Composites Science and Technology 63 (2003) 861–869

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Effect of fibre surface modification on water-sorption

characteristics of oil palm fibres
M.S. Sreekala1, S. Thomas*
School of Chemical Sciences, Mahatma Gandhi University, Kottayam, Kerala, 686 560, India

Received 16 May 2002; received in revised form 6 November 2002; accepted 8 November 2002

Abstract
Natural fibres have proved to be an excellent reinforcement in polymers. The main disadvantage of the natural fibres to be used
as reinforcement in polymers for structural applications is their hydrophilic nature. Oil palm fibres have been found to be an
excellent reinforcement in phenolic matrices. A detailed investigation on the water sorption characteristics of oil palm fibres has
been carried out. Various fibre surface modifications such as mercerization, latex coating, gamma irradiation, silane treatment,
isocyanate treatment, acetylation and peroxide treatment were tried to reduce the hydrophilicity and thereby decreasing the sorp-
tion characteristics. The effects of treatments on the sorption characteristics of oil palm empty fruit bunch fibre in distilled water at
four different temperatures were investigated. Changes in physical and chemical modifications of fibres upon different treatments
changed the water sorption behaviour. Treatment reduced overall water uptake at all temperatures. Hydrophilicity of the fibres
decreased upon many modifications, which decreases water uptake. The effect of sorption on the mechanical performance of the
treated and untreated fibres was also investigated. It was found that the mechanical properties of the fibres decrease upon sorption
and regains on desorption.
# 2003 Elsevier Science Ltd. All rights reserved.
Keywords: D. Scanning electron microscopy; Natural fibre; Water sorption; Chemical modification; Tensile properties

1. Introduction The present investigation dealt with the treatment

Natural fibres have proven their applicability as rein-
forcement in polymers. The main disadvantage con-
cerning the use of natural fibres are their suceptibility to
moisture uptake [1–5]. Recently we have succeeded in
utilizing oil palm empty fruit bunch fibre as a reinfor-
cement in phenol-formaldehyde resin and the resulting
composites have shown excellent mechanical perfor-
mance [1]. We have already reported elsewhere, the
structural and physical properties of these fibres [2].
Yamini et al. investigated the strength properties of par-
ticle boards prepared from OPEFB fibre and UF resin
[3]. We have investigated water sorption abilities of the
untreated oil palm fibres and reported elsewhere [6].
* Corresponding author. Tel.: +91-481-598015/598303; fax: +91-
481-561190.
E-mail addresses: sreekalams@yahoo.co.in (M.S. Sreekala),
sabut@md4.vsnl.net.in (S. Thomas).
1
Present address: Institute for Composite Materials Ltd.,
University of Kaiserslautern, Erwin-Schrödinger-Strasse, D-67663,
Kaiserslautern, Germany.
0266-3538/03/$ - see front matter # 2003 Elsevier Science Ltd. All rights reserved.
doi:10.1016/S0266-3538(02)00270-1
effects on the water sorption characterisatics of oil palm
fibres in distilled water. The influence of temperature on
the sorption was investigated. Distilled water contains
no impurities. They contain mainly calcium, magnesium
and carbonate ions. Mercerization, introduction of
coupling agents like isocyanate and silane, g irradiation
effects, latex coating, acetylation and peroxide treat-
ment on fibre were done to reduce the water sorption.
Tensile properties of untreated and treated fibres in
swollen stage and in the desorbed stage were analysed.
Tensile strength, percentage elongation at break and
tensile modulus at 5% elongation were evaluated. Ten-
sile fracture mechanism of the fibres were analysed
using scanning electron microscopic examination of the
fracture surfaces.
2. Materials and experimental
The fibres were collected from local sources. The
empty fruit bunch is subjected to retting. OPEFB fibres
862 M.S. Sreekala, S. Thomas / Composites Science and Technology 63 (2003) 861–869

