Enhanced properties of lignin-based biodegradable polymer composites

using injection moulding process

Saswata Sahoo
a
, Manjusri Misra
a,b
, Amar K. Mohanty
a,b,
a
Bioproducts Discovery and Development Center (BDDC), Department of Plant Agriculture, University of Guelph, Ontario, Canada N1G 2W1
b
School of Engineering, University of Guelph, Ontario, Canada N1G 2W1
a r t i c l e i n f o
Article history:
Received 2 December 2010
Received in revised form 21 July 2011
Accepted 21 July 2011
Available online 28 July 2011
Keywords:
A. Thermoplastic resin
B. Strength
D. Mechanical testing
E. Extrusion
a b s t r a c t
Composites from polybutylene succinate (PBS) and lignin-based natural material were fabricated using a
melt mixing process. The effects of lignin material and polymeric methylene diphenyl diisocyanate
(PMDI) compatibilizer on the properties of composites were investigated. Incorporation of 65% lignin
material into PBS was achieved with an improvement in the tensile and exural properties of composites.
Incorporation of 1% PMDI in 50% lignin lled composites enhanced the tensile, exural and impact
strength simultaneously. Heat deection temperature (HDT) of the virgin plastic also increased with lig-
nin and PMDI incorporation. Improved interfacial adhesion was observed from SEM micrographs of the
compatibilized composites.
2011 Elsevier Ltd. All rights reserved.
1. Introduction
Lignin, the second most abundant natural biopolymer in the
world, serves as a matrix component for cellulose and hemicellu-
lose in plant cell walls and provides mechanical strength to bio-
bres. Currently, about 70 million tons of lignin are generated
annually as a co-product in the paper pulp industry [1]. Further-
more, in order to fulll the demand for lignocellulosic bioethanol
in the United States in the near future, about 225 million tons of lig-
nin generation is expected from the cellulosic bioethanol industry
[1]. Only about 2% of the generated lignin is being used for value
added applications while the rest is used as burning fuel in the same
generating industries. Sustainability of these industries greatly de-
pends upon the value added applications of this co-product.
Lignin is an amorphous substance that has potential for mate-
rial applications. It is a complex polyfunctional macromolecule
which is composed of a large number of polar functional groups
[2]. Important functional groups, chemical units and inter unit
linkages present in lignin are phenolic AOH, aliphatic hydroxyl,
carbonyl, alkyl aryl ether, biphenyl, diaryl ether, phenylpropane,
guaiacyl, syringyl, etc. [1,2]. The details of the chemical functional-
ities and inter unit linkages are reported in literature [1,2]. Traces
of carbohydrates also remain with lignin. Lignin nds applications
in adhesives, asphalts, polyurethanes, and phenolformaldehyde
resin formulations [1,3]. Lignin has interesting grafting and cross-
linking abilities that makes it an interesting material for its use
in polyurethanes and other polymeric systems [3]. However, very
limited studies have been conducted on lignin-based polymer
composites or polymer blends. Ligninpolymer blends and com-
posites have been reviewed recently [1]. Lignin forms miscible
blends with polyethylene terephthalate (PET) and polyethylene
oxide (PEO) and immiscible blends with polypropylene (PP) and
polyvinyl alcohol (PVA) [4]. LigninPP, ligninPET, ligninPVC
(polyvinyl chloride) and ligninPS (polystyrene) composites have
also been reported in literature [57]. Lignin is compatible with
polystyrene (PS) [7] and its compatibility increases with increasing
lignin content. In case of ligninPVC blends, lignin is more compat-
ible to unplasticized PVC than plasticized PVC [7]. Ligninpolyeth-
ylene composites compatibilized with ethylene vinyl alcohol
copolymer was studied by Samal et al. [8]. Incorporation of lignin
in low density polyethylene (LDPE), linear low density polyethyl-
ene (LLDPE), and high density polyethylene (HDPE) slightly in-
creased the modulus but decreased the tensile strength and
elongation of the blends [9]. However, coupling agents have been
used to improve the mechanical properties of lignin composites
[10]. Lignin itself has also been used as a compatibilizer in natural
bre composites [11]. It has been reported that lignin acts as b
nucleating agent, re retardant and toughening agent for neat PP.
However, very limited studies have been done on lignin blended
with biodegradable biopolymers such as starch, polyhydroxyalk-
anoates and polylactic acid. Lignin acts as a plasticizing agent for
starch [12], nucleating agent for polyhydroxybutyrate (PHB) poly-
mers [13] and adhesion promoter in cotton brePLA composites
1359-835X/$ - see front matter 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.compositesa.2011.07.025

