Beruflich Dokumente
Kultur Dokumente
cn
Received 19 September 2000; received in revised form 11 January 2001; accepted 13 March 2001
Abstract
The present paper investigates the eect of ber treatment on the mechanical properties of unidirectional sisal-reinforced epoxy
composites. Treatments including alkalization, acetylation, cyanoethylation, the use of silane coupling agent, and heating were
carried out to modify the ber surface and its internal structure. As indicated by infrared spectroscopy, X-ray diraction and tensile
tests, variations in composition, structure, dimensions, morphology and mechanical properties of the sisal bers can be induced by
means of dierent modication methods. When the treated bers were incorporated into an epoxy matrix, mechanical characterization of the laminates revealed the importance of two types of interface: one between ber bundles and the matrix and the other
between the ultimate cells. In general, ber treatments can signicantly improve adhesion at the former interface and also lead to
ingress of the matrix resin into the bers, obstructing pull-out of the cells. As a result, the dependence of laminate mechanical
properties on treatment methods becomes complicated. On the basis of a detailed analysis, the relationship between optimized ber
treatment and performance improvement of sisal composites was proposed. # 2001 Published by Elsevier Science Ltd. All rights
reserved.
Keywords: A. Sisal; A. Natural ber; E. Chemical and physical treatment; A. Unidirectional laminates; B. Interface
1. Introduction
The use of natural vegetable bers as reinforcements
in polymer composites to replace synthetic bers like
glass is presently receiving increasing attention because
of the advantages, including cost eectiveness, low density, high specic strength, as well as their availability as
renewable resources [13]. Owing to the poor wettability
and adsorbability towards polymers resulting from the
hydrophilicity of plant bers, however, the adhesion
between the bers and polymer matrices is generally
insucient. To improve the interfacial bonding, either
surface modication of the bers [4] or plasticization of
the bers [5] can be carried out.
It is worth noting that chemical composition and cell
structure of natural bers are quite complicated. Each
ber is essentially a composite in which rigid cellulose
* Corresponding author. Tel.: +86-20-84034385; fax: +86-2084036564.
E-mail address: cesrmz@zsulink.zsu.edu.cn (M.Z. Rong).
microbrils are embedded in a soft lignin and hemicellulose matrix (Fig. 1). In addition, the microbrils are
helically wound along the ber axis to form ultimate
hollow cells. Uncoiling of these spirally oriented brils
consumes large amounts of energy and is one of the
predominant failure modes. As a result, pretreatment of
the bers would result in chemical and structural changes not only on the ber surface but also in the distinct
cells, which in turn also inuences the properties of the
bers and composites.
Possessing high content of cellulose and high tensile
strength in comparison with other natural bers [6],
sisal ber in chopped, continuous and woven forms has
been shown to be suitable for application in polymer
composites [7]. For purposes of having a thorough
understanding of the mechanical role of sisal bers in
composites and the eects of ber treatment, unidirectional sisal/epoxy laminates (instead of short-ber composites which are more dicult to analyze owing to the
complexity of their microstructure) with chemically and
physically modied bers are produced and evaluated in
0266-3538/01/$ - see front matter # 2001 Published by Elsevier Science Ltd. All rights reserved.
PII: S0266-3538(01)00046-X
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this paper. In particular, it is expected that the relationship between mechanical behavior and interfacial
adhesion can be known.
2. Experimental
2.1. Materials
All of the materials employed in this work were
obtained from commercial sources and used as received.
Untreated sisal bers (UTSF) with diameters ranging
from 100 to 200 mm were provided by Dongfanghong
State Farm in Guangdong. The epoxy resin was a product of the Guangzhou East Chemistry Company (E51,
molecular weight=392). A mixture of tetraethylene
pentamine (TEPA) and acrylonitrile (1.2/1 by weight
ratio) was used as the curing agent.
2.2. Fiber treatment
2.2.1. Alkali-treated sisal-ber (ATSF)
Sisal ber was immersed in a solution of 2% NaOH for
4 h at 60 C, in which ber-to-solution weight ratio was
1:25. The ber was then washed thoroughly with water to
remove the excess of NaOH, and air dried at 80 C. The
weight loss after treatment was measured accordingly.
