Bioresource Technology 100 (2009) 17051710

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Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

Review

The anaerobic degradability of thermoplastic starch: Polyvinyl alcohol blends:

Potential biodegradable food packaging materials
Melissa A.L. Russo a,b,*, Cathryn OSullivan c, Beth Rounsefell c, Peter J. Halley a,b, Rowan Truss a,
William P. Clarke c
a
The Centre for High Performance Polymers, The University of Queensland, Queensland 4072, Australia
b
The Australian Institute of Bioengineering and Nanotechnology (AIBN), St Lucia, The University of Queensland, Queensland 4072, Australia
c
Division of Environmental Engineering, The University of Queensland, Queensland 4072, Australia

a r t i c l e i n f o a b s t r a c t

Article history: A systematic study on the anaerobic degradability of a series of starch:polyvinyl alcohol (TPS:PVOH)
Received 29 July 2008 blends was performed to determine their fate upon disposal in either anaerobic digesters or bioreactor
Received in revised form 15 September landlls. The aims of the study were to measure the rate and extent of solubilisation of the plastics.
2008
The extent of substrate solubilisation on a COD basis reached 60% for a 90:10 (w/w) blend of TPS:PVOH,
Accepted 17 September 2008
Available online 5 November 2008
40% for 75:25, 30% for 50:50 and 15% for PVOH only. The rate of substrate solubilisation was most rapid
for the 90:10 blend (0.041 h1) and decreased with the amount of starch in the blend in the following
order 0.034 h1(75:25); 0.023 h1(50:50). The total solids that remained after 900 h were 10 wt.%
Keywords:
Anaerobic digestion
(90:10); 23 wt.% (75:25); 55 wt.% (50:50); 90 wt.% (0:100). Starch containing substrates produced a
Degradation higher concentration of volatile fatty acids (VFAs) and biogas, compared to the 0:100 substrate. The major
Carbohydrates outcome was that PVOH inhibited the degradation of the starch from the blend.
Starch Crown Copyright 2008 Published by Elsevier Ltd. All rights reserved.
Polyvinyl alcohol

1. Introduction energy production. However, the effect of the synthetic polymer

Thermoplastic starch (TPS) materials present several advanta-
ges to the plastic industry due to their biodegradability, low cost
and wide availability (Avrous, 2004; Avrous et al., 2000). How-
ever, applications of TPS materials are limited by poor mechanical
strength properties and high moisture sensitivity (Avrous, 2004;
Avrous et al., 2000). Researchers have overcome these challenges
by successfully blending starch with other synthetic polymers
(Follain et al., 2005; Huneault and Li, 2007; Li et al., 2007; Martin
et al., 2007; Matzinos et al., 2002). Thermoplastic starch: polyvinyl
alcohol (TPS:PVOH) blends are of particular interest due to excel-
lent compatibility of these components (Kondo et al., 1994; Nwufo
and Grifn, 1985) and improved properties such as tensile
strength, elongation (Mao et al., 2000) and processability, predom-
inantly due to an improvement in melt strength (Fishman et al.,
2006; Mao et al., 2000), compared to pure TPS materials. Under
anaerobic conditions, such as a bioreactor landll, the starch will
digest to biogas (CH4 and CO2), thereby decreasing the volume of
organic wastes in the bioreactor landll and enhancing renewable
* Corresponding author. Address: The Australian Institute of Bioengineering and
Nanotechnology (AIBN), St Lucia, The University of Queensland, Brisbane, Queens-
land 4072, Australia. Tel.: +61 7 3346 3525; fax: +61 7 3346 3973.
E-mail addresses: m.russo@uq.edu.au, russo.mel@gmail.com (M.A.L. Russo).
matrix on the degradation of the starch is unknown.
Starch is a natural polymer that is comprised of linear amylose
and branched amylopectin where the amounts of each vary
according to the source and plant type (Dean et al., 2008). Recent
work has extended the use of starch in thermoplastic starch poly-
mer blends (Chaleat et al., 2008; Russo et al., 2007).
Starch can be readily metabolised by a range of microorganisms
(Weurding et al., 2001) to fermentation products such as ethanol
(Bai et al., 2008; Jamai et al., 2007), hydrogen (Okamoto and
Mityahara, 1999; Tadasa and Takeda, 1986; Yang and Shen,
2006) and methane (Amon et al., 2007; Carbone et al., 2002). PVOH
is susceptible to biological degradation; however, the process is
slow (Gartiser et al., 1998) especially under anaerobic conditions.
TPS and PVOH can be blended at varying concentrations, to tai-
lor the mechanical properties of the material for a variety of appli-
cations. The effect of blend composition on degradability should
also be considered. The rate and extent of biodegradation of the
blend could be estimated from the biodegradation behaviour of
the individual components. However, interactions are likely, par-
ticularly because the less degradable phase can inhibit access to
the more degradable phase. Therefore, the rate and extent of
degradation of the blend may not be directly predictable from
the extent and rate of degradation of the components. This needs
to be determined experimentally.

