Composites: Part A 39 (2008) 13621369

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Composites: Part A
journal homepage: www.elsevier.com/locate/compositesa

Cellulose and cellulignin from sugarcane bagasse reinforced polypropylene

composites: Effect of acetylation on mechanical and thermal properties
S.M. Luz a, J. Del Tio a, G.J.M. Rocha a, A.R. Gonalves a,*, A.P. DelArco Jr. b
a
b

Escola de Engenharia de Lorena/USP, CP 116, 12602-810 Lorena/SP, Brazil

Diviso de Materiais IAE/CTA, Pa Mar-do-Ar Eduardo Gomes, 50, 12228-904 So Jos dos Campos/SP, Brazil

a r t i c l e

i n f o

Article history:
Received 24 February 2007
Received in revised form 29 March 2008
Accepted 28 April 2008

Keywords:
A: Polymer-matrix composites (PMCs)
B: Mechanical properties
B: Thermal properties
Acetylation

a b s t r a c t
This current work is concerned with the development of polypropylene composites reinforced with cellulose and cellulignin bers attained from sugarcane bagasse. Moreover, the bers were chemically modied by acetylating process and its effects on the ber/matrix interaction were also evaluated. The
chemical modication efciency was veried by FTIR analysis and the bers morphological aspects of
bers by SEM. Likewise, the inuence of modied bers content in the composites was studied by
mechanical (tensile, shear and exural tests) and thermal analyses (TGA and DSC). After the chemical
modication, the FTIR results showed the appearance of acetyl groups and reduction of OH bonds for
all bers. Together with, SEM characterization showed that the acetylation changed the morphology of
bers, resulting in mechanical properties decreases, probably because of the new morphological aspect.
The thermal characterization of composites based on untreated and treated cellulose and cellulignin presented intermediary stability in respect to matrix and ber. Finally, DSC results revealed that the composites reinforced with untreated bers were more crystalline than neat PP.
2008 Elsevier Ltd. All rights reserved.

1. Introduction
Recently, the composites reinforced with ller have received
crescent interest from industries for application in components
with individual mechanical properties. Reinforcement of polymer
matrix using inorganic llers is widely used, resulting in materials
with excellent mechanical and thermal properties [1].
However, in recent years, organic llers, such as cellulose-based
bers have slowly taken root in the market to replace synthetic
materials [2]. Cellulose-based bers (natural bers) come from
renewable and relatively inexpensive resources, and because of
that, the addition of natural bers, such as wood bers, ax or sisal
to polymeric matrices can result in feasible composites concerning
mechanical and economic points of view [3]. Composites based on
natural bers are environmentally superior to those based on
synthetic bers, such as berglass. Recent studies reported that
the incineration of components with natural bers uses 45% less
energy, and results in lower air emissions [4]. Another main point
is the recyclability and biodegradability potential of natural bers
composites and the wide sources of natural bers, which are
renewable [5].
The production of biomass in Brazil is higher than 20  109
ton/year and gure has been shown that only 1% is necessary to
* Corresponding author. Tel.: +55 12 31595033; fax: +55 12 3153 3165.
E-mail address: adilson@debiq.eel.usp.br (A.R. Gonalves).
1359-835X/$ - see front matter 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.compositesa.2008.04.014

replace the petroleum consumed in the country, without impacts

on the food and feed production or even damaging effects on
native forests [6]. Integral utilization of this biomass (and not
simply using part of it) is the most rational way to promote an
alternative usage of this high-value raw material. In the case of
Brazil, regional particularities should be also taken into account.
In respect to sugarcane, the main residue and by-product is the
bagasse that can be used as reinforcement for natural ber composites [7].
Sugarcane bagasse is constituted by three main components:
cellulose, lignin and hemicelluloses [8]. In this work, both cellulose
and cellulignin (ber without hemicelluloses) were attained
through sugarcane bagasse. First, cellulignin was obtained by soft
hydrolysis from sugarcane bagasse, resulting in bers with high
content of cellulose and lignin [9]. Even though the hemicelluloses
were removed during the hydrolysis, the ber shape was preserved. After that, the cellulignin was treated in alkaline medium
for lignin removal, obtaining the cellulose ber. Cellulose is a
raw material applied in cellulose derivatives manufactured products such as ethers and esters [10]. Cellulignin is a new and promising material and, like cellulose, can be used as reinforcement of
polymers due its brous structure.
Enhanced moisture absorption and poor adhesion between
hydrophilic bers and hydrophobic polymer matrix may be a
disadvantage for their successful application. Chemical or physical
modication of reinforcement or matrix should be lately

