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JCMR
Journal of Chemistry and Materials Research Journal of Chemistry and
Materials Research
Vol. 5 (1), 2016, 212
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Original Research

Solvent Transport through Oil Palm Fibre filled Low Density Polyeth-
ylene Composites
H.C. Obasi1,*, B.C. Aharanwa1, F.O. Aguele2, P.C. Uzoma1, C. Nwapa1, U.L. Ezeamaku1, I.C Chukwujike3
1
Department of Polymer and Textile Engineering, Federal University of Technology, Owerri, Nigeria
2
Department of Chemical Engineering, Michael Okpara University of Agriculture, Umudike, Nigeria
3
Department of Polymer and Textile Engineering, Nnamdi Azikiwe University, Awka, Nigeria

Received 01 March 2016; accepted 29 March 2016

Abstract
The transport behaviour of toluene through oil palm fibre (OPF) filled low density polyethylene (LDPE) composites have been investigated in
the temperature range 313–353 K. The effects of filler content, particle size and temperature on the transport behaviour of solvent through
OPF/LDPE composites were studied. It has been observed that all the systems follow Fickian mode of transport on increasing temperature. The
effect of alkali treatment on solvent uptake and swelling parameters was also analyzed. The estimated Arrhenius activation energies for the
processes of diffusion, and permeation indicated that the activation energies showed no particular trend with filler content, filler treatment and
particle size.The enthalpies, and entropies of sorption for the solvent have been investigated and the change in the estimated free energies of
sorption were all positive; an indication of the non-spontaneity of the solubility of oil palm fibre in the aromatic solvent at 313 K.The first
order kinetic model has been used to follow the kinetics of diffusion of solvent through OPF/LDPE composites.

Keywords: Oil palm fibre, sorption, activation energy, swelling parameters, first order rate constant, alkali treatment.

