Composites: Part B 56 (2014) 279–283

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Composites: Part B
journal homepage: www.elsevier.com/locate/compositesb

Characterization and biodegradability of polypropylene composites

using agricultural residues and waste fish
Amir Nourbakhsh a, Alireza Ashori b,⇑, Ali Kazemi Tabrizi c
a
Department of Wood and Paper Science, Research Institute of Forests and Rangelands (RIFR), Tehran, Iran
b
Department of Chemical Technologies, Iranian Research Organization for Science and Technology (IROST), Tehran, Iran
c
Department of Wood and Paper Science and Technology, Karaj Branch, Islamic Azad University, Karaj, Iran

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

Article history: The objective of this research was to study the potential of waste agricultural residues such as rice-husk
Received 11 January 2013 fiber (RHF), bagasse fiber (BF), and waste fish (WF) as reinforcing and biodegradable agents for thermo-
Received in revised form 10 June 2013 plastic composites. Addition of maleic anhydride grafted polypropylene (MAPP) as coupling agent was
Accepted 12 August 2013
performed to promote polymer/fiber interfacial adhesion. Several composites with various polypropylene
Available online 21 August 2013
(PP) as polymer matrix, RHF, BF, WF, and MAPP contents were fabricated by melt compounding in a twin-
screw extruder and then by injection molding. The resulting composites were evaluated through
Keywords:
mechanical properties in terms of tensile, flexural, elongation at break and Izod notched impact following
A. Fibers
B. Mechanical properties
ASTM procedures. Biodegradability of the composites was measured using soil burial test in order to
B. Environmental degradation study the rates of biodegradation of the composites. In general, the addition of RHF and BF promoted
Bagasse fiber an increase in the mechanical properties, except impact strength, compared with the neat PP. According
to the results, WF did not have reinforcing effect on the mechanical properties, while it could consider-
ably improve the biodegradation of the composites. It was found that the composites with high content of
WF had higher degradation rate. Except impact strength, all mechanical properties were found to
enhance with increase in cellulosic fiber loading In addition, mechanical properties and biodegradability
of the composites made up using RHF was superior to those of the composites fabricated with BF, due to
its morphological (aspect ratio) characteristics.
Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction
Sustainability and eco-efficiency in technical applications has
become quite important during the last two decades resulting from
ecological concern, environmental awareness, new legislative reg-
ulations, and Greenpeace groups [1]. Petroleum-based synthetic
polymers are widely used in modern society. However, the annual
worldwide disposal of approximately 170 million tons of petro-
chemical plastics in commonly used commodities such as polyole-
fin in packing, bottle and molding products is a significant
environmental problem, especially with the continuously increas-
ing production and consumption of these materials (Fig. 1) [2,3].
Furthermore, plastic wastes are an undesired pollutant in soil, riv-
ers and marine. Because of their resistance to microbial attack,
they tend to accumulate in the natural environment. Although
the biodegradable polymers can partially solve the problem of
non-biodegradable plastic waste pollution, the majority of biode-
gradable polymers are not widely used because they are too expen-
⇑ Corresponding author. Tel.: +98 21 5627 6637; fax: +98 21 5627 6265.
E-mail address: ashori@irost.org (A. Ashori).
sive and the range of the material selection suitable for various
end-use products is limited [4].
Wood plastic composite (WPC) is part of a new generation of
reinforcing products in recent years. It composes of a thermoplastic
polymer as matrix and cellulosic material which act as the rein-
forcing filler. There are many studies concerning the use of natural
fiber as reinforcing in polymer composite systems. These reinforc-
ing materials can be naturally degraded by microorganisms and
play a significant role in degrading natural organic substances in
the ecosystem [5]. Polypropylene (PP) undoubtedly has been one
of the best candidates as matrix material for WPCs because of its
low price, thermal stability, and widespread use in technical appli-
cations, e.g. in the automotive industry. Numerous publications
can be found on the effect of addition of cellulosic fibers on the
physical and mechanical properties of polymer matrix composites
with focus on PP matrices [1,6,7].
Biodegradation occurs with enzymatic action and involves liv-
ing microorganisms. Almost all microbial degradations are carried
out by both fungi and bacteria. There are four biodegradation envi-
ronments for polymeric products namely soil, aquatic, landfill and
compost. Each environment contains different microorganisms and
has its special conditions for degradation. In soil, fungi are mostly

1359-8368/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.compositesb.2013.08.028
280 A. Nourbakhsh et al. / Composites: Part B 56 (2014) 279–283

Table 2
Material formulations used to prepare composites.