Corresponding author at: Bioproducts Discovery and Development Center

(BDDC), Department of Plant Agriculture, University of Guelph, Ontario, Canada
N1G 2W1. Tel.: +1 519 8244120x56664; fax: +1 519 763 8933.
E-mail address: mohanty@uoguelph.ca (A.K. Mohanty).
Composites: Part A 42 (2011) 17101718
Contents lists available at SciVerse ScienceDirect
Composites: Part A
j our nal homepage: www. el sevi er . com/ l ocat e/ composi t esa
[14]. It has been reported that tensile strength and elongation at
break of polylactic acid (PLA) decreased with lignin incorporation.
As well, thermal degradation was accelerated when lignin content
reached 20% [15].
PLA and polyhydroxyalkanoates (PHAs) are the most widely
used biopolymers but they are facing challenges due to their infe-
rior impact performance. Polybutylene succinate (PBS) is a com-
paratively tough polymer and is capable of incorporating a high
volume of biomass. PBS can be made from both fossil and renew-
able resources which offer a great future for the composite indus-
tries regarding availability of raw material. The growing interest
for PBS manufacturing predicts a future cost reduction which is
signicantly lower than the current price. Natural bre reinforced
PBS composites have been studied by many authors [1619]. Nat-
ural bres are not compatible with hydrophobic polymers and
hence result in inferior material properties. In order to improve
the properties of natural bre composites, surface treatments of -
bres have been reported in literature [17,18]. Compatibilizers/cou-
pling agents have also been used to improve the performance of
composites. Various types of compatibilizers have been tested
are silanes, titanates, maleic anhydride grafted polymers and isoc-
yantes. Use of polymeric methylene diphenyl diisocyanate (PMDI),
one of the isocyanate compatibilizers, has improved the tensile
strength and elongation of natural ller based composites [20,21].
Lignin-based PBS composites are very rarely reported in litera-
ture. In the present study, a lignin-based natural material with the
trade name Arboform

F 45 has been used as reinforcing ller in a

PBS matrix. Arboform

F 45 is a melt processable thermoplastic

material available in pellet form. It contains modied alkali lignin
(obtained from paper pulp industry), natural additives, and 45%
ground plant bres like hemp, ax and wood particles [22,23].
Arboform

F 45 pellets (described as lignin in this manuscript)

were used as received in this study. It is believed that lignin is
more compatible with polar polymers due to the presence of polar
functionality in its chemical structure. Poor compatibility of lignin
with conventional polyolen polymers can be understood from the
inferior mechanical properties of lignin lled polyolen compos-
ites. The tensile strength of polyethylene drastically decreased
with 27% lignin incorporation [10]. Similarly, incorporation of lig-
nin to polypropylene gradually decreased the tensile strength of
composites [6,24]. Incorporation of lignin to PLA also reduced the
properties of the polymer [15]. PBS was selected as the polymer
matrix for our study because of its toughness, polar nature, nearly
similar solubility parameter with lignin, biodegradability, and pos-
sible renewability. In this research, the effect of lignin (Arboform

F 45) content and the effect of polymeric dimethylene diphenyl

diisocyanate (PMDI) compatibilizer were tested with respect to
the mechanical, thermal and thermo-mechanical properties of
the generated composite materials.
2. Experimental
2.1. Materials and method
2.1.1. Materials
Lignin Arboform

F 45 was received from Tecnaro GMBH, Ger-

many. PBS (Bionolle

1020), a product of Showa Highpolymers Co.

Ltd., Japan, was received from Toyo Plastics Co. Ltd., Osaka, Japan.
Polymeric methylene diphenyl diisocyanate (PMDI) under the
trade name Rubinate

M was used in this study. Rubinate

M used
was a product of Huntsman polyurethanes, NJ, USA.
2.1.2. Composites fabrication
Lignin (Arboform F 45) was not melt processable alone in a
15 cc microextruder (DSM Xplore, Netherland). Hence, it was melt
mixed with PBS to develop composites from lignin. Before compos-
ite processing, PBS and lignin pellets were dried at 80 C for 3 and
4 h respectively using a convection oven. Lignin of varying weight
percentages (30%, 50% and 65%) with calculated quantities of PBS
were melt mixed in a 15 cc microextruder at 160 C barrel temper-
ature, 150 rpm screw rotation (co-rotation conguration) and
compounded for 6 min. The hot melt was collected and composites
were fabricated using a 12 cc microinjection moulder (DSM
Xplore) at 160 C melt temperature and 30 C mould temperature.
Composites with compatibilizer were made by adding 12 wt.%
PMDI to 50% lignin lled PBS composites. All the composites were
made at similar processing conditions. All the composite speci-
mens acquired a lignin like dark reddish brown colour.
2.2. Characterisation
The effect of lignin (Arboform

