Industrial Crops and Products 76 (2015) 725733

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Industrial Crops and Products

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

Processing, mechanical and thermal behavior assessments of

polycaprolactone/agricultural wastes biocomposites
Aleksander Hejna a , Krzysztof Formela a, , Mohammad Reza Saeb b
a
Department of Polymer Technology, Chemical Faculty, G. Narutowicza Str. 11/12, Gdansk University of Technology, 80-233 Gdansk, Poland
b
Department of Resin and Additives, Institute for Color Science and Technology, P.O. Box: 16765-654, Tehran, Iran

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

Article history: In this paper, brewers spent grain (BSG) was applied as potential lignocellulose bioller in biocompos-
Received 20 March 2015 ites based on polycaprolactone (PCL). The PCL/BSG biocomposites lled with varying content of biollers
Received in revised form 17 July 2015 were prepared via low-temperature melt-compounding. These conditions allow limiting thermal degra-
Accepted 22 July 2015
dation of used biollers during processing. The inuence of bioller content (ranging from 25 to 200
Available online 12 August 2015
parts by weight on 100 parts of PCL) on processing, static and dynamic mechanical properties, thermal
properties and water absorption was investigated. For better characterization of interfacial interactions
Keywords:
between PCL and BSG obtained results were compared with properties of biocomposites lled with other
Biocomposites
Polycaprolactone
agricultural waste - wheat bran (WB). It was observed that higher amount of amino-acids present in the
Brewers spent grain BSG (21 wt.%), in comparison to WB (4 wt.%), caused partial plasticization of PCL matrix, which improved
Wheat bran processing but simultaneously deteriorated the mechanical properties of PCL/agricultural wastes bio-
Thermomechanical properties composites. The melt ow index of PCL/BSG was two-folds higher than for PCL/WB composites. The best
mechanical properties were achieved in case of PCL/WB biocomposites, which showed higher values of
storage modulus, 5% higher values of hardness and at least 30% higher tensile strength in most cases.
Obtained results suggest better compatibility between the PCL matrix and WB in comparison to the BSG,
which were explained by differences in the content of proteins in applied biollers. The conducted inves-
tigations showed that BSG and WB could be successfully applied as a low-cost substitute of lignocellulose
llers in polymer wood composites and biocomposites.
2015 Elsevier B.V. All rights reserved.

1. Introduction
The idea of using agricultural wastes as ller and/or reinforcing
agent, and commercializing the resulting products has become a
matter of growing interest during the last decades. Investigations
devoted to brewers spent grain (BSG), a major by-product of brew-
ing industry generated in the mashing process, have enlivened this
area of research (Fillaudeau et al., 2006). Moreover, the abundance
and low cost of BSG gives it the potential to become a candidate
for different industrial and/or environment-related applications
(Ishiwaki et al., 2000; Robertson et al., 2010). It has been docu-
mented that BSG accounts for 85% of the total by-products of
beer manufacturing, on average 31% of the original malt weight
(Mussatto et al., 2006; Tang et al., 2009). Assuming that for each
100 liters of the product 20 kilograms of malt are used (value for
the most popular type of beer light lager, exceeding 45 kg for
Corresponding author.
E-mail address: krzysztof.formela@pg.gda.pl (K. Formela).
strong stouts), 6.2 kg of the BSG is generated for one hectoliter of
the produced beer. According to the 2012 edition of The Brewers
of Europe Beer Statistics Report, 40 billion liters of beer are pro-
duced annually in Europe, which gives around 2.5 million tonnes
of BSG (The Brewers of Europe, 2012).
Nowadays BSG is mainly used for animal nutrition, either in
wet or dried form (Dhiman et al., 2003). According to the litera-
ture, BSG is a very advantageous feed, rich in protein, ber and
energy (Mussatto and Roberto, 2006; Waters et al., 2012), which
results in an increased milk production of cows (Belibasakis and
Tsirgogianni, 1996). Application of BSG has been also reported for
other animals feeding such as sh, pigs and chickens, resulting in
positive impact on the animal nutrition (Kaur and Saxena, 2004;
Muzinic et al., 2004).
Several attempts have been made to incorporate BSG into
human nutrition regime, like quite popular biscuits and snacks con-
taining prepared BSG. Kanauchi et al. reported that BSG is a valuable
source of vitamins, minerals and amino acids. Though the content
of protein in the dried BSG exceeds 20 wt.% (Kanauchi et al., 2001),
its usage in white bakery products is limited because of appearance

