a theoretical amount of car-
bon in the sample, and expressed in terms of percent
mineralization.
Determining Biodegradability in Activated Sludge
Preparation of inoculum: Activated sludge from a local
wastewater treatment plant was centrifuged (5,0009g,
20 �C, 10 min) and washed three times with drinking
water. The required volume was centrifuged again and the
biomass was suspended in mineral medium [16] to reach
0.5 g L-1 of dry mass.
Testing: Respirometric determination according to the
Czech EN ISO 9439 norm [16] was employed, utilizing a
Micro-Oxymax respirometer (Columbus Instruments Co.,
USA). Samples of concentrations of 0.2 g L-1 were used
and reactor flasks were placed in a water bath at 25 ± 1 �C.
CO2 production and O2 consumption were periodically
measured.
A ratio of the CO2 actually produced (corrected by a
blank) to the theoretical quantity given by the carbon
content in the sample was employed and the biodegrada-
tion was expressed in terms of percent mineralization.
Determining Biodegradability in Compost
Preparation of inoculum: Commercial compost produced
by the AGRO CS Comp. was used throughout the study. It
was sieved through a screen of approximately 0.7 cm mesh
and left to mature for about 6 weeks at 58 �C, 50 %
humidity and under continuous aeration. After this period,
dry matter of 55.17 % and pH 6.85 were found.
Inert material: Agroperlite (AGRO CS Comp.) was used
for maintaining humidity and increasing the homogeneity
of the mixture. Water content \ 2.0 %, pH 6.0–7.5.
Mineral medium: Composition (in g per litre): KH2PO4
1.64, K2HPO4.12H2O 4.35, Na2HPO4.12H2O 8.94,
(NH4)2SO4 0.50, CaCl2 0.275, MgSO4.7H2O 0.225,
FeSO4.7H2O 0.003 and 1 ml of trace element solution
(MnSO4.4H2O 0.043, H3BO3 0.057, (NH4)6Mo7O24.4H2O
0.037, CuSO4.5H2O 0.040, Co(NO3)2.6H2O 0.025,
ZnSO4.7H2O 0.043).
Testing: A modification of the Czech EN ISO 14885-2
norm [17] was used. All the tests were conducted in gas-
tight flasks with 1,140 ml of total volume. A mixture of
10 g of compost dry matter and 20 g of Agroperlite was
dosed into the each test flask. Each sample (1.7 g) was
dissolved in 20 ml of mineral medium and added into the
flask. Blank bottles without a sample were prepared in
parallel. All reaction flasks were sealed with caps equipped
with a gas-tight sampling valve and incubated at 58 �C in
the dark. Concentrations of CO2 and O2 were determined
twice a week using an Agilent 7890A gas chromatograph
equipped with a Porapak Q column (80/100 MESH) and a
5A molecular sieve (60/80 MESH), with a TCD detector.
Aeration of all the flasks via CO2-free air was performed
after each sampling attempt and water content was checked
by weighing every entire bottle.
CO2 production was calculated for each flask, corrected
by a blank and compared to carbon content in each sample.
The level of biodegradation was expressed in terms of
percent mineralization.
Determining Biodegradability in Soil
Preparation of inoculum: Three soil types (commercial
garden soil and two types of agriculture soil) were sieved
through a screen of 0.7 cm, mixed at the ratio 2:1:1 and
kept at 5 �C and humidity of 50 %. After this, dry matter of
50.4 % and pH 6.2 were found.
Testing: A modification of the ISO 17556 method [18]
was used. All the tests were carried out in gas-tight flasks
with a total volume of 1,140 ml. 30 g of soil mixture and
30 g of Agroperlite (see above) were dosed into each flask
and 0.6 g of sample (dissolved in 20 ml of water) was
added. Solutions of (NH4)2SO4 and K2HPO4 were added to
reach the C:N:P ratio of 100:10:1. Blank bottles without
90 J Polym Environ (2013) 21:88–94
123
samples were prepared in parallel. All the flasks were
sealed with gas-tight caps equipped with a gas-tight sam-
pling valve and incubated at 25 �C in the dark. The process
of determining the CO2 and O2 concentrations, aerating the
flasks as well as evaluating biodegradability was carried
out in an identical manner to the compost tests.
Obtaining FTIR Spectra
FTIR-ATR spectra of the PVA, xanthan, gellan and blend
foils were measured using the Nicolet iS10 instrument
(Thermo Scientific, USA) with the ATR Smart MIRacleTM
adapter containing a diamond crystal, the spectral range
being 4,000–525 cm-1, resolution 4 cm-1, and the number
of scans 32. The spectra obtained were processed via
Omnic 8 software (Thermo Scientific, USA).