F 45) content (30%, 50% and 65%)

on the PBS matrix was studied and the properties of the resulting
composites were compared with neat PBS polymer (control). Com-
posites with 50% lignin content were selected for PMDI incorpora-
tion. Composites were prepared with the incorporation of 1 and
2 wt.% PMDI compatibilizer. The properties of the compatibilized
composites were compared with the properties of 50% lignin lled
composites and neat PBS. The types of characterisations carried out
are discussed below. All results presented are the average values of
ve replications for mechanical properties and three replications
for thermal and physical properties.
2.2.1. C, N, S analysis
Total carbon, nitrogen and sulphur content of lignin pellets
were evaluated through elemental analysis at Laboratory Services,
University of Guelph.
2.2.2. Mechanical testing
Tensile and exural properties of the composites were mea-
sured by a Universal testing machine, Instron 3382, according to
standards ASTM D 638 and ASTM D 790 respectively. System con-
trol and the data analysis were done using Blue Hill software. The
notched Izod impact strength was measured with a TMI Monitor
Impact tester (model No. 4302-01) according to ASTM D 256
using a pendulum of 5 ft-lb.
2.2.3. Fourier transform infrared spectroscopy (FTIR)
Thermo Scientic Nicolet 6700 FTIR spectrometer in attenu-
ated total reection infrared (ATR-IR) mode with a resolution of
4 cm
1
and a number of 32 scans per sample was used to obtain
the spectra.
2.2.4. Differential scanning calorimeter (DSC)
Heat ow as a function of temperature was studied by a Differ-
ential scanning calorimeter (DSC Q 200, TA Instruments Inc.) using
heatcoolheat mode. Nitrogen was used as purge gas during the
experiment. The data was collected by heating the specimen from
50 to 200 C at a constant heating and cooling rate of 10 C per
minute. The data was analysed through TA instrumentss Universal
analysis software.
2.2.5. Dynamic mechanical analysis (DMA)
The storage modulus, loss modulus and tan delta of the com-
posite specimens as a function of temperature were measured
using a Dynamic mechanical analyser (TA Instrument Inc. DMA Q
800). Experiments were carried out by heating the specimens from
50 to 110 C at a constant heating rate of 3 C/min, 20 lm oscil-
lating amplitude, and 1HZ frequency. Heat deection temperature
(HDT) measurements were done at 0.455 MPa load (ASTM D 648).
Specimens were heated from room temperature to 110 C using a
S. Sahoo et al. / Composites: Part A 42 (2011) 17101718 1711
heating rate of 2 C /min. A three point bending clamp was used for
all the tests.
2.2.6. Thermogravimetric analysis (TGA)
Thermogravimetric analysis was carried out by a Thermogravi-
metric analyser (TA Instrument Inc. Q500).The samples were
scanned from room temperature to 600 C at a heating rate of
20 C/min in a nitrogen atmosphere.
2.2.7. Density measurement
The density of polymer and composites was measured by an
Electronic densimeter MD-300S (Alfa Mirage) that takes measure-
ments according to Archimedes principle.
2.2.8. Scanning electron microscopy (SEM)
The morphology of tensile fractured surfaces of the composites
was observed through a Hitachi S-570 scanning electron micro-
scope (Hitachi High Technologies, Tokyo, Japan) at room tempera-
ture. The samples were gold sputtered up to a thickness of 21 nm
by means of a Emitech K-550 sputter coater (Ashford Kent, UK).
An accelerating voltage of 10 kV was used to collect the
micrographs.
3. Results and discussion
3.1. Characterisation of lignin
Lignin pellets were analysed for density, elemental composi-
tion, functional groups, and thermal properties. The density of lig-
nin was 1.34 g/cm
3
. The total carbon, nitrogen and sulphur content
in the material were 57.2%, 0.27% and 0.6% respectively. This lignin
material showed thermal degradation onset at about 179 C (Ta-
ble 1). Lignin degrades at a very broad range of temperatures, be-
tween 150 and 800 C. Lignin decomposition occurs by several
competing reactions during which various bonds cleave at wide
range of temperatures releasing gases like CO, CO
2
, H
2
O and CH
4
[25]. The FTIR spectrum of lignin (Fig. 1) shows a strong and broad
peak at 3342 cm
1
which depicts the presence of OH group in the
material. Peaks due to a CAH stretching vibration appear at 2920
2845 cm
1
. Characteristic peaks in the spectra appear at
1685 cm
1
, 1590 cm
1
, 1511 cm
1
are due to aromatic C@C
stretching, and peaks at 1040 cm
1
and 1260 cm
1
appear due to
CAOAC stretching from ether groups (broader peak than CAO
stretching of polyester). Weak peaks appear at 1220 cm
1
and
1370 cm
1
(not very clearly distinguished due to the overlapping
of spectra) also indicate phenolic CAO and phenolic OH in lignin
respectively. A chemical and structural analysis of this material
was also reported by Haensel et al. [26].
3.2. Mechanical properties
3.2.1. Tensile properties
Tensile properties of composites are shown in Table 2. It is ob-
