International Journal of Environmental Studies

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Studies on mechanical and biodegradability

properties of PVA/lignin blend films

Issa Korbag & Salma Mohamed Saleh

To cite this article: Issa Korbag & Salma Mohamed Saleh (2015): Studies on mechanical and
biodegradability properties of PVA/lignin blend films, International Journal of Environmental
Studies, DOI: 10.1080/00207233.2015.1082249

To link to this article: http://dx.doi.org/10.1080/00207233.2015.1082249

Published online: 14 Sep 2015.

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 International Journal of Environmental Studies, 2015
http://dx.doi.org/10.1080/00207233.2015.1082249

Studies on mechanical and biodegradability

properties of PVA/lignin blend films
ISSA KORBAG* AND SALMA MOHAMED SALEH
Department of Chemistry, Faculty of Arts and Sciences, University of Benghazi, Al Kufrah, Libya
Downloaded by [University of Nebraska, Lincoln] at 15:38 19 September 2015

The mechanical and biodegradation properties of polyvinyl alcohol/lignin blended films have been
studied. The biodegradable composite films were developed by mechanical mixing followed by
film casting method using poly (vinyl alcohol) (PVA), with lignin in different compositions. The
progress of biodegradation was evidenced by means of the soil burial test. There was also an
evaluation of the weight loss of the samples at the end of the biodegradation process. Blending the
PVA with lignin improves tensile strength and the modulus of elasticity and causes a slight
decrease in the elongation at break. The best tensile mechanical properties of a PVA/lignin blend
were at ratio 2:30 where the tensile strength was 38 MPa, elastic modulus 83.22 MPa and elonga-
tion at break 213.9%. Blends of various PVA/lignin ratios have shown transparency, flexibility and
good mechanical properties. Film composites also showed good biodegradability. The addition of
lignin to the PVA matrix increases the degradation rate of the blends. The weight loss is affected
by the composition of the blend, and by the nature of the microorganisms in the soil. PVA/lignin
film may be potentially suitable as eco-friendly packaging materials.

Keywords: Mechanical; Biodegradable; PVA; Lignin

1. Introduction

Lignin, the second most abundant bio-macromolecule existing in the plant kingdom, is
relatively inexpensive and widely available [1]. Commercially, lignin is obtained as a
by-product of ‘wood-free’ paper making. Lignin is mainly burnt as an energy source. Some
industrial processes consistently produce standard well-defined lignins as part of a complex
chemical recovery system [2]. Lignin peroxidases, manganese peroxidases, and laccases are
three families of enzymes that are implicated in the biological degradation of lignin [3,4].
Natural fibres have advantages over man-made glass and carbon fibres. These advantages
include low cost, low density, and comparable specific tensile properties. Natural fibres are
not abrasive to equipment. They do not irritate the skin. They have reduced energy con-
sumption. They generally present no health risk. They are renewable, recyclable, and
biodegradable. Being eco-friendly, these materials are considered as strong candidates to
replace conventional glass and carbon fibres. These composite materials are suitably
applicable for aerospace, leisure, construction, sport, packaging and automotive industries,
especially for the last mentioned application according to Ku et al. [5] and Malkapuram
et al. [6]. Biodegradable polymers can be decomposed into carbon dioxide, methane, water,
inorganic compounds or biomass by the actions of microorganisms. The rate of