0960-8524/$ - see front matter Crown Copyright 2008 Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2008.09.026
1706 M.A.L. Russo et al. / Bioresource Technology 100 (2009) 17051710
Limited research has been conducted on the biodegradation of
TPS:PVOH blends. Researchers have employed aqueous anaerobic
environments (Peja et al., 2006), starch-specic degrading bacte-
rium (Bacillus subtilis) and a PVOH degrading bacterium (Pseudo-
monas vesicularis var. povalolyticum strain PH) (Fujita and
Hashimoto, 1985) to degrade the TPS:PVOH blends. There has been
no systematic study on the effect of blend ratios on the degradabil-
ity of the TPS and PVOH components.
This study investigates the degradability of TPS and PVOH
blends under anaerobic conditions to simulate the most common
disposal environment for household wastes. Anaerobic digestion
of organic material is a microbially mediated set of reactions that
convert complex polymers to biogas, inorganic nutrients and hu-
mic matter in the presence of a mixed consortium of Bacteria and
Archaea. The overall process can be split into four steps: hydrolysis,
acidogenesis, acetogenesis and methanogenesis (Wheatley, 1990).
The study focuses on hydrolysis, which is dependent on the struc-
ture of the polymer substrates and the density of microbial coloni-
sation on the particle surfaces (OSullivan et al., 2008). Although
volatile fatty acids (VFAs) produced during the acidication step
can accumulate and cause pH inhibition of all microbial activity
(Inanc et al., 1999), pH can be easily buffered to prevent inhibition
(Huser et al., 1982). Hydrolytic organisms typically thrive in acidic
conditions down to pH 5 and are therefore insensitive to mild
acidication.
2. Methods
2.1. Preparation of substrate
Four different mixtures were prepared with varying TPS:PVOH
w/w%: 90:10, 75:25, 50:50, 0:100. Chemically modied high-amy-
lose starch sourced from maize was purchased from Penford Aus-
tralia. The PVOH was purchased from DuPont Australia. These
mixtures were extruded using water as a plasticiser then processed
into lms of 1 mm thickness using a compression moulder. Com-
pression moulding was conducted at temperatures from 125 C
160 C for 57 min, depending on the PVOH content, using platens
of dimensions 150 mm  150 mm at a force of 100 kN. After com-
pression moulding, all substrate lms were cut into small squares
of dimensions 5 mm  5 mm  1 mm and then placed into a
closed, dry chamber of silica gel for at least two weeks to allow
for drying. The moisture content within each sample was un-
changed after equilibration at these conditions.
2.2. Preparation of media
Media was prepared according to the recipe by Owen et al.
(Owen et al., 1979). This dened media contains nutrients and vita-
mins for mixed anaerobic cultures (Speece and McCarty, 1964;
Wolin et al., 1963). Resazurin was added for detection of oxygen
contamination and cysteine hydrochloride to provide a reducing
environment.
2.3. Preparation of assay bottles
The BMP assays were conducted in sterile 200 ml Wheaton ser-
um bottles tted with aluminium capped butyl rubber septums for
sampling of biogas and liquid. Three types of tests were assayed
during the trials: a blank, a reference and a substrate test. The
blank contained BMP media and inoculum, the reference contained
BMP media, inoculum and microcrystalline cellulose (sigmacell
20 lm particle size) and the substrate test contained BMP media,
inoculum and a TPS:PVOH blend. Each test was performed in trip-
licate. 2 g of cellulose or TPS:PVOH blend was used in each test.
70 ml of BMP media equilibrated to room temperature was then
transferred into each serum bottle. Anaerobic conditions were
maintained during the media transfer by bubbling N2 into the ser-
um bottle. Supernatant from the second stage of an established
two stage, laboratory scale digester feed with a mixture of primary
domestic sludge and food waste was used as an inoculum. This
reactor had been operating for 18 months at the time of sampling.
10 ml of inoculum was transferred into each serum bottle under a
N2 atmosphere as performed previously for the media transfer. The