1. Introduction llulosic fibre composites which include inadequate dispersion

Eco-friendly materials and the concept of sustainable
development are the keys to consideration of environmental
issues. The idea suggests the use materials from renewable
resources for the future so that after their uses, they could
rapidly degrade naturally. There has been for the past few
decades a growing interest in the use of lignocellulosic fibres
or particles as reinforcing components in polymeric matrices
[1,2]. Natural lignocellulosic fillers when compared to
inorganic fillers offer low cost, low density, renewability,
biodegradability, abundant availability in variety of forms as
advantages. As a result, a large number of researchers have
focused in investigating the examination of lignocellulosic
fibres as load-bearing constituents in composite materials.
However, there are inherent problems associated with lignoce-
* Corresponding author:
E-mail address: neduobasi23@gmail.com (H.C. Obasi).
All rights reserved. No part of contents of this paper may be reproduced or
transmitted in any form or by any means without the written permission of
ORIC Publications, www.oricpub.com.
and bonding between fibre and polymer matrix, moisture
absorption by natural fibres, and non-uniform mechanical and
physical properties of natural fibres [3].
Nowadays, oil palm fibres (OPF) have been used as natural
fillers to develop thermoplastic-based composites. Large
quantities of palm pressed fibres are accumulated every year in
the south eastern part of Nigeria. OPF’s are by-products of Oil
palm processing industries. The fibres generally have a
specific use as biomass fuel in the oil mills which leave behind
large chunk of ashes. The ash from the burning of palm press
fibre does not contain sufficient nutrients to be used as a
fertilizer, and dumping creates an airborne hazard and
pollutant. However, composting palm pressed fibre with
poultry litter and urea has been successfully tested and studies
indicate that this compost mixed in sand and loam may
enhance crop production [4]. The chemical composition of the
untreated palm-pressed fibres is estimated to be 39.9 %
cellulose, 28.9 % hemicellulose, 20.3 % lignin and 3.6 % ash
content [5].
Low density polyethylene (LDPE) was originally prepared
by the high pressure polymerization of ethylene. Its compara-
tively low density arises from the presence of a small amount
 H.C. Obasi et al. / Journal of Chemistry and Materials Research 5 (2016) 2–12
of branching in the chain. Chemically LDPE is un-reactive at
room temperature, although it is slowly attacked by strong
oxidizing agents and some solvents will cause softening or
swelling. It may be used at temperatures up to 95 °C for short
periods and at 80 °C, continuously [6]. Low-density polyethy-
lene is a semi-crystalline solid with a degree of crystallinity in
the 50–60 % range that leads to several properties such as
opacity, tensile strength, tear strength, rigidity and chemical
resistance, flexibility even at a low temperature [7,8].
LDPE is one of the most commonly used thermoplastics to
develop composites reinforced by different natural materials,
cellulose [9], lignin [10], starch [11]. Therefore, blending the
fibres with thermoplastic polymers such as LDPE could be a
novel way of turning waste into wealth.
Molecular transport of small molecules through polymeric
materials has significant importance in different scientific and
engineering fields such as medicine, textile industry, membr-
ane separations, packaging in food industry, extraction of
solvents and of contaminants etc. The transport behavior of the
filler/polymer systems depends on the filler size, surface area,
state of aggregation, the amount of filler and the interaction
between the filler and the matrix. The compatible inert fillers
will take up the free volume within the polymer matrix and
creates a tortuous path of the permeating molecules. When the
filler is not compatible with the polymer, voids tend to occur at
the interface, which leads to an increase in free volume of the
system and consequently permeability increases. Interaction of
different fillers with the matrix can be understood from the
studies of swelling and transport characteristics [12]. The
diffusion characteristics of aromatic solvents into polypropyl-
ene, and polyethylene films have been reported in the literature
[13,14]. The permeability, solubility, and diffusivity of the
aromatic solvents in polyethylene were found to increase with
increase in temperature, and the calculated enthalpies of
sorption for the solvents in polyethylene were positive while
the calculated entropies of sorption were negative.
Several researchers have used the equilibrium swelling
technique to evaluate the interactions of different fillers with
polymers. The diffusion characteristics of toluene, an aromatic
solvent into natural rubber/linear low-density polyethylene
blends were investigated by Obasi, et al. [15]. The transport of
toluene through most of the blend compositions was anomal-
ous, although at 55 °C, the transport of toluene through the
60/40 NR/LLDPE blend was Fickian, and at 35 °C, pseudo-
Fickian. The diffusion coefficient and permeability to toluene
in 50/50 and 60/40 NR/LLDPE blends were found to increase
with increase in sorption temperature. Mathew and Kuriakose
[16] and Sareena, et al. [17] in their separate studies observed
that at higher concentration of lignin rich fillers, there is a