*Corresponding author. Email: issa2zoay@yahoo.com

© 2015 Taylor & Francis

 2 I. Korbag and S. Mohamed Saleh

decomposition, residuals, and by-products can be measured in standardized tests [7]. In nat-
ure, basidiomycetes white-rot fungi is the main mechanism for efficient lignin degradation
during the process of wood decay. Dashtban and Schraft report that many white rot fungi
simultaneously attack lignin, hemicelluloses and cellulose whereas some other white-rot
fungi preferentially work on lignin in a selective manner [8]. Natural polymers do not
always possess the characteristics desired in a plastic. It is usual for natural polymers to be
mixed with petroleum-based polymers to obtain desired properties [9]. The use of biologi-
cally derived polymers (bio-macromolecules) is emerging as an important component for
economic development. New renewable, biodegradable, and biocompatible materials
(biomaterials) are being produced by transforming forest and agricultural feedstock [10].
Biodegradable plastics made from renewable resources can provide all the advantages of
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petroleum based plastic without the negative environmental effects [11]. The use of
biodegradable polymers obtained from renewable resources for use in packaging has been
implemented in recent years. Lignin degradation in the soil forms the main material of soil
humus. Lignin can be used as the degradation primer applied to plastics to increase their
degradation [12,13].
Poly (vinyl alcohol) (PVA), a highly polar, water-soluble polymer, has been well used in
polymer blends with natural polymeric materials. Compatible with many biopolymers,
PVA is biodegradable [14]. Recently, it was reported that 55 species of microorganisms
(including bacteria, fungi, yeast and mould) participate in the degradation of polyvinyl
alcohol. Scientists have isolated the Pseudomonas bacteria from the soil bacterium growing
on PVA as the source of carbon. Pseudomonas is the main PVA degrader [15]. Among all
vinyl polymers manufactured, PVA is the only one known to be biodegradable by microor-
ganisms, but its biodegradation rate is too small for practical use as a degradable polymer
in environmental conditions. The most effective approach to improve its degradability is
by blending it with a suitable biopolymer [16]. Lignocellulosic materials, which are among
the most environmentally friendly agro wastes were used as reinforcing filler as a substi-
tute for synthetic materials to obtain more biodegradable composites [17]. Polyvinyl alco-
hol has excellent film forming, emulsifying, and adhesive properties [18]. Miscible PVA
blends with cellulose and chitosan have been reported by Nishio et al. [19], Lee et al. [20]
and Kim et al. [21]. In these systems, good material performance was obtained and attribu-
ted to the formation of intermolecular hydrogen bonds between the hydroxyl groups of the
respective polymers. PVA blends have also been reported with lignin ethers and alkali lig-
nin derived from biomass [22,23]. PVA is a polymer partially miscible with lignin, and a
high degree of intermolecular interaction takes place between lignin and the PVA chains.
The miscibility between lignin and polar polymer materials such as PVA and PVC favours
the formation of hydrogen bonding at the interface [24].
Inspired by those studies, the aim of this work was to investigate the blend properties of
a PVA/lignin blend system. The tensile test is used to study the mechanical properties of
the blends, and the soil burial test is used to study the biodegradability of PVA/lignin
blended films.

2. Experimental
2.1. Materials
The material used in this journal are PVA with molecular weight Mw = 205,000 purchased
from Sigma-Aldrich, Germany, lignin, acetic acid, and distilled water.
 Properties of PVA/lignin blend film 3

2.2. Experimental procedure

2.2.1. Preparation of films
Polyvinyl alcohol films were prepared using a casting method of aqueous polymer solu-
tions. Lignin solutions were obtained by adding 20 g of lignin to 350 g of distilled water
and then adding drops of acetic acid each half hour to increase solubility of lignin and
keep pH 4 during the stirring and heating of the mixture at 80 °C for 2 h. Then, polyvinyl
alcohol in amounts of 10, 20, 30 and 40 g were added to 300 g of lignin solution. The
mechanical mixing was performed at range 60–70 °C for 6 h. Finally, the produced
mixture was poured onto Petri dishes to make films. All films were kept for 1 h at 25 °C
temperature and then oven dried at about 50 °C for 24 h. The dried films were peeled from
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the Petri dishes and then stored in desiccators at room temperature.

2.3. Analysis
2.3.1. Tensile test
The tensile properties (tensile strength, elongation at break, and modulus elasticity) of the
blended films were preformed according to ASTM D882 method using an Instron univer-
sal tensile testing machine (Model 3366, Instron). The tensile test was conducted using a
cross head speed of 10 mm/min. The width of each specimen was set at 6.4 mm. The ini-
tial gauge length between grips was set at 50 mm.

2.3.2. Soil burial test

The soil burial test was carried out on a laboratory scale to examine the biodegradability
using the method reported by Behjat et al. [25] and Laxmeshwar et al. [26]. The initial
weight of the dry specimens was 0.65 g. The dry specimens were buried by random
pattern in a perforated box containing moisturized soil. The pot containing the soil and
samples was incubated at almost constant temperature of 25 °C for one month. The mois-
ture content was maintained at 40–50% of the soil’s maximum water holding capacity.
This humidity is optimal for microbial activity [27]. In addition, the pots were covered
with plastic film to avoid water evaporation from the soil surface. Biodegradation was
estimated by monitoring changes in weight as a function of burial time. The samples were
removed from the soil every 5 days. The specimens were then carefully washed with water
several times in order to remove debris and soil from the film and to ensure that the
degradation stopped. After that, the samples were dried at room temperature to a constant
weight. After drying, they were weighed using a GR200 model analytical balance in order
to determine the percentage values of weight loss as by the following equation:

