Polymer Degradation and Stability 95 (2010) 225e233

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Polymer Degradation and Stability

journal homepage: www.elsevier.com/locate/polydegstab

Lignin and starch as potential inductors for biodegradation of lms based

on poly(vinyl alcohol) and protein hydrolysate

ta Julinova

a, *, Jan Kupec a, Pavol Alexy c, Jarom
r Hoffmann a, Vladim
r Sedlar
k b,
Marke

kova

a, Peter Bugaj c

s Vojtek a, Jitka Chrom
ca
Toma
a
b
c

Department of Environmental Protection Engineering, Faculty of Technology, Tomas Bata University in Zlin, TGM Square 5555, 760 01 Zl
n, Czech Republic
Polymer Centre, Faculty of Technology, Tomas Bata University in Zlin, TGM Square 5555, 760 01 Zl
n, Czech Republic
Slovak University of Technology, Faculty of Chemical and Food Technology, Department of Plastics and Rubber, Radlinsk

eho 9, 812 37 Bratislava, Slovak Republic

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 17 April 2009
Received in revised form
4 September 2009
Accepted 15 October 2009
Available online 21 October 2009

The objective of this work was to study the biodegradation of blow-moulded lms of poly(vinyl alcohol)
(PVA)/protein hydrolysate (PH) which contain biodegradation inductors of the starch (S) and lignin (LI)
types. These increase the biodegradation rate of PVA while preserving or improving the technical and
usage properties of blends. The aim of the work was to reach the maximum breakdown rate so that rapid
disintegration of PVA could take place at a wastewater treatment plant. The biological material chosen
was activated sludge from a municipal wastewater treatment plant. Preparation of the blends required
that a plasticiser be used, in this case glycerol (G). This allowed for successful processing but prolonged
the lag phase of PVA breakdown as well as reducing its nal biodegradation percentage. The inuence of
G, in this respect, was not affected by incorporating PH. S and LI reduced the inuence of the plasticiser
but caused a breakdown rate comparable to PVA itself. Contrarily, after adapting biomass to PVA,
applying G produced a PVA breakdown rate three times greater, albeit with a lag phase prolonged
vefold. However, due to the duration of breakdown (the period above the retention time of wastewater
during activation), this effect was not positive. The addition of PH to the blends mentioned did not
exhibit any clear favourable inuence. Adding S resulted in a shorter lag phase, in addition to which the
degradation rate increased by approximately 1.5 times. Combining LI and S distinctly accelerated the
degradation of a blend, although a disadvantage of doing so is an incomplete breakdown of the substrate,
which lowers the nal biodegradation percentage. Therefore, an eventual compromise was arrived at,
this being a blend of PVA/G PH S. Its breakdown time is half that of pure PVA, and the lms produced,
from a mechanical standpoint, are more convenient.
2009 Elsevier Ltd. All rights reserved.

Keywords:
Poly(vinyl alcohol)
Lignin
Protein hydrolysate
Starch
Biodegradation
Activated sludge

1. Introduction
With a view to utilising existing polymers, an important trend
today is their modication into forms more susceptible to natural
biodegradation under aerobic and/or anaerobic conditions. One
way of achieving this consists of incorporating readily degradable
additives that, rst and foremost, have to be inexpensive and
should not affect the mechanical and practical properties of a nal
product. From this perspective, waste materials (e.g. lignocellulose,
waste gelatin, protein hydrolysate) appear to be prospective llers,
the same goes for renewable sources (starch, chitin, derivatives of
chitin and others) or products made from these. If these plastics are
to nd a wider role commercially, they have to be easily processed,

* Corresponding author. Tel.: 420 57 603 1220; fax: 420 57 721 0172.

).
E-mail address: julinova@ft.utb.cz (M. Julinova
0141-3910/$ e see front matter 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.polymdegradstab.2009.10.008

possess properties comparable to usual plastic types and be

competitively priced.
PVA ranks among the few forms of biodegradable synthetic
polymer that are frequently modied owing to their properties.
After being employed by industry, it is carried away in wastewater
to treatment plants, where it is more or less successfully degraded.
Nevertheless, it remains in soil [1] and displays low biodegradation
when applied in agriculture. Another use of it is as packing material
for anglers' bait-bags. Consequently, PVA turns up in surface and
ground water, where it is susceptible to biological processes. Its
course, however, is quite lengthy and continuous effort is made for
this reason, with the endeavour to shorten the biodegradation time
of PVA to the maximum possible extent, simultaneously attempting
to preserve or improve its technological and usage properties.
There are numerous well-known PVA-based blends, but only a few
papers have concentrated on describing the consequences of
making blends with a view to the biodegradability of PVA. Its