http://dx.doi.org/10.1016/j.indcrop.2015.07.049
0926-6690/ 2015 Elsevier B.V. All rights reserved.
726 A. Hejna et al. / Industrial Crops and Products 76 (2015) 725733
concerns (Ktenioudaki et al., 2012). Nevertheless, replacement of
10 wt.% of traditional our with the our made from BSG increases
the protein content by 50% (Hassona, 1993). Addition of BSG our
to bread or cereals also decreases its caloric density, because of the
starch being removed during mashing (Huige, 1994).
Another application of BSG is related to the energy production,
by direct combustion, pyrolysis or manufacturing of charcoal bricks
(Okamoto et al., 1999; Sato et al., 2001). Raw BSG has caloric value
of 20 MJ/kg (Russ et al., 2005), while its processing into charcoal
bricks increases the caloric value to 27 MJ/kg. This is similar to (or
even higher than) the caloric value of charcoals produced from
other raw materials (Okamoto et al., 2002). It is also possible to pro-
cess BSG through fermentation which yields biogas or bioethanol
to be used as an alternative fuel (Meneses et al., 2013; Mussatto
et al., 2010a; Sezun et al., 2011).
Some attempts were also made to implement BSG in chemi-
cal and biotechnological processes, for example as a substitute of
glucose or sucrose in the lactic acid production (Mussatto et al.,
2007) or incorporation of BSG in xylitol production (Carvalheiro
et al., 2007; Mussatto and Roberto, 2005). Hydroxycinnamic acids
such as ferulic or p-coumaric acids, which show antioxidant prop-
erties, can be successfully extracted from BSG and applied in food
or cosmetic production (Moreira et al., 2012; Xiros et al., 2009).
BSG can also be used at cultivation of microorganisms and
enzymes production (Dhillon et al., 2012; Hashemi et al., 2011;
Souza et al., 2012). Among other applications of BSG, there is
adsorption of different compounds from gases or wastewater. For
example, adsorption of cadmium, lead, chromium or copper ions
from aqueous solutions (Li et al., 2012; Lu and Gibb, 2008); appli-
cations related to dyes used in paper and textile industries (Silva
et al., 2004); extraction of volatile organic compounds from waste
gases (Chiang et al., 1992). Moreover, BSG can be converted into
activated carbon (Mussatto et al., 2010b).
Investigations regarding the structure of BSG reveal that it is
mainly composed of cellulose, hemicellulose and lignin bres. Its
composition is comparable to wood our, ax ber, kenaf ber,
and wheat bran, already applied in composites based on poly-
mers and polymer blends (Andersons et al., 2006; Bedzki et al.,
2014; Graupner et al., 2009; Tawakkal et al., 2014). The relatively
low price of BSG is the next good reason for incorporation of this
agricultural waste as pro-ecologic ller in polymer compositions.
Cunha et al. developed polyhydroxybutyrate-valerate/BSG com-
posites and produced lms for food packaging applications (Cunha
et al., 2014). Their investigations showed that addition of BSG bers
decreases the stiffness and crystallinity of the resulting lms. The
obtained lms revealed increased permeability when subjected to
O2 , CO2 and water vapor, which affects their biodegradability. On
the other hand, considerable aggregation of BGS bers was found to
impose serious limitation on processing of PHBV/BSG composites
(Berthet et al., 2015). This shortcoming was arising from the treat-
ment of some llers applied for removal of proteins and sugars from
the BSG. Recently, green composites based on polyurethane and
ginger spent were prepared where a signicant rise in the mechan-
ical properties was reported with respect to neat polyurethane
upon addition of 2.57 wt.% of ginger spent to the polyurethane
(Chethana et al., 2015). This was ascribed to the sufcient adhesion
at the matrix-ller interface. It was also found that the lignocellu-
losic bers impose signicant impact on the physical, mechanical,
and thermal properties of such biocomposites (Liu et al., 2014).
In the light of above discussions, agricultural by-products rich in
cellulose are valuable sources for production of polymer compos-