were then cleaned, washed and dried. The physical and
chemical characteristics of the fibres are given in Table 1.
Chemicals used for fibre surface modifications were of
reagent grade which includes sodium hydroxide, NR
latex, acetic anhydride and benzoyl peroxide. The cou-
pling agents used are triethoxy vinyl silane and toluene
diisocyanate. They were procured from Union Carbide
Company, Montreal, Canada and PolySciences, USA
respectively.
2.1. Fibre treatments
2.1.6. Acetylation
Fibres were pretreated with 2% sodium hydroxide for
about half an hour in order to activate the OH groups
on the cellulose and lignin. Fibres were then subjected
to acetylation with acetic anhydride in acetic acid med-
ium. Concentrated H2SO4 acts as a catalyst in this
reaction.
2.1.7. Peroxide treatment
Fibres were treated with benzoyl peroxide from acce-
tone solution after alkali pretreatment.

The OPEFB fibre was subjected to the following
treatments in order to improve sorption characterstics.
2.1.1. Mercerization
Fibres were immersed in 5% sodium hydroxide solu-
tion for about 48 h. Fibres were then washed many
times in distilled water and finally washed with water
containing little acid and dried.
2.1.2. Latex coating
Fibres were given a latex coating by dipping it into
natural rubber latex having 10% DRC content after
pretreatment with NaOH.
2.1.3. g radiation treatment
Fibres were exposed to g radiation at a dose rate of
0.1 Mrad/h for about 30 h.
2.1.4. Silane treatment
The fibres were pretreated with alkali and dipped in
alcohol-waxes mixture (60:40) containing tri-ethoxy
vinyl silane coupling agent. The pH of the solution is
maintained between 3.5 and 4. Fibres were then washed
in distilled water and dried.
2.1.5. TDIC treatment
The alkali treated fibres were taken in a round bot-
tomed flask and soaked in chloroform containing dibu-
tyl tin dilaurate catalyst. Toluene diisocyanate was
added dropwise into the flask using a pressure equaliz-
ing funnel. The reaction was allowed to take place for 2
h with continuous stirring. Fibres were purified by
refluxing with acetone and then washed with distilled
water and dried in an oven.
2.2. Water sorption studies
About 0.5 g of dried oil palm empty fruit bunch fibre
having an appropriate length of 5 cm were taken for the
water sorption study. The diameters of the fibres were
noted. The samples were immersed in distilled water
having different temperatures 30, 50, 70 and 90
C in a
thermostatically controlled air oven. Increase in weight
of the samples was noted at specific time intervals. This
process is continued until equilibrium is reached. The
values obtained are found to be perfectly reproducible.
The mole percent uptake Qt for water by 100 g of the
polymer was plotted against the square root of time.
The Qt value can be expressed as
MeðwÞ=MrðwÞ
Qt ¼  100 ð1Þ
MiðsÞ
where Me(w) is the mass of water at equilibrium, Mr(w)
is the relative molecular mass of water i.e. 18 and Mi(s)
is the initial mass of the sample. When equilibrium was
reached, Qt was taken as the mole per cent uptake at
infinite time. i.e. Q1. The water sorption of fibres was
calculated as number of moles of water absorbed by 100
g of the fibre.
Values of the kinetic parameters n and k for sorption
by oil palm fibres in all the systems are calculated using
Eq. (2) [7]
log ðQt =Q1 Þ ¼ logk þ nlogt ð2Þ
where
Qt=mol% water uptake at time t;
Q1=mol% water uptake at equilibrium;
k=a constant;
t=time.

Table 1 Linear regression analysis is used to calculate the

Physical and chemical characteristics of oil palm fibres values. The value of n represents the mechanism of
sorption which lies around 0.1 for oil palm fibres. It
Fibre Lignin Cellulose Density Diameter Ash
denotes a non-Fickian mode of diffusion. The deviation
content content (g/cc) (mm) content
(%) (%) (%) from the linear diffusion is due to the time dependent
response of the natural fibre. The k value indicates the
OPEFB fibre 19 65 0.7–1.55 0.015104– 2 interaction between the penetrant and the fibre. The
0.05104
value is found to increase as the temperature increases.
 M.S. Sreekala, S. Thomas / Composites Science and Technology 63 (2003) 861–869 863