tendency for sorption to decrease and this can be explained on
the basis of increase stiffness which is imparted to the polymer
matrix by the addition of the filler lignin. Also, Kwei and
Kunins [18] observed that the sorption of chloroform by an
3
epoxy resin was lowered by about 70 % when 5 % filler was
incorporated. Similarly, George, et al. [19] investigated the
effect of different types of fillers such as cork, silica and
carbon black on the transport of aromatic solvents in isotactic
polypropylene/acrylonitrile-co-butadiene rubber blends.
In this study, we report the transport of toluene, an aromatic
solvent through OPF-filled LDPE at different temperatures.
The sorption of oil palm fibre composites are studied at three
different temperatures. The effect of penetrant molecule, filler
concentration, and particle size are also studied. From the sor-
ption data, matrix-solvent interaction parameter, mechanism of
swelling, thermodynamic parameters likeentropy, enthalpy,Gibbs
free energy and first order kinetics of swelling are evaluated.
2. Materials and Methods
2.1.Materials
Pellets of Low density polyethylene (LDPE) (Density:
0.915g/cm3; Melt flow index: 8 g/10 min measured at 190 °C
using 2.16 kg standard weight; melting temperature: 110 °C)
were purchased from Cee Plast Industries Ltd, Aba, Abia
State, Nigeria. Oil palm fibre (OPF) was obtained from Ada
Palm Industry, Ohaji, Imo State, Nigeria. The solvent, toluene
used in this study was purchased from a chemical vendor at
Onitsha main market, Anambra State, Nigeria. It is of an
analytical grade with a density of 0.865 g/cm3 and was used
without further purification.
2.2.Preparation/Treatment of Oil Palm Fibre
Wet extraction method was employed to leach out the
remaining residual oil from the OPF which was retained after
processing, that used hot water as described elsewhere, [20]
was used. The fibres were thoroughly washed with distilled
water to further remove impurities followed by sun drying for
five days. The dried fibres were then treated with 5 % solution
of NaOH for about 2 h to avoid fibre damage. The fibres were
later severally washed with distilled water to remove excess
NaOH and dried at 80 °C for 12 h. The dried OPF was then
pulverized and sieved to obtain different particle sizes.
2.3.Preparation of OPF/LDPE Composites
Different mixtures alkali treated oil palm fibre (AOPF)
and untreated of oil palm fibre (OPF) and low density
polyethylene (LDPE) were melt blending similar to polymer
blending in an injection machine with a screw speed of 50 rpm
and at a temperature of 105–130°C to obtain AOPF/LDPE and
OPF/LDPE composites. Composites with different fibre
contents (10, 20, and 30 wt. %) were prepared. After injection
molding, the sheets were conditioned for 24 h at 70 °C and
stored in desiccators for further use.
4 H.C. Obasi et al. / Journal of Chemistry and Materials Research 5 (2016) 2‒12
2.4.Sorption Experiments
The sorption behavior of the alkali-treated and untreated
OPF/LDPE composites, prepared at three different particle
sizes of OPF, viz. 425, 500, and 600 µm were studied at three
different temperatures namely; 40, 60, and 80 °C. Uniform size
cut samples of dimensions 2.5 x 2.5 cm2 were used in sorption
experiments. Initially, the samples were dried in a vacuum
oven at room temperature for about 24 h. The original weight
and thickness of the samples were measured before sorption
experiments. They were then immersed in TOLUENE (20 mL)
in closed diffusion bottles, kept at particular temperature in a
thermostatic water bath. Periodically, the samples were
removed from the bottles and damp dried between filter papers
to remove excess solvent on the surface. They were then weig-
hed immediately using an electronic balance that measured to
the nearest 0.0001 g. The samples were immediately placed
back into the test bottles. The process was continued until
equilibrium sorption was reached.
3. Results and Discussion
3.1.Analysis of swelling data
3.1.1. Determination of Qt (mol % uptake of toluene)
The sorption data of aromatic solvent, toluene into OPF/
LDPE blend composites at different blend composition and
filler concentration have been determined. It is expressed as
the molar percentage uptake (Qt %) of solvent per gram of
OPF/ LDPE blends and was calculated using the equation;
 W W 
Qt   t 0  /W0 (1)
 Ws 
where Wt is the mass of the sample at time t; Wo is the initial
mass of the sample and Ws is the molecular weight of the
solvent. The molar percentage uptake (Qt %) for the solvent
was plotted against the square root of time ( t ) to obtain the
sorption curves. The diffusion of solvent through a composite
has been observed to depend on the geometry of the filler
(size, shape, size distribution, concentration and orientation),
properties of the matrix and interaction between the matrix and
filler.
3.1.2. Effect of filler content on sorption properties of
OPF/LDPE composites
The effect of filler content at 40 °C on the mole percent
uptake byOPF/LDPE and AOPF composites was plotted against
the square root of time ( t ) as shown in Fig. 1. An initial
increase in uptake was shown for the entire blend composite
studied. This is due to the high concentration gradient of
solvent molecules with the composites. This initial solvent
absorption rates in polymers have been explained in terms of
rapid cavitations, which expose a greater surface area, thus
enhancing solvent percolation [21]. However, the solvent