Results and Discussion
Base Mechanical Properties of the Blends
The results of measuring the base mechanical properties of
the plastics produced are shown in Table 2. As expected,
all the blend samples showed lower tensile strength com-
pared to PVA foil, with the rate of the decrease corre-
sponding to an increasing proportion of polysaccharides.
The samples containing xanthan reached approximately
half of the value of strength compared to PVA. Regarding
the values of elongation at break, blends containing 10.5
and 21 % of polysaccharides demonstrated properties rel-
atively close to pure PVA and only those samples con-
taining 42 % of polysaccharides proved markedly fragile.
A comparison of the mechanical properties of the blends
showed that using xanthan was more favourable, this is
because adequate samples of gellan always produced
slightly worse results.
Biodegradability of PVA, Xanthan and Gellan
Firstly, the biodegradability of all the basic components
under the conditions studied were observed. The results
obtained are summarized in Table 3.
In accordance with previous papers [2, 19], PVA was
found to be completely degradable in activated sludge over
18 days; after a acclimation period lasting several days
final CO2 production equalled 72 %. Further tests of PVA
biodegradation in compost and soil, as well as in meso-
philic anaerobic sludge, proved its low degradability under
these conditions. The data observed showed that, in these
cases, PVA mineralization did not exceed values corre-
sponding to the content of residual acetate groups. Similar
results have formerly been described by Gartiser and
Chiellini [1, 2]; these all indicate the need to lower the
amount of waste containing PVA entering such environ-
ments.
Important differences were observed in the biodegrad-
ability of the two polysaccharides studied. Whereas xan-
than revealed complete biodegradability in all the
environments tested, gellan was proven to gradually
degrade in the compost and soil tests. The course of its
biodegradation in soil was characterized by an acclimation
period of nearly 1 month in length followed by partial
degradation phase, suggesting a low number of degrading
microbes in the soil used. Quite a different degradation
curve was noted in the gellan compost test. The carbohy-
drate was continuously and slowly degraded, so that after
2 months the level of CO2 production reached only 40 %,
compared to nearly 98 % of CO2 production originating
from xanthan decay. In aerobic and mesophilic anaerobic
sludge, similar levels of biodegradation for both carbohy-
drates were found, where over 80 % of CO2 production
and 60 % of carbon mineralization, respectively, were
determined.
Biodegradability of Polymer Blends
All the polymer blends prepared were tested for biode-
gradability in the same way as the individual components;
the results of these tests are summarized in Fig. 1. As
expected, for all blend types, the best biodegradability was
observed in activated sludge, without any evident accli-
mation period. Under such condition due to mixed char-
acteristics of the samples immediate CO2 production from
glycerol mineralization arose, followed by consecutive
degradation of the other two components making a certain
step-like characteristic of all the curves (data not shown).
The biodegradability of the samples in all other envi-
ronments was influenced by the low degradability of PVA
under the given circumstances; however, all the results
clearly indicate that the degree of blend mineralization
corresponded to the proportion of natural components.
Therefore, the highest values originated from samples with
Table 2 Base mechanical properties of the final polymer blends and
PVA foil
Tensile strength [MPa] Elongation at break [MPa]
PVA 35.8 ± 0.68 161.9 ± 14.55
PVA/G10 16.8 ± 1.25 141.6 ± 29
PVA/G21 14.3 ± 0.31 126.7 ± 37.27
PVA/G42 12.2 ± 0.63 10 ± 1.0
PVA/X10 20 ± 0.59 205 ± 52.18
PVA/X21 17.5 ± 0.20 134.2 ± 14.9
PVA/X42 15 ± 0.94 20 ± 1.5
J Polym Environ (2013) 21:88–94 91
123
a 42 % proportion of polysaccharides. This especially
applies to the PVA/X42 sample, for which the results from
anaerobic mesophilic sludge and compost showed miner-
alization at 60 %, while for the soil environment this value
was only about 50 %. Lower levels of decomposition were
found in blends containing 21 % of polysaccharides, where
the balance of the biodegradation products showed rates of
mineralization from 28 to 35 % for the PVA/X21 sample
and 21–25 % for the PVA/G21 sample, depending on the
type of environment. For the blends containing 10.5 % of
polysaccharides, the mineralization results not exceeded
25 %.
Increasing the degree of mineralization of samples with
an increased proportion of natural components indicates an
important characteristic of blends prepared by extrusion.