S.M. Luz et al. / Composites: Part A 39 (2008) 13621369

investigated for improvement of mechanical and thermal properties. In this work, the acetylation of bers was the chemical process
used. Recent works in the literature have applied this modication
successfully for sisal/polystyrene composites [11]. Performance
and properties of composite materials depend on the properties
of the individual components and their interfacial compatibility
[12]. Current literature has described the application of mechanical
tests in composites based on natural bers, evaluating the content
and chemical modication effects [1317].
Thermal analysis of polymers is an important study, covering a
broad eld of applications and is a method used for understanding the structureproperty relation and mastering the technology
for industrial production of different polymeric materials, especially ber-reinforced composites [18]. One of the accepted methods for studying the thermal properties of polymeric materials is
Thermogravimetry (TG). Both TG and Derivative Thermogravimetry (DTG) provide information about the nature and degradation
of the material. Some works apply this technique for characterization after chemical modication of lignocellulosic materials
[19,20]. In Differential Scanning Calorimetry (DSC), the heat ow
rate associated with a thermal event can be measured as a function of time and temperature allowing obtaining quantitative
information about melting and phase transitions of the composite
system [21]. For composites based on semicrystalline matrix
polymers, crystallinity is an important factor that determines
the stiffness and fracture behavior of the crystallized matrix
polymer [22]. Current studies have revealed that the presence
of natural bers and chemically modied bers acts on bers
as nucleating agents of semicrystalline thermoplastics, causing
change in crystallization and melting heat of the nal composite
[23,24].

2. Experimental
2.1. Materials
Cellulignin: in natura sugarcane bagasse was pretreated with
10% aqueous solution in a 350-mL stainless steel reactor at
120 C for 10 min; with solid/liquid ratio of 1:20 (w/v). Therefore,
cellulignin, cellulose and lignin free of hemicelluloses were attained [25].
Cellulose: the cellulignin was submitted in alkaline medium in
a 350 L stainless steel reactor with 150 L of distilled water, 10 kg
pretreated sugarcane bagasse and 30 L of aqueous solution containing 3 kg NaOH. The reaction was performed at 98100 C for
1 h under stirring at 100 rpm. Final concentration of the mixture
was 1.5 wt% NaOH and solid/liquid ratio of 1:20 (w/v). After delignication, the mixture was carried to centrifugation at 1700 rpm.
Cellulose, the nal product, was washed and dried under room
temperature [25].
Acetylated cellulose and cellulignin: initially, 90 g of sample
(cellulose or cellulignin) was placed in a round bottom ask with
456 g of glacial acetic acid. The reaction was performed in thermostatic bath at 35 C for 45 min under mechanical stirring. After that,
more 150 g of glacial acetic acid was added with 0.6 mL concentrated H2SO4 and the bath was maintained for more 1 h. After this
step, the mixture was cooled at 18 C for slow addition of anhydride acetic (264 g) with 3.6 mL concentrated H2SO4 during 3 h under constant stirring. Temperature of 18 C was maintained for
more 15 min and later than, was slowly increased to 5055 C to
nalize the esterication process.
PP (polypropylene) used as matrix was kindly provided by Braskem. H 503 isotatic polypropylene presented 0.9 g cm1specic
weight; 1.16 GPa exural modulus; 33 MPa tensile strength; 11%
elongation at break [26].

