Composites: Part B 40 (2009) 628–632

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

Effect of surface treatment on performance of pineapple leaf

fiber–polycarbonate composites
P. Threepopnatkul a,b,*, N. Kaerkitcha a, N. Athipongarporn a
a
Department of Materials Science and Engineering, Faculty of Engineering and Industrial Technology, Silpakorn University, Nakorn-pathom 73000, Thailand
b
Center for Petroleum, Petrochemicals, and Advanced Materials, Chulalongkorn University, Bangkok 10330, Thailand

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

Article history: This research is to study the properties of pineapple leaf fiber reinforced polycarbonate composites (PC/
Received 9 October 2008 PALF). Surface of pineapple leaf fiber (PALF) was pre-treated with sodium hydroxide (PALF/NaOH) and
Received in revised form 11 January 2009 modified with two different functionalities such as c-aminopropyl trimethoxy silane (PALF/Z-6011)
Accepted 16 January 2009
and c-methacryloxy propyl trimethoxy silane (PALF/Z-6030). The effects of PALF content and chemical
Available online 18 April 2009
treatment were investigated by Fourier transform infrared spectroscopy, scanning electron microscopy
and mechanical testing. The modified pineapple leaf fibers composite also produces enhanced mechan-
Keywords:
ical properties. Young’s modulus is the highest in the case of the PALF/NaOH composites. The PALF/Z-
E. Surface treatments
A. Natural fibres composites
6011 composites showed the highest tensile strength and impact strength. In thermal property, the
B. Mechanical properties results from thermogravimetric analysis showed that thermal stability of the composites is lower than
B. Thermal properties that of neat polycarbonate resin and thermal stability decreased with increasing pineapple leaf fiber
content.
Ó 2009 Elsevier Ltd. All rights reserved.

1. Introduction eral vital and useful properties such as transparency, dimensional

Nowadays, natural fiber [1] such as hemp, jute, rice straw,
wood, bamboo, etc. has gained attention as an alternative to syn-
thetic fiber by using natural fiber as filler or reinforcement in plas-
tic to reduce cost, increase productivity and improve mechanical
properties of product. Mixing, especially with bio-plastic lead to
green composite that is easy to degrade by bacteria or enzyme
[2,3]. However, an important problem for using fiber as reinforce-
ment in plastic is poor adhesion between natural fiber and polymer
matrix. It is also reported by Abdelmouleh et al. [4], because fiber
has low interaction with matrix, load transfer from matrix into fi-
ber is not good. Therefore, fiber surface is needed to be modified to
reduce polarity of fiber and hence the compatibility at interface re-
gion is improved. The modification methods are alkaline treatment
[5,6], grafting with maleic anhydride copolymer [7] and using si-
lane coupling agent [8–10].
Polycarbonate (PC) is an amorphous thermoplastic polymer and
widely used as engineering thermoplastic because it possesses sev-
* Corresponding author. Address: Department of Materials Science and Engi-
neering, Faculty of Engineering and Industrial Technology, Silpakorn University,
Nakorn-pathom 73000, Thailand. Tel.: +66 86 882 8369; fax: +66 34 219 363.
E-mail address: poonsubt@yahoo.com (P. Threepopnatkul).
stability, flame resistance, high heat distortion temperature and
high impact strength. However, there are some disadvantages
which limit its use in some application. Relatively soft polymeric
surface of PC can easily scratch and notch sensitivity at lower tem-
peratures [11].
This research is to study the use of pineapple leaf fiber (PALF) as
reinforcement to improve mechanical properties of PC. Currently,
there is very little literature examining the reinforcement of PALF
in other polymers [12–14]. This research focused on the prepara-
tion of green composites by surface modification of PALF with
two types of silane coupling agent included with c-aminopropyl
trimethoxy silane (Z-6011) and c-methacrylate propyl trimethoxy
silane (Z-6030).
2. Experimental
2.1. Materials
Pineapple leaf fibers were used as reinforcement for compos-
ites. Polycarbonate (Jupilon, grade S-3000) obtained from Thai
Polycarbonate, Rayong, Thailand, was used as the matrix. Sodium
hydroxide (NaOH) was purchased from Ajax Finechem, Australia.
Acetic acid, methanol and acetone were supplied by Union Intraco
Co., Ltd., Bangkok, Thailand. Two silane coupling agents, c-(amino-
propyl) trimethoxy silane (Z-6011) and c-methacrylate propyl tri-
methoxy silane (Z-6030), whose chemical structures and
description are listed in Table 1. These coupling agents were

