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Composites Science and Technology 61 (2001) 14371447


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The eect of ber treatment on the mechanical properties


of unidirectional sisal-reinforced epoxy composites
Min Zhi Ronga,b,*, Ming Qiu Zhangb, Yuan Liub, Gui Cheng Yangb, Han Min Zengb
a
Materials Science Institute, Zhongshan University, Guangzhou 510275, PR China
Key Laboratory for Polymeric Composite and Functional Materials of Ministry of Education, Zhongshan University,
Guangzhou 510275, PR China

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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M.Z. Rong et al. / Composites Science and Technology 61 (2001) 14371447

Ref. [8], the resultant content of acetyl ranges from 1.6


to 2.4 wt.%.

Fig. 1. Structural constitution of a natural vegetable ber cell, in


which the secondary wall S2 makes up 80% of the total thickness
and thus acts as the main load bearing component.

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

2.2.3. Cyanoethylated sisal ber (ANSF)


Sisal ber was steeped in a 4% sodium hydroxide
solution saturated with sodium thiocyanate for 30 min.
Subsequently, the ber was pressed to drain o the
excess water and removed quickly into a round-bottomed
ask allowing a reaction with acrylonitrile (sisal berto-AN ratio=1:3) for 1 h at 4045 C. After the reaction, a solution of acetic acid was used to neutralize the
alkali catalyst to a pH value of 67. The product was
well washed with water and 95% alcohol, respectively.
Due to the chemical heterogeneity of sisal, degree of
substitution originating from cyanoethylation process is
hard to be measured. Instead, the extent of cyanoethylation reaction is characterized in terms of a weight gain
of 3.7%.
2.2.4. Organosilane coupling agent treated sisal ber
(SCSF)
Sisal ber was soaked in a solution of 2% aminosilane
(KH550, g-amine propyl triethoxysilane) in 95% alcohol. The treatment was carried out for 5 min at a pH
value of 4.55.5, and then the ber was kept in air for
30min for hydrolyzing of the coupling agent. Eventually, the reaction between hydroxyl groups of sisal
ber and silanols of KH550 was induced in an oven at
100 C for 2 h.
2.2.5. Heat treated sisal ber (HTSF)
Sisal ber was heated at 150 C in an air-circulating
oven for 4 h. The weight loss was measured when the
ber was cooled down to room temperature.
2.2.6. Mixed treatments
Besides the above methods of treatment, a combination of some of them was also tried. That is, alkali
treated sisal ber was further modied by KH550 coupling agent or by heat treatment. These bers are named
(AT+SC)SF and (AT+HT)SF, respectively.
2.3. Preparation of sisal composite laminates
Unidirectional composites laminates with various
ber volume fractions were prepared as follows. Treated
or untreated bers were dried prior to use. A resin formulation containing desired amount of hardener was used
for making prepregs. Composite laminates of 1315.53
cm3 were obtained by hot pressing 1014 pieces of prepregs (depending on the sisal contents) at 60 C for 30
min using a leaky mold, and then curing at 80 C for 6 h.
The mold was kept under pressure until the resin was set
into a hard mass. Composites sheets with dierent ber
contents were prepared under dierent pressures to
maintain a constant sample thickness.

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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

where I002 is the diracted intensity by (002) plane,


while I18:5 the diracted intensity at 2 18:5 .
For evaluating tensile properties of untreated and
treated sisal bers at ambient temperature, the bers were
tested by LWK-5 electronic tensile tester at a crosshead
speed of 2 mm/min. For each case, 10 bers were tested at
a gauge length of 20 cm. To calculate tensile strength
and Youngs modulus, the cross-sectional area of each
tested ber was determined by a S-520 scanning electron
microscope (SEM).
Tensile and exural properties of composite laminates
were also determined by the LWK-5 tester at a crosshead
speed of 10 mm/min in accordance with GB3354-82. The
reported data were the average of ve successful tests.
The fractured surface of sisal bers and the composites was observed by the aforesaid SEM. Prior to the
examination, the specimens were sputter-coated with
gold.