1363

2.2. Preparation of composites

Polypropylene composites reinforced with 10 and 20 wt% of untreated and treated cellulose and cellulignin bers from sugarcane
bagasse were prepared in a thermokinetic mixer at 5250 rpm. After
mixing, the composites were cooled with water and after that,
ground to 13 mm. The composites were dried in an oven at 80 C
for 3 h and thereafter injected directly in a mold with specic
dimensions for tensile, shear and exural specimens. Part of the
composites samples was also evaluated by thermal analysis.
2.3. Mechanical tests
For all standard tests, composites were analyzed in an Instron
universal-testing machine (model 4301), equipped with pneumatic
claws. In the tensile tests, ve specimens of composites were analyzed, with dimensions in agreement with the ASTM D 638 [27]
standard: 19 mm width, 165 mm length and 3.2 mm thickness
and 2 mm min1 crosshead speed. In the exural tests, a load
was applied on the specimen at 2.8 mm min1 crosshead motion
rate. Five specimens were analyzed with dimensions in agreement
with the ASTM D 790 [28] standard: 25 mm width, 76 mm length
and 3.2 mm thickness. The adopted exural test was the 4-point at
1/4 points method. In the shear tests [29], a load was applied at
1.3 mm min1 crosshead speed. The dimensions of the ve specimens was about of 6.5 mm width, 19.2 mm length and 3.2 mm
thickness.
2.4. Thermogravimetric analysis (TGA) and differential scanning
calorimetry (DSC)
TGA was carried out using a Perkin Elmer (TGA 7) instrument, in
N2 atmosphere at 10 C min1 heating rate, from 30 to 650 C. In
DSC analysis (Perkin Elmer instrument Pyris 1) the composites
samples were cut and placed in an aluminum plate in N2 atmosphere. The thermal programme for DSC measurements was performed as following: stage I = sample heating in the calorimeter
at 10 C min1 heating rate from 30 to 200 C; stage II = 200 C
for 3 min (applied to remove crystalline nuclei); stage III = cooling
the sample to 30 C in the calorimeter at 10 C min1 cooling rate.
DSC calibration procedure was made once a week or more often
when the baseline drift needed to be adjusted.

3. Results and discussion

3.1. Chemical characterization
In the beginning, the acetylated bers were characterized by
FTIR analysis. This analysis was able to reveal the main differences
between the untreated and treated bers, and then the changes and
appearance of new bands could provide information about the efciency of chemical modication. Spectra in Fig. 1 show the differences between bands before and after bers acetylation, where
the main differences are related to nger print region from 1900
to 600 cm1. The main change of treated bers in comparison to untreated bers spectra is related to the appearing of band at
1758 cm1, this band is proceeding from wide C@O carbonyl peak
from bonded acetyl group. Moreover, bands at 1050 cm1, proceeding from CO alcoholic stretch and at 1390 cm1 from CH from cellulose and hemicelluloses are observed in both spectra. After ber
acetylation, there was a decrease in OH band and its displacement
was from 3400 to 3700 cm1. In chemical modication, the hydrogen of hydroxyl group was substituted by acetyl groups, resulting in
lower hydroxyl groups able to carry through hydrogen bonds. The
band displacement occurred due to high energy of OH bonds.

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S.M. Luz et al. / Composites: Part A 39 (2008) 13621369

pits could be observed. The presence of the orices can permit a

better interaction of these bers with the matrix, because of the
surface of contact after mixing. After acetylation, the material
was similar to acetylated cellulose, with less dimensions varying
from 20 to 90 lm.
The SEM micrographs conrmed the chemical modication and
its inuence in the morphological aspects of bers. Because of
chemical modication, the mechanical and thermal properties
could be strongly inuenced.