226

et al. / Polymer Degradation and Stability 95 (2010) 225e233

M. Julinova

biodegrading qualities may not only be affected by this primary

modifying property, but also by processes running during blend
preparation, such as heat treatment. In addition, they need not be
quantied by an effective sum of the degradability of particular
components.
Biodegradation of pure PVA and its blends has been given
considerable attention in the past. Beside the blends discussed
later, other combinations have also been prepared, examples
including polyphenols/PVA [2], poly(lactic acid)/PVA [3], poly
(propylene carbonate)/PVA [4], polyhydroxybutyrate/PVA [5],
chitin/PVA [6,7], chitosan/PVA [8,9] and chitosan/PVA/gelatin [10].
Literature mostly refers to combinations of PVA with various kinds
of starch [11,12]. Indeed, the authors mentioned did not study the
biodegradability of these materials.
Ishigaki et al. [13] have studied the biodegradability of blends
containing 60% Mater-Bi AF 10H starch and 40% PVA in an aqueous
environment, applying inoculum of various origins (activated
sludge, Bacillus subtilis, Pseudomonas vesicularis var. Povalolyticus,
enzyme a-amylase). In their work, they state that when activated
sludge with the dry matter content of 50e2000 mg l1 (a mixed
liquor suspended solid concentration) was employed, a 40%
decrease in substrate (lm) appeared in 30 days. A degradation test
using the bacteria B. subtilis (isolated from soil) showed concentration reduced by 45% in 5 days. The reduction in substrate was in
accord with the enzymatic activity examined. In the presence of
bacteria of the P. vesicularis species, isolated by these authors from
activated PVA-adapted sludge, the blend was degraded by 50% in 30
days. Biodegradation in the presence of the enzyme a-amylase
(catalysing the breakdown of starch) led to a 50% reduction in
concentration in one day.
Typically, blends based on PVA/starch possess inferior technical
and usage properties; hence efforts to modify starch physically or
chemically. For example, water resistance and the mechanical
properties of PVA/methylated cornour are described in a work by
Zhao et al. [14]. The authors Yang Sung-Yeng et al. [15] proposed
using plasma treatment to increase the mechanical and thermal
properties of PVA/S blends. A current trend is also the application of
nanollers for preparing PVA/S blends; a paper [16] describes the
effect of nano-SiO2 on the performance of lms based on a PVA/
starch blend. Nonetheless, even in this manner, properties comparable to those of polymers presently available were not achieved,
and the authors again omitted an examination of biodegradability.
A promising and potential ller for PVA, as regarded by the
authors of references [17,18] is lignocellulose, which is obtained
from food and agricultural industry waste (pressed sugar cane,
orange and apple peelings). Water-soluble mixed lms were
prepared, employing plasticiser G with urea. According to the
authors, urea was utilised to allow the blends to be additionally
applied as a farm fertiliser. Nevertheless, the resultant blends were
very sensitive to atmospheric humidity. The authors, therefore, also
included cross-linking agents (hexamethoxymethylmelamine or
formaldehyde) in their following paper [18]. The mixed lms thus
prepared (PVA:lignocellulose 1:1) with added urea and glycerol,
as well as PVA alone, were subjected to biodegradation tests in an
aerobic aqueous environment in the presence of adapted activated
sludge. After a 45-day incubation, a 45% breakdown occurred in
pure PVA and 30e35% breakdown occurred in mixed lms. Filler
itself (lignocellulose) was degraded by only 17% in the presence of
PVA-adapted inoculum. Adapting the inoculum resulted in reduced
breakdown of the readily degradable component. The authors
concluded from these results that the presence of lignocellulose
containing residual concentrations of glucose diminishes the
activity of PVA-degrading bacteria.
From among a number of waste materials, gelatin has been
tested as a ller too. Chiellini et al. [19] prepared blends containing