uptake is counter balanced by solvent extraction from the
polymer at equilibrium. Similar trend have been reported for
other polymer systems [17,22,23]. The maximum solvent
uptake was observed for 10 wt.% and the minimum by 30 wt.%.
The mol solvent uptake increases in the order 30, 20, and 10
wt.%. It is very clear that the mol solvent uptake increases
with decrease of filler contenting the blend composition. This
can be explained based on the fact that the local mobility of
the polymer gets restricted by reinforcement fillers and
improves resistance to solvent. Again, because LDPE is non-
polar while OPF is polar, the absorption of toluene is seemed
to depend solely on the matrix alone. As the fibre content is
increased the cellulose content increased, which in turn
resulted in the less absorption of solvent. Thus, the
reinforcement of blend by reinforcing filler improves the
resistance to solvent to a great extent. The diffusion of the
penetrant solvent also depends on the concentration of free
space available in the matrix to accommodate the penetrant
molecule. The increase in filler content reduced the availability
of free spaces and also creates a tortuous path for transport of
solvent molecules. The degree of tortuosity is tied to the
volume fraction of the filler and the shape and orientation of
the particles [24]. If the filler is incompatible with the
polymer, voids tend to occur at the interface which leads to an
increase in free volume of the system, decrease in interfacial
strength and consequently to an increase in permeability
3.1.3. Effect of particle sizes on sorption properties of
OPF/LDPE composites
The effect of particle as function of toluene uptake by the
different compositions of polymer composites is shown in
Fig.2. For the given blend composites, the solvent uptake was
found to reduce with decrease in particle size. The dispersion
of the particles differs with particle size when the content is
the same and the average interparticle distance reduces with
the decrease of particle size. The lowest micron size filler is
predominantly finer with higher surface and understandably
improves filler/ polymer interactions. The intercalated
morphology of the blend composites hinders the movement of
penetrant molecules. As the particle size decreases, the mole
uptake decreases, showing a decreasing order
450m  500m  600m . The trend is the same for all the
composite compositions but with reduced values for treated
composites. Reduced movement of the penetrant molecules in
the presence of particle size are already reported [17, 25].
 H.C. Obasi et al. / Journal of Chemistry and Materials Research 5 (2016) 2–12
Fig. 1. Effect of filler content on Qt of OPF/LDPE Composites at 80°C for
425µm
Fig. 2. Effect of particle size on Qt of OPF/LDPE Composites at 40°C for 10
wt. %
3.1.4. Effect of temperature on sorption properties of
OPF/LDPE composites
The dependence of transport properties of solvent, toluene
on temperature was studied by conducting the experiment at
40, 60, and 80 °C. The change in mol % values for the different
filler loading at different temperature is presented in Fig. 3.
Irrespective of the solvent, blend composition, filler content,
treatment and particle size, sorption increases with increase of
temperature in all the systems studied. The figure shows that
solvent uptake for all the blend composites generally increased
with increase in sorption temperature. Temperature considera-
bly activates the diffusion process. At higher temperature the
polymer chains become more flexible and the kinetic energy of
the molecules is also higher. This results in a subsequent
reduction in the viscosity of the solvent, and a further increase
in the segmental mobility of the polymer. This increase in the
mass of solvents sorbed by polymer composites with increase
in temperature as observed here had similarly been reported
elsewhere [17, 25-27].
5
Fig. 3. Effect of Temperature on Qt of OPF/LDPE composites at 500µm for
10 wt. %
Fig. 4. Effect of filler treatment on Qt of OPF/LDPE Composites at 60⁰ C for
20 wt. %
3.1.5. Effect of alkali treatment on sorption properties
of OPF/LDPE composites
The effect of alkali treatment as function of toluene uptake
by the different blend compositions of polymer composites is
shown in Fig. 4. The figure shows that the toluene uptake for a
given filler concentration and particle size used is lower for
treated OPF/LDPE composites than the untreated counterpart.
It is obvious to say that treatment of the fibres with chemical
modifiers provides enhanced adhesion between fibre and
matrix as this result in a decrease in voids between fibre and
polymer matrix. Furthermore, alkali treatment seems to be the
factor of providing a chemical strength between filler and
matrix [28]. In this study, alkali treatment shows a positive
impact on the toluene absorption behavior of the composite as
shown in Fig. 4. The first attempt of alkali treatment on the oil
palm fibre/ low density polyethylene composite at 5 % NaOH
shows decrease in toluene absorption behavior. Dissolving the
hemicelluloses and volatile extractives has contributed in
reducing the numerous hydroxyl groups that are available on
the filler surfaces thus resulting in more interaction of the filler
and matrix as more rigid and crystalline packed of cellulose
surfaces are exposed.
6 H.C. Obasi et al. / Journal of Chemistry and Materials Research 5 (2016) 2‒12