W0  Wt
Weight loss ð%Þ ¼  100
W0

where W0 is the initial mass and Wt is the remaining mass at any given time, t.
 4 I. Korbag and S. Mohamed Saleh

3. Results and discussion

3.1. Tensile test
A tensile test was performed to investigate the tensile properties of the PVA/lignin films.
Figure 1 shows the effect of the blend ratio on the tensile strength, modulus of elasticity,
and elongation of PVA/lignin blend films. Tensile properties of pure PVA film were
266.50%, 19.12 and 9.52 MPa for elongation, tensile strength, and elastic modulus
respectively. It can be noted that the tensile strength of PVA/lignin films increased with the
addition of lignin amount.
The experimental data show that the film with acceptable values for elongation, tensile
strength, and elastic modulus is obtained using the mass ratio 2:30 of the blend. The
Downloaded by [University of Nebraska, Lincoln] at 15:38 19 September 2015

elongation at break and tensile strength of PVA/lignin (2:30) were 213.9% and 38.44 MPa
respectively. The elongation at break slightly decreased with the addition of the lignin
amount in the blends, perhaps because of the low ductility of lignin. The elastic modulus
of PVA/lignin (2:30) increased to 83.22 MPa in comparison with pure PVA. The results
show that the incorporation of lignin into PVA improves both tensile strength and modulus
of elasticity with slight decreases in the elongation at break. The values obtained for the
elongation at break are high enough to allow the use of the films in various fields [28]. In
general, the higher the modulus of elasticity and tensile strength the stronger will be the
film. It is clear that significant improvement in the tensile properties of PVA was achieved
via inclusion of even small amounts of lignin in the blend. This behaviour can be
explained by creation of strong hydrogen bonds between lignin and PVA which contribute
to a high level of interfacial adhesion and also dispersion of lignin, so that there is a sig-
nificant decrease in the deformability of PVA. An additional consideration is that lignin
can act as a rigid structural component, which behaves as a cross-linker in linear-structured
polyvinyl alcohol. Therefore, the composite films formed by this method showed signifi-
cantly improved mechanical properties compared with PVA film, which is in agreement
with the results obtained by Su et al. [12], Xu et al. [24], Simmons et al. [29], and Kubo
and Kadla [30].

3.2. Soil burial test

Figure 2 illustrates the effect of lignin content on the biodegradability of PVA/lignin films.
It can be observed that the highest values of weight loss were recorded for the PVA/lignin

300 266.5
251.8
250 213.9
177.4 184.2
200 166.4
Tensile strength Mpa
136.9
150
Precent elongation
83.22
100 71.45 Young's modulus Mpa
28.49 38.44 28.97
50 19.12 21.54
9.521

0
pure PVA PVA/Lignin PVA/Lignin PVA/Lignin PVA/Lignin
1:30 2:30 3:30 4:30

Figure 1. Mechanical properties of pure PVA and PVA/lignin films.

 Properties of PVA/lignin blend film 5

7
6

Weight loss %
5
4 PVA/Lignin 1:30
3 PVA/Lignin 2:30
2
PVA/Lignin 3:30
1
0 PVA/Lignin 4:30
0 10 20 30 40
Burial time (Days)

Figure 2. Weight losses of PVA/lignin films.

Downloaded by [University of Nebraska, Lincoln] at 15:38 19 September 2015

blend with less content of PVA in the mixture. The PVA/lignin blend with ratio 1:30
recorded the highest value of weight loss (6.61%) after 30 days buried in soil. The lowest
value of weight loss (3.84%) was recorded for PVA/lignin with ratio 4:30 caused by the
large amount of PVA added to the blend.
In general, there are drastic increases in weight losses in the first 5–10 days, and there
are slight increases in the degradation process of all films from 10–25 days. After 25 days
the rate of the degradation process slightly increased and levelled off in all blended films.
The weight losses are influenced by the composition of mixture, as well as by several
physicochemical and biological parameters including the number and species of
microorganisms present, the conditions for microbial degradation activity (e.g. presence of
nutrient, oxygen, pH and temperature) the quality, quantity and bioavailability of the con-
taminants; and the soil characteristics such as particle size distribution in the soil [28,31].
The results suggested that it is possible to blend polyvinyl alcohol polymer with lignin in
order to improve its biodegradability.