3. Results and discussion


3.1. Treatments induced variation in sisal ber
Sisal ber, principally consisting of 65.8% cellulose,
9.9% lignin and 12.0% hemicellulose, has been shown
to be very sensitive to caustic soda [10]. In agreement
with other lignocellulose bers, the signicant weight
loss of sisal ber after alkali treatment (Table 1) can be
ascribed to the partial dissolution of hemicellulose [11].
This is further convinced by the FTIR curves in Fig. 2,

where the carbonyl band at 1730 cm1 corresponding to


hemicellulose disappears when the ber is treated by
NaOH. Comparatively, the acetylated ber has a spectrum prole similar to that of the alkali treated one,
representing a similar extent of alkali treatment and a
rather low acetylation degree. After cyanoethylation, chemical structure of sisal bers has been changed as reected
by the presence of a strong adsorption at 2240 cm1 due to
nitrile (CN) stretching. Vibrations of amino and carboxyl groups are also perceivable as a result of hydrolysis
of nitrile groups. In the case of organosilane coupling
agent treated sisal ber, amine was introduced to the
bers as demonstrated by the NH2 band at 3200 cm1. In
addition, strong absorptions related to SiO and SiOSi
are observed at 1285, 1075 and 1018 cm1, respectively.
With respect to thamal treatment, it might not induce
any chemical changes as expected conventionally. Hence
the FTIR spectra of both the untreated and treated bers
look almost the same except the slightly diminished
intensity at 1650 cm1 of the HTSF. Removal of some
aromatic lignin-like impurities should be responsible for
it [12].
The results of X-ray diraction show that sisal ber
with and without treatment exhibits the same crystalline
lattice of cellulose I, in which the resolution of (101) and
101 reections is poor due to the semi-crystalline nature crystallization of the cellulose (Fig. 3).
However, a slight change in the crystallinity of cellulose I can be seen in Table 1. Compared with UTSF, the
crystallinity of ATSF becomes lower owing to swelling
and partial removal of the cementing materials, which
result in a slight disturbance of cellulose chain arrangement rather than a better packing as found in coir [13].
On the contrary, acetylated sisal ber has a higher
crystallinity even though the acetyl groups on cellulose
chains might reduce molecular regularity. This can be
reasonably explained by the fact that a small amount of
acetyl groups usually softens the cellulose chain (as
demonstrated by the reduced stiness shown in Table 1)
and thus facilitates ordered rearrangement of the molecules through a chainfold conformation mechanism. On
the other hand, the increase in crystallinity for heat
treated sisal ber can be attributed to the adjustment in
molecular structure at elevated temperature.

Table 1
Physical and mechanical properties of sisal bers
Fibers

Crystallinity
of cellulose (%)

Weight loss after


treatment (%)

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. 2. FTIR spectra of sisal bers treated by dierent methods.

that sisal ber becomes relatively ductile after the


removal of some hemicellulose and lignin. It is interesting that HTSF shows a much more signicant increase
in tensile strength due to the improved crystallinity of
cellulose. Similarly, ACSF exhibits an improved tensile
strength while ANSF and SCSF are provided with
lower tensile strength, which is consistent with the
changes in cellulose crystallinity.
From Table 1, it is noted that all chemical treatments
result in greater extensibility and lower modulus. These
phenomena must be related to the structural variation in
the ultimate cells. That is, swelling and partial removal of
lignin and hemicellulose, the cementing materials in
vegetable bers [14], decrease the resistance of microbrils to stretching [10]. Coinciding with this explanation, Fig. 4 illustrates a rougher and more uneven surface
morphology of ATSF and ACSF in comparison with
untreated and heat treated bers. Besides, some loosely
spiraled brils are even exposed [Fig. 4(c), (d) and (f)]
because the primary wall was dissolved away. Uncoiling
of these brils can easily occur if a tensile force is applied.
3.2. Eect of alkali treated sisal ber on the mechanical
behavior of composite laminates

Fig. 3. X-ray diraction spectra of sisal bers treated by dierent


methods.