ites or biocomposites due to their low price as well as reinforcing
features. In the presented state of knowledge, only a few recently
published papers concerned using of brewers spent grain (BSG) in
polymer composites.
Table 1
Chemical composition of BSG and WB.
Components Weight content in bioller, %
BSGa WBb , c
Cellulose 17 25
Hemicellulose 19 32
Lignin 15 5
Proteins 21 4
Ashes 3 4
Starch 12
Others (lipids, moisture, ash etc.) 25 18
a
According to ztrk et al. (2002).
b
According to Saunders (1978).
c
According to Caprez et al. (1986).
In this work the potential of BSG as a bioller in biocompos-
ites with polycaprolactone (PCL) matrix was evaluated. Highly lled
PCL/BSG biocomposites were prepared via melt-compounding and
the inuence of BSG content on processing, static mechanical prop-
erties (tensile strength, elongation at break, hardness), dynamic
mechanical properties, thermal behavior, and water uptake of
PCL/BSG biocomposites was determined. For better understanding
the interfacial interaction between PCL and BSG, the characteris-
tics of PCL/BSG biocomposites were compared with properties of
biocomposites lled with another agricultural waste by-product -
wheat bran (WB).
2. Experimental
2.1. Materials
Polycaprolactone (PCL), CapaTM FB100 with molecular weight
of 100,000 g/mol and melting point of 5860 C was obtained from
Perstorp Holding AB (Sweden). PCL as matrix was selected because
of its good mechanical properties, biodegradability and relatively
low processing temperature in comparison with conventional poly-
mers (Terzopoulou et al., 2015). Processing of biocomposites at
low temperatures allows for the reduction of energy consumption
and prevents degradation of some biopolymers (e.g. cellulose based
llers).
Brewers spent grain (BSG) was provided by home brewery Dno
Bojlera (Poland) as a by-product from the production of weissbier
(pale German wheat beer). Initial composition of the malted grain
used during beer production contained (wt.%): 68.2% pale wheat
malt; 22.7% pilsner malt; 5.7% wheat bran and 3.4% buckwheat
husk. Wheat bran (WB) was purchased from Myn Gospodarczy
Sp. J. (Poland).
The chemical composition of BSG and WB is presented in Table 1.
The main difference between BSG and WB llers refers to content of
proteins, lignin (higher content in BSG) and starch (higher content
in WB).
It is well known that the size of ller imposes a signi-
cant inuence on its disperseability in the polymer matrix. From
this perspective, prior to processing, BSG and WB were dried at
80 C and then mechanically grinded in a co-rotating twin-screw
extruder at 120 C to obtain particles with a narrow size distribu-
tion. The particle size distribution and the appearance of the used
BSG and WB can be seen in Fig. 1 and Fig. 2, respectively.
Caprez et al. analyzed different methods of WB treatment and
their inuence on the chemical composition of resulting samples.
The authors investigated extrusion of WB by changing the process-
ing parameters like temperature and screw speed. Their results
indicated that modication of WB via extrusion insignicantly
affects its chemical composition (Caprez et al., 1986).
 A. Hejna et al. / Industrial Crops and Products 76 (2015) 725733
Fig. 1. Particle size distribution of used biollers.
2.2. Biocomposites preparation
Biocomposites were prepared in a GMF 106/2 Brabender batch
mixer at 135 C and rotor speed of 100 rpm. The mixing time
equaled 8 min and included 3 mins of preliminary plasticization
of PCL, then introduction of BSG or WB followed by mixing for
5 mins. The ller content in the biocomposites was altered from 25
to 200 parts by weight of ller (pbw). The obtained biocomposites
were compression molded into 2 mm-thick samples at 135 C and
4.9 MPa applied for about 1 min. Neat PCL processed at the same
conditions was used as reference sample. Samples of composites
were coded as PCL/BSGXpbw or PCL/WBXpbw , where X stands for the
amount of ller used, expressed in parts by weight.
2.3. Measurements
The density of the samples was measured based on the
Archimedes method, as described in ISO 1183. Accordingly, all
