fibre..........................................................

Study on the interface

modification of bagasse fibre and
the
mechanical properties of its
composite with PVC

Yu-Tao Zheng b,c, De-Rong Cao a,b,*,

Dong-Shan Wang b, Jiu-Ji Chen b
a College of Chemistry, South China University of Technology,
Guangzhou 510641, China
b LCLC, Guangzhou Institute of Chemistry, Chinese Academy of
Sciences, Guangzhou 510650, China
c Graduate School of the Chinese Academy of Sciences, Beijing
100039, China
Received 15 April 2005; received in revised form 21 December 2005;
accepted 28 January 2006

Tabla de contenidos.

1.Introduction..........................................................................................................................3
2. Experimental.......................................................................................................................3
2.1. Materials.......................................................................................................................3
2.2. Treatment of BF...........................................................................................................4
2.3. Preparation of the composites and samples.................................................................4
2.4. Mechanical properties of the composites.....................................................................4
3. Results and discussion.........................................................................................................4
3.1 Tensile strength..............................................................................................................5
3.2. Impact strength.............................................................................................................6
.............................................................................................................................................7
3.3. Elongation at break......................................................................................................8
3.4. Tensile modulus............................................................................................................9
3.5. Analysis of the SEM pho tographs of BF/PVC..........................................................10
4. Conclusions.......................................................................................................................12
Acknowledgement.................................................................................................................12
References.............................................................................................................................12

Tabla de figuras y tablas.

Ilustración 1.............................................................................................................................6
Ilustración 2.............................................................................................................................7
Ilustración 3.............................................................................................................................8
Tabla 1.....................................................................................................................................4
Tabla 2.....................................................................................................................................5
Tabla 3.....................................................................................................................................6
Tabla 4.....................................................................................................................................6

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2
doi:10.1016/j.compositesa.2006.01.023
* Corresponding author. Address: LCLC, Guangzhou Institute of
Chemistry, Chinese Academy of Sciences, Guangzhou 510650, China.
Tel.: +86 20 85231666; fax: +86 20 85232903.
E-mail address: caodr@mail.gic.ac.cn (D.-R. Cao).
 1. Introduction
In recent years, significant efforts have been directed to investigating the use of natural fibres as a
reinforcement
in thermoplastics. Natural fibres, such as wood fibre, wheat straw, jute fibre and bagasse fibre
have several benefits: low cost, low density, high toughness, acceptable specific strength
properties, enhanced energy recovery and biodegradability [1–3]. The use of natural fibres in
plastic matrix includes many benefits, such as low volumetric cost,
increase of heat deflection temperature, increase of stiffness of thermoplastics and improvement
of ‘‘wood’’ surface appearance. So natural fibres reinforced plastic composites have achieved
applications in decking, furniture components, door moldings, packing pallets and interior panels
of automobiles [4–6]. However, there is poor interfacial adhesion between the hydrophobic matrix
and the hydrophilic fibre. If no modification
of fibre or compatibilization of the two materials is developed, the weak interfacial adhesion
between fibre and
matrix usually results in poor mechanical properties of the composites. Obviously, improvement of
the compatibility between the two components is a key to success in the area. In order to
introduce natural fibres profitably into hydrophobic thermoplastics, such as HDPE, PP and PVC, a
pretreatment
of the fibre surface or the incorporation of interface modifiers is generally required. In order to
improve the compatibility of the wood fibre/polymer composites, a lot of chemicals and methods
have been developed, such as the different treatments [7,8] of the polymer matrices (e.g. graft
copolymerization or grafting fibre), coupling agents [9–11] (e.g. silanes and isocyanates) and
interface compatibilizer [11–14] (e.g. maleic anhydride grafted polyolefin or elastomer). In the
previous studies, the use of the organic carboxylic acids [15–17] (e.g. stearic acid, acetic
anhydride, maleic anhydride and phthalic anhydride) have also drawn considerable attention, due
to their effectiveness in improving adhesion between natural fibre and thermoplastic matrix.
According to the principles of interface coupling, the hydrophilic carboxyl group of organic acid as
the modifier is expected to react with the hydroxyl groups of natural fibre in the surface, and the
hydrophobic group should react or have relatively high compatibility with the polymer matrix. The
combined effects of these interactions will effectively improve the fibre dispersion and resultant
adhesive coupling. In this work we focused on the effect of benzoic acid as the surface modifier on
the mechanical properties of the natural fibres/reinforced plastic composites. The surface of BF
was modified by benzoic acid, and then compounded with PVC resin to prepare the composite. The
main objective of this study was to evaluate the effects of the content of BF, the content of benzoic
acid and BF-treated temperature on the mechanical properties of BF/PVC composites by the
orthogonal optimal method. The processing conditions was used according to the general
procedure [18].

