Composites Science and Technology 41 (1991) 165-178

The Effect of Silane Treatment on the Mechanical and

Physical Properties of Sisal-Epoxy Composites

E. T. N. Bisanda* & M. P. Ansell:~

School of Materials Science, University of Bath, Bath, UK

(Received 1 November 1989; revised version received 15 May t990:

accepted 23 May 1990)

ABSTRACT

The surface of sisal fibres has been modified by mercerization and silane
treatment to #nprove adhesion characteristics andmoisture resistance. Silane
treatment is" most effective in reducing moisture uptake q[fibres bl humid
environments. Sisal fibres with and without surface pretreatments hat'e been
combined with epoxy resin to Jorm composite materials. The compressive
strength of these composites is improced by pretreatment but the flexural
strength and st!~hess are not affected. However. in moist environments all
mechanical properties are #nprot'ed by silane treatment.

INTRODUCTION

Cellulose-based natural fibres are a potential resource for making low cost
composite materials, especially in developing tropical countries where these
fibres are abundant. Sisal and jute fibres possess moderately high specific
strength and stiffness and can be used as reinforcement in polymeric resin
matrices to make useful structural composite materials, t Lack of good
interracial adhesion and poor resistance to moisture absorption make the
use of cellulosic fibre reinforced composites less attractive. In this work sisal
fibre surfaces have been treated by mercerization and silane coating and the
resulting physical and mechanical properties of dry and wet sisal-epoxy
composites have been assessed.
* On study leave from the University of Dar es Salaam, Tanzania.
,~ To whom correspondence should be addressed.
165
Composites Science and Technology 0266-3538/91/$03-50 ~ 1991 Elsevier Science Publishers
Ltd, England. Printed in Great Britain
 166 E. /2 3,'. Bisan~h~, M. Pr ,~TgSC//

Fig. I. Fractured sisal fibre bundles.

Sisal fibre is composed of cellulose (78 wt %), lignin (8%), hemicellutoses

(10%), waxes (2%) and about 1% ash.-' Sisal is classified as a hard fibre and is
between 1"0 and 1-5 m in length and 0-1-0.3 mm thick. Fractured fibres are
shown in an electron micrograph in Fig. 1. The fibre is in fact a bundle of
sub-fibres each of which is hollow and the cell walls of which are reinforced
with spirally oriented cellulose in a hemiceltutose and lignin matrix. The
external surface of the fibre cell wall is, however, covered by a layer of
lignaceous material and waxy substances that bond the fibre cell to its
adjacent neighbours. This surface will, therefore, not form a strong bond
with a polymeric matrix. Cellulose is a hydrophilic glucan polymer
consisting of a linear chain of 1,4-fl-bonded anhydroglucose units. 3 The
large amount of hydroxyl groups which occur throughout the structure
accounts for the hydrophilic nature of cellulose. Consequently, in order to
improve interracial bonding, modification of the fibre surface is essential.
Mercerization is one of the oldest methods of treating textile fibres. The
treatment involves soaking the fibres in a dilute solution of sodium
hydroxide. The mercerization treatment improves the fibre surface adhesive
characteristics by removing natural and artificial impurities, thereby
producing a rough surface topography. X-ray examination of native and
mercerized cotton fibres 4 has shown that mercerization changes the form of
the cellulose crystaltites, increasing the amount of amorphous cellulose at
the expense of crystalline cellulose. In addition mercerization leads to fibre
fibrillation, that is, breaking down the composite fibre bundle into smaller
fibres, increasing the effective surface area available for contact with a wet
matrix.
Chemical or irradiation induced removal of some hydroxyl groups has
 Silane treatment and the properties of sisal--epoxy composites 167

been used to improve hydrophobicity and chemical bonding at the

interface. 5-7 Silane interfacial coupling agents widely used on glass fibre to
form stable covalent bonds to both the mineral fibre surface and the resin are
potentially suitable for use on cellulosic fibres. Studies on paper sheetsa that
had been chemically modified with trichloro-s-triazine showed an increase
in contact angle against water, which means the paper became more
hydrophobic. Furthermore, the treatment of wood with an alkoxysilane
coupling agent, 9 ),-methacryloxy-propyltrimethoxysilane decreased its
hygroscopicity and improved the dimensional stability of the wood.
In view of the potential use of sisal reinforced composites in developing
countries, mercerization has been chosen as a surface modification
treatment and in addition silane treatment has been used in view of its
known water-repellent and adhesion-promoting properties.