Fig. 2. The appearance of BSG (A) and WB (B): 1 - before and 2 - after the grinding.
727
measurements were carried out at room temperature in methanol
medium.
Melt ow index (MFI) of the biocomposites was investigated
using Zwick mFlow plastometer according to ISO 1133 (170 C,
5 kg).
The tensile strength and elongation at break were estimated
in accordance to ASTM D638. Tensile tests were performed on a
Zwick/Roell Z020 apparatus with cell load capacity of 20 kN at
a constant speed of 50 mm/min. Direct extension measurements
were conducted periodically using an extensometer with sensor
arms. Shore hardness type D was estimated using Zwick 3131
durometer in accordance with PN-ISO 868.
Dynamic mechanical analysis was conducted on a DMA
Q800 TA Instruments apparatus. Samples with dimensions of
40 10 2 mm were loaded with variable sinusoidal deformation
forces in the single cantilever bending mode at the frequency of
1 Hz under the temperature rising rate of 4 C/min, ranging the
temperature from 70 to 100 C.
The differential scanning calorimetry (DSC) was performed on a
DSC 204 F1 Phoenix apparatus under nitrogen atmosphere provid-
ing purge ow rate of 20 ml/min, in the temperature range of 80
to 200 C, and at a heating rate of 10 C/min. First, samples 10 mg in
weight were heated from 30 to 200 C to eliminate thermal history,
then cooled down to 80 C and reheated to 200 C.
Degree of crystallinity of PCL phase was determined according
to Formula (1):
Hm
Xc = 100% (1)
Hc 
where, Xc : degree of crystallinity (%); Hm : melting enthalpy (J/g);
Hc : melting enthalpy at 100% crystallinity, the value of which has
been reported to be 136 J/g (De Kesel et al., 1999) and : the weight
fraction of PCL phase in the blend.
Thermogravimetric analysis (TGA) was performed under nitro-
gen atmosphere on a NETZSCH TG 209 apparatus using 5 mg
samples in the temperature range of 25600 C at a heating rate
of 20 C/min.
The water-uptake of the biocomposites were studied over a
period of one week. Biocomposites (1 g samples) were conditioned
at room temperature and then immersed in sea water (taken on
728 A. Hejna et al. / Industrial Crops and Products 76 (2015) 725733
Fig. 3. MFI of biocomposites as function of bioller content.
22/07/2014 from Baltic Sea in Gdansk-Brzezno). Sea water was
chosen for to simulate the disposal of biocomposites in the natu-
ral environment. Specimens were taken out of the medium after
7 days, blotted on lter paper and weighed. Water-uptake was
determined according Formula (2):
mt mo
W= 100%
mo
where W: water-uptake; mt : mass of the sample after 7 days in g
and mo : initial mass of sample, g.
3. Results and discussion
3.1. MFI analysis
The effect of ller type and its content on the MFI value of the
prepared biocomposites was estimated and the results are pre-
sented in Fig. 3. It can be seen that the type of agricultural waste
ller has signicant inuence on the MFI values of biocomposites.
PCL/WB biocomposites were characterized by lower values of MFI,
than PCL/BSG biocomposites. It was noticed that addition of smaller
amount of BSG ller (to 100 pbw) causes increase of MFI. This phe-
nomenon can be attributed to the higher content of proteins within
the BSG, comparing to WB (see Table 1). Amino acids presented on
the surface of BSG are natural low-molecular-weight compounds,
which can act as plasticizers (Stein and Greene, 1997; Stein et al.,
1999; Selmin et al., 2015). This phenomenon causes an increase
in MFI value (decrease of viscosity of material). Incorporation of
higher amount of ller leads to decrease in MFI of biocomposites.
These results conrm increase in the viscosity of the biocomposites.
Incorporation of biollers imposed some limitation on the mobility
of PCL, which is liable for its lower ow ability.
3.2. Density and water uptake
Densities of biocomposites lled with different amounts of agri-
cultural llers are given in Table 2. As it can be seen, signicant
differences in the densities of PCL/BSG and PCL/WB composites
were observed. Higher values were noticed for PCL/WB composites,
which was expected considering the density of llers. As mentioned