Specimen no. PP MAPP RHF BF WF

(wt.%) (wt.%) (wt.%) (wt.%) (wt.%)
RHF1 58 2 40 0 0
RHF2 58 2 30 0 10
RHF3 58 2 25 0 15
BF1 58 2 0 40 0
BF2 58 2 0 30 10
BF3 58 2 0 25 15

Fig. 1. World plastic production in 2011 [3].
responsible for degradation of organic matter including cellulosic
fibers and polymers [8]. The biodegradation rate in WPCs depends
on a number of factors including fiber content, the biodegradability
of each component and the quality of the interface. The fiber addi-
tion generally increases the degradation rate of composites and
alkaline treatment of fibers produce a slightly higher degradation
rate than pure matrix [9]. In addition, the additives used (e.g. plast-
icizers, fillers, etc.) are important in biodegradation kinetics as well
as the type of polymer reflected in molecular weight, structure and
crystallinity [10]. In addition, the rate of biodegradation depends in
general on the substrate composition and the existing
microorganisms.
The main objective of this work was to study the potential of
waste materials such as rice-husk fiber (RHF), bagasse fiber (BF),
and waste fish (WF) as reinforcing and biodegradable fillers for
WPCs in order to evaluate and compare their mechanical proper-
ties and biodegradability. In addition, the effects of fiber loading
and WF contents on the above-mentioned properties were studied.
2. Methods
2.1. Materials
Two types of agricultural residues were investigated in this
study: RHF and BF. The important chemical components and fiber
morphology of lignocellulosic materials are given in Table 1. In or-
der to reduce extractives effects, the lignocellulosic materials were
treated with water at 50 °C for 48 h. RHF and BF were produced by
refiner mechanical pulp (RMP) process. Consequently, the samples
were oven-dried and stored in sealed plastic bags for subsequent
use. The moisture content of oven-dried fiber was lower than 3%.
Table 1
Chemical and morphological properties of used materials.
Properties RHF
Cellulose (%) 48.9
Lignin (%) 19.1
Extractives (%) 2.5
Ash (%) 12.3
Fiber length (mm) 0.80
Aspect ratio 89
Injection molding grade PP, with trade name V30S, was sup-
plied by Arak Petrochemical Co. (Iran). The PP was in the form of
pellets with a melt flow index of 18 g/10 min and density of
0.92 g/cm3.
Maleic anhydride functionalized polypropylene (MAPP) with a
molecular weight of 52,000, acid number of 9 mg KOH/g, and melt-
ing point of 158 °C was provided by Eastman Chemical Products,
Inc.
Kilka (Clupeonella engrauliformis), obtained from Iranian waters
of the Caspian Sea, was used as WF. It is the most abundant fishes
in the Caspian Sea [11]. The chemical analysis of WF showed 70%
protein, 7.8% fat and 6.6% moisture content.
2.2. Preparation of samples
Formulation of the mixes and abbreviation used for the respec-
tive mixes prepared are given in Table 2. Composites were pro-
duced in a two-stage process. In the first stage, fibers, PP, WF,
and MAPP pellets were premixed by hand at various formulations,
and the mixtures were then fed into a laboratory co-rotating twin-
screw extruder. The temperature profile in the extruder was 165/
170/175/180/185 °C and the screw speed was set at 70 rpm. In
the second stage, the extrudate in the form of strands were allowed
to cool to room temperature and then granulated using a CW Brab-
ender Granulator. The resulting granules were dried at 105 °C for
24 h before being injection-molded.
2.3. Mechanical testing
The specimens were tested following ASTM standard D 638 for
tensile properties, ASTM D 790 for flexural properties and D 256 for
notched Izod impact strength (ASTM 1999). Tensile and bending
tests were conducted using a Universal Testing Machine (Santam
model STM-150) at a speed of 5 and 10 mm/min, respectively. Isod
impact test was performed with a pendulum apparatus (Zwick
model 1446) using conventional V notched specimens. Four repli-
cates were tested for each property under each formulation.
2.4. Soil burial test
The soil burial test was carried out on a laboratory scale to
examine the biodegradability using the method which reported
by Behjat et al. [8] briefly as follows. First, rectangular sheets
(10 cm  10 cm  1 mm) of specimens were buried in the soil by
random pattern. The pot containing the soil and samples were
incubated at almost constant temperature of 27 °C for four months.
The moisture content was maintained at 45–60% of the soil’s max-
BF imum water holding capacity. This humidity is optimal for micro-
55.3
bial activity. In addition, the pots were covered with plastic film to
21.0 avoid water evaporation from the soil surface. Biodegradation was
2.9 estimated by monitoring changes in weight as a function of burial
1.9 time. The samples were removed from the soil every 20 days. The
0.96
debris on the specimens was removed by washing with water. The
42
samples were then dried in an oven at 100 ± 5 °C for 24 h. After
 A. Nourbakhsh et al. / Composites: Part B 56 (2014) 279–283 281