20% waste gelatin and PVA. They studied the thermomechanical

properties and biodegradability in a soil environment. Applying
gelatin when preparing PVA-based blends is also described in
a work by Mendieta-Taboada et al. [20], although the authors
merely examined thermomechanical properties.
A substance sharing similar qualities to gelatin is PH commercially designated as Hykol E. It is made by enzymatic hydrolysis of
chrome-tanned leather waste (shavings). Alexy et al. [21,22],
prepared blends of various PH and PVA contents, the plasticiser
utilised being G. Their attention focused on usage and technological
properties, though principally on water solubility and water
penetration. Despite the high content and wide concentration
range of protein hydrolysate in a blend, all blends were able to be
processed and provided very high quality lms (assessed through
melt ow index e MFI, thermogravimetric analysis and torque). Via
a planned test system, they observed the inuence of G and PH
contents on the properties of lms. Comparing the results obtained,
the authors concluded that lms containing PH displayed markedly
better water solubility in comparison with lms prepared on the
basis of sole PVA. They further found that PH very signicantly
affects the water solubility of lms at low temperatures too, its
increasing content reducing the time to rst lm dissolution. In
addition, the G/PH ratio may signicantly affect the content of
insoluble fractions and PH of solutions (adding PH increases the PH
level of a 2% aqueous solution of a blend from approximately 5.75 to
approx. 6.5). The biodegradability of these blends is described in
a work by Hoffmann et al. [23]. In order to evaluate the biodegradation of mixed lms, the authors rst chose activated sludge from
a wastewater treatment plant as the inoculum. A two-stage course
of biodegradation curves was recorded in all cases.
It follows from the survey of literature presented that adding PH
(or gelatin) is associated with improvements in the technological
and usage properties of PVA-based mixed lms. However, the
biodegradation time and biodegradation percentage of PVA itself
are usually less favourable. By contrast, the starch contained in the
PVA-blends has a positive inuence on the biodegradation of PVA,
although technological and usage properties proved unsatisfactory.
The facts above have brought about the use of more types of
llers for preparing mixed PVA-based lms, preserving or
improving their technical and usage properties via adding PH and
supporting the biodegradation of PVA alone with added S. Literature also mentions that enzyme lignin-peroxidase may also
participate in PVA biodegradation. In a paper [24,25], it was proven
that lignin-peroxidase (Phanerochaete chrysosporium) increased the
degradation of PVA chains by forming carbonyl groups and double
bonds. A signicant (approximately 80%) reduction was observed in
its mean molecular mass [24]. For this reason, the additional ller
chosen for our work was modied lignin.
Hence, the objective of this study was to examine the biodegradability of blow-moulded PVA lms based on PVA and PH, with
added S and LI for increasing the biodegradation rate of PVA, while
preserving or improving the technical and usage properties of
mixed lms.
2. Experimental
2.1. Materials and chemicals
The materials employed for the experiments were mainly
commercial products currently available. POVAL 205 (PVA),
viscosity 5 mPa s, hydrolysis degree 88%mol, produced by Kuraray,
Japan; Hykol E (PH) collagen hydrolysate, prepared via enzymatic
hydrolysis of chrome-tanned shavings, nitrogen content 14%,
molecular mass 1000 g mol1, powdery in form, produced by Tanex
r, the Czech Republic; MERITENA 100 (starch, S) natural
Co e Jarome


et al. / Polymer Degradation and Stability 95 (2010) 225e233

M. Julinova

untreated cornour, produced by Amylum Co e the Slovak

Republic; LIGNIN 2 (LI) e modied lignin obtained from beechwood, a product under development at the SAV Chemical Institute
in Bratislava, the Slovak Republic; GLYCEROL (G), delivered by H.C.I.
Slovak Republic; STEARIN III e a blend of stearic and palmitic acids,
specied for pharmaceutical purposes, produced by SETUZA Co e

nad Labem, the Czech Republic; SIPERNANT 22 S e precipitated
Ust

silicon dioxide for pharmaceutical purposes, produced by DEGUSSA
Co- Germany; TALC e Mg3(OH)2(Si4O10) from Magnatech Co e

sta, the Slovak Republic.
Hnu
All other chemicals employed were of analytical purity,
produced or supplied by Pliva Lachema Brno, the Czech Republic.
2.2. Film preparation
The percentage of the particular components present in the
mixed blow-moulded lms and blends (Table 1) was chosen on the
basis of a compromise between the necessary and envisaged processing and biodegradation properties. When preparing the lms,
one requirement involved the application of an anti-blocking agent
e silicon dioxide (or talc) e present in the quantity of 0.37e0.57%
mass depending on blend composition. The agent preventing the
adhesion of PVA melt to processing equipment and reducing shear
stress in the melt was a blend of stearic acid and palmitic acid
(Stearin III) used in the mass quantity of 0.3%.
2.2.1. Thermoplastic starch (TPS) e plasticisation of starch
The agent employed as a plasticiser for S was a mixture of G and
water (Meritena 100:glycerol 2:1). The mixtures for plasticising
were prepared in a high-speed uid mixer at laboratory temperature. The mixtures of water, G and S were then heated to 80  C in
a hot-air drier for 2 h. During this time, a paste of S was created,
which was then left to stand for 24 h at laboratory temperature.
Drying the mixture was nished at 60  C in order to produce a loose
material.
The mixtures for preparing blends and blow-moulded lms
were prepared in a Brabender Plasticorder planetary mixer, and in
such manner that all the powdery components were dosed rst
into the planetary mixer whilst G was gradually added during the
action of continuous stirring (50 rpm). After adding all the G, the
mixture was heated to 130  C for 5 min. The mixture was discharged from the mixer after this time and cooled to laboratory
temperature. The blow-moulded lms were subsequently prepared
on the laboratory Plasticorder Brabender extruder in the following
specication: screw diameter 19 mm, L/D 25, compression ratio
1:3, the blow extruder head employed was of a special type; the
regime of temperatures from the feeding hopper to the head was
210e220e230e200  C, with a rotation speed of 35 rpm.