in previous section, BSG contains more than 20 wt.% of proteins. It
is generally assumed that the density of proteins can be considered
to be 1.35 g/cm3 , independent of the nature and molecular weight
of the protein (Fischer et al., 2004). On the other hand, density of
natural bers like cellulose, hemicellulose, and lignin, which are
the main components of WB takes values around 1.5 g/cm3 (Faruk
et al., 2012; Mwaikambo and Ansell, 2001). Experimental values of
the density of the incorporated biollers are corresponding to data
from the literature. The ascending trend in the density of green
composites prepared in this work upon ller content ts well with
previous studies (Datta and Gowinska, 2011; Li et al., 2008).
In order to determine the porosity of the materials, values of
theoretical densities of investigated samples are used and listed
in Table 2. This estimation brings some more insights about the
nature of porosity in the studied biocomposites and will be further
compared with mechanical and thermal properties. The theoretical
densities of biocomposites were calculated using the Eq. (3):
C = PCL (1 X) + F X (3)
where, C is the theoretical density of the biocomposite, g/cm3 ; 
PCL
is the density of the PCL, g/cm3 ; F is the density of the bioller,
g/cm3 ; X is the fraction of the ller. Using the theoretical and exper-
imental values of the density, porosity of biocomposites was also
calculated according to Formula (4):
(theo exp )
p= 100% (4)
theo
where, p is the porosity of the material in volume percent; theo is
the theoretical value of density, g/cm3 ; and exp is the experimental
density determined for biocomposite, g/cm3 .
In case of composites containing llers, water uptake is strictly
related to the porosity of the material. Fillers incorporated into
(2) polymer matrix occupy the pores between polymer chains. This
causes a decrease of porosity and immobilization of polymer chains,
which results in stiffening of the material (Bindu and Thomas,
2013). However, it can be seen that the incorporation of BSG and WB
into the PCL signicantly increases the water uptake of the prepared
samples. This can be ascribed to the fact that both biollers (WB
and BSG) are mainly composed of lignin, cellulose, hemicellulose
and other polysaccharides, which show high values of water bind-
ing capacity and swelling capacity (Kozio et al., 2012; Zhu et al.,
2010). Higher values of water uptake were observed for samples
containing WB, which is associated with the difference in chemical
compositions of WB and BSG (20 wt.% of proteins in BSG, 12 wt.%
of starch in WB) (Hu and Yu, 2014).
Assessment of water uptake could be a very positive feature
of the prepared samples considering biodegradation of investi-
gated biocomposites, which will be the topic of further researches,
together with the analysis of compounds presented in the degra-
dation medium.
Sol fraction values, associated with the mass of biocomposite
dissolved in the water during the test, are also presented in Table 2.
It can be realized that introduction of WB, which is composed
mainly of polysaccharides, has small inuence on the sol fraction in
the composites, which is related to the very low solubility of lignin
and cellulose in water (Horvath, 2006). In case of BSG, which con-
tains about 20 wt.% of proteins as mentioned before, values of sol
fraction are signicantly higher due to differences in composition
between WB and BSG (see Table 1). According to the literature, the
main amino acids presented in the BSG are glutamine, asparagine,
leucine, lysine, phenylalanine and arginine, which show good sol-
ubility in water (Robertson et al., 2010).
3.3. Static mechanical properties
The values of tensile strength and elongation at break of
investigated biocomposites are presented in Figs. 4 and 5. The
incorporation of 100 pbw of agricultural waste ller into the PCL
matrix expectedly caused ve-fold drop in the tensile strength
from 40 MPa to 8 MPa, while addition of 200 pbw of BSG/WB
ller caused ten-fold decrease in the tensile strength (from 40
 A. Hejna et al. / Industrial Crops and Products 76 (2015) 725733 729