served that the tensile strength of the composites rst decreased
with 30% lignin incorporation and then increased gradually by
increasing lignin content to 65% (Table 2). Tensile strength of com-
posites also decreased with increasing ller (agro bre) content in
biodegradable polymers like PLA and PBS [27,28]. This outcome
was attributed to the weak interfacial adhesion between the
hydrophilic ller and the hydrophobic polymer matrix. However,
improvement in the tensile properties of composites at higher lig-
nin content (65%) was observed in this investigation. At 65% lignin
content, the tensile strength increased by a factor of 10 over the
50% lignin lled composites, and the strength was about 13% high-
er than the neat polymer. The increase in the tensile strength at
higher lignin content indicates the reinforcing effect of lignin in
PBS polymer that may be attributed to the similarity in the solubil-
ity parameter of lignin and PBS, crosslinking ability and adhesive
nature of lignin. A highly viscous appearance of the composite melt
was observed during the processing of 65% lignin lled compos-
ites; however, the composite melt at 30% and 50% lignin content
was comparatively less viscous. This result may be attributed to
the crosslinking ability of lignin that increased with increasing lig-
nin content in the composites. The tensile modulus of the compos-
ites gradually increased with increasing lignin content in the
composites. The improvement in the properties of composites indi-
cates an interaction, possibly polarpolar interaction between lig-
nin and the polyester matrix. Improvement of the tensile strength
of the hydroxypropyl lignin and polyethylene blend with the
Table 1
Thermo gravimetric analysis of composites.
Specimens Degradation onset
(C)
Weight loss at degradation onset
(%)
Maximum
degradation
temperature (C)
Weight loss at 400 C
(%)
Charred residues at 600 C
(%)
PBS 306.4 1.0 402.9 57.1 0.2
30% LigninPBS 260.3 2.4 392.3 67.8 12.0
50% LigninPBS 237.6 2.6 387.9 343.2 63.8 20.4
65% LigninPBS 236 2.7 383.7 341.3 57.5 27.3
50% LigninPBS-1% PMDI 244.5 2.4 388.1 344.2
h
61.7 22.1
50% LigninPBS-2% PMDI 236.7 2.6 357.8 353.1 62.6 21.8
Lignin 179 3.2 341 380480
b
53.4 31.6
b
Broad.
h
Hump.
Fig. 1. FTIR spectra of lignin, PMDI and composites.
1712 S. Sahoo et al. / Composites: Part A 42 (2011) 17101718
addition of vinyl acetate, a polar component in non polar polyolen
matrix, also supports this interaction concept [29]. Authors have
interpreted that the interaction was due to the presence of polar
carbonyl group [29]. Therefore, a hydrogen bond formation could
be possible between the carbonyl group of the polyester matrix
and the hydroxyl group of lignin.
Based upon the processing suitability and properties combina-
tion, 50% ller based composites were selected for incorporation
of PMDI compatibilizer. Incorporation of 1% and 2% PMDI increased
the tensile strength by 27 and 44% over the uncompatibilised com-
posites, and was about 7.5% and 22% higher than the neat polymer
respectively (Table 2). From these results it was concluded that
PMDI improved the interfacial adhesion in the composites
[20,21]. Addition of PMDI expects the formation of a urethane
(AHNACOOA) linkage due to the reaction between the ANCO
group of PMDI and the AOH group of lignin [30]. Furthermore,
the urethane linkage leads to possible secondary intermolecular
bonding (i.e. the hydrogen bonding between NAH group of ure-
thane linkage and carbonyl group of polyester [30]) which could
be the cause of improved interfacial adhesion of PMDI compatibi-
lized composites. The schematics of the possible interactions are
shown in Fig. 2.
The modulus of the composites decreased slightly with 1% PMDI
addition (Table 2) and was reduced further by increasing PMDI
concentration from 1% to 2%. Lowering of the modulus may be
attributed to possible plasticisation of the composite materials
due to the PMDI addition. It is reported that the moisture present
in the bioller reacts with PMDI producing amine or urea com-
pounds. These compounds plasticize the composites [21] resulting
in a lowering of modulus and an increase in the elongation. The
stressstrain curves of the composites are shown in Fig. 3. Brittle
failure of composites can be observed from the gure. Strain at
break of materials decreased with ller incorporation and slightly
improved by PMDI addition. Reduction of elongation at break with
the ller incorporation and slight improvement by PMDI addition
can also be observed from Table 2. It is reported that PBS is a quite
ductile polymer and the percentage elongation reduces signi-
cantly even with 10% bioller incorporation [17]. Similar trends
in properties by the addition of PMDI to sugar beet pulp based
polylactide composites have also been reported [21].
The rule of mixtures as presented in Eq. (1) was used to predict
the modulus of composites. The rule is generally applied to random
oriented short bre composites [27].
E
c
V