Table 1 Swelling Parameters and Penetration rate of OPF/LDPE Composites at different temperatures and particle sizes
TEMP. FILLER SWELLING PARAMETERS AND PENETRATION RATE OF OPF/LDPE COMPOSITES
⁰C WT.%
SWELLING INDEX, % SWELLING COEFFICIENT, β
425µM 500µM 600µM 425µM 500µM 600µM
40 AOPF OPF AOPF OPF AOPF OPF AOPF OPF AOPF OPF AOPF OPF
10 11.96 12.51 12.51 13.16 13.25 13.80 1.51 1.57 1.57 1.65 1.65 1.73
20 11.50 12.05 12.05 12.70 12.60 13.43 1.44 1.51 1.51 1.59 1.58 1.68
30 11.13 11.50 11.68 12.14 12.33 12.88 1.40 1.44 1.46 1.52 1.55 1.64
60 10 12.33 12.88 12.97 13.62 13.71 14.26 1.55 1.61 1.63 1.71 1.72 1.77
20 11.87 12.51 12.70 13.16 13.43 13.80 1.49 1.57 1.59 1.65 1.68 1.73
30 11.50 12.14 12.14 12.60 12.77 13.25 1.44 1.52 1.52 1.58 1.60 1.66
80 10 12.77 13.34 13.34 14.08 14.17 14.81 1.60 1.67 1.67 1.76 1.78 1.86
20 12.33 12.88 12.97 13.52 13.71 14.26 1.55 1.61 1.63 1.69 1.72 1.79
30 11.96 12.42 12.51 13.06 13.25 13.71 1.50 1.56 1.57 1.64 1.66 1.72
PENETRATION RATE, X10-3 CMS-1/2