Diffusion coefficient, sorption coefficient and perme-
ability coefficient of oil palm fibres for all the systems
tried. Diffusion coefficient explains the rate at which a
diffusion process takes place. It is the rate of transfer of
the diffusing substance across unit area of a section
divided by the space gradient of concentration at the
section [8]. The diffusion coefficient, D is calculated
using the following equation [7],
D ¼ ðh=4Q1 Þ2
where
uptake due to the capillary action is also reduced. The
equilibrium mol% uptake for the treated fibres in dis-
tilled water at different temperatures are given in
Table 2. As the temperatures increase generally the
uptake decreases. However, there are irregularities
observed for different treated systems. The decrease in
uptake value for treated fibres will be attributed to the
ð3Þ

h=Initial average diameter of the fibres; and

=Slope of the initial linear portion of the sorption
curves.

The diffusion coefficient characterizes the ability of

water molecule to diffuse into the fibre.
The sorption coefficient (S) is calculated using Eq. (4)
S ¼ M1 =M0 ð4Þ
where

M1=Mass of the water sorbed at equilibrium swelling,

M0=initial mass of the sample.

It gives a measure of the extent of sorption.

Permeability coefficient, a net effect of diffusion and
sorption are also calculated. It gives an idea about the
amount of water permeating through uniform area of Fig. 1. Sorption curves for distilled water/treated OPEFB fibre at
the sample per second. The permeability coefficient is 30
C.
given by Eq. (5).
P ¼ D:S ð5Þ
Tensile testings of the fibres were done on a FIE ten-
sile testing machine TNE-500 according to ASTM
standards. The scanning electron microscopic studies
were done inorder to understand the surface character-
istics and fibre structure.

3. Results and discussion

3.1. Effect of OPEFB fibre treatment on the mechanism

of sorption

Figs. 1–4 give the sorption behaviour of untreated

and treated OPEFB fibre in distilled water at 30, 50, 70
and 90
C respectively. The porous structure of oil palm
fibres lead to an initial capillary uptake which results in
the large initial uptake in all cases. At lower tempera-
ture the untreated oil palm fibre shows a two step sorp-
tion behaviour. It is already reported that in cellulosic
fibres a two step behaviour can occur as case II sorption
behaviour [6,8]. Treatment considerably reduces the Fig. 2. Sorption curves for distilled water/treated OPEFB fibre at
overall water uptake at all temperatures. The initial 50
C.
864 M.S. Sreekala, S. Thomas / Composites Science and Technology 63 (2003) 861–869

physical and chemical changes occurred to the fibres
upon different treatments. The scanning electron
micrographs of the untreated and treated fibre surfaces
reveals the changes in the porous structure of the fibre
(Fig. 5). Fig. 6 shows schematically the different chemi-
cal bonds formed on the fibre surface during treatments.
Mercerization results in the leaching out of the amor-
phous waxy cuticle layer (Fig. 5b). This may reduce the
sorption. Latex coating on the fibre partially masks the
pores on the fibre surfaces (Fig. 5c). Decreased sorption
at the capillary region is observed for the latex coated
fibres. Gamma ray irradiation partially eliminates the
porous structure and causes microlevel disintegration of
the fibre (Fig. 5d). Reduced sorption is observed due to
decreased capillary action. Introduction of coupling
agents and acetylation make the fibre hydrophobic and
thus reducing moisture absorption. Silane treatment
gives a coating on fibre surface (Fig. 5e). Adhering par-
ticles are observed on the TDIC treated fibre surface
(Fig. 5f). Acetylation also removes the waxy layer from
the surface (Fig. 5g). Fibrillation is observed in the per-
oxide treated fibres and may be due to the leaching out
of the waxes, gums and pectic substances (Fig. 5h).
Shrinkage of the micropores, collapse of the capillaries
upon treatments may block the capillary absorption. It
is found that TDIC treated fibre shows least water

Table 2
Values of Q1 for the treated OPEFB fibres in distilled water at
different temperatures

Treatment Temperature (
C) Q1 (mol%)