Table 2
Density, porosity, water uptake and sol fraction experimental data of the biocomposites.

Sample Experimentaldensity, g/cm3 Theoreticaldensity, g/cm3 Porosity,% Water uptake, % Sol fraction, %

PCL 1.14 0.01 - - 0.43 0.15 0.29 0.02

PCL/BSG50pbw 1.17 0.01 1.25 7.27 9.79 0.98 1.68 0.12
PCL/BSG100obw 1.19 0.01 1.31 9.60 20.51 2.60 3.38 0.07
PCL/BSG150pbw 1.22 0.02 1.34 9.34 24.72 0.62 7.44 1.28
PCL/BSG200pbw 1.24 0.02 1.36 9.70 30.44 2.25 11.61 0.61
PCL/WB50pbw 1.18 0.01 1.26 6.42 10.97 0.14 0.48 0.07
PCL/WB100pbw 1.25 0.02 1.32 6.44 21.92 0.17 0.68 0.36
PCL/WB150pbw 1.28 0.01 1.36 6.37 31.25 1.05 0.84 0.13
PCL/WB200pbw 1.31 0.01 1.38 5.90 36.19 0.66 1.88 0.33

Fig. 4. Tensile strength of biocomposites as function of bioller content. Fig. 6. Hardness of biocomposites as function of bioller content.

related to chemical composition of the used biollers (see Table 1).

Since WB contains higher amount of polysaccharides and starch
than the BSG, an enhanced interactions between polar groups pre-
sented in this bioller (mainly hydroxyl groups) and ester groups
from PCL was expected. Stronger interactions explain the higher
tensile strength observed for PCL/WB biocomposites in compari-
son to PCL/BSG materials. Weak interfacial adhesion between the
BSG and PCL matrix may be also correlated with the partial plasti-
cization of PCL by amino-acids presented in BSG ller.
The hardness values of the studied biocomposites lled with
different amount of agricultural llers are plotted in Fig. 6. It is
evident that PCL/WB composites show higher (5 Sh D) hardness
in comparison to the neat PCL. On the other hand, the results of
hardness determined for the PCL/BSG composites were similar to
neat PCL, which conrms partial plasticization of PCL matrix in the
PCL/BSG composites.

3.4. Dynamic mechanical properties

Fig. 5. Elongation at break of biocomposites as function of bioller content.

MPa to 4 MPa). Furthermore, increasing the amount of ller in
PCL/agricultural waste ller composites caused a signicant fall
in the elongation at break (see Fig. 5). Such a descending trend in
the mechanical properties of biocomposites upon increase of ller
content can be explained by the weak compatibility between PCL
matrix and agricultural waste ller. In other words, incorporation
of higher amount of ller to PCL matrix has limited the mobility of
PCL chains, leading to a signicant deterioration of the mechanical
properties (Khan et al., 2013). Furthermore, PCL/BSG biocompos-
ites exhibit lower tensile strength and higher elongation at break
values compared to the PCL/WB composites. This phenomenon is
In Fig. 7, Fig. 8 and Table 3, the results of dynamic mechani-
cal analysis of the prepared composites are given. It can be seen
that addition of agricultural llers has signicantly increased the
storage modulus (E ) of PCL. It was also observed that stiffness of
composites was enhanced with the addition of BSG and WB. It is
well known that incorporation of llers into the polymer matrix
imposes serious limits on the mobility of polymer chains, which
is responsible for stiffness enhancement. Glass transition temper-
atures (Tg ), which corresponds to the maximum value of the curve
loss tangent (tan ) versus temperature, also conrm the changes
in the stiffness of the prepared biocomposites. As it can be seen in
the Fig. 8, addition of llers not only shifts the tan peak towards
higher temperatures, but also lowers the peak magnitude. This is
730 A. Hejna et al. / Industrial Crops and Products 76 (2015) 725733

Table 3
Glass transition temperatures, volume fractions of immobilized polymer chains and adhesion factors of the biocomposites.