Tensile strength, RHF Tensile strength, BF

Tensile modulus, RHF Tensile modulus, BF
27.5 2.5
(a)

Tensile modulus (GPa)

Tensile strength (MPa)
26.0 2.4

24.5 2.3

23.0 2.2

21.5 2.1

20.0 2.0
PP 1 2 3 PP 1 2 3

Flexural strength, RHF Flexural strength, BF

Flexural modulus, RHF Flexural modulus, BF
36 3.7
(b)

Flexural modulus (GPa)

Flexural strength (MPa)

34 3.5

32 3.3

30 3.1

28 2.9

26 2.7
PP 1 2 3 PP 1 2 3

Impact strength, RHF Impact strength, BF

Elongation, RHF Elongation, BF
26 2.5
(c) Elongation at break (%)
Impact strength (J/m)

24 2.2

22 1.9

20 1.6

18 1.3

16 1.0
PP 1 2 3 PP 1 2 3
Specimen No.

Fig. 2. Mechanical properties of various composites using RHF, BF, and WF contents.

drying, they were weighed using an electronic balance with a pre-
cision of 0.1 mg. For comparative reason, the weight of treatments
was normalized to 10 g in the first measurement.
3. Results and discussion
3.1. Mechanical properties
The average measured values of mechanical properties in terms
of tensile, flexural, impact and elongation at break are plotted in
Fig. 2. Except impact strength, all mechanical properties were in-
creased with addition of RHF and BF, while WF was not able to
reinforce the mechanical properties.
3.1.1. Tensile properties
The tensile properties of composites as functions of the filler
type and content are presented in Fig. 2a. It is evident that moder-
ate increase in tensile strength occurred upon filling the polymer
matrix with fibers, indicating a considerable reinforcing effect from
these fibers. The phenomenon was stronger for the composites
filled by RHF. Similar behavior can be observed in Fig. 2a, where
the significant increase in tensile modulus is plotted versus fiber
content. Same results have been published by Karmarkar et al.
[12] and Ashori and Nourbakhsh [7] who studied the properties
of WPCs. Their data show that the tensile strength of cellulosic fi-
ber/PP composites increases with increasing fiber content. The pos-
sible reasons proposed for this kind of behavior may be due to the
282 A. Nourbakhsh et al. / Composites: Part B 56 (2014) 279–283
10.0
9.8
Weight (g)
9.6
9.4
Neat PP BF1
9.2 BF2 BF3
9.0
0 20 40 60 80
Time (days)
Fig. 3. Biodegradability of (a) BF/PP composites and (b) RHF/PP composites during burial time.
improved interfacial adhesion between the matrix and fibers. In
addition, various parameters influence the mechanical properties
of fiber-reinforced composites including the fiber aspect ratio, fi-
ber-matrix adhesion, stress transfer at the interface and mixing
temperatures. The BF fiber, which had a low aspect ratio (Table 1),
showed inferior strength to the RHF filled composites. In other
words, the aspect ratio of the RHF fibers is much higher than that
of the BF, which permits better stress transfer between the matrix
and the fibers.
In general, all mechanical properties were decreased with addi-
tion of WF content from 0% to 15%. The low specific gravity of the
WF causes to float on top of the mixture and it creates a lack of
homogenous mixture in the composite so that the top surface of
the composite fills with accumulated WF. After analyzing the bro-
ken pieces of the specimens, it was observed that some parts of the
WF could not distribute uniformly in the matrix, and a quantity of
WF was clamped together and placed in some points of the speci-
men. This means that some areas of the specimens were without
WF, which could result in the reduction in WF-matrix interfacial
area and hence lower strength properties than the expected.
3.1.2. Flexural properties
The effect of fiber loading on the flexural strength and modulus
for RHF/PP and BF/PP composites are presented in Fig. 2b. Similar
with the trend results of tensile properties, the addition of fibers
results in significant improvement in flexural properties of the
composites. The improvement in mechanical properties achieved
can be attributed to high strength and modulus of cellulosic fibers
(RHF and BF) and to improved interfacial adhesion between the
matrix and fiber. Flexural strength and modulus values are found
to be much higher in composites filled with RHF compared to BF
fiber. The mentioned properties reached the maximum values at
40% of RHF fiber content. As it can clearly be seen from Fig. 2b, with
increase in WF contents from 0% to 15%, the flexural properties are
considerably decreased. In both RHF and BF composites the flex-
ural strength and modulus values increased with increasing fiber
content.
3.1.3. Elongation at break
The elongations at break values of the composites are plotted
against filler type and content in Fig. 2c. The two cellulosic materi-
als have different effects on this property as well, i.e. they influence
the deformation and failure of the composites slightly differently.
Composite type BF2 shows brittle behavior, with 60% lower elon-
gation at break than RHF2 composite. The higher elongation at