2. Experimental
2.1. Materials
PVC (LS080S, K value 84), supplied by LG Chem.; Waste BF (100-mesh); Liquid tin stabilizer (SS-
218, Shanghai Plastic Auxiliary Co., China); Calcium stearate and household PE wax (H110,
Shanghai Naduo Co., China);
acrylic processing aid (ACR-401, Shanghai Plastic Auxiliary Co., China).

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doi:10.1016/j.compositesa.2006.01.023
* Corresponding author. Address: LCLC, Guangzhou Institute of
Chemistry, Chinese Academy of Sciences, Guangzhou 510650, China.
Tel.: +86 20 85231666; fax: +86 20 85232903.
E-mail address: caodr@mail.gic.ac.cn (D.-R. Cao).
2.2. Treatment of BF
BF (150-lm sieve) was treated with H2O2 solution under ultrasonic condition for 15 min and dried at
60 _C for 48 h. BF was then mixed at room temperature with the solution of benzoic acid in a small
quantity of ethanol. After the solvent was evaporated, BF was dried in air circulating oven at 105
_C for 24 h. The treated-BF was added to the rolls, heated at different temperature (140 _C, 150 _C
or 160 _C) and ground simultaneously for 4 min. The surface of fibre contacted and reacted with
benzoic acid in situ during
grinding.

Tabla 1

2.3. Preparation of the composites and samples

BF and PVC were compounded in a two-roll mill for 7 min. The temperatures of the two rolls were
at 150 _C
and 170 _C, respectively. After the addition of the matrix, the fibre was added as soon as the
polymer had reached a steady plastifying state which needed about 3 min. After mixing for 3–4
min, the resulting mixture was compressionmolded into panels to produce the specimens for
mechanical property test. All of the samples were performed in a preheated press at 185–190 _C
under a pressure of 10 MPa for 8 min, and followed by cooling to room temperature in another
press equipped with refrigeration
facilities. The dogbone-shaped specimens were made for tensile test (1.0 mm thick, 4.0 mm
width). Rectangular specimens were cut from the pressed sheet (80 * 10 * 4 mm) for impact
test. The untreated BF/PVC composite was prepared with BF (25%) and the same dosage in Table
1.

2.4. Mechanical properties of the composites

The tensile properties of the composites were measured in an Universal Tensile Machine at a
crosshead speed of 5 mm/min. Three tensile properties were tested: (i) the tensile strength; (ii) the
tensile modulus; and (iii) the elongation at break. The unnotched Charpy impact strength was
measured in a Charpy Impact Test Machine. All evaluation reported were the average values of at
least five
measurements.