1359-8368/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.compositesb.2009.04.008
 P. Threepopnatkul et al. / Composites: Part B 40 (2009) 628–632 629

Table 1 3. Results and discussion

The chemical structures and descriptions of silane coupling agent.

Silane Chemical description Chemical structures 3.1. Characterization of composites by FTIR

type
Z-6011 c-(Aminopropyl) trimethoxy OCH3 Both untreated and silanized PALF were characterized by FTIR
silane to confirm the chemical reaction between silanes and cellulose
NH2-(CH2)3-Si-OCH3
backbone of PALF. The FTIR spectrum of PALF and two types of si-
OCH3 lane are presented in Fig. 1. Characteristic peak of Z-6011 reveal at
O OCH3 around 3379 cm1 corresponds to a C—NH2 bond and transmission
peak at 1715 and 1597 cm1 could be due to the presence of NH2 .
Z-6030 c-Methacrylate propyl trimethoxy CH2=C-CO-(CH2)3 Si-OCH3
silane Another peak appears at 1720 cm1 in Z-6030 come from carbonyl
CH3 OCH3 group (C@O) [15].
Fig. 2 shows the spectrum of PALF which is pre-treated with
NaOH, treated with Z-6011 and Z-6030. All treated PALF reveal
board peaks at around 3300 cm1 which could be attributed by
supplied by Acros Organics, New Jersey, USA and Fluka, Germany, OH. In PALF/Z-6011 spectra, characteristic peak of Z-6011 at
respectively. 1715 cm1 for NH2 assures some silane reactions with pineapple
leaf fibers occurring through direct condensation reactions be-
2.2. Fiber surface modification tween the hydrolyzed silane and hydroxyl groups of the pineapple
leaf cellulose as shown in Fig. 3. But in PALF/Z-6030 spectra cannot
2.2.1. Alkaline pre-treatment confirms bonding between these two phases.
Pineapple leaf fibers were washed and immersed in water for
24 h at room temperature. Then the fibers were washed with ace- 3.2. Mechanical properties of composites
tone and dried in an oven at 120 °C for 3 h. After that, fibers were
immersed in NaOH solution (5% w/v) in water bath at 30 °C for 5 h. Young’s modulus, tensile strength, percentage elongation at
Next the fibers were washed with distilled water until all NaOH break obtained from stress–strain curve as shown in Fig. 4 of neat
was eliminated, that is until this water no longer indicated any PC and its composites were investigated in order to observe the
alkalinity. After washing, the fibers were dried in an oven at reinforcement effect of NaOH and silanized PALF. The behaviour
60 °C for 3 h. of PC/PALF composites was changed from ductile to brittle.
Fig. 5 shows the tensile modulus of the untreated, NaOH trea-
2.2.2. Silane treatment ted, and two different silanized PALF/PC composites at various
The fibers were cut into 2 mm. For the fibers surface treat- PALF concentrations. Young’s modulus of the PC composites signif-
ment, 1% w/w silane (weight percentage compared to the fi-
ber) was dissolved for hydrolysis in methanol solution. The
pH of the solution was adjusted to 3.5 with acetic acid and
PALF
stirred continuously for 10 min. Next, the fibers were soaked
in the solution for 6 h and then dried in ambient
temperature. Z-6011