1240
1.5

1051
1758

1.1

Absorbance

1388

acetylated cellulose
0.7

3.3. Mechanical behavior

3370

cellulose

608

0.3

3646

-0.1
3900

3400

2900

2400

1900

1400

900

400

Wavenumber (cm-1)
1240

1.9

1760
1050
1.5

Absorbance

1380
1.1

acetylated cellulignin

0.7

3400
0.3

cellulignin
606

3650

-0.1
3900

3400

2900

2400

1900

1400

900

400

Wavenumber (cm-1)
Fig. 1. FTIR spectra of untreated and treated cellulose and cellulignin bers (400
4000 cm1).

3.2. Morphological characterization of bers

Not only had the FTIR spectra showed the main changes in the
modied bers but also the SEM analysis of morphology. The SEM
evaluations were applied for cellulose and cellulignin bers characterizations before and after chemical modication by acetylation. Thereby, the shape of bers, dimension and morphological
aspects were determined. Then, the main reasons for application
of this technique were to verify if the mechanical and thermal
properties could depend on these characteristics. Fig. 2 exhibits
the SEM micrograph of untreated and treated cellulose at 300
and 1000 times magnication.
SEM micrographs of cellulose showed cylindrical shape bers
with 10 lm diameter, presence of bundle of bers and attened
shape bers. The main aspect of these micrographs was to observe
the huge supercial area of cellulosic bers that can promote a better contact with matrix after mixing. After acetylation, the bers
became agglomerated with globular and amorphous shapes and
the particle dimensions varied from 17 to 200 lm. These aspects
showed that the chemical modication was not so soft and promoted the hard changes in the morphological aspects of bers that
could inuence in the composites properties, mainly in the
mechanical properties.
The same behavior could be observed for the cellulignin bers.
Fig. 3 shows that the cellulignin presented brillar morphology,
keeping bundle of cells shape, where the presence of lumen and

The mechanical measurements of composites were made by

three different tests: tensile, shear and exural. The fundamental
differences between the tests are the type of force that the specimen was submitted. The tensile test could show the response by
composite material to forces submitted for stress in the longitudinal part of the specimen. On the other hand, in the exural tests,
the load was applied in the transversal session of the specimen,
causing deformations of compression inside the specimen and tension outside of it. In addition, the shear measurements could cause
internal deformations in the specimen because of the debonding
between bers and matrix.
Polypropylene composites reinforced with cellulose and cellulignin were obtained and the inuence of chemical modication
by acetylation was studied in respect to mechanical properties. Table 1 shows the tensile, exural and shear strength. Composites
presented tensile strength between 20.1 and 26.2 MPa, values lower than neat polypropylene (27 MPa). The highest tensile strength
values were obtained for cellulose/PP composites (10 and 20 wt%)
and the lowest ones were obtained for acetylated cellulignin/PP
(10 and 20 wt%). The performance for composites with 10 wt%
was superior than 20 wt%, showing that the ber content decreased the tensile strength. Most of the results showed that the
chemical modication did not contribute for the mechanical properties improvements and because of that, the composites reinforced with treated bers presented the worse results.
Afterwards, the SEM evaluations could conrm these results,
showing that the bers dimension decreased after the chemical
process.
Elongation at break of composites was inferior for neat PP (11%).
This aspect reveals that the composites are rigid materials when
compared to matrix; and with a lower ber content, a higher elongation at break was attained. Acetylated cellulignin (10 wt%)/PP
composite presented the highest elongation at break (10%) and cellulose 20 wt%/PP presented the lowest value (6%). Natural bers
present higher elastic modulus than neat polypropylene. Because
of that, when the bers were inserted in the matrix, the rigidity
was strongly increased. Moreover, the addition of bers caused
failure between ber and matrix and this failure depending on
the stress transference, could cause a beforehand rupture, and
thereby the elongation at break was decreased. As a conclusion,
high bers content can cause higher failure and consequently the
elongation is anticipated.
Flexural strength was inuenced by bers content and type. Besides the tensile properties, the bers chemically modied by acetylation inside the matrix also contributed negatively for exural
strength. However, the ber content contributed for the improvement of this property. Cellulose/PP composites presented the highest exural strength, reaching 39.8% compared to neat PP.
Shear strength test is related to the slipping between ber and
matrix and is normally called as short beam measurements. In
this current test, a short specimen was submitted to an apparatus
similar to the one used in the procedure of the three point exural
test. The load was placed in the center of the specimen on a two
cylinder support. Due to the short specimen, the load was better

S.M. Luz et al. / Composites: Part A 39 (2008) 13621369

1365

Fig. 2. SEM micrograph of cellulose (a: 300 and b: 1000) and acetylated cellulose (c: 300 and d: 1000).