EXPERIMENTAL METHODS
Fibre treatment

Sisal fibres (Agave sisalana) have been supplied by the Tanzania Sisal
Authority. Only the central part of the fibres, at least 20 cm from each end,
has been used. The fibres have been subjected to the following treatments.

Mercerization
The fibres were first dewaxed by soaking batches of about 200 g of sisal
fibres, 30 cm long, in a 2000 ml solution of benzene and alcohol (methylated
spirit), ratio 1:1, in a sealed glass vessel. The fibres were soaked for 24 h,
rinsed in alcohol, and then rinsed in distilled water. These fibres were then
mercerized by soaking in a 0"5N solution of sodium hydroxide, for about
72 h, rinsed in distilled water and dried.

Silane treatment
An organofunctional silane, A1100 (gamma-aminopropyltriethoxysilane),
was supplied by Union Carbide (UK) Ltd. The A l l 0 0 silane, chemical
formula NH2(CH2)3Si(OC2Hs)3, reacts with water to form a silanol and an
alcohol:
NH2(CH2)3Si(OC2Hs)3 + 3H20 = (HO)3Si(CH2)3NH 2 + 3(C2HsOH)
In the presence of moisture the silanol then reacts with the hydroxyl groups
attached to the glucose units G of the cellulose molecules in the cell wall,
thereby bonding itself to the cell wall with further rejection of water:
NH3(CH2)3Si(OH)a + H20 + GOH = NH2(CH2)aSi(OH)2OG + 2H20
168 E. T. N. Bisanda. M. P. Ansell

To assess the effectiveness ofsilane in providing moisture resistance to fibres,

a 100% solution of A l l 0 0 silane was used. For work on the moisture
resistance of composites, the fibres were treated using silane that had been
diluted to 5% in methylated spirits, for reasons of economy. A 0" 1,~1solution
of ceric a m m o n i u m nitrate (CAN) was used as catalyst. The fibres used for
making composites were treated in batches by soaking about 150g of the
mercerized fibres in 1500 ml of the silane/CAN solution (2:1), for about 24 h
at room temperature. The fibres were then rinsed in distilled water and dried.

Resin system

A room-temperature cure epoxy resin system, supplied by Ciba Geigy

Plastics, Araldite LY 1927 GB plus hardener HY 1927 GB, has been used in
this work.

Moulding and cure of unidirectional composites

Two compression moulds shown in Figs 2(a) and (b), have been used to
produce rectangular section and round section unidirectional bars tbr
flexural bending and compression tests, respectively. In small batches, a
known weight of fibres was soaked with resin inside the mould, followed by
cold compression to 5 tonnes in a press to remove all excess resin and attain
designated dimensions. The composites were first allowed to gel at room
temperature for about 24 h while under pressure. The composites were then
released from the mould and cured by heating at 60°C for 2 h, at 80°C for
another 2 h, and then postcured at 100°C overnight.

Physical properties

Fibre volume fraction

The fibre volume fraction vr, was calculated from the equation

~,f = (mf/pf)/ V
where mf is the weight of fibres in a composite of volume II, and pf is the
density of the fibres, taken as 1.45 g/cm 3 for sisal. 1°

Moisture absorption
The fibres to be tested were in the following conditions:
(a) original or 'as received' condition;
(b) dewaxed by soaking in benzene/alcohol 1:1 solution for 72 h;
(c) mercerized in a IN solution of sodium hydroxide for 72 h;
(d) mercerized as above, then treated in 100% A1100 silane for 2 h.
 Silane treatment and the properties of sisal-epoxy composites 169

(z) (b)

Fig. 2. Compression moulds for producing (a) flexural and (b) compressive
unidirectionally-reinforced samples.