425µM 500µM 600µM

AOPF OPF AOPF OPF AOPF OPF
40 10 2.51 2.57 2.64 2.72 2.77 2.07
20 2.44 2.57 2.58 2.69 2.72 2.83
30 2.39 2.42 2.51 2.56 2.82 2.70
60 10 2.48 2.58 2.62 2.69 2.77 2.83
20 2.73 2.81 2.57 2.67 2.42 2.53
30 2.36 2.38 2.50 2.53 2.66 2.67
80 10 2.48 2.51 2.61 2.64 2.77 2.79
20 2.41 2.46 2.55 2.60 2.71 2.76
30 2.33 2.37 2.46 2.52 2.62 2.67
The values of the swelling index, swelling coefficient and
3.1.6. Swelling Parameters penetration rate are shown in Table 1. From the table, the
swelling index and swelling coefficient of the composites were
The swelling studies of /low density polyethylene found to decrease with increase in fibre content and decrease
composites containing alkali treated and untreated oil palm in particle size. This is evidently due to the increased
fibres were conducted in aromatic solvent like toluene. The restriction exerted by the fibres at higher fibre concentrations
swelling parameters like swelling index and swelling and also due to good fibre/matrix interactions facilitated by
coefficient were evaluated. Swelling index depends on the higher surface area at lower particle sizes. The alkali treated
molar volumes of polymer and solvent and their cohesion fibre composites exhibited lower swelling behavior than the
energy whereas swelling coefficient is an index of the ability untreated ones. Understandably, this may be attributed to
with which the sample swells. The swelling coefficient and enhanced interfacial adhesion between the matrix and fibre. In
swelling index of the OPF/LDPE composites were assessed this study, the swelling parameters did not show any
using Eq. 2, and 3 respectively. dependence on temperature.
Swelling coefficient,
 M  M 0  1 3.2.Kinetic Parameters
      s (2)
 M0  3.2.1. Diffusion Coefficient (D)
where Mo and M∞ are mass of the sample before and after The mechanism of transport of toluene into OPF/LDPE
swelling, respectively, and ρs is the density of the solvent. composite systems is akin to Fickian and therefore the
Swelling Index, diffusion mechanism has been calculated accordingly.
 M  M0  For a Fickian model of transport of a thin polymer film of
%    100 (3) thickness h having boundary conditions at;
 M0  t  0, C  0 and t  0 and C  C (4)
 H.C. Obasi et al. / Journal of Chemistry and Materials Research 5 (2016) 2–12 7

Table 2 Sorption values of PPF/LDPE Composites at different temperatures and mesh sizes
TEMP. FILLER KINETIC PARAMETERS OF OPF/LDPE COMPOSITES AT DIFFERENT TEMPERATURES AND PARTICLE SIZES
⁰C WT.%
DIFFUSION COEFFICIENT, D, X 10-6 SORPTION, S, %
2
CM /S
425µM 500µM 600µM 425µM 500µM 600µM
40 AOPF OPF AOPF OPF AOPF OPF AOPF OPF AOPF OPF AOPF OPF
10 4.96 5.21 5.47 5.83 6.04 3.83 3.39 3.50 3.55 3.69 3.75 3.92
20 4.67 5.18 5.24 5.68 5.81 6.29 3.50 3.66 3.66 3.86 3.83 4.08
30 4.50 4.62 4.97 5.15 6.27 5.73 3.66 3.80 3.80 4.00 4.00 4.20
60 10 4.84 5.24 5.41 5.69 6.04 6.31 3.50 3.69 3.69 3.83 3.89 4.03
20 4.62 6.21 5.20 5.59 5.84 5.02 3.61 4.20 3.86 4.00 4.08 3.80
30 4.39 4.45 4.93 5.01 5.57 5.6 3.75 3.92 3.94 4.14 4.17 4.34
80 10 4.82 4.93 5.34 5.49 6.01 6.10 3.64 3.78 3.80 3.97 4.03 4.17
20 4.57 4.76 5.12 5.33 5.77 5.97 3.75 3.92 3.94 4.11 4.17 4.34
30 4.28 4.42 4.74 4.99 5.39 5.62 3.89 4.06 4.06 4.28 4.31 4.50
-6 2
PERMEATION COEFFICIENT, P, X10 CM /S

425µM 500µM 600µM

AOPF OPF AOPF OPF AOPF OPF
40 10 16.81 18.23 19.42 21.51 22.65 13.25
20 16.34 18.96 19.18 21.92 22.25 25.66
30 16.47 17.56 18.89 20.60 25.08 24.07
60 10 16.94 19.34 19.96 21.79 23.50 25.43
20 16.48 26.08 20.07 22.36 23.83 19.08
30 16.46 17.44 19.42 20.74 23.23 24.30
80 10 17.54 18.63 20.29 21.79 24.22 25.44
20 17.14 18.66 20.17 21.91 24.06 25.91
30 16.65 17.94 19.24 21.36 23.23 25.29
where C is the penetrant concentration in the polymer matrix at and Q∞ is the equilibrium absorption. It is evident that as the
a time t. If there is a negligible concentration dependence of OPF content increases, the diffusion coefficient decreases due
diffusivity over the concentration interval studied, a value of mainly to high resistance of OPF to toluene ingression (Table
mutual diffusion coefficient D can be calculated using Eq.5 2). Oil palm fibres having high cohesive energy density
[29]. because of the functional groups present in it. Thus, the