Untreated 30 13.37
50 11.17
70 10.15
90 8.71
Fig. 3. Sorption curves for distilled water/treated OPEFB fibre at
Mercerization 30 7.26
70
C.
50 7.74
70 6.91
90 7.37
Latex 30 7.65
50 6.15
70 6.06
90 5.89
g irradiation 30 7.36
50 7.17
70 6.68
90 7.37
Silane 30 8.51
50 6.90
70 7.14
90 6.27
TDIC 30 6.94
50 6.15
70 6.61
90 6.68
Acetylated 30 7.48
50 6.94
70 6.44
90 6.59
Peroxide 30 7.44
50 6.56
70 6.76
Fig. 4. Sorption curves for distilled water/treated OPEFB fibre at 90 6.59
90
C.
 M.S. Sreekala, S. Thomas / Composites Science and Technology 63 (2003) 861–869
Fig. 5. Scanning electron micrographs of OPEFB fibre surface, (a) untreated (400), (b) mercerized (400), (c) latex coated (200), (d) g irradiated (200), (e) silane treated (101), (f) TDIC
treated (100), (g) acetylated (200), (h) peroxide treated (200).

865
866 M.S. Sreekala, S. Thomas / Composites Science and Technology 63 (2003) 861–869
Fig. 6. Major chemical modifications happened to the fibres on treatments.
sorption due to its high hydrophobic nature. It is
reported by Joly and coworkers that alkyl isocyanate
treatment on cotton cellulose fibres leads to decreased
water uptake [9]. The interstices between the groups of
microfibrils of the fibre would be blocked by the linked
agents which reduce the water accessibility.
Table 3 gives the values of parameters n and k. In
most cases the value of n lies around 0.1. Diffusion and
sorption of moisture are maximum at 30
C (Table 4).
Values of diffusion coefficient, sorption coefficient and
permeability coefficient show major decrease upon fibre
treatment. The free hydroxyl groups on the fibre surface
are ammenable to modifications. Treatments make the
fibre surface less hydrophilic. This will decrease the
water uptake and thus the diffusion coefficient. Excep-
tionally there is a very high increase in diffusion coeffi-
cient observed for all treatments at 30
C. At lower
temperature the amorphous waxy materials binds the
water molecules to the fibre surface which facilitates the
water sorption. This accounts for the increase in diffu-
sion coefficient at lower temperatures. Moisture is
mainly absorbed in the amorphous region of the fibre.
Decrease in the diffusion coefficient on treatments
points out the changes occured in the amorphous region
of the fibre.
3.2. Tensile tests
3.2.1. Untreated fibre
Major tensile properties of the fibres in the swollen
stage and in the desorbed stage are given in Table 5.
Large fibre to fibre variations in tensile properties are
observed for the fibres. Therefore an average value of
each property is reported. The tensile strength values
decreased upon sorption. The decrease in the tensile
strength is most prominent in salt water sorbed fibre.
Around 30% decrease is observed in this case. The ten-
sile strength of the desorbed fibres also shows consider-
able decrease. The elongation at break of the fibres
increased considerably in the swollen stage. The elon-
gation at break of the desorbed fibre is greater than the
original value. Fig. 7 shows the stress–strain chracter-
istics of OPEFB fibre, both in the desorbed stage and in
the swollen stage. A major slope change is observed at
lower elongations for the swollen and desorbed fibres
irrespective of the virgin fibre. Swollen and desorbed
fibres show initial crystalline, then elastic and finally
crystalline stress–strain behaviour. Water sorption
reduces the crystallinity of the fibres. Modulus of the
fibres shows considerable variation on sorption. Mod-
ulus at 5% elongation of OPEFB fibres decreases upon
 M.S. Sreekala, S. Thomas / Composites Science and Technology 63 (2003) 861–869 867