2.3. Composites compounding and processing NH2

C-NH2 Z-6030
Both untreated and silane-treated PALFs were compounded
with PC using diisononyl phthalate 3% w/w (weight percentage
compared to the PC) as plasticizer in an internal mixer, Brabender
C=O
Corp., with rotor speed of 10 rpm and mixing chamber tempera-
ture of 230 °C for 3–6 min. Various fiber concentration (0, 5, 10 3800 3400 3000 2600 2200 1800 1400 1000 600
and 20 wt%) were prepared. After compounds were removed from -1
Wavenumber,cm
the internal mixer, they were cut into small pieces using grinder.
An injection molding machine, Battenfeld Corp. UNILOG B2, was Fig. 1. FTIR spectrum of PALF, Z-6011 and Z-6030.

used to prepare the specimens for mechanical tests.

2.4. Characterization and testing

PALF/NaOH
The modified fiber was identified using a Fourier transform
infrared spectroscopy (FTIR, Nicolet impact 410). Thermal prop-
erties of PC/PALF composites were tested using thermogravimet-
PALF/NaOH/Z-6011
ric analysis (TGA, Perkin Elmer Corp.). A universal testing NH2
machine (LLOYD Instruments Corp. LR 50K) was used for tensile
properties measurements, according to ASTM D638. All tests
were performed at room temperature with a crosshead speed PALF/NaOH/Z-6030
of 5 mm/min. Izod impact tests, following ASTM D256, were per-
formed on a Zwick Testing Machine. The interfacial PALF/PC
adhesions were investigated using a JEOL scanning electron 3800 3400 3000 2600 2200 1800 1400 1000 600
microscopy (SEM) operated at 15 keV. The composite fracture -1
Wavenumber,cm
surfaces for examination were obtained immersion in liquid
nitrogen. Fig. 2. FTIR spectrum of PALF/NaOH, PALF/Z-6011 and PALF/Z-6030.
630 P. Threepopnatkul et al. / Composites: Part B 40 (2009) 628–632

OCH3 OH 2500
H2O HO-Si-(CH2)3NH2
CH3-O-Si-(CH2)3NH2

Young' s modulus (MPa)

OH 2000
OCH3

OH OCell 1500
HO-Si-(CH2)3 NH2 + Cell-OH Cell-O-Si-(CH2)3 NH2
OH OCell 1000
Fig. 3. Reaction between pineapple leaf fibers and c-aminopropyl trimethoxy PC+PALF/NaOH
silane. 500 PC+PALF/NaOH/Z-6011
PC+PALF/NaOH/Z-6030
PC+Untreated PALF
0
0 5 10 15 20 25
80 % PALF content
70
Fig. 5. Comparison of Young’s modulus of ðÞ untreated, ðrÞ NaOH treated, ðjÞ Z-
60 6011 treated and ðNÞ Z-6030 treated PALF/PC composites.
Stress (MPa)

50
PC+5% PALF/ NaOH PC+10% PALF/ NaOH
40
PC+20% PALF/ NaOH PC+5% PALF/ Z-6011
30
PC+10% PALF/ Z-6011 PC+20% PALF/ Z-6011
20
PC+5% PALF/ Z-6030 PC+10% PALF/ Z-6030
10
PC+20% PALF/ Z-6030 PC
0
0 50 100 150 200
%Strain

Fig. 4. Comparison of stress and strain curve of treated pineapple leaf fiber and
polycarbonate composites at different fiber content and neat polycarbonate.

Fig. 6. Reaction of silane polymerization.