Qt  8 OPF/LDPE composites exhibit lower diffusivity value at
e  ( 2 X 1)  ( Dt / h )
2 2 2
 1 (5)
Q X  0 (2 X  1) 
2 2 higher OPF content. This behavior has been reported in the
literature that the presence of polar or bulky groups also
where t is the time and h is the initial thickness of the influence the diffusion properties [30].The presence of OPF in
composite sheet. Although this equation can be resolved, it is LDPE matrix fills any free space present, thus the solvent
imperative to examine the short-time limiting expression as passing through the matrix must travel in a more tortuous path.
well (Eq. 5).
The reinforcement of the polymer matrix with filler reduces
  1
Qt  4  Dt  2 the mobility of polymer chains near the phase boundaries. It
   (6) was observed from the table that diffusivity decreases with
Q  1  h 2 
 2  alkali treatment. This might be attributed to the same reason
earlier advanced for swelling parameters. However, the
A plot of Qt vs. t1/2, gives a curve with initial linear portion. diffusivity increases with increase in particle size and sorption
Thus, D can be calculated from the rearrangement of Eq. 6 as temperature. The rate of diffusion of solvent into composite is
shown in Eq. 7. time and temperature dependent. Temperature increase
2
 h  facilitates activation of diffusion, leading to weakening of
D     (7)
 4Q  filler/matrix adhesion and creation of micro cracks or voids in
the system. The increase in the mass of solvent sorbed by
where h is the initial sample thickness, θ is the slope of the polymers with increase in temperature had been reported.
linear portion of the sorption curve of the plot of Qt against t1/2
8 H.C. Obasi et al. / Journal of Chemistry and Materials Research 5 (2016) 2‒12

Table 3 Table 3.Values of n and k (g/g/min-n of OPF/LDPE Composites.

TEMP FILLER TRANSPORT MECHANISM
. ⁰C WT. %
n k
425µM 500µM 600µM 425µM 500µM 600µM
AOPF OPF AOPF OPF AOPF OPF AOPF OPF AOPF OPF AOPF OPF
40 10 0.45 0.43 0.46 0.44 0.47 0.44 0.084 0.097 0.082 0.092 0.077 0.090
20 0.46 0.46 0.48 0.47 0.49 0.49 0.077 0.080 0.073 0.077 0.070 0.073
30 0.48 0.48 0.49 0.49 0.50 0.50 0.068 0.074 0.065 0.070 0.061 0.067
60 10 0.43 0.41 0.45 0.43 0.47 0.44 0.091 0.104 0.086 0.097 0.080 0.092
20 0.45 0.45 0.47 0.48 0.49 0.48 0.084 0.084 0.077 0.080 0.072 0.077
30 0.47 0.47 0.49 0.48 0.50 0.49 0.074 0.077 0.070 0.076 0.066 0.072
80 10 0.42 0.41 0.43 0.43 0.45 0.45 0.098 0.105 0.094 0.098 0.087 0.092
20 0.45 0.43 0.46 0.45 0.48 0.47 0.084 0.092 0.081 0.087 0.076 0.082
30 0.46 0.45 0.48 0.46 0.49 0.47 0.077 0.087 0.074 0.082 0.069 0.079

Table 4 Values of activation energy (ED and EP) of OPF/LDPE Composites

FILLER
ENERGY OF ACTIVATION
WT. %

-ED, X103 KJ/Mol EP, X103 KJ/Mol

425µM 500µM 600µM 425µM 500µM 600µM
AOPF OPF AOPF OPF AOPF OPF AOPF OPF AOPF OPF AOPF OPF
10 1.16 1.07 1.04 0.70 3.47 0.43 0.20 0.46 0.44 0.83 -1.78 1.10
20 0.47 1.90 0.52 1.41 0.15 1.20 1.11 -0.35 1.18 0.02 1.82 0.27
30 0.91 1.23 0.53 1.37 0.10 +1.38 0.94 0.52 1.01 0.27 1.53 15.30

Table 5 Values of enthalpy of absorption (ΔHs), entropy of absorption (ΔSs), and Gibbs free energy (ΔGs) of OPF/LDPE Composites.
FILLER WT.% THERMODYNAMIC PARAMETERS OF THE OPF/LDPE COMPOSITES
(ΔHs), X 103KJ/Mol (ΔSs), J/Mol /K
425µM 500µM 600µM 425µM 500µM 600µM
AOPF OPF AOPF OPF AOPF OPF AOPF OPF AOPF OPF AOPF OPF
10 1.37 1.42 1.43 1.58 1.75 1.63 41.61 41.09 41.05 40.17 39.64 39.61
20 1.58 1.48 1.70 1.43 1.92 1.37 41.29 41.19 40.48 40.94 39.39 40.68
30 1.63 1.76 1.59 1.64 1.64 1.42 41.40 40.68 41.12 40.64 40.53 40.87
(ΔGs), X 103 KJ/Mol
425µM 500µM 600µM
AOPF OPF AOPF OPF AOPF OPF
10 14.40 14.28 14.28 14.16 14.15 14.03
20 14.51 14.38 14.37 14.24 14.25 14.10
30 14.59 14.49 14.16 14.36 14.32 14.21