2.2.2. Acetylated sisal ber (ACSF)
Sisal ber was subjected to a solution of 18% NaOH
for 5 min at ambient temperature followed by washing
with distilled water. After that, the ber was treated
with a solution of 2.5% H2SO4 as neutralizing agent,
washed, and air dried. Then the ber was soaked in a
50% acetic acid aqueous solution for 5 min (ber-tosolution ratio=1:25), washed and air dried [8]. Because
there were no other catalysts except acetic acid, acetylation can only occur on the easily accessible hydroxyl
groups on the cell walls of the bers, implying a low
degree of acetylation under this condition. According to
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2.4. Characterization
In order to identify the inuence of treatment on
bers chemical composition, Fourier transform infrared
(FTIR) spectra were measured by MS-X infrared spectroscopy. Wide angle X-ray diraction spectra were
collected by a D/max-3A apparatus to detect the crystalline structure of cellulose in sisal. The crystallinity
index, which is adapted only to crystalline cellulose I,
was calculated by [9]:
Crystallinity% I002 I18:5 =I002 100
Table 1
Physical and mechanical properties of sisal bers
Fibers
Crystallinity
of cellulose (%)
Density
(g/cm3)
Tensile strength
(MPa)
Youngs modulus
(GPa)
Elongation at
break (%)
UTSF
ATSF
ACSF
ANSF
SCSF
HTSF
62.8
61.4
64.8
58.3
55.6
66.2
13.5
8.2
1.6
1.29
1.27
1.32
1.31
391.1 45.2
495.6 40.1
423.0 27.3
375.8 31.4
387.5 34.5
535.1 42.3
15.0 0.9
12.9 0.8
4.5 0.3
11.3 0.8
12.6 0.6
15.5 0.8
2.5 0.3
3.8 0.4
8.3 0.7
4.5 0.3
4.7 0.4
3.5 0.2
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Fig. 4. SEM micrographs of sisal bers: (a) untreated, (b, c) alkali treated, (d) acetylated, (e) cyanoethylated, (f) alkali and heat treated, (g) heat
treated. The arrows in (d) and (f) indicate the exposed helical brils.
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Fig.6. Fiber volume fraction versus weight fraction, Wf, of unidirectional sisal/epoxy composites.
due to decohesion of the cells as represented by cell pullout [Fig. 8 (a)]. On the other hand, the decreased adhesion in some locations of the intercellular region, where
the binder was extracted, can be compensated by the
immigrated epoxy. The above cohesive failure has to be
hindered at these ultimate cells. Since the immigrated
epoxy is connected to the bulk matrix forming a network,
no extension and deconvolution of microbrils in these
cells can occur. Hence, the strengthening eect of ATSF
can not be brought into full play in the composites. As
can be seen in Fig. 5, there is about 15% improvement in
tensile strength of ATSF reinforced composite in comparison with the UTSF composite at Vf=58 vol.%,
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Fig. 8. SEM micrographs of fractured surface of unidirectional sisal/epoxy composites due to tension. (a) ATSF/epoxy with traces of cell pull-out as
indicated by the arrow, (b) ATSF/epoxy, (c) ATSF/epoxy with immigrant resin adhered to the cells as indicated by the arrow, (d) UTSF/epoxy.
Fiber content in all the laminates is 58 vol.%.
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Fig. 11. Fiber content dependence of exural strength of unidirectional sisal/epoxy composites.
Fig. 12. Fiber content dependence of exural modulus of unidirectional sisal/epoxy composites.
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is believed that a treatment of sisal bers which increases (i) ber strength and (ii) the adhesion between the
ber bundles and the matrix, while it does not introduce
any new bonding to the intercelullar region to hinder
cell pull-out would favor an overall improvement of
mechanical properties (especially tensile properties) of
sisal laminates. This criterion can be used as a guide to
the development of techniques of ber modication for
the composites with pre-determined components.
Acknowledgements
4. Conclusions
1. Sisal bers can be eectively modied by chemical
and physical treatments. Chemical methods usually bring
about an active surface by introducing some reactive
groups, and provide the bers with higher extensibility
through partial removal of lignin and hemicellulose. In
contrast, thermal treatment of the bers can result in
higher ber stiness due to the increased crystallinity of
hard cellulose.
2. Adhesion at the interface between sisal bundles and
matrix and that between ultimate cells play a key role in
determining the mechanical behavior of the laminates.
In the case of tensile tests, an enhancement of the interaction at the rst type of interface prevents transverse
failure and serves as the prerequisite for an improvement
in strength and modulus, while a weaker intercelullar
bonding would facilitate pull-out of ultimate cells, leading to stretching and uncoiling of microbrils in the cells
which imparts high mechanical performance to the composites. Under the circumstances of three-point bending,
however, resistance to interlaminar failure controls the
ultimate properties of the laminates. An improved interfacial interaction results in high exural stiness.
3. Composites reinforced by treated sisal is a way of
heading for potential structural materials, as concluded
in a recent review on this topic [19]. Continuous eorts
should be made before a broad application is realized. It
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