Table 1
Composition of blends (lms) on the basis of polyvinyl alcohol in wt%.
Sample

PVA Protein
Glycerol Starch Thermoplastic Lignin
hydrolysate
starch

PVA/G
PVA/G
PVA/G
PVA/G
PVA/G
PVA/G
PVA/G
PVA/G
PVA/G
PVA/G
PVA/G

88.9
75.5
69.7
69.7
69.7
69.7
67.1
69.7
69.7
69.7
69.7

S (2:3)
S (1:1)
S LI
TPS
TPS LI
PH
PH S
PH S LI
PH TPS
PH TPS LI

e
e
e
e
e
e
16.7
5.1
2.5
5.1
2.5

11.1
9.4
15.2
15.1
7.6
10.1
16.2
15.1
15.1
10.1
10.1

e
15.1
15.1
10.1
e
e
e
10.1
10.1
e
e

Thermoplastic Starch (TPS), Meritena 100:glycerol 2:1.

e
e
e
e
22.7
15.1
e
e
e
15.1
15.1

e
e
e
5.1
e
5.1
e
e
2.5
e
2.5

227

2.3. Biodegradation tests

The biodegradability of samples tested was studied in an aerobic
aqueous environment. Inoculation was in the form of centrifuged
activated sludge from a wastewater treatment plant, either unadapted
(method I) or PVA-adapted in the laboratory [26] (method II). The
initial dry matter content of the sludge was 500 mg l1 and the
concentration of substrate (blend) was approximately 100 mg C per
litre (corresponding to COD 300 mg l1). The blends tested were
always dissolved in cold mineral medium and the only source of

organic carbon. A mineral medium according to CSN
EN 29439 [27]
was employed for preparing these solutions and for all dilutions. The
level of PH during testing was 7.0  0.5.
In order to determine the biodegradability of blends, two comparable instruments were chosen. For method I, an automatic respirometer of the MicroOxymax (Columbus Instruments Co-Ohio, USA)
type was used alongside laboratory apparatus with continuous
determination of CO2 production (acidimetry), in addition to which
samples were taken of activated sludge suspension (to determine PVA
and DOC) without corruption of the gas atmosphere in the bioreactor.
The comparative tests showed (with the help of a standard) that
satisfactory results through both methods were achieved [31].
2.3.1. Method I e tests with unadapted activated sludge
The method selected for tests with unadapted inoculum was the
determination of production of CO2 by the MicroOxymax respirometer [27,28]. Allyl thiourea was added to the suspension to
suppress potential nitrication processes whilst endogenous
respiration was also examined. The basic biodegradability criterion
was the ratio of CO2 actually produced during microbial breakdown
to the theoretical quantity of CO2, as given by the balance of carbon
present in a sample and expressed as DCO (%) in accordance with (1):

DCO2

nCO2sample  nCO2blank
ThCO2

 100

(1)

where: nCO2sample is the quantity of CO2 produced during breakdown

of the substrate (mmol), nCO2blank is the quantity of CO2 produced
during endogenous respiration of micro-organisms (mmol), and
ThCO2 is the theoretical production of CO2 from total substrate
breakdown (mmol) as determined by the balance of organically
bound carbon in mixed lm (TOC 5000A e (Shimadzu Corp e
Austria).
2.3.2. Method II e tests with PVA-Adapted activated sludge
The method [23] chosen for tests with adapted inoculum was
acidimetric determination of CO2 produced (1) and the decrement
of PVA from the cultivation medium by laboratory apparatus [23].
The decrease was determined by spectrophotometry. PVA with
iodine and boric acid forms a blue-coloured complex, whose
intensity changes with PVA concentration at l 658 nm [29].
Samples for spectrophotometrically determining PVA were taken at
24 h intervals and ltered through lter paper (surface mass
85 g m2). With help of this simple methodology, the biomass and
non-dissolved starch were removed from the sample analysed.
During application of this advance, the inuence of additives on
spectrometric determination of PVA was rendered [31], the data
concerning which is not presented here.
2.3.3. Mathematical description of experimental dates
Pure components or blend biodegradation time courses, DCO f
(t) or DPVA f(t), were described by regression, applying an equation for rst-order substrate kinetics (2) [30]:

D Dmax  1  ekttlag

(2)


et al. / Polymer Degradation and Stability 95 (2010) 225e233

M. Julinova

where Dmax is the regression coefcient representing the limit

value in innite time [%], k are the constant rates e kDPVA, kDCO are
[h1], and tlag is the shift on the time axis expressing lag phase [h].
So as to assess whether biodegradation proceeded in accordance
with the rule of additivity, meaning the nal biodegradation degree
in the given time is denoted by a sum of biodegradations of
particular components, or if physico-chemical and microbial reactions (positive or negative) occur in the system, the chosen calculation (3) applied was [31]:

kDCO2 W1  k1DCO2 W2  k2DCO2 . Wn  knDCO2

(3)

where: the particular values k1 e kn were calculated in accordance

with the equation for pure components (2), and values w1 e wn
represent mass fractions of particular components in the respective
blend (Table 1). Finally, (calculated theoretical blends kDCO eq. (3)), it
is possible to calculate additive curves at any time by an equation (2).
Over time, the course of additive curves of blends with the
content S and/or LI and/or PH showed that the percentage of other
components was not the expressive inuence (Figs. 1 and 2); hence
for comparison with real courses, it is possible to use the average
gure and standard deviation.