Fig. 3. SEM micrograph of cellulignin (a: 300 and b: 1000) and acetylated cellulignin (c: 300 and d: 1000).

transferred to the composite, improving the response between ber and matrix. This method has been widely applied for interfacial
interlaminar strength (IIS).
Fig. 4 gives the kinds of failure modes that can occur in composites. Shear strength values were higher than neat PP (7.3 MPa) and
the ber content contributed for the increase of this property. Cellulose/PP composites (10 and 20 wt%) presented increases of 34.2%
and 43.8%, respectively, compared to reinforced bers. The results
showed that the chemical modication negatively affected the
shear strength. The failure modes mechanisms observed in the

composites occurred according to Fig. 4, showing the shear with

inelastic typical deformation for polymeric composites.
Another way to measure the mechanical properties of the
composites materials is to analyze the tensile and exural moduli,
because the elastic modulus is directly related to the rigidity of
the material. Fig. 5 shows the results of tensile and exural moduli for polypropylene and composites reinforced with untreated
and treated bers as a function of ber content. As a result, the
neat PP presented lower values of modulus when compared to
composites. Generally, when the high modulus bers were

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S.M. Luz et al. / Composites: Part A 39 (2008) 13621369

Table 1
Mechanical results from tensile, exural and shear tests for neat PP and composites reinforced with untreated and treated cellulose and cellulignin
Sample

Tensile strength (MPa)

Elongation at break (%)

Flexure strength (MPa)

Shear strength (MPa)

Polypropylene
Cellulose 10 wt%/PP (C10)
Cellulose 20 wt%/PP (C20)
Acetylated cellulose 10 wt%/PP (AC10)
Acetylated cellulose 20 wt%/PP (AC20)
Cellulignin 10 wt%/PP (CL10)
Cellulignin 20 wt%/PP (CL20)
Acetylated cellulignin 10 wt%/PP (ACL10)
Acetylated cellulignin 20 wt%/PP (ACL20)

27 1
26.2 0.7
25.8 0.3
24.5 0.8
20.1 0.4
24.2 0.5
23.7 0.3
23.2 0.2
20.3 0.4

11.0 0.2
8.9 0.4
6.0 0.3
8.9 0,7
7.3 0.4
9.4 0.4
7.3 0.4
10.0 0.2
8.4 0.3

25.4 0.1
34.9 0.2
35.5 0.4
28.0 0.2
27.7 0.2
31.7 0.2
34.0 0.4
27.9 0.1
29.0 0.7

7.3 0.3
9.8 0.1
10.5 0.2
8.1 0.2
8.3 0.1
9.7 0.3
9.2 0.2
9.2 0.2
11.9 0.1

Fig. 4. Failure modes mechanisms in shear measurements.

ACL20
ACL10
CL20
CL10
AC20
AC10
C20
C10
PP
0

200

400

600

800

1000

1200

1400

1600

Tensile Modulus (MPa)