An evident decrease in crystallinity is found in the


case of silane coupling agent treated sisal ber (Table 1).
As it is generally accepted that when silane coupling agent
reacts with hydroxyl groups, alkoxysilanes undergo stages
of hydrolysis, condensation and bond formation. This
means that in addition to the reaction of silanols with
hydroxyls of the ber surface, formation of polysiloxane
structures also take place. Such a large coupling molecules would destroy the packing of cellulose chains to a
certain extent. As for cyanoethylated sisal, the crystalline
structure of cellulose might be disrupted by substituting
its hydrogen bonds with CH2CH2CN characterized by
decrystallization.
Tensile properties of sisal bers, selected at random,
are also listed in Table 1. Usually, eects of mercerization (i.e. alkali treatment) on the properties of natural
bers depend on the type and concentration of the
alkali solution as well as the temperature and time of
treatment [9]. The condition of mercerization chosen in
this work leads to an improvement of tensile strength
and elongation at break up to 27 and 52%, respectively,
but a decrease in Youngs modulus (Table 1). It suggests

Fig. 5 represents the dependence of tensile strength of


UTSF and ATSF reinforced epoxy on ber volume
fraction, Vf. In the case of untreated bers, tensile strength
of the composites increases with increasing Vf up to 58
vol.%. Thereafter, there is only a marginal increase with a
further addition of the ber. The fall of the strengthening
eectiveness should result from the increased amount of
cavities due to ber-to-ber contacts, as observed in
other ber composites. When sisal bers are treated by
NaOH, the strength of the composites becomes higher
than that of untreated versions due to the intrinsically
increased strength of the bers and shows a continuous
increasing trend within the whole ber content range of
interests, manifesting a better wetting of the bers by
epoxy. Usually, alkali treated natural ber has to shrink if
no tension is applied during the treatment. However, much
greater improvement of ber strength can be acquired
under isomeric condition when the ber is stretched [15],
which improves the packing of the crystallites and
reduces the weak links originated from voids in the cellulose microbrils. In the present work, the shrinkage of
ATSF is about 15% as demonstrated by the lower ber
volume fraction of ATSF/epoxy in comparison with
UTSF/epoxy when ber weight percentage being equal
(Fig. 6). It factually allows the weight of ATSF added to
the composite is higher than UTSF under the same
volume fraction. Provided interfacial adhesion is strong
enough, the strength of ATSF laminates is bound to be
superior to that of UTSF ones at high ber loading.
For a unidirectional composite, its strength depends
upon the failure strains of ber and matrix, "uf and "um ,

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M.Z. Rong et al. / Composites Science and Technology 61 (2001) 14371447

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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.

respectively. In the case "uf > "um and ber content is


high enough (>11 vol.% in general), the failure stress
of the composite, uc , varies with Vf in a linear way [16]:
uc uf Vf

where uf denotes the failure stress of ber. According


to this relationship, the tensile strengths of UTSF and
ATSF laminates are estimated and illustrated in Fig. 5.
It is found that all the experimental data are higher than
the calculated ones. Factually, epoxy is able to ll up
the apparent aws in sisal bers and results in better
load sharing. Neglect of this aspect must account for the
lower strengths predicted by Eq. (2) than the measured
ones. Regarding the argument in the last paragraph, it
can thus be concluded that interfacial eect greatly

Fig. 5. Fiber content dependence of tensile strength of unidirectional


sisal/epoxy composites.

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Fig.6. Fiber volume fraction versus weight fraction, Wf, of unidirectional sisal/epoxy composites.

inuences properties of sisal reinforced composites and


needs further investigation.
In general, mechanical performance of a ber composite basically depends on strength and modulus of the
reinforcement, strength and toughness of the matrix,
and eciency of interfacial stress transfer. For natural
ber reinforced polymers, some more factors including
interface between ultimate cells and orientation variation of microbrils in each cell are involved because of
the structural characteristics of the bers. In fact, a
piece of sisal ber is not a single lament like carbon or
glass ber but a bundle of cellular aggregate consisting
of more than 100 irregular hexagonal hollow ultimate
cells (Fig. 7). The binder that separates the cells makes
the governing contribution to stress development in
ber bundles. Therefore, two types of interface should
be considered when discussing sisal composites: one
between the ber bundle and the matrix and the other
between the cells [17]. A higher binding strength at the
former interface than the latter one is highly desired so
that the ultimate cells might decohere from each other,
probably leading to interbrillar failure and uncoiling of
the helical brils. The composites would be remarkably
strengthened and toughened in this way.
Returning to Figs. 2 and 4, hemicellulose and lignin in
sisal are found to be removed during alkalization and
the ber surface has a coarser appearance than the
untreated one. It is believed that the vacancies outside
and inside sisal bundles left by NaOH treatment facilitate
penetration of epoxy. That is, the removed cementing
materials can be partially replaced by epoxy. This greatly
improves ber bundle/matrix bonding because sisal bers
and epoxy resin exhibit polar characteristics and there is a
reactive bond between them rather than a wetted interface, besides the increased static frictional force originating from the irregular outlines of the bers. As a result,
adhesion between ber bundles and the matrix is stronger
than the intercelullar binding strength, on the whole.
Adhesive failure between sisal bundles and epoxy, a main
failure mechanism involved in untreated sisal composites,
could not take place. Instead, the ATSF laminates fail

Fig. 7. Schematic drawing of (a) cross-section of a piece of sisal leaf


and (b) inner construction of bunched sisal bers.