70
60

Biodegradation [%]

228

50
40
PVA
30

PVA/G
PVA/G PH

20

PVA/G PH S
PVA/G PH S LI

10

additivity*
0
0

100

200

300

400

500

Time [h]
Fig. 2. The course of aerobic biodegradation (according to CO2 produced) of polyvinyl
alcohol and blends containing protein hydrolysate, starch and lignin in the presence of
unadapted activated sludge. Additivity* is the average value of theoretical biodegradability of the blends PVA/G PH, PVA/G PH S and PVA/G PH S LI; (SD), according to
equation (3), Chapter 2.3.3.

3. Results and discussion

PH proved surprisingly suitable for improving the technological
and usage properties of PVA [21]. Blends containing starch [13]
exhibited an increased biodegradation rate of PVA due to the
presence of the enzyme a-amylase arising whilst S itself degraded.
Therefore, in accordance with the procedure described in the
Experimental section above, blends were prepared that contained
both PH and S. It was found in the literature that lignin-peroxidase
enzyme resulting from lignin biodegradation [25] may also
participate in biodegrading PVA. Consequently, modied lignin (a
breakdown inductor), present in a quantity of 2.5e5%, was chosen
as a ller. The plasticising agent employed in preparation was
always glycerol, which was additionally used for plasticising starch
(TPS) in the ratio of starch:glycerol 2:1.
During the technological incorporation of PH into PVA/G blends,
physico-chemical interactions between the PVA and protein
component demonstrably took place. It may be assumed [31] that

70

PVA
PVA/G

Biodegradation [%]

60

PVA/G S (2:3)
PVA/G S LI

50

PVA/G TPS LI
additivity*

40
30
20

unreacted acetate groups in PVA release acetic acid when heated,

and double bonds occur in the polymeric chain. In the presence of
compounds with free amino groups (e.g. as in PH), the original
acetate group may be replaced with the formation of an amide
bond. Free amino groups in PH react with acetic acid that has split
off to form acetamide, thereby partly eliminating a decrease in PH
and the course of acid-catalysed degradation reactions as a consequence. Hence, PH becomes a stabiliser for PVA. With higher PH
content (more amino groups), cross-linking then takes place [31].
In such a case, one may already speak of modifying PVA itself. This
should be taken into account when assessing the biodegradability
of blends under study. The possible interactions between the other
components of blends (S, LI) and PVA were not examined.
The inuence of particular components in mixed lms on PVA
breakdown was judged from two standpoints e ecology and
processing.
The objective of the environmental standpoint was to achieve
the maximum breakdown rate so that potentially rapid breakdown
of PVA would practically take place (at a wastewater treatment
plant). For this reason, the chosen biological material was a mixed
microbial culture (activated sludge from a wastewater treatment
plant). The results obtained from biodegradation tests were processed in this respect. An accent was laid on minimising the lag
phase and reducing the degradation period relative to the retention
time of wastewater in the activation tank, as well as on attaining
maximum breakdown with a view to residual values of efuent
from the wastewater treatment plant.
As regards processing, the chief purpose was to reduce the price
of polymer, increase the resistance of blends to atmospheric
humidity and enhance water solubility.

10

3.1. Biodegradation of particular components of blends

0
0

100

200

300

400

500

Time [h]
Fig. 1. The course of aerobic biodegradation (according to CO2 produced) of polyvinyl
alcohol and blends containing the additives of starch and lignin in the presence of
unadapted activated sludge. Additivity* is the average value of theoretical biodegradability of the blends PVA/G S, PVA/G S LI and PVA/G TPS LI; (SD), according to
equation (3), Chapter 2.3.3.

In accordance with literature [1] and previous experiments

[21,23], it was found that with current unadapted wastewater
treatment culture, pure PVA degraded during a lag phase of
140e290 an hour for approximately 400 h (70% DCO2 ), under
conditions presented in Section 2.3. In reality, PVA does not appear
in municipal wastewater, the relevant biomass is not adapted,
and as a consequence the lag phase is disproportionately long