3. Results and discussion

A L9(33) three factor three-level orthogonal optimal method was chosen by Orthogonal Experiment
Assistant

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doi:10.1016/j.compositesa.2006.01.023
* Corresponding author. Address: LCLC, Guangzhou Institute of
Chemistry, Chinese Academy of Sciences, Guangzhou 510650, China.
Tel.: +86 20 85231666; fax: +86 20 85232903.
E-mail address: caodr@mail.gic.ac.cn (D.-R. Cao).
II 3.1 (Sharetop Software Studio). BF content (A), content of benzoic acid (B) and fibre-treated
temperature (C) were the three key variables, whereas the mechanical properties were the
variable responses. The analysis of the data was made to identify the key factors which affected
the tensile and impact strength properties.
Table 2 presents these factors with their normalized levels. Factor A is BF content, Factor B is the
content of benzoic acid, and Factor C is the fibre-treatment temperature. Table 3 shows the
corresponding experimental units and the results of the experimental matrix. The mechanical data
generated by Orthogonal Experiment Assistant II 3.1 software were entered into the design matrix
(Table 3) and a corresponding analysis was carried out. Table 4 shows

Tabla 2

Table 4
indicates that the content of BF
(A) and content of benzoic acid (B) had more e ect than
the fibre-treated temperature (C) on the tensile strength
123
of the rigid BF/PVC composites. Content of BF was the
Level
most significant factor.’
Fig. 1

3.1 Tensile strength

shows the interaction graphs
Fig. 1. Interaction graphs of tensile strength against three variables. (n)
of tensile strength against the three variables, which illus-
BF content, (n) benzoic acid content, (.) treatment temperature.
trates the changes of tensile strength with di erent factors.
The tensile strength clearly increased as the content of BF
composite (38 MPa). The maximum values (52 MPa) was
and the content of the modifier increased. This phenome-
non can be explained in terms of the strong interface inter-
obtained with the maximum amount of fibres, and also
actions of BF with PVC matrix. It also indica tes that
the maximum amount of the modifier, which was con-
benzoic acid had reacted with the hydroxyl groups of BF
firmed by the entry 9 in
Table 3

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doi:10.1016/j.compositesa.2006.01.023
* Corresponding author. Address: LCLC, Guangzhou Institute of
Chemistry, Chinese Academy of Sciences, Guangzhou 510650, China.
Tel.: +86 20 85231666; fax: +86 20 85232903.
E-mail address: caodr@mail.gic.ac.cn (D.-R. Cao).
Tabla 3

Tabla 4

Ilustración 1

3.2. Impact strength

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doi:10.1016/j.compositesa.2006.01.023
* Corresponding author. Address: LCLC, Guangzhou Institute of
Chemistry, Chinese Academy of Sciences, Guangzhou 510650, China.
Tel.: +86 20 85231666; fax: +86 20 85232903.
E-mail address: caodr@mail.gic.ac.cn (D.-R. Cao).
of BF in PVC matrix. The improvement of the interfacial
adhesion made the fibre act as an agent of reinforcement
The e ects of the three variables on the unnotched
in PVC matrix. So the addition of benzoic acid brought
Charpy impact property are shown in
Table 4
and
Fig. 2
.
about an increase in tensile strength instead of decrease
From
Table 4
we can see that the content of BF was the
comparing to the tensile strength of untreated BF/PVC
Table 3

Ilustración 2

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doi:10.1016/j.compositesa.2006.01.023
* Corresponding author. Address: LCLC, Guangzhou Institute of
Chemistry, Chinese Academy of Sciences, Guangzhou 510650, China.
Tel.: +86 20 85231666; fax: +86 20 85232903.
E-mail address: caodr@mail.gic.ac.cn (D.-R. Cao).
Ilustración 3

Results of the orthogonal optimal method

2
Composite Factors Tensile strength (MPa) Impact strength (kJ/m
) Elongation at break (%) Tensile modulus (MPa)
ABC
Interaction graphs of tensile modulus against three variables. (j)
Level
BF content, (n) benzoic acid content, (.) treatment temperature.
Fig. 2. Interaction graphs of unnotched Charpy impact strength against
three variables. (j) BF content, (n) benzoic acid content, (.) treatment
temperature.
Figs. 1 and 2
. Thus, better result (13 kJ/m
) was obtained
2
with the minimum content of fibre, as shown by entry 2
in
Table 3