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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M.Z. Rong et al. / Composites Science and Technology 61 (2001) 14371447

which is much lower than the increment of tensile


strength of sisal ber itself after alkalization (Table 1).
The fractured surface of both ATSF and UTSF reinforced epoxy due to tension is shown in Fig. 8. Clearly,
the ATSF composite has a stronger interface bonding
than the UTSF one. A larger quantity of residual resin
can be observed on the surface of ATSF [Fig. 8(b)] and
even at the gaps between the ultimate cells [Fig. 8(c)],
proving the penetration of epoxy into alkali treated sisal
ber bundles.
The increased interfacial adhesion is also perceived in
Fig. 9. The decreasing trend in Youngs modulus with
ATSF loading represents the lower stiness nature of
alkali treated sisal bers. In addition, transverse failure
in UTSF laminates corresponding to the rst cracking in
the tensile curve is no longer detectable in ATSF laminates (Fig. 10), which helps to enhance the stability of
the composites.
In contrast to tensile properties, an overall enhancement in exural strength and modulus with a rise in ber
content can be seen in ATSF laminates (Figs. 11 and 12).
This actually reects the structural characteristics of the

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laminates in response to dierent stress states. As the


upper and lower surfaces of the specimen under threepoint bending load are subjected to bending stress (compression and tension) and the axisymmetric plane is subjected to shear stress, there are two failure modes in
materials: exural and shear failures. The specimen fails
when the bending or the shear stress reaches the corresponding critical value. Usually, the force-deection
curve obtained by three-point bending is able to reveal
the modes of failure [18]. That is: when the specimen fails
so abruptly that the curve is practically linear, it can be
attributed to exural failure mode. When the specimen
fails in the way that the slope of the force-deection
curve decreases gradually to zero, shear failure takes
place. The appearance of a curve shown between these
two forms can be considered a result of mixed failure
mode. According to this criterion, it is clear that the contribution of shear deformation plays the leading role in
UTSF laminates (Fig. 13). In this case, exural properties
of these unidirectional composites are factually controlled by the resistance to interlaminar failure. Therefore, the enhanced interfacial adhesion in ATSF/epoxy

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. 9. Fiber content dependence of Youngs modulus of unidirectional sisal/epoxy composites.

Fig. 11. Fiber content dependence of exural strength of unidirectional sisal/epoxy composites.

Fig. 10. Typical tensile stressstrain curves of unidirectional sisal/


epoxy composites (Vf=50 vol.%).

Fig. 12. Fiber content dependence of exural modulus of unidirectional sisal/epoxy composites.

mentioned above is responsible for the signicantly high


exural modulus of the laminates in comparison with
their Youngs modulus (Figs. 9 and 12). Besides, the
lower strength of the interlaminar resin should account
for the fact that exural strengths of the laminates are
lower than tensile strengths when the same ber loading
is dealt (Figs. 5 and 11).

before acetylation. It is reasonably deduced that the


interfacial interaction either outside or inside ACSF
bundles in the presence of epoxy is stronger than the
case of ATSF. Similar to the case of ATSF/epoxy discussed above, nevertheless, intercelullar adhesion is
weaker than ber bundles/matrix bonding and cohesive
breakage of ultimate cells is still the main failure mechanism. Moreover, obstruction to cell pull-out and microbril
stretching, exerted by the epoxy sticking to the cell walls,
is much more severe and the increased strength of
acetylated sisal is completely shielded. A relatively high
exural performance of ACSF composite compared to
ATSF and UTSF composites (Fig. 15) give evidence of
the strong interfacial interaction at the two types of
interface proposed in Section 3.2.
Among the composites reinforced by chemically treated bers studied in the current paper, ANSF laminates
have the lowest tensile and exural strengths (Figs. 14
and 15). This should be understood from both the
interfacial eect and the structural variation in the
modied ber itself. When ANSF is compounded with