This concerns the fact that in the plastic materials so pro-
duced there are no interactions between the polymers,
which would prevent biodegradation of natural compo-
nents. This was clearly visible in the PVA blends with
xanthan, where the values identified of the samples’ min-
eralization corresponded to the relative representation of
polysaccharide and glycerol in different types and showed
that it was only poly(vinyl alcohol) which remained a non-
decomposed component in soil, compost and anaerobic
sludge. These assumptions were confirmed by the results of
the diluted organic carbon found in supernatant liquors at
the end of tests in anaerobic sludge, since the DOC con-
centrations corresponded to the proportion of PVA in the
samples weight and the volume of the sludge suspension
used (data not shown).
FTIR Characterization
Infrared spectra of PVA, xanthan, gellan and final blends
are shown in Figs. 2 and 3. In FTIR spectrum of pure PVA
major bands related to hydroxyl and acetate groups are
present. The broad band observed at 3,300 cm-1 is asso-
ciated with the O–H stretching vibrations from the inter-
molecular and intramolecular hydrogen bonds. The
vibration band observed at 2,909 cm-1 refers to the C–H
stretching vibrations from alkyl groups. The bands at 1,731
and 1,245 cm-1 are associated to the C = O stretching
vibrations and C–O–C functional groups, respectively,
originating from remaining acetate groups [20].
FTIR spectrum of xanthan shows strong band at
3,300 cm-1 due to O–H stretching vibrations and two
carbonyl bands at 1,723 cm-1 corresponding to acetate or
Table 3 Biodegradability of
pure PVA, xanthan and gellan
under differing conditions
(mean ± SD, for n = 3 or 4)
Mineralization [%]
Activated sludge Anaerobic sludge Compost Soil
Test time 20 days 34 days 47 days 48 days
Gellan 86.92 ± 1.32 72.69 ± 3.85 35.21 ± 1.88 35.78 ± 1.40
Xanthan 91.39 ± 0.96 77.00 ± 0.67 97.76 ± 0.29 76.12 ± 1.83
PVA 68.13 ± 0.96 8.28 ± 0.17 8.48 ± 0.10 B1
Fig. 1 Mineralization of all
polymer blends under differing
conditions (mean ± SD, for
n = 3 or 4)
92 J Polym Environ (2013) 21:88–94
123
pyruvate groups, respectively, and at 1,600 cm-1 charac-
teristic of a carboxylate group [21].
FTIR spectrum of the pure gellan shows very large band
at 3,312 cm-1 corresponding to O–H stretching vibrations
from hydroxyl groups. The bands located in the range
2,882–2,926 cm-1 can be assigned to the CH3 and CH2
stretching vibrations groups. In the wavenumber regions
from 700 to 2,000 cm-1, a band at 1,600 cm-1 is attributed
to glycosidic bond and that at 1,404 cm-1 is associated to
the C–H bending [22]. The bands at 1,023–1,149 cm-1 are
due to ethereal and hydroxylic C–O stretching, respectively
[23].
In FTIR spectra of final blends the adsorption peaks at
1,600 cm-1 proportional to the xanthan or gellan content
are clearly visible, while the peaks at 1,731 cm-1 and at
1,245 cm-1, representing PVA ester groups, are reasonably
reduced. Similar trend is evident in the wavenumber region
of 1,100–1,000 cm-1 (C–O stretch and O–H bending).
Obtained results proved mixed character of the blends,
without formation of any new bonds; interaction in the
form of the hydrogen bonds between polysaccharides and
PVA in the blends described in the range of
3,000–3,500 cm-1 by Sudhamani et al. [12] were not by
our measures found.
Fig. 2 FTIR spectra of xanthan,
PVA and their blends
Fig. 3 FTIR spectra of gellan,
PVA and their blends
J Polym Environ (2013) 21:88–94 93
123
Conclusions
Plastic materials on the basis of poly(vinyl alcohol) that
contained xanthan or gellan were prepared. The results of
the base mechanical properties and biodegradability have
shown that, of the natural carbohydrate polymers, xanthan
was the more preferable type, as blends containing this
polysaccharide demonstrated more favourable properties
than samples with the same proportion of gellan. Even
though blends with a high proportion of carbohydrates
(42 %) were found to show a high degree of biodegrad-
ability, this occurred at the expense of their mechanical
properties. Therefore, PVA-based plastics with a content of
around 20 % of xanthan prepared through plasticization of
basic component with subsequent extrusion appear to be an
alternative for applications where maximum tensile
strength is not a requirement. Thus, such plastic materials
can help to reduce PVA inputs into the environment, where
PVA biodegradation proves rather limited.
Acknowledgments This work was supported by the Grant Agency
of the Czech Republic (GACR P108/10/0200) and also with support
from Operational Program Research and Development for Innova-
tions co-funded by the European Regional Development Fund
(ERDF) and the national budget of the Czech Republic, within the
framework of the project Centre of Polymer Systems (reg. Number:
CZ.1.05/2.1.00/03.0111).
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