Properties Sample symbol

PCL PCL/BSG100pbw PCL/BSG200pbw PCL/WB100pbw PCL/WB200pbw

Tg , C 39.93 37.28 35.12 36.40 35.43

Cv 0 0.1614 0.1791 0.1857 0.1975
A 1.3777 3.0174 1.2973 2.9680

W can be calculated from the tan in accordance to the following

relation (6):
 tan
W= (6)
 tan + 1
Volume fractions (Cv ) of the immobilized polymer chains are pre-
sented in Table 3. It should be noticed that Cv increase upon increase
of bioller content, which is consistent with storage modulus trend.
Moreover, higher Cv values are observed for biocomposites lled
with WB, which is associated with the difference in chemical
composition of the used llers (see Table 1) and suggests better
compatibility between PCL and WB. As mentioned earlier, WB, in
comparison to BSG, contains higher amount of polysaccharides
and starch, which results in an enhanced interfacial interactions
between the polar groups of biollers and ester groups of PCL.
Stronger matrix-ller interactions cause higher immobilization of
polymer chains, which itself affects on the mechanical properties
of PCL/agricultural waste biocomposites (see Figs. 4 and 5).
For better understanding the interfacial interactions between
Fig. 7. Storage modulus of biocomposites as a function of temperature.
PCL and used biollers, the adhesion factor (A) was calculated from
dynamic mechanical analysis results according to Wei et al. (Wei
et al., 2015) using the following Formula (7):
1 tan c
A=( )( )1 (7)
1 Vf tan m
where, c and m subscripts denote biocomposites and matrix, while
Vf is the ller volume fraction.
A low value for A indicates good adhesion and enhanced inter-
actions between the matrix and ller particles (Wei et al., 2013).
The A values presented in Table 3 were averaged from the temper-
ature range from 15 to 35 C, assuming the average temperature
at mechanical properties measurements was 25 C. It was noticed
that adhesion factors of the PCL/WB composites are slightly lower
comparing to those of PCL/BSG materials, which conrms the
conclusions about enhanced ller-matrix interactions. Presented
calculations explain the differences in static mechanical properties
between two types of composites.

3.5. Differential scanning calorimetry (DSC)

Fig. 8. Plot of tan of biocomposites as a function of temperature.

in agreement with previous studies (Cao et al., 2005; Sormana and
Meredith, 2004; Tarakcilar, 2011). Bindu and Thomas, based upon
the information and formulas presented by Abdalla and Kojima
(Abdalla et al., 2007; Bindu and Thomas, 2013; Kojima et al., 1993),
proposed a method for calculation of the amount of polymer chains
immobilized through matrix-ller interaction in accordance with
Formula (5):
(1 Co )W
Cv = 1
Wo
where, Cv is the volume fraction of the immobilized polymer chains,
Co stands for the volume fraction of the immobilized chains in the
pure PCL (taken to be 0), and W and Wo are energy loss fractions for
analyzed sample and pure PCL, respectively. Energy loss fraction
The results of DSC measurements are summarized in Table 4
and Table 5. In the presented data, number 1 in the subscript means
rst heating run and number 2 means second heating run. The dif-
ference between DSC results determined at the rst and second
heating run is related with thermal history of the studied samples.
It was noticed that incorporation of agricultural waste ller to PCL
have small effects on the thermal properties of PCL matrix. Simi-
lar observation was recently described in other work (Sabo et al.,
2013). Correspondingly, PCL/BSG and PCL/WB composites exhib-
ited similar melting temperatures (Tm ) ranging in 57.960.4 C,
which is similar to the Tm of neat processed PCL, that is 58.6 C. It
(5) was noticed that incorporation of higher amount of bioller caused
small decline in the crystallization temperature (Tc ). The lower Tc
values of biocomposites compared to the neat PCL can be related to
hindered diffusion of PCL segments into crystallization site caused
by limited mobility of PCL chains. Incorporation of 100 pbw and
200 pbw of agricultural waste to PCL matrix decreased the values
 A. Hejna et al. / Industrial Crops and Products 76 (2015) 725733 731

Table 4
Melting and crystallization temperatures together with corresponding enthalpy for biocomposites.

Sample Tm1 , C Hm1 , J/g Xc1 , % Tc , C Hc , J/g Tm2 , C Hm2 , J/g Xc2 , %

PCL 65.9 69.5 51.1 32.4 56.9 58.6 50.3 36.9

PCL/BSG100pbw 68.3 34.0 48.8 30.9 26.9 59.4 23.8 34.1
PCL/BSG200pbw 65.6 25.3 54.5 28.8 19.3 59.1 16.5 35.6
PCL/WB100pbw 68.9 32.9 47.2 29.2 25.9 60.4 23.7 33.9
PCL/WB200pbw 62.0 22.7 48.8 30.9 15.9 57.9 15.2 32.6

Hm enthalpy of fusion (melting); Hc enthalpy of crystallization; Xc degree of crystallinity; Tm melting temperature; Tc crystallization temperature; 1 rst
heating; 2second heating.

Fig. 9. Thermogravimetric curves determined for investigated biocomposites.