m
E
m
kV
f
E
f
1
E
c
, E
m
, E
f
are the elastic modulus of the composite, polymer matrix
and ller (lignin) respectively. A modulus of lignin of 6.27 GPa [22]
was considered for calculating the modulus of composites. V
m
and
V
f
are the volume fraction of polymer matrix and ller respectively.
A factor k (contribution of bre length and orientation) was used to
t the data. The volume fraction of the bre and matrix was calcu-
lated using the density of PBS (1.26 g/cm
3
) and lignin (1.34 g/cm
3
).
Correlation between theoretical modulus and experimental modu-
lus of composites is shown in Table 2. An increase in the modulus
with increasing lignin content can be observed from the Fig. 4.
The theoretical modulus calculated from the rule of mixture was
higher than the experimental modulus of composites. With a tting
parameter k = 0.67, the theoretical modulus exactly matches the
experimental modulus of 50% lignin lled composites. However,
modulus values obtained from 30% and 65% lignin lled composites
showed slightly lower and higher values than the respective calcu-
lated modulus. Considering the random orientation of wheat straw
bres, a bre efciency factor of k = 0.9 was reported by authors
[27]. However, in our research, lignin pellets (having 45% nely
Table 2
Tensile, exural, HDT and impact properties of composites.
Specimen label Tensile
strength (MPa)
Tensile
modulus (GPa)
Elongation at
break (%)
Flexural
strength (MPa)
Flexural
modulus (GPa)
Impact
strength (J/M)
HDT (C)
PBS 35 1.5 0.6 0.01 122 21 28 0.4 0.6 0.01 40 8.4 78 1.9
30% LigninPBS 26 1.8 1.1 0.03 4.6 0.3 40 0.5 1.1 0.01 29 1.0 83 3.0
50% LigninPBS 29 3.4 2.3 0.35 2.0 0.8 46 0.3 2.2 0.03 15 0.9 86 3.1
65% LigninPBS 39 1.1 3.3 0.04 1.5 0.1 52 1.1 3.8 0.15 11 0.9 85 0.6
50% LigninPBS-1% PMDI 37 6.1 2.0 0.03 3.1 1.3 68 1.8 2.3 0.07 29 2.3 90 1.9
50% LigninPBS-2% PMDI 42 4.7 1.9 0.19 4.3 0.7 66 0.7 2.1 0.03 24 3.7 94 1.6
-O-(CH
2
)
4
-O-C-(CH
2
)
2
-C-
OH
O
Lignin
O
n
a
O
O-C
OH
Lignin
OCN
CH
2
-
n
+
N-C=O
CH
2
-
n
H
O-Lignin
(b)
(a)
Lignin
Polyester
Polyurethane
linkage
PMDI
Fig. 2. Schematics of reaction between lignin, PBS and PMDI. (a) Interaction
between lignin and PBS through hydrogen bonding, (b) polyurethane linkage
formation.
i (at full strain)
i (within 6 % strain)
Fig. 3. Stressstrain curve of the composites. (i) Neat PBS specimen, (ii) 30% lignin
PBS composite, (iii) 50% ligninPBS composite, (iv) 65% ligninPBS composite, (v)
50% ligninPBS composite with 1% PMDI, (vi) 50% ligninPBS composite with 2%
PMDI.
S. Sahoo et al. / Composites: Part A 42 (2011) 17101718 1713
ground biobre, lignin particles and other additives [22,23]) were
used as ller instead of biobre alone, hence, a k value of 0.67 is
quite reasonable. The lower modulus values for 30% lignin lled
composites and the higher modulus values for 65% lignin lled
composites as compared to the theoretical modulus values may
be attributed to the ligninpolymer interaction which is not taken
into account in the equation.
3.2.2. Flexural properties
It can be observed from Table 2 that the exural strength and
exural modulus of composites increased gradually with increas-
ing lignin content. Flexural strength and modulus increased by
41 to 84% and 81 to 503% respectively with increasing lignin con-
tent from 30 to 65 wt.%. It is believed that, the polar biollers are
more compatible with the polar polymers that improves the misci-
bility of the two phases and promotes a good interfacial morphol-
ogy. However, the difference in the trend of the tensile and exural
properties was not clearly understood. The possible cause may be
the behaviour of the material towards the stretching and bending
forces. The addition of 1% PMDI improved exural strength by
48% compared to the uncompatibilised material and by 143% com-
pared to the neat polymer (Table 2). Greater stress transfer from
the matrix to the ller through a compatibilizer modied interface
is believed to be the cause of this signicant improvement. The
exural modulus of composites with 1% compatibilizer remained
almost the same as that of uncompatibilised materials (Table 2).
Increasing PMDI content to 2% slightly decreased the exural
strength and modulus of the composites. This result may be attrib-
uted to the resultant effect of various competing reactions such as
plasticisation, urethane linkage formation, and secondary hydro-
gen bonding.
3.2.3. Impact strength
Impact strength measures the ability of the material to resist
fracture under high rate stress applied at a high speed. Fibres play
a key role towards the impact resistance or toughness of a material.
In this research, impact strength of composites decreased drasti-
cally with ller incorporation (Table 2). A similar trend was
observed in the unnotched Izod impact strength of ligninPP com-
posites [24]. It is reported that the incorporation of lignin, a brittle
material, decreases the impact strength of composites. Incorpora-
tion of agrobres also decreases impact strength of composites