ACL20
ACL10
CL20

20 wt%) presented the best values (1182 and 1484 MPa, respectively) whereas, acetylated cellulignin/PP (10 and 20 wt%) presented lower values (937 and 964 MPa, respectively). The exural
modulus was also inuenced by bers content and type. All the
composites presented higher exural modulus in respect to neat
PP, reaching 90% increase for cellulose 20 wt%/PP composite. The
composites reinforced with 20 wt% presented higher modulus
showing that the addition of ber increased the exural modulus.
However, the chemical modication of bers resulted in composites with lower modulus in relation to those ones with untreated
bers.
Although the analyses indicated the existence of physical interaction between ber and matrix, it was not enough for the
improvement of some mechanical property when compared to
neat PP. It could be seen that tensile and exural moduli were increased and so the exural strength and shear, when compared to
neat PP. The added natural bers presented a weak interaction between ber and matrix, but enough to cause perceptive changes in
some properties like thermal and modulus. However, in this work,
it was clear that the chemical modication did not affect positively
the mechanical properties, only the thermal properties. The main
kind of interaction was the mechanical and physical adhesion; because of polarity, differences and presence of interstices can improve the contact between bers and matrix.
Indeed, the chemical modication negatively affected the tensile modulus. These results could be related to the shape and
dimensions of bers obtained after chemical modication. The
SEM results (Figs. 2 and 3) for bers before acetylation presented
brous aspect, while the acetylation resulted in globular and amorphous particles. Therefore, the particles shape could have inuenced ber/matrix adhesion.

CL10

3.4. Thermogravimetric analysis

AC20
AC10
C20
C10
PP
0

200

400

600

800 1000 1200 1400 1600 1800 2000 2200 2400

Flexure Modulus (MPa)

Fig. 5. Tensile and exural moduli of neat PP and composites reinforced with untreated and treated cellulose and cellulignin.

inserted in the matrix, the elastic modulus of composites was improved [11].
The tensile modulus (Fig. 5) changed between 937 and
1484 MPa and only cellulignin/PP and cellulose/PP composites
(20 wt%) presented 30.3% increase of tensile modulus compared
to neat PP (1139 MPa). The cellulose/PP composites (10 and

The composites reinforced with untreated bers or treated by

acetylation were evaluated by thermogravimetric analysis (TGA)
for verication of the thermal characteristics of the materials. Lignocellulosic bers were submitted to intense heat during composite fabrication. Therefore, a thermal analysis study was necessary
to determine the inuence of bers addition into polymer on thermal stability of composites and to conrm any degradation process
during composites production [30]. The thermal degradation and
stability were determinated by TG (thermogravimetric) curves.
This characterization allowed not only to evaluate the limit of temperature to which this material can be submitted, but also to study
the inuence of chemical modication and ber content in the
matrix.
Fig. 6 shows TG curves of PP, cellulignin and cellulignin/PP (10
and 20 wt%). Neat PP showed a one-step decomposition process,
while composites clearly showed a two-step process. In the rst
and second stages, the ber and matrix decompositions occurred,
respectively. The composites presented intermediary thermal

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S.M. Luz et al. / Composites: Part A 39 (2008) 13621369

110
100

PP

Fiber 10 wt%/PP

90
80

Weight (%)

70

Fiber 20 wt%/PP

60

fiber

50
40
30
20
10
0
-10
0

100

200

300

400

500

600

Temperature (C)
Fig. 6. TG curves of PP, cellulignin, cellulignin 10 wt%/PP and cellulignin 20 wt%/PP
composites.

stability between neat ber and matrix. The addition of bers decreased the thermal stability of the composite.
Table 2 shows the weight loss and degradation temperature
peak of composites, neat matrix and bers. At 400 C, polypropylene practically did not lose weight, however from 450 C on, the
weight loss was fast and accentuated, resulting in minimum residue. PP started decomposition at about 450 C (indicates the degradation of saturated and unsaturated carbon atoms in
polypropylene), which was higher than that for ber [23].
The TG curves for cellulignin exhibited two degradation stages.
The rst stage of weight loss occurred between 30 and 100 C (both
bers), and in many works of literature, this loss corresponds to
the water vaporization heat in the sample [18,30]. The lignocellulosic bers contain a signicant level of water, which is released
when bers/PP composites are produced, conrming the need to