3.3. Elongation at break

7.5
The e ect of three variables on the elongation at break
was shown in
Table 4
and
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doi:10.1016/j.compositesa.2006.01.023
* Corresponding author. Address: LCLC, Guangzhou Institute of
Chemistry, Chinese Academy of Sciences, Guangzhou 510650, China.
Tel.: +86 20 85231666; fax: +86 20 85232903.
E-mail address: caodr@mail.gic.ac.cn (D.-R. Cao).
Fig. 3
.
Table 4
indicates that
7.0
the content of BF was the main factor a ecting the elonga-
tion at break.
Fig. 4
shows that elongation at break
6.5
decreased, as expected, as the content of fibre increased.
The decrease of elongation at break might be due to the
higher brittleness introduced by blending BF with the
6.0
PVC matrix. As in the case of the benzoic acid treatment,
it did enhance the elongation at break (5.8%, comparing
5.5
to the elongation at break (3.5%) of untreated BF/PVC
composite), as expected, though the change was small.
5.0
The fibre-treatment temperature had a less significant
123
e ect.
Level
Fig. 3. Interaction graphs of elongation at break against three variables.

3.4. Tensile modulus

(n) BF content, (n) benzoic acid content, (.) treatment temperature.
The analysis of the e ect of the three factors on tensile
main factor a ecting the impact strength.
Fig. 2
shows a
modulus for BF/PVC composites is shown in
Table 4
linear decay on impact strength of the composites as the
and
Fig. 4
. The treatment of benzoic acid improved the
content of BF increased. BF in the PVC matrix restricts
modulus of the composite when it increased up to 5%
molecular motion, imposing more resistance to deforma-
and then decreased. The content of BF had a strong posi-
tion that could absorb impact energy, which explains the
tive e ect on the tensile modulus. When there was a good
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doi:10.1016/j.compositesa.2006.01.023
* Corresponding author. Address: LCLC, Guangzhou Institute of
Chemistry, Chinese Academy of Sciences, Guangzhou 510650, China.
Tel.: +86 20 85231666; fax: +86 20 85232903.
E-mail address: caodr@mail.gic.ac.cn (D.-R. Cao).
decrease of impact strength of the composites as the con-
dispersion of BF in PVC matrix the tensile strength was
tent of BF increased. Benzoic acid did not e ect the impact
expected to increase with the addition of fibre. This was
strength much as shown in
Fig. 2
. For example, the impact
reasonable because it demands a higher stress to su er
2
strength changed between 8.3 and 9.2 kJ/m
comparing to
some deformation as the fibre plays a reinforcing role. It
the impact strength of untreated BF/PVC composite
could be seen that as the content of BF increased the mod-
2
(7.5 kJ/m
) when the content of benzoic acid changed
ulus increased, especially when 35% of BF was used.
between 3% and 10%. The tensile strength and impact
According to the analysis above, the maximum values of
strength increased as fibre-treatment temperature rose
modulus were obtained with the maximum content of fibre
firstly (lower than 150 °C), and then decreased as tempera-
and lowest fibre-treatment temperature (see entry 8 in
ture continued to rise (higher than 150 °C) as shown in
Table 3
).