[27,28]. Incorporation of 1% PMDI compatibilizer to lignin compos-
ites improved the impact strength by 92% as compared to the
uncompatibilized counterpart. This improvement may be attrib-
uted to the possible plasticisation as discussed earlier. On increas-
ing the PMDI content from 1% to 2%, the impact strength of
composites decreased by a small extent. Decrease of impact
strength with increasing PMDI concentration was also reported
by the authors [20]. They observed a detrimental effect at 1% PMDI
while using bamboo pulp in composites however, the same was
observed at 2% for lignin lled composites in our study.
3.3. FTIR analysis
FTIR spectra of neat PBS, lignin, and 50% ligninPBS composites
with and without PMDI are shown in Fig. 1. Characteristic carbonyl
(C@O) stretching at 17351750 cm
1
, CAO stretching at 1145
1155 cm
1
, and CAH stretching at 28502950 cm
1
are present
in the spectra of PBS and all its composites. Broad peaks for hydro-
gen bonded AOH groups at 34003100 cm
1
appear in the spectra
of lignin and all the composites. Characteristic peaks of lignin have
been discussed in the characterisation of lignin. It can be observed
that all the characteristic peaks of PBS and lignin appear in the
composites. The peak at 1370 cm
1
in lignin spectra (due to pheno-
lic OH group) shifted to 1388 cm
1
in the spectra of composites
which is possibly caused due to the interaction between OH groups
of lignin and C@O groups of PBS matrix. No characteristic peak for
NCO (isocyanate) group at 2270 cm
1
appears in the spectra of
compatibilized composites which indicates a complete reaction
of isocyanate in the composite system. As shown in Fig. 2, NAH
and C@O bond formation are expected during the reaction. As
C@O is already present in the matrix and NAH stretching appears
at 33503180 cm
1
(overlapping with hydrogen bonded OH
stretching), disappearance of peak at 2270 cm
1
and increased
intensity of the peak at 33503180 cm
1
can be considered as a
conrmation of urethane formation in the composites.
3.4. Dynamic mechanical analysis (DMA and HDT analysis)
Dynamic mechanical analysis (DMA) is widely used for the
investigation of the viscoelastic behaviour and structure of com-
posite materials. Damping measurement (Tand) gives information
about the glass transition temperature (T
g
) and the storage modu-
lus gives information about the stiffness. The storage modulus ac-
counts for the elastic component of the complex modulus of
material. Storage modulus, loss modulus and tan delta of compos-
ites as a function of temperature are shown in Fig. 5. Storage mod-
ulus of the polymer and composites decreased with increasing
temperature (Fig. 5a). The reduction of storage modulus with tem-
perature can be attributed to the softening of the polymer due to
the increase in the chain mobility of the polymer matrix at high
temperatures. As compared to neat PBS, storage modulus of the
Fig. 4. Correlation analysis of experimental tensile modulus and rule of mixture
(ROM).
Table 3
Thermal properties of composites from DSC.
Types of specimen T
g
(C) T
m
(C) DH
m
(J/g) T
c
(C) DH
c
(J/g) v (%)
PBS 31.1 113.2 64.8 78.4 62.2 30.9
30% LigninPBS 26.4 112.0 57.3 71.6 43.7 39.0
50% LigninPBS 20.5 112.0 49.1 64.3 31.6 46.8
65% LigninPBS 12.1 110.4 31.6 63.9 21.6 42.9
50% LigninPBS-1% PMDI 15.8 111.6 25.7 77.2 25.5 24.7
50% LigninPBS-2% PMDI 21.1 110.9 26.3 76.9 27.03 25.6
1714 S. Sahoo et al. / Composites: Part A 42 (2011) 17101718
composites at room temperature (25 C) increased by 96495% at
3065 wt.% lignin loading. Similar results were observed in agro
our lled biodegradable composites [31]. The storage modulus
of composites remained almost constant at 1% PMDI addition.
However, the storage modulus decreased on increasing the PMDI
content to 2%. This observation may be attributed to various com-
petitive reactions caused by the addition of PMDI.
The loss modulus accounts for the contribution of the viscous
component in the complex modulus of the material. At room tem-
perature, the loss modulus of composites increased with increasing
ller content (Fig. 5b). However, very little difference in the loss
modulus was observed near the glass transition temperature. The
glass transition temperature (T
g
) obtained from the loss modulus
peak (Fig. 5b) increased with increasing lignin content. Two peaks
are observed in the thermogram of 65% lignin lled composites
where the rst peak corresponds to the T
g
of the polymeric phase
and the second possibly represents the ller (because of very high
content of ller). Addition of compatibilizer to 50% lignin lled PBS
composites decreased the glass transition temperature slightly.
The damping behaviour of the material is measured by the
magnitude of tan d since it is the ratio of loss modulus to stor-
age modulus or energy dissipated to energy stored during a
dynamic loading cycle [16]. Tand decreased with ller incorpora-
tion (Fig. 5c). The result indicates that addition of ller de-