sorption and desorption. Mannan and Talukder [10]
investigated the stress–strain behaviour and other ten-
sile properties of jute fibres. They have obtained a two
stage elastic elongation due to the amorphous and
crystalline phase of the fibres. Mechanical performance
of the fibres depends on the chemical structure, cellulose
content, microfibrillar angle etc. Decrease in the micro-
fibrillar angle and increase in cellulose content enhances
the mechanical properties of the fibre. Lignin and
hemicellulose play a cementing role in the three dimen-
sional network of the fibre structure. The amorphous
phase of the fibres accounts for the high elongation of
the fibres. On sorption, water molecules enter into the
spaces between the cellulose fibrils and microfibrils. The
microporous nature of the oil palm fibres helps the
retention of moisture on to the fibres. The presence of
water molecules destroys the lignin cellulose network
thereby decreasing the strength properties. The amor-
phous phase becomes more active in the swollen stage
which accounts for the high elongation behaviour.
Fig. 8 is the scanning electron micrograph of tensile
fracture surface of OPEFB fibre. The structural failure
of the fibres on application of stress is clear from the
micrograph. The fractured surface shows irregularities
in its morphology. As the applied stress increased the
weak primary cell wall collapses and decohesion of cells
occurs which leads to the failure of the fibre.
3.2.2. Effect of fibre treatment on the tensile properties
of the OPEFB fibre on sorption
Tensile properties of the treated OPEFB fibre in the
unswollen and swollen stage are given in Table 5.
Treatment reduces the strength of the fibres except for
silane treatment. Treatments lead to the breakage of the
bound structure and disintegration of the noncellulosic
materials. This will reduce the strength of the fibres. The

Table 4
Table 3
Values of diffusion coeffient, sorption coeffient and permeability coef-
Values of n and k for treated OPEFB fibres in distilled water at dif-
ficient at different temperatures for treated OPEFB fibre systems
ferent temperatures
Treatment Temperature D107 S P107
Treatment Temperature n k
(
C) (cm2 S1) (g/g) (cm2 S1)
(
C) (g/g min2)
Untreated 30 0.60 2.41 1.44
Untreated 30 0.049 0.438
50 13.00 2.01 26.15
50 0.149 0.481
70 38.49 1.83 70.31
70 0.209 0.509
90 26.71 1.57 41.89
90 0.155 0.621
Mercerization 30 4.93 1.31 6.44
Mercerization 30 0.131 2.000
50 0.62 1.39 0.87
50 0.043 1.270
70 0.70 1.24 0.87
70 0.038 1.230
90 1.02 1.33 1.35
90 0.050 1.310
Latex 30 12.30 1.38 16.93
Latex 30 0.265 4.120
50 56.38 1.11 62.45
50 0.137 1.970
70 5.46 1.09 5.96
70 0.118 1.730
90 7.61 1.06 8.07
90 0.158 2.100
g irradiation 30 6.21 1.33 8.23
g irradiation 30 0.171 2.570
50 1.50 1.29 1.94
50 0.077 1.550
70 6.35 1.20 7.64
70 0.114 1.650
90 3.43 1.15 3.95
90 0.120 2.040
Silane 30 7.99 1.38 10.99
Silane 30 0.200 3.350
50 2.78 1.24 3.46
50 0.116 2.030
70 6.28 1.28 8.07
70 0.134 1.920
90 4.68 1.13 5.28
90 0.122 1.810
TDIC 30 0.301 4.040 TDIC 30 20.18 1.25 25.22
50 0.266 3.230 50 17.61 1.11 19.48
70 0.235 2.500 70 19.49 1.19 23.18
90 0.206 2.390 90 14.72 1.20 17.70
Acetylated 30 0.194 3.370 Acetylated 30 5.36 1.35 7.22
50 0.146 2.490 50 4.87 1.25 6.08
70 0.109 1.860 70 3.52 1.16 4.07
90 0.159 2.310 90 7.62 1.19 9.03
Peroxide 30 0.130 2.100 Peroxide 30 4.33 1.34 5.80
50 0.080 1.590 50 0.72 1.18 0.85
70 0.085 1.540 70 2.50 1.22 3.04
90 0.079 1.450 90 0.81 1.19 0.96
868 M.S. Sreekala, S. Thomas / Composites Science and Technology 63 (2003) 861–869