break for the composites filled with RHF indicates the higher elas-
ticity of the RHF compared with the BF. As observed from the
graph, the composites filled with RHF exhibited a positive elonga-
tion at break effect with the addition of cellulosic fibers. The posi-
10.0
(a) (b)
9.8
Weight (g)
9.6
9.4
Neat PP RHF1
9.2
RHF2 RHF3
9.0
100 120 120 100 80 60 40 20 0
Time (days)
tive RHF effect of the elongation at break was also observed by
Srinivasa et al. [13], who concluded that in a composite, the addi-
tion of fibers with high elongation often increased the elongation
at break of the composite compared to the composite made from
low elongation fibers.
3.1.4. Impact behavior
Fig. 2c reports the result of notched Izod impact strength mea-
surement function of fiber contents. With increasing fiber contents
Izod impact strength decreased linearly. The RHF fiber appeared to
improve impact strength in comparison with the BF fiber. This was
expected because RHF fibers should be more resistant to crack
propagation in the matrix. This is consistent with the results re-
ported by most authors [6,7,14,15].
The impact performance of fiber reinforced composites depends
on many factors including the nature of the constituent, fiber/ma-
trix interface, the construction and geometry of the composite and
test conditions [16]. The presence of cellulosic fibers in the PP ma-
trix provides points of stress concentrations, thus providing sites
for crack initiation. Another reason for decrease in impact strength
may be the stiffening of polymer chains due to bonding between
wood fibers and matrix. For high impact properties, in fact, a
slightly weaker adhesion between fiber and polymer is desirable,
as it would result in a higher degradation of impact energy, sup-
porting the so-called fiber pull-out [12]. Good adhesion on the con-
trary results in abrupt fiber fracture with a minor energy
degradation [17]. The impact strength of the boards was found to
be a maximum when WF content was 0% such as RHF1 and BF1
samples. Addition of WF reduced the increases volume of fibers
and reduced interfacial area of contact between the fiber and the
PP matrix, and hence diminishes the potential of a given fiber to
be able to bond with the matrix.
3.2. Biodegradability
Fig. 3 shows the biodegradation test experimental data for the
blends of RHF and BF with various WF contents. As expected there
was no weight loss on neat PP during the 120 days observations.
The dispersion of integrity and breakup of samples was observed
after around 20 days and increased during burial time. It can be
noted that higher content of WF had lead to higher degradation.
These observations were in agreement with the findings reported
in the work by Kaczmarek and Oldak [18] and Oldak et al. [19].
They found that with a very small amount of cellulose (5–15%) in
polyethylene (PE) composite, it may not improve its biodegradabil-
ity. The biodegradability in PE films will only have the pronounced
effect if it contains 30% cellulose and more. Fig. 3 clearly presents
the effect of WF content on the biodegradation of RHF/PP and BF/
PP composites. The compounds show some degree of
 A. Nourbakhsh et al. / Composites: Part B 56 (2014) 279–283
biodegradability with increasing WF. The degradation is about 8%
for BF and 10% for RHF compounds after 120 days, respectively.
From the data in Fig. 3, it also shows the effects of different cel-
lulosic materials and their loading on biodegradability of compos-
ites. With addition of RHF, all samples show substantial decrease in
their weight in the first 40 days. It is noted that for RHF/PP
composites, addition of 25% RHF and 15% WF showed the highest
degradation rate among all treatments after 120 days.
4. Conclusions
Based on the results of this study the following conclusions can
be drawn:
1. The results showed that the fiber content had the greatest effect
on mechanical properties and biodegradation of PP/fibers
composites.
2. Except impact strength, all mechanical properties were found to
increase with increase in fiber loading.
3. The mechanical properties of PP filled with RHF were consider-
ably higher than BF in composites, due to its higher aspect ratio.
4. Based on the results of this investigation, the highest mechani-
cal properties of RHF composites can be reached with 40% fiber
content.
5. The highest biodegradation rate was achieved with the addition
of 25% RHB and 15% WF.
6. Based on the results of this investigation, it is possible to blend
the non-degradable PP matrix with RHF, BF, and WF in order to
improve its biodegradability.
7. The successful biodegradability test can be continued with
more percentage of WF; however, it may be weaken the
mechanical properties of the composites.
8. RHF could be considered as a potential source of low cost and
biodegradable material for composites.
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