et al. / Polymer Degradation and Stability 95 (2010) 225e233

M. Julinova

(a small fraction of micro-organisms are capable of metabolising

PVA). Conversely, adapting micro-organisms to PVA is associated
with the rather speedy development of PVA-degrading bacteria,
which showed in a degradation lag phase shortened to a maximum
of 24 h. Therefore, adapting micro-organisms brought about almost
immediate degradation of PVA.
As expected, adding PH, S and G meant that conditions for good
biodegradability were met, according to the production of CO2 [31];
the mineralization degrees register for PH 93%, S 86% and G 85%. It
was only whilst modied Lignin 2 was biodegraded under the given
conditions that complete biodegradation did apparently not occur
(20% DCO2 ), biodegradation products did not thus consist of solely
CO2 but probably humic compounds [31,32] hard to biodegrade.
This supposition was suggested by increasing the turbidity of the
reaction suspension e the absorbance level at 254 nm rose over
time [33] and levels of DOC during tests stagnated [31]. However,
virtually no lag phase (<5 h) was recorded during the biodegradation of Lignin 2.
Other additives (a mixture of palmitic and stearic e Stearin III
and silicon dioxide e Sipernat 22 S) were added to the blends to
improve their processing technically, being used in very low
concentrations (approx. 0.3e0.5%). For this reason, no attention
was paid to them concerning their biodegradability.
3.2. Biodegradation of blends of unadapted sludge
Multiple-component PVA-based blends are characterised by
a multi-stage (2e3) biodegradation course depending on the
character and number of additives [34]. In the case of blends under
study here, a 2-stage course (Figs. 1 and 2) was recorded in accord
with expectations. Spectrophotometric determination of PVA
proved the second breakdown degree corresponded to PVA
biodegradation.
Nevertheless, G added to the plastic brings about a PVA lag
phase prolonged by 72 h, in addition biodegradation reduced by
10%, thus markedly worsening breakdown in an unadapted
microbial environment, which is unacceptable as regards wastewater treatment plants. This highlights how the use of other

229

additives when making PVA-based lm is substantiated. Adding

S and LI to blends (Fig. 1) suppresses the negative effect of plasticising, but PVA biodegradation is always retarded. This is also
conrmed by analysing the additive curve (Fig. 1), calculated
according equations (2, 3). A required increase in PVA biodegradability does not occur but the negative effect of plasticising is
minimised.
In terms of blends containing PH, due to the PVA/PH interactions
proven, our team rst studied the inuence of protein hydrolysate
on biodegradability. Accordingly, the breakdown of a PVA/PH blend
was examined concurrently with that of a mixture of aqueous
solutions of PVA and PH, both of these being identical in mass
content. In 672 h, the blend as well as the mixture of solutions
exhibited DOC removal exceeding 97%. However, during biodegradation of the mixture of aqueous solutions, a longer lag phase (by
about 96 h) for the second biodegradation degree was recorded, as
was 20% lower degradation according to DCO2 [35]. This result is
unexpected as any potentially slower breakdown was rather
assumed to occur with heat-processed blends as a consequence
of interactions between PVA and protein molecules. Therefore, it
follows that physico-chemical interactions between PH and PVA
produced whilst heat processing a blend do not exert a negative
inuence on the biodegradation of these blends [35].
Nevertheless, adding PH again lowered the percentage of
biodegradation and prolonged lag phase in comparison with PVA
alone. The second-stage limit values of biodegradation were almost
identical (relative to additive content) to plasticised PVA. The
negative effect of plasticisation was not so suppressed by adding
PH, although it was achieved only when the blend was lled with
PH and S as well as LI. The lag phase extended merely by 1 day
longer as opposed to just PVA. When data is compared to the
additive course, the level of measured DCO2 is again markedly lower
than that of the theoretical (Fig. 2).
A comparison of limit values from the second stage of blend
biodegradation, calculated in accordance with the equation of rstorder kinetics (2), is shown in Fig. 3. A statistically signicant
difference was only recorded in the lag phase of the second stage of
breakdown, which depended in all cases on the contents of additives

PVA
PVA/G

DCO2 max
DCO2
[%]

PVA/G S (1:2)

t lag [h]
of 2nd stage
tlag
kk[10-3
DCO2 h-1]

PVA/G S LI
PVA/G TPS LI
PVA/G PH
PVA/G PHS
PVA/G PHS LI
PVA/G PH TPS
PVA/G PH TPS LI
0

25

50

75

100

125

150

175

200

225

DCO2 max [%]; t lag of 2nd stage [h]; kDCO2 [10-3 h-1 ]
Fig. 3. Limit values for the second stage of biodegradation of blends evaluated by CO2 produced in the presence of unadapted activated sludge (SD).


et al. / Polymer Degradation and Stability 95 (2010) 225e233

M. Julinova

230

Table 2
Limit values (SD) for the biodegradation of blends (lms) based on of polyvinyl
alcohol with adapted activated sludge.
kDCO [103 h1]

Theoretical kDCO [103 h1]

PVA
PVA/G
PVA/G
PVA/G
PVA/G
PVA/G
PVA/G
PVA/G
PVA/G
PVA/G
PVA/G

11.9 
10.3 
20.1 
9.1 
13.2 
10.6 
7.1 
17.9 
11.8 
11.8 
8.8 

e
11.7
11.9
11.2
11.9
11.2
11.4
11.7
11.5
11.8
11.5

S (1:1)
S LI
TPS
TPS LI
PH
PH S
PH S LI
PH TPS
PH TPS LI

90

Biodegradation of PVA [%]