Fibre samples of about I g were obtained from each of the above treated
fibres. The samples were dried in a vacuum chamber at 60°C and weighed on
a sensitive balance (___0.001 g). They were then exposed to moisture in a
conditioning chamber at 65% RH, 20°C, for short intervals of time in which
the weight changes of the sample were monitored.

Water absorption of composites

Water absorption tests of composites were carried out on cylindrical
specimens, with a diameter of 12 mm and a length of 18 mm, similar to those
used in compression tests. Specimens were first dried by heating in an oven at
100°C for about 2 h, weighed and then soaked in a bath of distilled water at
room temperature, After 72 h the specimens were weighed again.

Density
The density of the composites was determined by direct measurement of the
mass of a known volume of the composite. Again, cylindrical composites
were used for these tests.

Mechanical testing

Compression tests
These tests have been carried out on dry and wet composites in accordance
with BS 2782: Part 3: Method 345A: 1979. The specimens were in the form of
right cylinders 12 m m in diameter and 18 m m in height. An Instron 1195
machine was used and all tests were performed at a cross-head speed of
1 mm/min. The wet composites had been soaked in distilled water for 5 days.
For each composite rod produced with a particular fibre volume fraction,
five dry and five wet specimens were tested.
 170 E. 7". N. Bisanda, M. P. Ansel[

Flexural tests
Three-point loading tests have been performed on wet and dry composites in
accordance with ANSI/ASTM D 790-71 (1978) on an Instron 1122 machine.
Test specimens 125 mm long, 12.7 mm wide and about 5 mm thick were used
at a loading span of 80 ram. Owing to limitations on the length of composites
that could be moulded, only two specimens could be obtained for testing
from each composite rod produced.

E X P E R I M E N T A L RESULTS A N D DISCUSSION

Physical properties

Moisture absorption
The moisture gain as a percentage of sample dry weight has been plotted
against time, Fig. 3, and it is clear that only silane-treated fibres are able to
resist moisture uptake at 20°C and 65% RH. At all stages of treatment prior
to silane treatment, fibre moisture uptake is comparable.

8 .....

6'

• 4
@
Q
@
0~

A
NUN
•~ 0

-2

-4 I I I I I

0 2OO 4O0 60O 80O IOO0 1200

Time (rain}
Fig. 3. Effect of fibre treatment on moisture absorption~ at 20°C, 65% RH. [], untreated;
t , mercerized; m, silane treated; 0 , dewaxed.
 Silane treatment and the properties of sisal-epoxy composites 171

Water absorption of composites

The water absorbed by sisal-epoxy composites as a percentage of dry weight
after 72 h immersion has been plotted against the fibre volume fraction in
Fig. 4. Predictably, the composites containing untreated fibres absorb most
water and the silane-treated composites absorb least. Composites
containing mercerized fibres exhibit, perhaps surprisingly, intermediate
behaviour, suggesting that changes in surface chemistry have reduced the
affinity of fibres for moisture.
The results of density measurements on sisal--epoxy composites, Fig. 5,
subjected to various surface treatments, are coplotted with a theoretical line
based on the density of the epoxy resin and sisal fibres. Results for all but as-
received fibres lie close to the theoretical line, so that in general the
composite density increases linearly with the fibre volume fraction.
However, with untreated fibres, this increase is compromised by high
porosity resulting from poor wettability.

Mechanical testing

The effect offibre treatment on the compressive strength is shown in Fig. 6. A

linear regression line has been fitted through the strength values for the

30

y=-7.824+0.58flx R==0.99

Untreated
20'
Z \

J y • •
g

Silane treated

y= -1.871+0.180x R=0.94

Fibre v o l u m e fraction (%1

Fig. 4. The effect of fibre treatment on the resistance of sisal-epoxy composite to water
absorption, m silane treated; 0 , mercerized; E~, untreated.
 172 E. T. N. Bisanda, 34. P. Ansell

I..5"

L4
y=l.17*0.000x R=I.~ /
1.3

lU

1.2'

1.1 • n * u • i " l

120

Fibre V o l u m e fraction (%}

Fig. 5. Effect of fibre treatment on sisal-epoxy composite density. ~ , untreated;,@,
mercerized: I , silane treated; O , epoxy-sisal.

y = 120.314 + 1.60Sx R = 1.00

(Silane)