3.3. Eect of sisal ber treated by other techniques on


the mechanical behavior of composite laminates
According to the investigation on ber treatment, it is
known that both mercerization and acetylation can
improve tensile strength of sisal bers (Table 1). However, tensile strength of ACSF/epoxy composites is even
slightly lower than that of untreated sisal/epoxy (Fig. 14).
The improvement of interfacial bonding in ACSF/ epoxy
is the results of (i) hydrogen bonds between acetyl groups
and hydroxyl or amine groups in epoxy resin, and (ii)
mechanical interlocking between epoxy and the caved
ber surface [Fig. 4(d)] due to the alkali pretreatment

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M.Z. Rong et al. / Composites Science and Technology 61 (2001) 14371447

Fig. 13. Typical stress-deection curves of unidirectional sisal/epoxy


composites in three-point bending test.

Fig. 14. Comparison of tensile properties of unidirectional sisal/epoxy


composites.

epoxy, a chemical reaction in addition to hydrogen


bonding can occur between amino groups on the ber
and epoxide groups in the matrix, resulting in strong
adhesion of ber bundles/matrix interface as implied by
the exural modulus of the composites (Fig. 15). Unlike
ATSF and ACSF, nevertheless, the degree of alkali pretreatment of sisal bers prior to cyanoethylation is quite
low. Few original components in sisal were dissolved out.
According to the above analysis, it is known that pullout of ultimate cells has not become easier in this case.
Considering that the damage of cellulose crystalline
structure due to cyanoethylation reduces tensile strength
of the ber (Table 1), eventually ANSF can not impart
sucient reinforcing eect to the matrix like other chemically treated bers, even under bending tests.
For SCSF reinforced composites, both tensile and
exural strengths are slightly higher than those of UTSF
laminates (Figs. 14 and 15), because amine groups of the
coupling agent can react with epoxy resin. When sisal
ber was rst treated with alkali and then by silane
coupling agent, however, tensile strength of the composite decreased in comparison with ATSF composites

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Fig. 15. Comparison of exural properties of unidirectional sisal/


epoxy composites.

Fig. 16. Comparison of tensile properties of unidirectional sisal/epoxy


composites.

(Fig. 14). It is believed that the coupling agent can


immigrate into the alkali treated sisal bers easily and
its reaction with cellulose could lead to an interfacial
interaction even stronger than the case of ATSF provided the coupling agent takes part in the curing process
of epoxy. Consequently, pull-out of the ultimate cells
with the adhered epoxy and stretching of microbrils in
these cells become more dicult. The increased exural
performance of (AT+SC)SF/epoxy gives supporting
evidence (Fig. 15).
Heat treated sisal has shown superior tensile properties due to the increased crystallinity (Table 1). When
the ber is added to epoxy, tensile and exural strengths
of the composites are higher than those of untreated
sisal composites (Figs. 16 and 17). It should be noted
that exural strength of HTSF composites is lower than
ACSF/epoxy (Figs. 15 and 17), again demonstrating
that exural failure of the laminates depends mainly on
ber/matrix interface rather than ber strength. For the
ber which was treated by alkali and subsequently by heat
treatment, an evident increase in exural strength and
modulus of the composites can be seen when compared to

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M.Z. Rong et al. / Composites Science and Technology 61 (2001) 14371447

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

Fig. 17. Comparison of exural properties of unidirectional sisal/


epoxy composites.

ATSF/epoxy (Fig. 17). In this case, positive synergetic


eect of improved ber strength and strong interfacial
adhesion of ber bundles/matrix play the leading role.
Factually, Youngs modulus of the ATSF composite can
also be greatly increased when ATSF was subjected to
heat treatment [refer to (AT+HT)SF/epoxy in Fig. 16].
The results suggest that a combination of chemical and
physical treatments can leave space for property optimization of natural ber composites.

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

The nancial support by the National Natural Science


Foundation of China (Grant: 59725307), the Key University Teachers Training Program of the Ministry of
Education of China, the Team Project of the Natural
Science Foundation of Guangdong, and the Talent
Training Program Foundation of the Higher Education
Department of Guangdong Province are gratefully
acknowledged.

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