4. Conclusions

Based on the results, a series of PVA/lignin blended films were successfully prepared by
the solution casting method. The resulting polymer blend films were visually homoge-
neous. Tensile test and soil burial tests were performed to study the mechanical and
biodegradability properties of the blended films. The incorporation of lignin into PVA pro-
vides a gain in tensile strength and elastic modulus and slightly decreases in elongation to
breakage. When the mass ratio of PVA/lignin was 2:30 the obtained film had tensile
mechanical properties where the elongation at break was 213.9%, elastic modulus
83.22 MPa and tensile strength 38 MPa were greater than in the case of pure PVA film.
When the PVA content exceeded 6.6%, the tensile strength of the composite films tended
to decrease but it was still much higher than the pure PVA film. It was observed that addi-
tion of lignin can improve some of the mechanical properties of the blends; but each prop-
erty was modified differently with respect to lignin content. For example, tensile strength
and tensile modulus were improved by lignin addition through the formation of strong
intermolecular hydrogen bonds between the hydroxyl groups of PVA and lignin, while
elongation at break was decreased, perhaps because of the low ductility of lignin. The bio-
composite films also showed good biodegradability. The results suggested that it is possi-
ble to blend polyvinyl alcohol polymer with lignin in order to improve its biodegradability.
The data indicate that bio-composites have application in many areas of science and
eco-friendly packaging materials.
 6 I. Korbag and S. Mohamed Saleh

Disclosure statement

No potential conflict of interest was reported by the authors.

References

[1] Glasser, W.G., Northey, R.A. and Schultz, T.P., 1999, Lignin: Historical, Biological, and Materials
Perspectives. ACS Symposium Series, 742 (Washington, DC: American Chemical Society).
[2] Kennedy, J.F., Phillips, G.O. and Williams, P.A., 1992, Ligno-cellulosics: Science, Technology, Development
and Use. Ellis Horwood Series in Polymer Science and Technology. (New York, NY: Ellis Horwood Ltd.).
[3] Glenn, J.K., Morgan, M.A., Mayfield, M.B., Kuwahara, M. and Gold, M.H., 1983, An extracellular H2O2-
requiring enzyme preparation involved in lignin biodegradation by the white rot basidiomycete Phane-
rochaete chrysosporium. Biochemical and Biophysical Research Communications, 114(3), 1077–1083.
Downloaded by [University of Nebraska, Lincoln] at 15:38 19 September 2015