II

¢I

ra
~ 140

8
(Untreated)

! I I [ I

0 10 20 30 40 50 60

Fibre v o l u m e ~action (%}

Fig. 6. Effect of fibre treatment on the compressive strength. El, untreated;,~, mercerized;
I , silane treated.
 Silane treatment and the properties of sisal-epoxy composites 173

silane treated data points and this corresponds closely to the mercerized
data. Untreated fibres produce composites with significantly less strength
than treated fibres but in each case a consistent variation with fibre volume
fraction is observed.
The failure mode of unidirectional sisal-epoxy composites during
compression in the fibre direction is a combination of shear buckling,
bulging and cleavage in axial planes. Untreated fibre composites fail
predominantly by cleavage in loading planes with little bulging and shear
buckling. In a compression test the waxy surface of the untreated sisal fibre
allows an easy mode of failure which a strongly bonded interface is able to
resist. The silane treated composites on the other hand, undergo
considerable lateral deformation before finally failing by shear deformation,
usually indicated by a zone of kinked fibres making an inclination of about
45 ° to the loading axis.
In contrast the flexural strength and flexural modulus of sisal-epoxy
composites plotted versus volume fraction, Figs 7 and 8, respectively, show
that fibre treatment has little effect on flexural mechanical properties. In a
three-point bend test a sample will experience tensile, compressive and shear
loads and the failure mechanism, and hence strength, is likely to differ from
that in an all-compressive test. The fracture in silane treated and mercerized

40O

m II

B • tJ

W I tJ

81 g

100 '- e i |

20 3O 4O 8O
Fibre v o l u m e fzscUon (%)
Fig. 7. Effect of fibre treatment on the flexural strength. [], untreated; ~,, mercerized; l ,
silane treated.
174 E. 7". N. Bisanda, AI. P. An.w~~

24
a m

41,

@e

[]
g
0
@D

14

I~1 [3
ra I~
12 I I i

20 30 40 50 60

Fibre v o l u m e fraction (%)

Fig. 8. Effect of fibre treatment on the flexural modulus. [5], untreated; ~ , mercerized; as,
silane treated.

sisal-epoxy composite samples tested appears to start by tensile fracture of

the matrix on the tensile side of the loading plane. Other cracks that run in
the fibre direction (shear plane) develop from the initial crack as fracture
proceeds towards the neutral plane. In the untreated fibre composites, there
is less tensile fracture, excessive deformation and virtually no shear plane
cracking, possibly due to lack of bonding.
It is not surprising that the flexural modulus remains independent of fibre
treatment but dependent on volume fraction, Fig. 8, because the modulus is
calculated prior to the onset of failure.
When subjected to soaking in distilled water for 5 days the variation in
flexural strength with fibre volume fraction becomes dependent on fibre
treatment, Fig. 9. The silane treated sisal-epoxy composites are in general
more resistant to water uptake, and are hence stronger, than composites
containing fibres which have received other treatments. However, there is a
considerable amount of scatter and it is difficult to draw firm conclusions
relating to the relative merits of fibre treatments with respect to wet flexural
strength.
The mean compressive strength, flexural strength and flexural modulus
have been evaluated for composites containing 40 vol % fibres, and these
values are presented in Table 1 for dry and wet composites, respectively.
 Silane treatment and the properties of sisal-epoxy composites 175

~{= 1 5 1 . 0 3 8 ÷ 2 . 1 5 4 x R=0.78

(Stla.ne}
U

m @

y = 160.877 + 0 . 9 9 5 x R=0.45

• (Mercerized}

1.1~ -P
30 40 50 60
Fibre volume fraction (%}
Fig. 9. Effect of water absorption on the flexural strength. I-:7,u n t r e a t e d ; , , mercerized: U,
silane treated.