serum bottles were placed in an incubator set to 38 C 0.5 C. 2 M
NaOH (Sigma Aldrich, A.G) was used to maintain the pH of the
reactor above 6.5.
2.4. Volatile fatty acid (VFA) analysis
Liquid samples were analysed for VFAs after centrifugation
and ltration through a 0.22 lm lter to remove solids. VFAs
were measured with a PerkinElmer Autosystem gas chromato-
graph using a ame ionisation detector (FID) and a polar capillary
column (DB-FFAP) with a length of 15 m, an internal diameter of
0.53 mm and a lm thickness of 1 lm. A sample of 0.9 mL was
transferred into a GC vial followed by the addition of 0.1 mL of
10% (v/v%) formic acid. High purity helium at a ow rate of
17 mL/min and a head pressure of 37 kPa was used as the carrier
gas. The oven temperature was 100 C for 1 min then increased at
7 C/min until reaching 140 C, and then increased at 45 C/min
until reaching 220 C respectively. Calibration was performed
using six standard solutions of concentrations 20, 50, 100, 250
and 500 ppm containing up to six VFAs (acetic, propionic, iso-bu-
tyric, butyric, and iso-valeric, valeric and hexanoic acid). Calibra-
tion standards contained 1% v/v of formic acid to match the
preparation carried out for unknown samples. A quality control
sample containing only 1% v/v formic acid was run after every
1520 samples.
2.5. Biogas analysis
The volume of biogas produced in the serum bottles was deter-
mined by connecting the bottles to a water-lled manometer and
measuring the displacement of water at the beginning of each sam-
pling event. Volumetric gas production was normalised to standard
temperature and pressure conditions (25 C and 101.325 kPa)
using the ideal gas law.
The composition of the biogas (H2, CH4 and CO2) was mea-
sured using a PerkinElmer Autosystem gas chromatograph (GC)
(PerkinElmer, USA) equipped with a thermal conductivity detec-
tor and a 2.44 m stainless steel column packed with Haysep (80/
100 mesh). The GC was tted with a PerkinElmer GC Plus Data
Station (Model 1022). High purity nitrogen was used as the car-
rier gas at a ow rate of 24.3 mL/min and a head pressure of
55 kPa. The operation temperatures of the injection port, oven
and detector were 40 C, 40 C and 100 C respectively. Calibra-
tion was performed with three standards at the end of 57 sample
runs using external gas standards obtained from British Oxygen
Company (BOC).
2.6. Soluble chemical oxygen demand (SCOD)
SCOD analysis was carried out using a spectroquant analysis
system and a Merck SQ118 Spectrometer. Each sample was ltered
through a 0.22 lm membrane lter and diluted with milliQ water
before being combined with the chemical oxygen demand (COD)
reagents and digested at 148 C for 2 h in a Merck Thermoreactor
TR300. The SCOD of the digested samples was then measured by
comparing their absorbance at 585 nm against the standard blank
(MilliQ water).
 M.A.L. Russo et al. / Bioresource Technology 100 (2009) 17051710
2.7. Total solids (TS) and volatile solids (VS)
The total solids content of samples were determined by drying
to constant weight overnight at 110 C. The volatile solids content
was determined by then burning the dry sample at 550 C for 2 h
(APHA, 1998).
2.8. Chemical oxygen demand (COD) mass balancing
The absence of oxygen in anaerobic systems means that COD
will be conserved throughout the digestions. COD mass balances
can therefore be used to calculate the extent of substrate solubili-
sation that had occurred at each time step (Song et al., 2005). The
mass of the feed substrate, inoculum and all degradation products
(CH4, VFAs and biomass) are expressed in COD equivalents.
At each sampling point the cumulative amount of solubilised
substrate (SCOD) up to that time point was calculated as the sum
of the cumulative CH4 (SCODCH4) and H2 (SCODH2) production
and the instantaneous VFA mass in solution (SCODVFA). The extent
of substrate solubilisation was expressed as the SCOD divided by
the initial COD (CODinitial) in the system (the sum of the substrate
COD and COD of residual VFA in the inoculum and media). i.e,
SCOD
Extent of solubilisation
CODinitial
SCODCH4 SCODH2 SCODVFA
CODinitial
2.9. Degree of crystallinity