creased the molecular mobility of the composite materials and
the mechanical loss occurred to overcome the inter-friction be-
tween molecular chains was also reduced. Similar observation
was reported for biobre reinforced PBS [16] and PLA [27] com-
posites. Good interaction between PBS matrix and lignin can be
understood from the increased tan d peak temperature (often re-
ferred as glass transition temperature, T
g
) and broadening of
Tand thermograms due to lignin incorporation. Two effects are
taken into account as the cause of increase in the T
g
of the com-
posites. The rst one may be the creation of an amorphous com-
ponent in the composite structure where both the polymer and
the ller coexisted in a closely associated state reducing free vol-
ume in the composites and hence increased T
g
. Another cause of
increase in T
g
may be the possibility of secondary bonds that
acted as quasi-crosslinks and restricted the Brownian motion of
long chain molecules [29]. The T
g
of composites rst increased
at 1% and then decreased by about 6C at 2% PMDI addition. This
may be attributed to be effects such as improved interaction and
plasticisation due to PMDI addition. Improved interaction be-
tween polymer and ller improves the T
g
and plasticisation low-
ers the T
g
of a material.
Heat deection temperature (HDT) is a measure of the dimen-
sional stability of the material under a particular load and temper-
ature. It is considered as an essential property requirement for a
wide range of material applications. HDT values of neat PBS and
all composites are shown in Table 2. HDT of composites increased
with increasing lignin content up to 50 wt.% and remained almost
unaltered with further increasing the lignin content to 65%.
Improvement in the HDT values was also observed in composites
for biobre reinforcement [32,33]. It may be attributed to the high-
er crystallinity of the bio-composites [32] compared to the neat
polymers. Incorporation of compatibilizer further enhanced the
HDT of composites which is believed to have occurred due to im-
proved interfacial adhesion [32].
3.5. Thermal analysis
3.5.1. Differential scanning calorimetry
The effect of lignin on the crystallisation and melting behaviour
of composites was studied in non-isothermal DSC experiments (3).
The degree of crystallinity was calculated using Eq. (2), given be-
low [27,34]
v%
DH
m
f DH
0
m
100 2
where v = degree of crystallinity (%), DH
m
= enthalpy of fusion of
material studied, DH
0
m
= enthalpy of fusion of 100% crystalline PBS
i.e. 210 J/g [35], f = weight fraction of polymer in composite.
Glass transition temperature (T
g
) increased by 519 C with
increasing lignin content in the composites (Table 3) which indi-
cates good interaction between the polymer matrix and lignin. Lig-
nin acts as a nucleating agent for PHB composites and facilitates
crystallisation [13]. In our current study, the degree of crystallinity
increased with ller incorporation up to 50% and slightly decreased
at 65% ller content (Table 3). It is believed that the amount of lig-
nin content (amorphous in nature) might have played some role in
Fig. 5. Dynamic mechanical analysis. (a) Storage modulus, (b) loss modulus, (c) tan
delta of composites. (i) neat PBS specimen, (ii) 30% ligninPBS composite, (iii) 50%
ligninPBS composite, (iv) 65% ligninPBS composite, (v) 50% ligninPBS composite
with 1% PMDI, (vi) 50% ligninPBS composite with 2% PMDI.
S. Sahoo et al. / Composites: Part A 42 (2011) 17101718 1715
the nucleation activity of the polymer. The decrease in crystallinity
at 65% lignin lled composites may have been due to very high l-
ler content compared to the polymer matrix. Lignin had no effect
on the melting behaviour of the polymer. The addition of PMDI
compatibilizer decreased the crystallinity of composites however;
the effect is not consistent for varying PMDI content. Similarly,
the glass transition temperature showed varying trends with the
increased PMDI content. Although, the effect of PMDI on the ther-
mal properties of natural ller based composites is not very clear
[21], polymer-ller interaction and plasticisation due to the PMDI
addition could be considered as the possible causes for the ob-
served results in this study.
3.5.2. Thermogravimetric analysis
Thermal degradation onset, weight loss (%), major decomposi-
tion temperature and charred residue left after 600 C for lignin,
neat polymer and all composites are shown in Table 1. Degradation
onsets of lignin and PBS polymer are 179 and 306.4 C respectively.
Degradation onset and maximum decomposition temperature of
composites decreased on increasing lignin content in the compos-
ites. Composites with 50 and 65 wt.% lignin content showed very
close degradation onset temperatures. The addition of PMDI in lig-
ninPBS composites increased the degradation onset of composites
by 7 C. Weight loss around 100 C can be attributed to the loss of
moisture from the materials and degradation at the onset temper-