elongation properties show sharp increase on modifi- were found to decline. As expected higher elongation is
cations except for silane treatment. Young’s modulus of observed in the swollen stage.
the fibre shows enhacement upon mercerization and The tensile stress–strain behaviour of the treated
silane treatment. This may be attributed to the modifi- OPEFB fibre in the unswollen and swollen stage are
cations that occurred at the cellulose region of the shown in Figs. 9 and 10. The silane treated fibre can
fibres. In the swollen stage the strength and modulus withstand higher stress than the untreated fibre. The
fibre became more elastic upon treatments. This is evi-
dent from the slope change of the stress–strain curves
Table 5 after an initial linear sorption. Untreated, silane treated
Tensile properties of the treated OPEFB fibre and mercerized fibres exhibit brittle behaviour which is
Treatment Fibre Tensile Elongation Young’s due to its crystalline nature. The crystallinity of the fibre
strength at break modulus is due to the increased molecular interactions due to the
(MPa) (%) (MPa)

Untreated Unswollen 248 (12) 14 (0.8) 6700 (25)

Swollen 224 (11) 40 (1) 2200 (20)
Mercerization Unswollen 224 (11) 16 (0.9) 5000 (48)
Swollen 170 (9) 35 (1) 265 (15)
Latex Unswollen 98 (3) 23 (1) 1850 (14)
Swollen 82 (2) 29 (1) 455 (10)
g irradiation Unswollen 88 (4) 25 (0.9) 1600 (14)
Swollen 41 (4) 33 (0.8) 190 (12)
Silane Unswollen 273 (10) 16 (0.7) 5250 (60)
Swollen 238 (9) 20 (0.8) 2500 (30)
TDIC Unswollen 160 (4) 22 (1) 2000 (11)
Swolllen 84 (6) 37 (1) 341 (8)
Acetylated Unswollen 143 (8) 28 (1) 2000 (25)
Swollen 81 (7) 41 (1.1) 341 (10)
Peroxide Unswollen 133 (5) 24 (1.1) 1100 (12)
Swollen 84 (5) 30 (1) 190 (8)

Figures in parentheses=Standard deviation. Fig. 8. Scanning electron micrograph of tensile fracture of OPEFB
fibre.

Fig. 7. Stress–strain behavior of OPEFB fiber in virgin, desorbed and Fig. 9. Stress–strain behaviour of treated OPEFB fibre in the normal
swollen stage. stage.
 M.S. Sreekala, S. Thomas / Composites Science and Technology 63 (2003) 861–869
Fig. 10. Stress–strain behaviour of treated OPEFB fibre in the swollen
stage.
above treatments. Crystallinity of the fibre is dependent
on the structural regularity, cellular arrangement, sec-
ondary interactions within the fibre etc. Treatments like
latex coating leads to physical interaction through the
micropores present on the fibre surface. The elongation
of the fibre increased upon treatments such as isocya-
nate, peroxide, acetylation, latex coating and gamma
irradiation in the unswollen stage. In the swollen stage,
all treated fibres except silane treatment exhibit a linear
increase in stress without significant slope change. The
exceptional behaviour of the silane treated fibre will be
due to the decreased water absorption. The elongation
at break of the fibres considerably increased upon sorp-
tion. Fibre surface modification leads to major changes
in the fibrillar structure and removal of amorphous
components. This affects the slope changes and fracture
pattern of the fibres.
869
4. Conclusions
In this work, the effect of fibre surface modification
on water sorption behaviour of oil palm empty fruit
bunch fibre has been investigated. Sorption behaviour
of distilled water at 30, 50, 70 and 90
C was evaluated.
At lower temperature a two step behaviour is observed.
The diffusion mechanism for all the systems was found
to be non-Fickian. This is evident from the kinetic
parameters. Treatment reduces the water uptake at all
temperatures. The decrease is due to its physical and
chemical changes occurred to the fibres on modifi-
cations. The diffusion coefficient, sorption coefficient
and permeability coefficient decreased upon treatments.
Mechanical performance of the fibres decreases on
water sorption and it regains on desorption. However
modulus of the OPEFB fibre decreases on sorption and
desorption. Treatment reduces the mechanical strength
of the fibres. Strain to break of the fibres is considerably
increased upon treatments except silane. Young’s mod-
ulus shows enhancement on mercerized and silane
treatment. In the swollen stage the stiffness of the fibre
was considerably reduced.
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