Sample

100

0.97
0.86
1.55
0.91
0.68
1.32
0.72
0.93
1.07
0.63
0.77












0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01

80
70
60
50
40

PVA

30

PVA/G

20

PVA/G S (1:1)
PVA/G S LI

10
0

and protein hydrolysate. It ranged from 180 to 216 h. In almost all

instances it grew longer, the smallest difference against sole PVA was
discovered with the blend PVA/G PH S LI. The longest lag phase was
then recorded with the blend PVA/G PH (approximately 9 days).
From the facts above, it follows that adding S and LI (assumed
inductors of PVA breakdown) only leads to suppressing the negative plasticising inuence of G. When choosing such blends for use
in an environment with unadapted microbial culture (anglers'
sacks for bait, seed sowing tapes and the like), the decisive factors
will obviously be their practical and processing properties in
addition to the economic demands of manufacture.

50

100

150

200

250

Time [h]
Fig. 5. The course of aerobic biodegradation affecting polyvinyl alcohol and the same
substance present in blends containing the combined additives of starch and lignin in
the presence of activated PVA-adapted sludge.

On evaluating the acidimetric determination of DCO2 and processing data via rst-order kinetics, no marked difference was
found in breakdown rate e kDCO of individual blends (Table 2).
2
When comparing values actually measured with those calculated
according to the rule of additivity (the mass of individual components that contributed to blend breakdown), relatively good
agreement was demonstrated in most cases. The only exceptions
were PVA/G S and PVA/G PH S blends, for which the breakdown
rate almost doubled according to DCO2 .
Together with assessing the breakdown rate of individual blends
in accordance with carbon dioxide produced, decreases in the
polymeric component e PVA e were also analysed, the data again
being processed via rst-order kinetics. This criterion indicated the
potential for yet more important connections between blend
composition and PVA breakdown (Figs. 4e6).

3.3. Biodegradation of blends by adapted activated sludge

The biodegradability of prepared blends in the presence of
activated PVA-adapted sludge was tested via the carbon dioxide
produced as determined by acidimetry e equation (1), and the
decrement of PVA from the cultivating environment [23].
Adapting micro-organisms to PVA signicantly reduced a lag phase
of blend to approximately 24e48 h and a one-stage course [23]. The
values of DCO2max uctuated at around 80%, and a 99% removal of PVA
from suspension occurred in all cases.

100

Biodegradation of PVA [%]

90
80
70
60
50
PVA

40

PVA/G

30

PVA/G PH

20

PVA/G PH S

10

PVA/G PH S LI

0
0

50

100

150

200

250

300

350

Time [h]
Fig. 4. The course of aerobic biodegradation affecting polyvinyl alcohol and of the same substance present in blends containing protein hydrolysate, starch and lignin in the
presence of activated PVA-adapted sludge.


et al. / Polymer Degradation and Stability 95 (2010) 225e233

M. Julinova

100

Biodegradation of PVA [%]

90
80
70
60
50
PVA

40

PVA/G TPS

30

PVA/G TPS LI

20

PVA/G TPS PH

10

PVA/G TPS PH LI

0
0

50

100

150

200

250

Time [h]
Fig. 6. The course of aerobic biodegradation affecting polyvinyl alcohol and the same
substance present in blends containing protein hydrolysate, thermoplastic starch and
lignin in the presence of activated PVA-adapted sludge.

Contrary to the results obtained by tests with an unadapted

microbial culture, plasticising PVA with G here positively affected
polymer biodegradation, and biodegradation did occur, with a rate
as much as three times greater. In one respect, the presence of
a readily degradable substrate (G) led to a lag phase prolonged from
around 10 h to 50 h, but nal degradability was comparable with
that of sole PVA e more than 99%. However, a generally shorter
breakdown time occurred, namely by 48 h (Fig. 4).
When the PVA/G blend received an added PH fraction about as
large as that of G, no change took place in degradation time, lag
phase or PVA breakdown rate. The inuence of an interaction
between PVA and PH on the biodegradation of PVA was not
recorded (Fig. 4).