The degree of crystallinity for substrates containing PVOH, was
calculated by comparing the heat of crystallisation of a starch and
PVOH blend, DH, to the heat of crystallisation of 100% crystalline
PVOH, DHc. The theoretical heat of crystallisation for 100% crystal-
line PVOH used in this study was 138.6 J/g (Hassan and Peppas,
2000). The degree of crystallinity (X) was calculated as:
DH
X  100%
DH c
The heat of crystallisation was carried out on a PerkinElmer
DSC7 with a TAC7 computer interface. Pyris, a thermal analysis
program, was used to record and analyse the DSC (Differential
Scanning Calorimetry) data. The instrument was calibrated using
Indium (Tm = 165.8 C) and Zinc (Tm = 419.5 C). Samples of
TPS:PVOH blends of 510 mg were packed into aluminium DSC
sample pans with the lid tightly crimped. Specic heat transition
was measured under a nitrogen atmosphere at a scanning rate of
20 C/min from 50 C to 300 C.
3. Results and discussion
3.1. Total solids (TS) and extent of solubilisation
The TS and extent of solubilisation data have shown that starch
is highly degraded under anaerobic conditions, whereas the degra-
dation of PVOH is slow and primarily PVOH remains at the end of
the digestion.
Fig. 1 illustrates the rate and extent of solubilisation for each
substrate over an incubation time of 100 h. It is evident from this
graph that the rate and extent of solubilisation is dependent upon
the starch content within the substrate. The extent of substrate
solubilisation decreased with the percentage of starch in the
blend. For the 90:10 TPS:PVOH blend, 60% of the blend was solu-
bilised on a COD basis (Eq. (1)). The extent of solubilisation of the
other blends was: 75:25 (40%), 50:50 (30%) and 0:100 (15%). The
1707
Fig. 1. The extent of solubilisation for each TPS:PVOH substrate; j 90:10, e 75:25,
N 50:50 and s 0:100.
TS data showed that only 10 wt.% of the 90:10 TPS:PVOH blend
remained as either undegraded solid or solid degradation product
after 900 h, 25 wt.% of the 75:25 substrate and 55 wt.% and 90
1
wt.% of the 50:50 and 0:100 substrate respectively. Given the
TS data, it was expected for the extent of solubilisation on a
COD basis would be higher than 60% and 40%, respectively, for
the 90:10 and 75:25 substrates. There are two possible explana-
tions for this result. Firstly, biomass was not included in the
100 h COD mass balance. Some of the COD that is present as bio-
mass or other non-soluble products such as extracellular poly-
mers is eventually degraded to either methane or soluble COD
by 900 h. Secondly, PVOH has a higher COD value (1.8 g COD)
than starch (1.06 g COD). Therefore, if PVOH predominantly re-
mains, as demonstrated by the TS data, the extent of COD solu-
bilisation will underestimate the extent of solubilisation on a
2
weight basis.
3.2. The rate of substrate and starch solubilisation
The anaerobic solubilisation of organic solids is most commonly
expressed as a rst order process with respect to the amount of
residual substrate (OSullivan et al., 2008). The rate of substrate
solubilisation can be calculated by tting post-lag data to:
SCOD
ln1   k1 t c 3
CODinitial
where k1 is the rst order rate constant for the solubilisation of the
substrate (Song et al., 2005).
The rate analysis, summarised in Table 1, has shown that diges-
tion followed rst order kinetics with respect to the substrate in all
cases but with a rate constant, k1, that varied with blend
composition.
Product accumulation (Eq. (3)) is only indicative of overall deg-
radation and does not distinguish the source of the products. How-
ever, the yield data presented in Table 2, shows that effectively all
degradation products are sourced from starch as the mass of solu-
bilised COD is relatively constant when normalised by the mass of
starch in the blend (i.e. grams solubilised COD per gram starch). If
the degradation of PVOH is assumed to be negligible compared to
starch degradation, then all degradation products can be assumed
to be sourced from the starch, and the 1st order rate constant
re-evaluated with respect to residual starch only:
1708 M.A.L. Russo et al. / Bioresource Technology 100 (2009) 17051710