Fig. 7. Reaction mechanism of a Z-6011 silane-treated PALF–PC composite.

icantly increased with increasing PALF content. Young’s modulus,
in particular, increased from 1120 MPa for neat PC to 1960 MPa
for PALF/NaOH composites. The increase in modulus of composite
was caused by improved adhesion between the PALF and the PC
matrix. Improved adhesion between PALF and PC makes it feasible
for stress transfer to take place from the plastic matrix to the PALF,
thereby improving the strength of the composites. The silanized
composites have lower modulus than NaOH-treated composites.
This could be resulted from a formation of flexible polysiloxane
(Si–O–Si) from self-condensation reaction of silane [16,17] as
and two different silanized PALF/PC composites. Tensile strength
of the PC composites slightly increases with the PALF content
increment. At 20% fiber content, the PALF/Z-6030–PC composites
decreases because the fibers may act as flaws in the matrix and
the higher void contents could occur are depicted in Fig. 9c and
subsequently showing the low interfacial strength.
80
70
Tensile strength (MPa)

shown in Fig. 6. Moreover, it was found that the PALF/Z-6011–PC 60

composites showed higher modulus than PALF/Z-6030–PC com-
posites. These could be explained by the chemical structure of 50
the two silane coupling agents used and are also listed in Table 40
1. Z-6011 consists of amino silanes having NH2 group which has
30
more polar than carbonyl (C@O) group in Z-6030. Therefore, inter-
facial adhesion between PALF/Z-6011 and PC is stronger because 20 PC+PALF/NaOH
PC+PALF/NaOH/Z-6011
the functional group of Z-6011 may react with –[O–CO–O–] group 10 PC+PALF/NaOH/Z-6030
of PC as seen in Fig. 7 and as a consequence polysiloxane would be PC+Untreated PALF
0
formed. Meanwhile the PALF/Z-6030 would be less likely to inter-
0 5 10 15 20 25
act with the carbonyl group of PC because of the existence of vinyl
% PALF content
end group in the treated system.
Fig. 8 illustrates the tensile strength of the PALF/PC composites Fig. 8. Comparison of tensile strength of ðÞ untreated, ðrÞ NaOH treated, ðjÞ
without surface treatment in comparison with the alkali treated Z-6011 treated and ðNÞ Z-6030 treated PALF/PC composites.
 P. Threepopnatkul et al. / Composites: Part B 40 (2009) 628–632 631

14

12

Elongation at break (%)

10

4
PC+PALF/NaOH
2 PC+PALF/NaOH/Z-6011
PC+PALF/NaOH/Z-6030
0
0 5 10 15 20 25
% PALF content
Fig. 10. Elongation at break of ðrÞ NaOH treated, ðjÞ Z-6011 treated and ðNÞ
Z-6030 treated PALF/PC composites.

10
9

Impact strength (kJ/m2 )

8
7
6
5
4
3
2 PC+PALF/NaOH
PC+PALF/NaOH/Z-6011
1 PC+PALF/NaOH/Z-6030
0
0 5 10 15 20 25
% PALF content
Fig. 11. Impact strength of ðrÞ NaOH treated, ðjÞ Z-6011 treated and ðNÞ Z-6030
treated PALF/PC composites.

for neat PC. As the PALF contents increased, the impact strength
tended to drop dramatically as seen in Fig. 11. Specifically, at low
PALF content (e.g., 5% wt), impact strength of composites depends
on polymer matrix. The effect of interfacial adhesion between PALF
at its high content (10 and 20% wt) and polymer matrix has more
influence on the impact strength. Therefore, the PALF/Z-6011 com-
posites have highest impact strength due to the interaction be-
tween the functional group of the treated PALF and polycarbonate.