231

Adding S (Fig. 5) or TPS (Fig. 6) to a PVA/G blend favourably affected

the PVA degradation rate (compared to PVA itself). The breakdown
rate increased by 1.5 times and lag phase was 33 h shorter.
As is obvious in Fig. 7, the best results were obtained with PVA
modied by means of PH and S (PVA/G PH S). A markedly shortened
breakdown time of the blend occurred, and the same dropped by
50% when compared with PVA itself (67 h), in addition to which the
breakdown rate increased by approximately 4.5 times, with
a minimum lag phase (18 h).
As blends that are based only on LI and plasticised PVA cannot
be prepared (not being capable of forming lm), the direct inuence of LI on PVA degradation was not studied, although an effect
analysed was that of its addition to plasticised PVA containing
S and/or PH. As follows from Figs. 4e7, LI strongly accelerated the
PVA breakdown rate. In terms of kPVA, the optimum blend was PVA/
G PH S LI, which resulted in an increase of approximately thirteen
times in breakdown rate. The biodegradation of blends containing
LI admittedly was strongly accelerated in all cases, although biologically resistant humin compounds were produced, and as
a consequence the levels of residual DOC (undesirable in efuent
from a wastewater treatment plant) rose. However, owing to lag
phase (approx. 65 h), the total breakdown time of PVA, being
reduced as required, was not exhibited. This is the limiting factor
from the viewpoint of water treatment technology and, for this
reason, blends of the composition as proposed cannot be regarded
as promising.
A comparison is depicted in Fig. 7 showing the limit values of
blend biodegradation calculated in accord with the equation of
rst-order kinetics (2). From the data presented, it is obvious that in
the case of PVA degradation by an adapted microbial culture, the
additives S and LI act as breakdown accelerators for PVA itself.
However, this was at the expense of lag phase and breakdown time
for most blends. Furthermore, it is PVA breakdown time alone that
is the key to assessing the convenience of the blend in a real-world
application, e.g. packing materials for used hospital linen. Bearing
this in mind, the only blend of note appears to be PVA/G PH S.

PVA

tPVA [%]
tPVA
t lag [h]
tlag

PVA/G

kk PVA
[10-3 h-1]
PVA/G S (1:1)
PVA/G S LI
PVA/G TPS
PVA/G TPS LI
PVA/G PH
PVA/G PHS
PVA/G PHS LI
PVA/G PH TPS
PVA/G PH TPS LI
0

25

50

75

100

125

150

175

200

225

t PVA [h]; t lag [h]; k PVA [10-3h-1]

Fig. 7. Limit values for the biodegradation of blends evaluated by DPVA in the presence of adapted activated sludge (SD), tPVA e time of 99% removal of PVA from suspension.

232

et al. / Polymer Degradation and Stability 95 (2010) 225e233

M. Julinova

4. Conclusions

References

From the point of view of utilising biodegradable blends, nding

a certain middle ground between requirements of manufacture and
following breakdown of the product (after use) in the environment
is very difcult. The ideal state is a mechanically valuable product
which shortly after application decomposes with maximum
possible efciency under the inuence of suitable biological
conditions. PVA is one of the few polymer matrices that can be
subject, in a satisfactory time and quantity, to biodegradation in an
aqueous aerobic environment. Practical biotechnologies in this line
include treatment of wastewater with heterogeneous technical
biomass e activated sludge e the process this paper was geared
towards. Biodegradation of PVA is supported in this work by both
adding suitable biopolymers (inductors) as well as by adapting
a given microbial culture. As preparing blends (blow-moulded
lms) for processing requires a plasticiser (here G) to be used, its
inuence on biodegradation also had to be taken into account.
Admittedly, G makes successful processing possible but it prolongs
the lag phase of biodegradation while simultaneously reducing its
nal biodegradation percentage. According to the data herein
presented, this is true of an unadapted culture, and this situation is
undesirable in terms of the technology found at wastewater
treatment plants. Incorporating PH does not suppress the inuence
of G, but it may be proven that assumed PVAePH interactions
probably running during thermal processing do not exert a negative inuence on the result of biodegradation. Employing inductors
(S e native as well as plasticised, and LI) lessen the mentioned
effect of a plasticiser, although a biodegradation rate comparable to
that of sole PVA is not achieved.
After adapting biomass to PVA, applying G contrarily increased
the breakdown rate threefold but with a lag phase prolonged by
ve times in length. The nal biodegradation percentage was
comparable to that of unplasticised plastic. However, due to the
duration of breakdown (the period above the retention time of
wastewater in activation), this fact is not favourable. Protein
hydrolysate present in the blends described did not exhibit
a noticeably favourable inuence. Adding inductors demonstrated
a shortened lag phase (by approximately 30 h) and an increased
degradation rate (1.5 times). Lignin combined with starch strongly
accelerated a blend's breakdown, probably due to the inuence of
an enzyme produced supporting PVA breakdown (forming CO
groups and breaking down more sensitive double bonds).
However, the disadvantage of adding LI is incomplete breakdown of
substrate (the production of intermediate humin compounds and,
thus, a high content of residual carbon), which decreases the nal
biodegradation percentage. Furthermore, the possibility should not
be overlooked as regards preparing lms based merely on PVA and
LI (the blend in question lacked the quality to form lm).
From the results of this work, it follows that the efciency of the
PVA biodegradation inductors selected greatly depends on the
microbial environment under study. The resultant compromise
(ensuing from the facts presented) between composition, mechanical properties and desired optimum biodegradation is the blend
designated PVA/G PH S. In an unadapted microbial environment, the
negative inuence of plasticising is most reduced, and in a PVAadapted environment its breakdown time is half that of sole PVA.
From a mechanical point of view, the lms produced are applicable.

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