Table 1 be occurring where the PVOH becomes the continuous phase,

A summary of the rates of blend solubilisation, k1, for each TPS:PVOH substrate. The encapsulates the starch and prevents access of enzymes to the
error represented for k1 is the 95% condence interval of calculated rate
starch, thus slowing solubilisation. Secondly, the interaction be-
Substrate First 95% Lag YVFA/ YCH4/ Y(VFA + tween starch and PVOH at the interface may include inter-chain
order condence according to total solid total solid CH4)/total mixing and partial miscibility that prevents starch solubilisation.
rate interval on intercept of (g (g solid (g
constant k1 1st order COD/g COD/g COD/g
Chaleat and et al. have suggested the same mechanism in their
k1 (h1) plot (h) COD) COD) COD) investigations on structure properties of TPS:PVOH blends (Chal-
90:10 0.041 0.001 12.84 0.57 0.06 0.63
eat, 2008). It was found that excellent compatibility between
75:25 0.036 0.002 5.35 0.45 0.05 0.50 starch and PVOH related to inter-chain mixing and that partial
50:50 0.020 0.001 17.73 0.30 0.04 0.34 miscibility at the interface between the two phases prevented
0:100 0.002 0 39.36 0.12 0 0.12 the determination of distinct phases within the blends (Chaleat,
2008). Additionally, Follain et al. have conrmed that strong
interactions exist between starch and PVOH by performing water
sorption and chemical reactivity experiments (Follain et al.,
Table 2 2005).
A summary of the rates of starch solubilisation, k2, for each TPS:PVOH substrate. The
error represented for k1 is the 95% condence interval of calculated rate 3.3. The effect of crystallinity
Substrate First 95% Lag YVFA/ YCH4/ Y(VFA +
order condence according to starch starch CH4)/starch DSC was used to characterize the degree of crystallinity of
rate interval on intercept of COD(g COD(g COD(g each blend. The blends with the highest proportion of PVOH,
constant k2 1st order COD/g COD/g COD/g
k2 (h1) plot (h) COD) COD) COD)
50:50 and 0:100, were the only blends that exhibited crystallin-
ity. The degree of crystallinity within each substrate was 4%
90:10 0.041 0.001 11.91 0.72 0.07 0.79
75:25 0.043 0.007 0 0.78 0.09 0.87
and 31% respectively.
50:50 0.020 0.001 12.96 0.81 0.11 0.92 Crystallinity within blends was investigated to assess whether
0:100 blend crystallinity exhibited an affect on the rate and extent of
substrate solubilisation (Arshady, 2003). The starch used in this
study was predominantly gelatinized amylose (P90%) and has an
amorphous structure. Permeation of liquids into amorphous struc-
SCOD tures is more favourable due to a disordered structure compared to
ln1   k2 t c 4 an ordered, densely packed crystalline structure. PVOH has been
CODstarch initial
reported to crystallise after processing (Chiellini et al., 2003). The
where CODstarch_initial is the initial amount of starch COD, and k2 is crystallinity within the 50:50 substrate is minimal but this may
rst order rate constant with respect to starch. have been enough to signicantly reduce accessibility to the starch
Regressions according to Eq. (4) are shown in Fig. 2 for each phase, as indicated by the reduced hydrolysis rate in Table 2. The
TPS:PVOH substrate. crystallinity within the 0:100 substrate would reduce the rate of
It is evident from this graph that the linear relationship be- media permeation throughout the substrate and as a result reduce
tween the log of starch COD concentration and time are rst or- the rate of solubilisation.
der. The values of k2, the associated 95% condence intervals and
lag times are represented in Table 2. The lag times are extrapo- 3.4. VFA and biogas production