pre-dry these bers prior to processing, or to employ devolatilization procedures to remove steam [30].
The second stage of weight loss for neat ber presented thermal
degradation peaks around 340 C. This weight loss was attributed
to the cleavage of chemical bonds of glucosidic linkages of cellulose
[11]. The thermal degradation peak furthered breakage of berdecomposition products, leading to the tar formation through levoglucosan [18].
At 350 C, the formation of aromatic compounds started, and
between 400 and 500 C, they were constituted 88% of ashes. Ash
produced by cellulose consists mainly of polycyclic aromatic compounds. All bers have a residual weight between 20.5 and 31.6%
at 600 C. Devallencourt et al. [31] observed residual weight about
17% for cellulose ashless lter paper after heating from 20 to
900 C. Under an inert atmosphere, the nal-products from degradation of cellulose are carbonaceous residues plus undegraded bers when they do not remain after heating. As during the plant
growing, inorganic compounds are needed as nutrients, and these
inorganic compounds will generate ash.
Despite the loss in the mechanical properties, the chemical
modication inuenced on the thermal stability of the ber. The
Table 2 shows that the composites reinforced with treated bers
presented higher thermal stability than the composites reinforced
with untreated bers (at 400 C).
3.5. Differential scanning calorimetry studies
The thermal properties such as Tc, melting temperature (Tm),
crystallization heat (DHc), melting heat (DHm) and percentage of
crystallinity (Xc) obtained from DSC studies are summarized in Table 3. The crystallinity of the PP component was determined by
using the relation below:

Xc

DHm  100
DHom  w

Table 2
Weight loss at different temperatures and degradation temperature peak of polypropylene and bers/PP composites
Sample

Polypropylene
Cellulose
Acetylated cellulose
Cellulignin
Acetylated cellulignin
Cellulose 10 wt%/PP
Cellulose 20 wt%/PP
Acetylated cellulose 10 wt%/PP
Acetylated cellulose 20 wt%/PP
Cellulignin 10 wt%/PP
Cellulignin 20 wt%/PP
Acetylated cellulignin 10 wt%/PP
Acetylated cellulignin 20 wt%/PP

Weight loss (%)

Degradation temperature peak (C)

100 C

200 C

300 C

400 C

500 C

0.0
7.3
3.7
2.1
1.8
0.3
1.5
0.4
0.5
0.3
0.8
0.3
0.4

0.0
7.6
4.0
3.4
2.8
0.3
2.0
0.4
0.5
0.8
1.2
0.3
0.9

0.4
13.4
8.2
19.5
14.0
2.1
4.0
0.9
1.6
3.2
5.7
1.5
0.4

6.5
78.7
80.5
74.3
75.3
8.7
20.5
11.7
19.4
11.0
17.7
10.2
11.7

99.7
81.5
83.4
79.4
81.0
99.6
100.0
98.8
100.0
97.9
95.7
97.7
95.5

309.9

344.9
338.5
343.8
344.2
330.2
333.8
349.2
358.4

450.5
352.6
345.7
334.7
330.2
456.2
458.2
456.2
453.7
453.9
457.8
456.0
455.9

Table 3
DSC results of PP and composites reinforced with cellulose and cellulignin, untreated or treated by acetylation
Sample

Tc (C)

DHc (J g1)

Tm (C)

DHm (J g1)

Xc (%)

Polypropylene
Cellulose 10 wt%/PP
Cellulose 20 wt%/PP
Acetylated cellulose 10 wt%/PP
Acetylated cellulose 20 wt%/PP
Cellulignin 10 wt%/PP
Cellulignin 20 wt%/PP
Acetylated cellulignin 10 wt%/PP
Acetylated cellulignin 20 wt%/PP

110.3
124.3
126.0
116.9
116.9
118.8
122.3
119.1
116.8

88.1
85.2
68.3
62.5
74.3
71.2
69.6
82.4
80.8

170.4
165.2
165.4
164.7
166.8
164.8
163.8
166.3
165.8

64.6
70.9
53.0
53.8
57.7
59.1
50.8
69.8
64.8

46.8
57.1
48.0
43.3
52.3
47.6
46.0
56.2
58.7

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S.M. Luz et al. / Composites: Part A 39 (2008) 13621369

35
33

Heat Flow (mW)

31
29

27

d
e

25
23
21

19

17

the addition of chemically treated bers (Fig. 8). Because of ber

surface modication by chemical treatments, the behavior of each
ber is different. The acetylation of cellulose favors the DHc increase; contrarily, this was not observed after acetylation of cellulignin. In most cases, the untreated bers are agents more effective
for nucleation sites. The higher crystallinity of composites showed
interaction between ber and matrix, resulting in the improvement of the mechanical properties, as observed by shear and exural data. However, the acetylation was not an effective process for
treatment of bers because the mechanical properties decreased
with the acetylation.