[4] Tien, M. and Kirk, T.K., 1983, Lignin-degrading enzyme from the hymenomycete Phanerochaete
chrysosporium burds. Science, 221(4611), 661–663.
[5] Ku, H., Wang, H., Pattarachaiyakoop, N. and Trada, M., 2011, A review on the tensile properties of natural
fiber reinforced polymer composites. Composites Part B: Engineering, 42(4), 856–873.
[6] Malkapuram, R., Kumar, V. and Negi, Y.S., 2009, Recent development in natural fiber reinforced polypropy-
lene composites. Journal of Reinforced Plastics and Composites, 28(10), 1169–1189.
[7] Greene, J., 2007, Biodegradation of compostable plastics in green yard-waste compost environment. Journal
of Polymers and the Environment, 15(4), 269–273.
[8] Dashtban, M., Schraft, H., Syed, T.A. and Qin, W., 2010, Fungal biodegradation and enzymatic modification
of lignin. Journal of Biochemistry and Molecular Biology, 1(1), 36–50.
[9] Sreekala, M.S., Kumaran, M.G., Joseph, S., Jacob, M. and Thomas, S., 2000, Oil palm fibre reinforced
phenol formaldehyde composites: influence of fibre surface modifications on the mechanical performance.
Applied Composite Materials, 7(5/6), 295–329.
[10] Imam, S.H., Greene, R.V. and Zaidi, B.R., 1999, Biopolymers: Utilizing Nature’s Advanced Materials. ACS
Symposium Series, 723. American Chemical Society: Washington, DC.
[11] Farrin, J., 2007, Biodegradable plastics from natural resources. Rochester Institute of Technology Report for
the Institute of Packaging Professionals, 13. Available online at: http://www.iopp.org/files/public/FarrinJen
niferRITBiodegradablePlastics.pdf.
[12] Su, L., Xing, Z., Wang, D., Xu, G., Ren, S. and Fang, G., 2013, Mechanical properties research and struc-
tural characterization of alkali lignin/poly (vinyl alcohol) reaction films. BioResources, 8(3), 3532–3543.
[13] Abdul Khalil, H., Marliana, M. and Alshammari, T., 2011, Material properties of epoxy-reinforced
biocomposites with lignin from empty fruit bunch as curing agent. BioResources, 6(4), 5206–5223.
[14] Matsumura, S., Tomizawa, N., Toki, A., Nishikawa, K. and Toshima, K., 1999, Novel poly(vinyl alcohol)-
degrading enzyme and the degradation mechanism. Macromolecules, 32(23), 7753–7761.
[15] Leja, K. and Lewandowicz, G., 2010, Polymer biodegradation and biodegradable polymers – A review.
Polish Journal of Environmental Studies, 19(2), 255–266.
[16] Tudorachi, N. and Lipsa, R., 2010, Synthesis and characterization of poly (vinyl alcohol-co-aspartic acid)
copolymers. Polymer, 55(7/8), 562–567.
[17] Premalal, H.G.B., Ismail, H. and Baharin, A., 2002, Comparison of the mechanical properties of rice husk
powder filled polypropylene composites with talc filled polypropylene composites. Polymer Testing, 21(7),
833–839.
[18] Jelinska, N., Kalnins, M., Tupureina, V. and Dzene, A., 2010, Poly (vinyl alcohol)/poly (vinyl acetate) blend
films. Scientific Journal of Riga Technical University, 21, 55–61.
[19] Nishio, Y., Haratani, T., Takahashi, T. and St. John Manley, R., 1989, Cellulose/poly(vinyl alcohol) blends:
an estimation of thermodynamic polymer-polymer interaction by melting-point-depression analysis. Macro-
molecules, 22, 2547–2549.
[20] Lee, Y.M., Nam, S.Y. and Kim, J.H., 1992, Pervaporation of water-ethanol through poly(vinyl alcohol)/chi-
tosan blend membrane. Polymer Bulletin, 29(3-4), 423–429.
[21] Kim, J.H., Kim, J.Y., Lee, Y.M. and Kim, K.Y., 1992, Controlled release of riboflavin and insulin through
crosslinked poly(vinyl alcohol)/chitosan blend membrane. Journal of Applied Polymer Science, 44, 1823–
1828.
[22] Corradini, E., Pineda, E.A.G. and Hechenleitner, A.A.W., 1999, Lignin-poly (vinyl alcohol) blends studied
by thermal analysis. Polymer Degradation and Stability, 66(2), 199–208.
[23] Ciemniecki, S. L. and Glasser, W. G., 1988, Multiphase materials with lignin: 2. Blends of hydroxypropyl
lignin with poly(vinyl alcohol). Polymer, 29(6), 1030–1036.
[24] Xu, G., Ren, S. and Hechenleitner, A.A.W., 2013, Fabrication and properties of alkaline lignin/poly (vinyl
alcohol) blend membranes. BioResources, 8(2), 2510–2520.
 Properties of PVA/lignin blend film 7

[25] Behjat, T., Russly, A.R., Luqman, C.A., Yus, A.Y. and Nor Azowa, I., 2009, Effect of PEG on the
biodegradability studies of kenaf cellulose-polyethylene composites. International Food Research Journal,
16(2), 243–247.
[26] Laxmeshwar, S.S., Madhu Kumar, D.J., Viveka, S. and Nagaraja, G.K., 2012, Preparation and properties of
biodegradable film composites using modified cellulose fibre-reinforced with PVA. ISRN Polymer Science,
2012, 1–8.
[27] Chandra, R. and Rustgi, R., 1998, Biodegradable polymers. Progress in Polymer Science, 23, 1273–1335.
[28] Tudorachi, N., Cascaval, C.N. Rusu, M. and Pruteanu, M., 2000, Testing of polyvinyl alcohol and starch
mixtures as biodegradable polymeric materials. Polymer Testing, 19(7), 785–799.
[29] Simmons, T.J., Lee, S.H., Miao, J., Miyauchi, M., Park, T.J., Bale, S.S., Pangule, R., Bult, J., Martin J.G.,
Dordick, J.S., and Linhardt, R.J., 2011, Preparation of synthetic wood composites using ionic liquids. Wood
Science and Technology, 45(4), 719–733.
[30] Kubo, S. and Kadla, J.F., 2003, The formation of strong intermolecular interactions in immiscible blends of
poly(vinyl alcohol) (PVA) and lignin. Biomacromolecules, 4(3), 561–567.
[31] Margesin, R. and Schinner, F., 1997, Efliciency of indigenous and inoculated cold-adapted soil
Downloaded by [University of Nebraska, Lincoln] at 15:38 19 September 2015

microorganisms for biodegradation of diesel oil in alpine soils. Applied and Environmental Microbiology,
63(7), 2660–2664.