lated based on the x-intercept of Fig. 2. The data has shown that
the rate of starch solubilisation, k2, varies with blend composition, Fig. 3ad shows the type and concentration of VFAs produced
indicating that the presence of PVOH impacts on the rate of over a 900 hour digestion period. It is evident that the higher the
starch solubilisation. If there was no effect of the PVOH on the starch content within the substrate, the higher the concentration
rate of starch hydrolysis, values of k2 would be uniform for each of VFAs produced during the digestion. After 100 h incubation, pre-
blend. Two mechanisms have been proposed to explain this effect dominantly the starch had rapidly solubilised from the 90:10,
of PVOH on the hydrolysis of starch. A barrier mechanism could 75:25 and 50:50 substrates and resulted in the high concentration
of VFAs in the media of the reactor, particularly butyric acid for the
90:10 and 75:25 substrates. Zhang et al. found that an increase in
starch concentration within the substrate resulted in a decrease of
acetic acid but an increase in butyric acid production (Zhang et al.,
2003). Due to the accumulation of VFAs in the 90:10, 75:25 and
50:50 reactors, the pH of the reactor decreased from  8 to 5,
inhibiting the production of methane. Fig. 3d shows the concentra-
tion of VFAs from the 0:100 substrate climaxed at 100 h then rap-
idly declined as the VFAs were converted to methane. The 0:100
reactor was the only test that did not result in an accumulation
of VFAs or souring of the reactor.
Fig. 4 illustrates the cumulative biogas production normalised
to the total initial g COD where the pH of the reactor was con-
trolled within pH 6.88.0 using 2M NaOH. Monitoring the pH
within optimum methane production conditions resulted in a
higher concentration of methane production for the 90:10,
75:25 and 50:50 substrates. The higher the starch content within
the substrate the higher the quantity of biogas produced, further
iterating that starch degrades more rapidly than polyvinyl
Fig. 2. Log of starch COD degradation versus time; j 90:10, e 75:25, N 50:50. alcohol.
 M.A.L. Russo et al. / Bioresource Technology 100 (2009) 17051710
Fig. 3. A summary of the concentration of VFA production during the digestion under soured digestion conditions; (a) 90:10, (b) 75:25, (c) 50:50 and (d) 0:100. N butyric acid,
e acetic acid, d propionic acid, s valeric acid, D hexanoic acid, h iso-valeric acid, j iso-butyric acid.
Fig. 4. Cumulative biogas production normalised to the total initial g COD for each
substrate under optimum methane production conditions; j 90:10, e 75:25, N
50:50, s 0:100. The dotted red line denotes methane production; dashed red line
denotes hydrogen production and the solid blue line denotes the total biogas
production (CH4, H2 and CO2).
4. Conclusions
The aims of this study were to measure the rate and extent of
solubilisation for a series of TPS:PVOH blends. The extent of solu-
bilisation data has shown that predominantly PVOH remained at
the end of the digestion and that starch is almost entirely de-
graded. The PVOH content signicantly impacted on the rate of
starch solubilisation. The calculated 1st order rate constant for
1709
starch solubilisation, k2, decreased with increasing amounts of
PVOH. It is possible that PVOH forms a continuous phase and
encapsulates the starch and that inter-chain mixing and partial
phase miscibility between starch and PVOH at the interface may
be contributing to the reduced rate of starch hydrolysis in blends
with more than 50% starch.
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