3.3. Thermal properties of composites

Fig. 9. SEM micrograph of (a) NaOH treated, (b) Z-6011 treated and (c) Z-6030
treated PALF/PC composites.
As seen in Fig. 9, the surface of PALF in NaOH-pre-treated com-
posites is relatively smooth whereas in the silane treated compos-
ites, the fiber has been covered with some polymer matrix and thus
better stress transfer could be predicted in the PALF/Z-6011 com-
posites. For PALF/Z-6030 composites, void between two phases
lead to poor adhesion and decreased in properties.
Fig. 10 shows that elongation at break of PC composites de-
creased significantly from 140% for neat PC and decreased with
PALF content increment. Because of fibers obstructed a chain
mobility of matrix polymer. Elongation at break of silanized com-
posites is higher than NaOH-treated composites because of plasti-
cization behaviour of polysiloxane in polymer phase, thus polymer
chain can slip easily.
Impact strength is ability of material to absorb energy. Impact
strength of composites decreased significantly from 111:4 kJ=m2
From TGA thermogram of neat PC, PALF and its composites, as
seen in Fig. 12, indicated that neat PC possesses a single stage in
the thermal degradation at around 440–520 °C. TGA was per-
formed on the neat PALF degraded in three stages. The first at from
40 to 130 °C was due to the release of absorbed moisture in the fi-
bers. The second transition (the temperature range of the decom-
position was from 195 to 360 °C) was related to the degradation
of cellulosic substances such as hemicellulose and cellulose. The
third stage (360–470 °C) of the decomposition was due to the deg-
radation of non-cellulosic materials in the fibers [18]. The PALF
composites showed the onset temperature for thermal degradation
at lower temperature (approximately 270 °C). This could be inter-
preted that the composites has low thermal stability compared
with neat PC resin because of low thermal stability of PALF (rapid
degradation at 270 °C). Almost all of the composites possess a same
trend of thermal degradation even though at a lower temperature
comparing to the one of the neat PC. The high PALF content (20%
wt) composites with alkali treatment were thermally examined
and found that the onset temperature occurred at lower tempera-
632 P. Threepopnatkul et al. / Composites: Part B 40 (2009) 628–632

PC+5% PALF/ NaOH PC+10% PALF/ NaOH Materials. The authors also wish to express their appreciation to
120 PC+20% PALF/ NaOH PC+5% PALF/ Z-6011
PC+10% PALF/ Z-6011 PC+20% PALF/ Z-6011 Thai Polycarbonate Co., Ltd., Rayong, Thailand for supplying the
PC+5% PALF/ Z-6030 PC+10% PALF/ Z-6030 polycarbonate. The authors wish to thank Asst. Prof. Dr. Chanchai
100
Thongpin, Dr. Wimonrat Sricharussin (Silpakorn University, TH)
80 PALF PC
and Dr. Chanin Kulsetthanchalee (Suan Dusit Rajabhat University,
TH) for their comments and suggestions during preparation of this
% Weight

60 PC+20%PALF/NaOH article.

40
20
0 Polym Sci 1999;24(2):221–74.
0 100 200 300 400 500 600 700
o based resin. Compos Sci Technol 2004;64(9):1135–45.
Temperature ( C)
Fig. 12. Thermogravimetric curves of the neat PC, PALF and treated-PALF/PC
composites.
ture among the other composites studied. This is caused by the
presence of low thermal stability of high content of PALF. However,
20% wt PALF composites with silane treatment performed a better
thermal stability.
4. Conclusion
From FTIR characterization, the spectra of PALF/Z-6011 has new
transmittance peak of amino group. While PALF/Z-6030 character-
istic peak of carbonyl group is not found, this could confirm the
fact of no chemical bonding between PALF and Z-6030. Young’s
modulus of composites are better than neat PC. The silanized com-
posites have lower modulus than NaOH-treated composites re-
sulted from a formation of flexible polysiloxane. For tensile
strength of the composites, the values showed slight increase with
the increment of PALF content. At 20% fibers content, the PALF/Z-
6030–PC composites illustrated a decrease in tensile strength. This
could be explained as a result of an abundant amount of the fibers
which may act as flaws in the matrix. Thus, the higher void con-
tents could occur and ultimately reflected on the low interfacial
strength of the matrix. Elongation at break and impact strength
of composites decreased significantly with the comparison of the
neat PC. The tendency was also the same for all the determined al-
kali and silanized composites, i.e., elongation at break as well as
impact strength had decreased with the higher amount of PALF
content presence. Thermal stability of composites decreased when
compared with neat PC.
Acknowledgements
The authors acknowledge the financial support of the National
Center of Excellence for Petroleum, Petrochemicals and Advanced
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