3.5. Analysis of the SEM pho tographs of BF/PVC

pellets. The samples were prepared as follows: (a) untreated
composites
BF (BF1); (b) BF with benzoic acid (5%) (BF2); (c) BF
with benzoic acid (5%) was ground at 160 °C for 4 min
The SEM micrographs of a fractured surface of the trea-
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doi:10.1016/j.compositesa.2006.01.023
* Corresponding author. Address: LCLC, Guangzhou Institute of
Chemistry, Chinese Academy of Sciences, Guangzhou 510650, China.
Tel.: +86 20 85231666; fax: +86 20 85232903.
E-mail address: caodr@mail.gic.ac.cn (D.-R. Cao).
(BF3); (d) BF with benzoic acid (5%) was ground at
ted BF/PVC composites and the untreated BF/PVC com-
150 °C for 4 min (BF4); (e) BF with benzoic acid (5%)
posite are shown in
Fig. 5
. The untreated BF was pulled
was ground at 140 °C for 4 min (BF5).
Fig. 6
shows their
out of the PVC matrix with smooth and clean surfaces
IR spectra. The characteristics absorption band of car-
because of the poor interfacial adhesion as shown in
bonyl group of benzoic acid at 1714 cm
(BF2), and the
À1
Fig. 5
c. However, the treated BF with benzoic acid was
peak decreased in intensity when it was ground at 140 °C
pulled out of the PVC matrix with little rough surfaces
for 4 min (BF5) due to the partly esterification of benzoic
because the interfacial adhesion was better, as shown in
acid. The absorption band of carbonyl group of benzoic
Fig. 5
d. There were many empty spaces due to the forma-
acid at 1714 cm
disappeared when it was ground at
À1
tion of aggrega tes of fibers as shown in
Fig. 5
a. But these
160 °C for 4 min (BF3). A new band appeared at
empty spaces disappeared mostly in the treated BF/PVC
1735 cm
which belongs to the ester carbonyl stretching.
À1
composites as shown in
Fig. 5
b. It is evident that treated
It illustrated that esterification between benzoic acid and
BF is more compatible with PVC rather than untreated
bagasse fiber occurred in situ during grinding.
BF, which can be explained that the hydrophilic carboxyl
groups of benzoic acid react with the hydroxyl groups of

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doi:10.1016/j.compositesa.2006.01.023
* Corresponding author. Address: LCLC, Guangzhou Institute of
Chemistry, Chinese Academy of Sciences, Guangzhou 510650, China.
Tel.: +86 20 85231666; fax: +86 20 85232903.
E-mail address: caodr@mail.gic.ac.cn (D.-R. Cao).
4. Conclusions
natural fibre in the surfa ce, and the hydrophobic group
has relatively high compatibility with the polymer matrix.
The e ect of the content of the modifier (3, 5 or 10 wt%
by fibre), the content of the composition (15, 25 or
3.6. Fourier transform infrared spectroscopy (FTIR)
35 wt%), and fibre-treatment temperature (140, 150 or
160 °C) were studied on the mechanical properties of BF/
The BF treated and untreated with benzoic acid were
PVC composites. The following conclusions could be
analyzed by FTIR (Analect, model RFX-65 A) with KBr
drawn from the experimental results: Benzoic acid was an
e ective adhesion promoter for BF/PVC composites. The
treatment of BF with benzoic acid improved significantly
dispersion of BF in PVC matrix, which could be supported
by SEM micrographs of impact fractured BF/PVC com-
posites and the fact that the addition of benzoic acid
BF1
(10%) brought about an increase in tensile strength
(52 MPa) of the BF/PVC composite comparing to the ten-
BF3
sile strength (38 MPa) of untreated BF/PVC composite.
BF5

Acknowledgement
BF2
Funding for this project was provided by the Chinese
Academy of Sciences (KJCXZ-SW-04).
BF4

References
2 0 00 18 0 0 1 60 0 1 4 00 12 0 0 1 00 0 8 00 6 0 0 40 0
[1] Rana AK, Mandal A, et al. Short fiber-reinforced polypropylene
Wavenumbers (cm
)

-1
composites: e ect of compatibilizer. J Appl Polym Sci 1998;69:
Fig. 6. FTIR spectra of BF1, BF2, BF3, BF4, BF5.
329–38.