Table 5
Thermal decomposition characteristics of biocomposites.

Sample Mass loss, % Tmax1 , C Tmax2 , C Tmax3 , C wtr560 , %

2 5 10 50 Exp. Theo.
Temperature, C

BSG 68.2 135.5 220.4 349.1 297.5 359.7 25.0

WB 58.0 96.4 243.0 331.7 308.4 26.5
PCL 364.6 380.4 391.1 417.4 420.3 0.5
PCL/BSG100pbw 150.4 243.0 282.3 408.4 295.3 359.9 417.4 12.7 12.7
PCL/BSG200pbw 128.1 210.8 263.0 404.5 294.3 361.7 417.8 16.4 16.8
PCL/WB100pbw 158.3 256.9 288.4 408.2 305.1 416.3 14.7 13.5
PCL/WB200pbw 136.7 233.1 277.8 400.9 304.1 415.8 19.2 17.8

of enthalpy of crystallization (Hc ) and enthalpy of melting (Hm ),
which is associated with higher content of amorphous phase (ller
content) in the investigated systems and with interfacial interac-
tions between PCL and used biollers. PCL, PCL/BSG and PCL/WB
composites showed very similar degree of crystallinity (Xc ).
Slight differences between presented results can be related to
the heterogeneous nucleation on the surface of agricultural wastes,
which is the main mechanism responsible for the crystallization
behavior of the PCL matrix (Luduena et al., 2012).
residue values determined at 560 C (wtr560 ) are shown in Table 5.
The theoretical values for composites have also been estimated
based on experimental data for neat PCL and the used biollers.
In case of PCL/BSG composites, the experimental values are well
consistent with the theoretical calculations. On the other hand, for
the PCL/WB biocomposites, the experimental values exceed predic-
tions by more than 1%, which suggests slightly better compatibility
between the PCL matrix and WB when compared to PCL/BSG sys-
tem. To sum up, the results corresponding to the static and dynamic
mechanical properties analyses are in agreement.

3.6. Thermogravimetric analysis (TGA)

The results of the thermogravimetric analysis of PCL/agricultural
waste biocomposites are summarized in Fig. 9. Presented data indi-
cate signicant decrease in the thermal stability with the addition
of either BSG or WB bioller, in other words, arising from their
rather poor thermal stability. It was observed that highly-lled
biocomposites (with 200 pbw of bioller) are thermally stable at
temperature 130 C. This creates a safe temperature window for
the processing of studied biocomposites, considering the fact that
melting temperature takes values around 6065 C. The weight
4. Conclusions
In this study, PCL/BSG biocomposites were prepared via
melt-compounding and their thermomechanical properties were
compared with PCL based biocomposites lled with the other agri-
cultural waste by-product - wheat bran (WB). This allowed better
characterization of the interfacial interactions in such systems. It
was noticed that chemical composition of the applied bioller has
a signicant inuence on the processing, mechanical and thermal
properties of the studied biocomposites. Sufciently high amount
732 A. Hejna et al. / Industrial Crops and Products 76 (2015) 725733
of amino-acids present in the BSG helps for partial plasticiza-
tion of PCL matrix, which has benecial inuence on the melt
ow index (processing) and sol fraction soluble in water (hydroly-
ses/degradation). On the other hand, PCL/WB biocomposites were
characterized by their higher tensile properties, hardness and ther-
mal stability. This phenomenon was related to the polymer chains
immobilization due to possible matrix-ller interfacial interac-
tions. This was further conrmed by dynamic mechanical analysis,
calculation of volume fraction of the immobilized polymer chains,
and adhesion factor. Presented calculations suggest better compat-
ibility between the PCL matrix and WB in comparison to the BSG,
which is supported by mechanical and thermal properties analyses.
Presented results conrmed that BSG and WB can be considered
as a substitute of cellulose based biollers in polymer composites
due to its low-cost as well as acceptable properties. We also dis-
close more ideas here to be followed in the future: (i) modication
of BSG/WB (e.g. removal of amido-acids, starch); (ii) application of
BSG/WB together with other llers as hybrid llers in biocompos-
ites; (iii) optimization of biocomposites processing and recycling
conditions (e.g. mixing at lower temperature, evaluation of degra-
dation products).
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