15
25

75

125

175

4. Conclusions

Temperature (C)
Fig. 7. DSC curves for melting of (a) PP and untreated cellulose containing, (b)
10 wt%, (c) 20 wt%, and acetylated cellulose containing, (d) 10 wt%, (e) 20 wt%.

35

Heat Flow (mW)

30

d
e

25
20

15

10
5
35

85

135

185

Temperature (C)
Fig. 8. DSC curves for cristallization of (a) PP and untreated cellulose containing, (b)
10 wt%, (c) 20 wt%, and acetylated cellulose containing, (d) 10 wt%, (e) 20 wt%.

The 138 J/g DHom value was determined taken for 100% of crystalline
isotactic PP, and w was given as the mass fraction of PP in the composite [23]. Fig. 7 and Table 3 show that the Tm decreased with ber
content and in some cases, DHm was also inuenced. For cellulignin/PP composites, those containing the acetylated bers consumed
higher energy for material fusion, resulting in the increase of crystallinity percentage. The addition of bers caused different crystallization in the matrix, because they are nucleating agents and
changed the crystallization of the matrix around the ber. Because
of that, the contact between ber and matrix promoted a weak
bond, decreasing the Tm.
Fig. 8 and results of Table 3 reveal that the melting prole of
composites reinforced with untreated and treated cellulose did
not change with ber content or chemical modication. Only a little displacement was observed in respect to neat PP. The temperature peak of melting decreased because of the inuence of added
bers, showing an interaction between ber and matrix.
Fig. 8 shows the crystallization heat of neat PP and composites
reinforced with untreated and treated cellulose. The ber content
and treatment inuenced the crystallization heat and also, the bers addition decreased the melting temperature and crystallization enthalpy.
Fig. 8 and Table 3 clearly demonstrate that the addition of ber
to PP resulted in an increase in Xc and Tc of the PP matrix. This can
be explained due to the nucleating ability of untreated and treated
cellulose and cellulignin ber for the crystallization of PP. As the
amount of added ber increases, Tc tends also to increase. Tc and
enthalpy of crystallization (DHc) of the PP phase increase with
the addition of bers, indicating that bers accelerate the crystallization process. The Tc of the PP phase is further decreased by

The chemical modication of cellulose and cellulignin by acetylation was conrmed by FTIR analysis. The appearing of acetyl
groups and decreasing of OH bonds were evidenced. SEM characterization showed that the acetylation changed the morphology
of bers, resulting in agglomerates with globular form. The addition of untreated and treated bers to the matrix resulted in composites with inferior tensile strength, when compared to neat PP.
Composites were more brittle than matrix and tensile modulus
indicated that only cellulose 20 wt%/PP and cellulignin 20 wt%/PP
composites were more rigid than neat PP and other composites.
However, the exural properties of composites were higher than
those ones of neat PP. Overall, the addition of bers increased
the exural strength and modulus, however, the chemical modication decreased these mechanical properties. Thermogravimetric
analysis showed that the composites based on untreated and treated cellulose and cellulignin presented intermediary stability in respect to matrix and ber. DSC results revealed that the composites
reinforced with untreated bers were more crystalline. The acetylation was not an effective process for treatment of bers because
the mechanical properties decreased with the acetylation. Consequently, these results could be proceeding from the change of bers morphology.
Acknowledgements
The authors would like to thank FAPESP, CNPq and CAPES for
nancial support.
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