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12
doi:10.1016/j.compositesa.2006.01.023
* Corresponding author. Address: LCLC, Guangzhou Institute of
Chemistry, Chinese Academy of Sciences, Guangzhou 510650, China.
Tel.: +86 20 85231666; fax: +86 20 85232903.
E-mail address: caodr@mail.gic.ac.cn (D.-R. Cao).
Y.-T. Zheng et al. / Composites: Part A 38 (2007) 20–25 25
[2] Mitra BC, Basak RK, Sarkar M. Studies on jute-reinforced
[12] Oksman K, Clemons C. Mechanical properties and morphology of
composites: its limitations, and some solutions through chemical
impact modified polypropylene–wood our composites. J Apply
modifications of fibers. J Apply Polym Sci 1998;67:1093–100.
Polym Sci 1998;67:1503–13.
[3] Bledzki AK, Gassan J. Composite reinforced with cellulose based
[13] Kazayawoko M, Balatinecz JJ, Woodhams RT. Di use re ec-
fibres. Prog Polym Sci 1999;24:221–74.
tance Fourier transform infrared spectra of wood fibers treated
[4] Selke SE, Wichman I. Wood fiber/polyolefin composites. Compos
with maleated polypropylenes. J Appl Polym Sci 1997;66:
Part A 2004;35:321–6.
1163–73.
[5] Clemons C. Wood-plastic composites in the United State. Forest
[14] Rana AK, Mandal A, Bandyopadhyay S. Short jute fiber reinforced
Prod J 2002;52(6):10–8.
polypropylene composites: e ect of compatibiliser, impact modifier
[6] Nabi Saheb D, Jog JP. Natural fiber polymer composites: a review.
and fiber loading. Compos Sci Technol 2003;63:801–6.
Adv Polym Technol 1999;18(4):351–63.
[15] Kokta BV, Maldas D, Daneault C, et al. Composites of poly(vinyl
[7] Shukla SR, Rao GVG, Athalye AR. Improving graft level during
chloride) and wood fibers. Part II: e ect of chemical treatment. Polym
photoinduced graft-copolymerization of styrene onto cotton cellu-
Compos 1990;11(2):84–9.
lose. J Appl Polym Sci 1993;49:1423–30.
[16] Mahlberg R, Paajanen L, Nurmi A, et al. E ect of chemical
[8] Liao B, Huang YH, Cong GM. In uence of modified wood fibers on
modification of wood on the mechanical and adhesion properties of
the mechanical properties of wood fiber-reinforced polyethylene. J
wood fiber/polypropylene fiber and polypropylene/veneer compos-
Appl Polym Sci 1997;66:1561–8.
ites. Holz als Roh–und Werksto 2001;59:319–26.
[9] Pickering KL, Abdalla A, Ji C, et al. The e ect of silane coupling
[17] Zafeiropoulos NE, Williams DR, Baillie CA, et al. Engineering and
agents on radiata pine fibre for use in thermoplastic matrix
characterisation of the interface in ax fibre/polypropylene composite
composites. Compos Part A 2003;34:915–26.
materials. Part I. Development and investigation of surface treat-
[10] Raj RG, Kokta BV. Reinforcing high density polyethylene with
ments. Compos Part A 2002;33:1083–93.
cellulosic fibers. I. The e ect of additives on fiber dispersion and
1359-835X/$ - see front matter _ 2006 Published by Elsevier Ltd.
13
doi:10.1016/j.compositesa.2006.01.023
* Corresponding author. Address: LCLC, Guangzhou Institute of
Chemistry, Chinese Academy of Sciences, Guangzhou 510650, China.
Tel.: +86 20 85231666; fax: +86 20 85232903.
E-mail address: caodr@mail.gic.ac.cn (D.-R. Cao).
[18] Matuana LM, Kamdem DP, Zhang J. Photoaging and stabilization
mechanical properties. Polym Eng Sci 1991;31(18):1358–62.
of rigid PVC/wood-fiber composite. J Appl Polym Sci 2001;80:
` s P, et al. E ects of di erent treatments
[11] Colom X, Carrasco F, Page
1943–50.
on the interface of HDPE/lignocellulosic fiber composites. Compos
Sci Technol 2003;63:161–9.

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14
doi:10.1016/j.compositesa.2006.01.023
* Corresponding author. Address: LCLC, Guangzhou Institute of
Chemistry, Chinese Academy of Sciences, Guangzhou 510650, China.
Tel.: +86 20 85231666; fax: +86 20 85232903.
E-mail address: caodr@mail.gic.ac.cn (D.-R. Cao).