Fig. 6. SEM micrograph of composites. (a and c) 50% LigninPBS composite (lower magnication and higher magnication respectively), (b and d) 65% LigninPBS composite
(lower magnication and higher magnication respectively), (e) 50% ligninPBS with 1% PMDI (lower magnication).
1716 S. Sahoo et al. / Composites: Part A 42 (2011) 17101718
ature may correspond to the scission of weak ether bonds [36]
present in lignin inter units (b-O-4 linkage). Maximum decomposi-
tion temperature of lignin was much lower than the neat polymer.
Unlike the polymer, additional peaks appeared in the derivative
curves of lignin. Second major decomposition peaks between
340345 C appeared in composites having higher lignin content
(50 and 65 wt.%). As discussed before, lignin decomposition occurs
by several competing reactions that release many gaseous compo-
nents. A lowest percentage of weight loss was observed for lignin
at 400 C compared to neat polymer and composites. The charred
residue left after 600 C was highest (31.6%) for lignin due to the
presence of high ratio of highly condensed aromatic structures.
Charred residue increased with the increase in lignin content in
the composites. The addition of PMDI compatibilizer slightly in-
creased the percentage of charred residues in the composites,
which may be attributed to the presence of aromatic components
of PMDI. Char yield is directly related to the ame retardant poten-
tial of the material [17]. Hence, the ame retardant ability of lignin
is reected from this result which is again synergized by PMDI
addition.
3.6. Density of composites
Density of lignin, 1.34 g/cm
3
, was obtained from the composites
by using the rule of mixtures. The density of the neat polymer and
the composites were measured by a densimeter. The composites
and neat polymer showed densities of nearly 1.3 g/cm
3
and
1.26 g/cm
3
respectively.
3.7. Surface morphology
The SEM photographs of the composites are shown in Fig. 6.
Phase separation between polymer and ller can be clearly ob-
served from a polymer rich part in 50 wt.% lignin lled PBS com-
posites (Fig. 6a).This might have been caused due to lower
amounts of crosslinking components in the ller present in the
composites. However, more homogeneous distribution of polymer
and lignin ller can be observed in the micrograph of the 65% lig-
nin lled composite (Fig. 6b). Tensile strength data for these com-
posites (50 and 65% lignin lled) also supports this observation.
Micrographs at higher magnication (Fig. 6c and d) clearly depict
the exact fracture surface morphology of these two composites.
More pulled out bres and holes in 50% lignin lled composites
indicate poor interfacial adhesion. The possible cause for the more
bres pull-out in 50% lignin lled composites may be the phase
separation owing to lower lignin content compared to 65% lignin
lled composites. More interaction in 65% lignin lled composites
possibly occurred due to higher lignin content. Pulled out bre
with adhered resin matrix and a more compatibilized phase indi-
cate a stronger interface in the composites having 1% PMDI
(Fig. 6e). The improved interface is well reected in the mechanical
properties of the compatibilized composites.
4. Conclusions
Lignin acted as reinforcing ller in PBS matrix that synergisti-
cally improved tensile, exural, some thermal and thermo-
mechanical properties of composites. Incorporation of a high
weight fraction (65%) of lignin was achieved. Impact strength and
thermal degradation onset of the composites gradually decreased
with increasing lignin content. The addition of PMDI compatibiliz-
er to 50 wt.% lignin lled composites improved all mechanical
strength of the composites at 1 wt% incorporation. Increasing PMDI
content to 2 wt% further improved tensile strength of composites
while the exural and impact strength reduced very negligibly.
The effect of PMDI was not very consistent for tensile and exural
moduli of composites however, both the moduli showed a slight
reduction with increasing PMDI content from 1 to 2%. A higher
amount of char content obtained from lignin indicates that it can
act as a ame retardant in the composites. Degree of crystallinity
of composites increased by the incorporation of lignin up to
50 wt.% and slightly decreased with increasing lignin content to
65%. Incorporation of PMDI to the composite blends resulted in
an improvement of HDT but decreased the degree of crystallinity
drastically compared to the composite with no PMDI. A strong -
brematrix interface was observed from the fractured surface mor-
phology of PMDI compatibilized composites.
Acknowledgements
Authors are thankful to 2009 Ontario Ministry of Agriculture,
Food and Rural Affairs (OMAFRA)/U of G project Renewable, recy-
clable lightweight hybrid green composites from lignin, switch-
grass, miscanthus and bioplastics and Ontario BioCar
Initiative, Ontario Ministry of Research and Innovation for the
nancial support to this research work.
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