General discussion

The data presented in Table 1 show that sisal fibre generally improves the
overall mechanical properties of epoxy in composites. Both the strength and
stiffness are improved. However, the use of these fibres in wet environments
may compromise some mechanical properties of the resin, as shown by the
decrease in compressive strength.
Mercerization greatly improves the resin pick up, or wettability of the
fibres as is evidenced by the increase in density of the composite. It is believed
that this treatment results in improvement in the interfacial bonding by
giving rise to additional sites of mechanical interlocking, hence promoting
more resin/fibre interpenetration at the interface. This is reflected in the 21%
rise in the compressive strength (Table I) of dry composites. The higher
amount of resin pick up could also account for the reduction in water
absorption (Fig. 4) and hence improved mechanical properties under wet
conditions.
The treatment of mercerized sisal in silane produces very little change in
the mechanical properties of dry composites. The compressive strength (Fig.
6), the flexural strength (Fig. 7) and the flexural modulus (Fig. 8) remain
176 E. 7". N. Bisanda. M. P. Ansell

TABLE 1
Mean Mechanical and Physical Properties of Sisal-Epoxy Composites of Fibre Volume
Fraction 0-40

Material,, / Compressive Flexural Flexural Relative Water

treatment strength strength modulus density absorbed (%)
(MPa) (MPa) (GPa) after 72h

Epoxy resin 120.0 95.0 31 1-17

Untreated/dry 148.0 266.5 15.93 t' 14 ....
Mercerized/dry 183.1 262.1 l 7.63 1.24 .....
Silane/dry 184'8 244.5 17.36 1"25 ~--
Untreated/wet 62.53 221.7 9.15 -- 15.6
Mercerized/wet 75-83 200.7 10-12 -- 9.0
Silane/wet 98.53 237.2 12.33 -- 5.0

unchanged. However, improvements in the mechanical performance of wet

composites, and hence water resistance, are achieved. The treatment in
100% silane produces fibres that are almost hydrophobic, as has been shown
in Fig. 3. The flexural properties of wet silane treated sisal-epoxy composites
are superior to those not treated in silane (Fig. 9). The compressive strength
is increased by a further 30%, the flexural strength by 18%, and the flexurat
modulus by 21% in the composite of 0-40 fibre volume fraction. This is
perhaps due to improved interfacial bonding arising from the use of the
silane together with the low water absorption of the composites with silane
treated fibres (Fig. 4). The presence of water molecules at the interface tends
to replace the resin-fibre covalent bond by weaker hydrogen bonds, hence
silanes can play an important role in reducing the water absorption in
cellulosic-fibre reinforced composites. As expected, the flexural strength of
mercerized and silane treated composites increases linearly with fibre
volume fraction in accordance with the rule of mixtures.
Although a hydrophobic fibre surface may be created by silane treatment,
as has been demonstrated in Fig. 3, it is not possible to prevent water from
entering the composite by capillary action, as long as the fibre ends are
exposed to the external surface. The fibres have a central hollow region, the
lumen, which may give access to water penetration by capillarity, more so in
composites with high fibre content. For practical purposes, it may therefore,
be necessary to seal offthe external surface by water-repellents, so as to keep
water uptake in the composite to a minimum.

CONCLUSIONS
. Treatment of mercerized sisal in silane results in improved moisture
resistance in both unbonded and bonded fibres.
 Silane treatment and the properties of sisal-epoxy composites 177

2. Mercerization of sisal fibres leads to improved wettability and resin

uptake so water absorption in sisal-epoxy composites is reduced.
3. It is possible to produce sisal--epoxy composites with up to 60% sisal
fibre by compression moulding, and the mechanical properties of the
composites increase linearly with fibre volume fraction.
4. Mercerization and silane treatment improve the compressive
strength without significant effect on flexural properties of dry sisal
epoxy composites.
5. Water absorption leads to considerable reduction in the mechanical
properties of sisal-epoxy composites. However, these properties are
improved by silane treatment of mercerized fibres.
Overall, the incorporation of sisal fibres in an epoxy resin matrix produces
stiff and strong structural composite materials. The treatment of the sisal
fibres in silane, preceded by mercerization, provides improved wettability,
mechanical properties and water resistance.

ACKNOW LEDGEM ENTS

We wish to acknowledge our thanks to the Swiss Development Cooper-

ation, for their financial support through the Tanzania government that has
made this work possible. We also thank Union Carbide for providing free
samples of Al100 silane, and Tanzania Sisal Authority for donating the
sisal.

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