Johnson and Thomas [22] had reported an increase in the
diffusion coefficient (D) with increase in sorption temperature.
Penetration rate defines the role played by a solvent as to
33 an osmotic stress in a polymer matrix. The penetration
exert
rate may be expressed by the rate of the advancing swollen
fronts which could be calculated from the linear portion of the
sorption curve and it is related to diffusion coefficient. The
relation between penetration rate (Pr) and the diffusion
coefficient of solvent is given by the equation:
Pr2
D
4
The penetration rate of the solvent toluene decreases with
the increase in filler concentration as shown in Table 1.
Similar trend observed in the case of diffusion coefficients
calculated for the composites at various filler concentrations in
toluene played out here. However, penetration rate did not
show any temperature dependent. This is attributed to the fact
that with increasing filler content and alkali treatment the
penetration of solvent among macromolecular chains are
prevented.
(8)
 H.C. Obasi et al. / Journal of Chemistry and Materials Research 5 (2016) 2–12
Fig. 5. Variation of Diffusion and Permeation with Filler Content
Fig. 6. Variation of Diffusion and Permeation with Filler Particle sizes
The variations of the diffusion and permeation with filler
content and particle sizes in the composite were also evaluated
and are presented in Figs. 5 and 6 respectively. The 10 wt.%
OPF has the highest diffusion and permeation values. This
may be attributed to the difference in polarity between the
solvent and filler used which favored diffusion rate at low
filler content (Fig. 5). The diffusion and permeation values
were highest for 600µm (Fig. 6).
3.2.2. Sorption Coefficient (S)
The sorption coefficient that is related to the equilibrium
sorption of the penetrant is calculated using the equation (9)
[14],
W
S  (9)
Wp
where W∞ is the mass of the solvent at equilibrium swelling
and Wp is the mass of the polymer composite sample. The
sorption coefficient (S) was obtained from the equilibrium
sorption curves and is presented in Table 2 for the different
compositions. From the table it is clear that the sorption
coefficient increases with oil palm fibre content, and sorption
temperature but decreased with alkali treatment in the
9
composite for any given filler particle size, indicating that
sorption is somewhat restricted by the alkali treatment of filler.
This observation is in agreement with earlier researchers.
Mathai and Thomas [31] who studied the transport of
substituted benzene through natural rubber/nitrile rubber blend
membranes and found that the sorption coefficient value
decreased with increase in nitrile rubber content. Johnson and
Thomas [22] also in their sorption studies reported that the
sorption coefficient increased with increase in sorption
temperature and in filler particle size too.
3.2.3. Permeation Coefficient (P)
The permeability coefficient gives an idea about the
amount of solvent permeated through uniform area of the
sample per second. The permeation process through any
matrix is a product of diffusion and sorption; hence it depends
on the sorption and diffusion coefficients. The permeation
coefficient, P, is determined using Eq. 10 [32].
P  D.S (10)
where D is the diffusion coefficient and S is the sorption
coefficient. The values of P are shown in Table 2. For different
OPF/LDPE composites, it was shown that the permeation
coefficient increases with particle size and sorption temperat-
ure which might due to presence of voids at high particle sizes
and weakening of the interface at high temperature. But
permeation showed a decreased trend with treatment which
can be well-explained by the improved interfacial adhesion
causing tortuous path for the solvent in the composites.
Permeation did not show any particular order but was found to
higher in most cases at 20 wt.%. In this study, diffusion
coefficient was observed to be inversely related to sorption
coefficient with respect to filler content.
3.3.Transport Mechanisms
A Fickian model is the most common and the easiest means
of analysis, but in some cases, it is not valid. To investigate its
applicability to this study, the results have been subjected to a
time power law equation [33],
Mt
 K .t n (11)
M
where Mt and M∞ are the mol % sorption at time t, and
equilibrium, respectively. k is a constant that depends upon the
structural characteristics of the polymer, in addition to its
interaction with the solvent. The value of the exponent n
indicates the nature of the transport mechanism. When the
value of n=0.5, the mechanism of transport is termed as
Fickian and this occurs when the rate of diffusion of the
penetrant molecule is much less than the relaxation rate of the
polymer chains. When n =1, it is termed as non-Fickian (case
II-relaxation controlled) which arises when the rate of
10 H.C. Obasi et al. / Journal of Chemistry and Materials Research 5 (2016) 2‒12
diffusion of the penetrant molecule is much greater than the
relaxation process. When the value of n between 0.5 and 1
indicates anomalous transport behavior and it is due to the fact
that the rate of diffusion of the penetrant molecule and the
relaxation rate of the polymer are similar. Super-case II
transport occurs when n  1.0 ; in that case, the release rate is
time-dependent and it is pseudo-Fickian (less Fickian
behaviour) when n  0.5 . Equation (11) can be linearized by
taking logarithms of both sides such that,
M Number of moles of the solvent absorbed at equilibrium
Log t  Logk  nLogt (12)
M
The values of n and k for the OPF/LDPE composites in
toluene are shown in Table 3, and were got by regression
analysis of plot of log (Mt/M∞) against log t. For the present
composites system, the mode of transport is found to be
Fickian (n=0.5) and pseudo-Fickian behavior (0.4< n <0.5. This
observation had been reported elsewhere in the literature
[15,34,35]. k is the constant which is entirely based on the
solvent and polymer interaction. The values of k increased
with filler content and are higher for the untreated composites
but showed no dependence on particle size and temperature.
This might be linked to the higher interfacial adhesion between
the treated fibres and the matrix.
3.4. Energy of Activation
Activation energy of diffusion was determined from the
solvent diffusion studies of OPF/LDPE composites at three
different temperatures(40, 60 and 80 °C) using the Arrhenius
relation, Eq. 13 [36]
 EX  contributions from (a) Henry’s law needed for the formation of
LogX  LogX 0    (13)
 2.303RT 
where, X is P or D and Xo represents Po or Do, which are
constants; Ex is the activation energy, R, the universal gas
constant and T, the absolute temperature. From the slopes of
the Arrhenius plots of Log D and Log P against 1/T, ED, and
EP can be calculated by linear regression analysis. The
activation energy of permeation (EP) was found to be generally
greater than that of the activation energy of diffusion (ED). The
activation energy of diffusion obtained from
The activation energy of diffusion obtained from Arrhenius
plot is given in Table 4. The negative value of the activation
energy suggested that the rise in the solution temperature did
not favor toluene absorption into OPF/LDPE composites. The
negative value also indicates an exothermic reaction and the
low value of the activation energy, E, indicates that the
absorption process of toluene adsorption into LDPE filled
composites might be by a physical absorption. It means that
the rate-limiting step of toluene absorption into OPF/LDPE
composites involved predominantly a physical process. It is
reasonable to believe that diffusion process results from the
movement of penetrant molecule from cavity to cavity under
the influence of concentration gradient. Here, the activation
energy did not show strong dependence on fibre treatment,
particle size and temperature.
3.5.Thermodynamic Parameters
In order to evaluate ΔHs and ΔSs for the toluene solvent in
the OPF/LDPE composites, the equilibrium absorption const-
ant (Ks) of the solvent was first obtained using Eq. 14 [37];
Ks 
Mass of the composite sample
(14)
The results obtained were used to evaluate the enthalpy of
sorption ΔHs and entropy of sorption ΔSs in the composites.
The values of Ks were substituted into the van’t Hoff’s
equation (Eq. 15)[22];
S s H s
LogKs   (15)
2.303R 2.303RT
Plots of van’t Hoff’s equations made were used to estimate
ΔHs and ΔSs in the LDPE filled composites. A plot of Log Ks
versus 1/T for both treated and untreated fibre in toluene is
shown in Fig. 7. It was noticed that the plot is linear within the
temperature interval of 40 – 80°C.
Also, the values of ΔHs and ΔSs obtained in toluene at all
the three temperatures are given in Table 5. The obtained ΔHs
is generally positive, indicating endothermic sorption behavior
and is also found to increase with increase in filler content but
showed no particular trend with filler particle size and alkali
treatment. The ΔHs is a composite parameter having the
a site and the dissolution of the species into that site, the
formation of the site involves an endothermic contribution and
(b) Langmuir’s (hole filling) type sorption mechanism, in
which case the site already exists in the polymer matrix and
sorption by hole filling gives exothermic heat of sorption.
Thus, the positive ΔH values of the composites suggest a
Henry’s type sorption behavior [38]. The calculated ΔSs values
forthesolvents in OPF/LDPE composites were all negative, and
Fig. 7. Variation of equilibrium absorption constant with temperature
 H.C. Obasi et al. / Journal of Chemistry and Materials Research 5 (2016) 2–12 11

Table 6 Values of Kinetic data (k’ x103 min-1) of OPF/LDPE Composites. The plot of “Log (C∞- Ct)” against “t” gives a straight line
TEMP. FILLER 1ST ORDER KINETIC RATE CONSTANTS with slope equal to –K’/2.303. From the slope of the plot, the
⁰C WT. % values of K’ are calculated and shown in Table 6. The kinetic
rate constant is a measure of the speed with which toluene
425µM 500µM 600µM molecule penetrates through the medium. The modified fibre
40 AOPF OPF AOPF OPF AOPF OPF composites have lower rate constant values than the
10 3.45 3.48 3.63 3.79 3.74 4.08 unmodified fibre composites which is evident from Table 6.
20 3.72 3.94 3.90 4.13 4.11 4.49 Values are found to increase with increase of fibre content,
particle size and temperature. The increase of rate constant
30 4.06 4.15 4.34 4.40 4.57 4.63
with temperature supports the fact that the rate of diffusion is
60 10 3.88 4.06 4.09 4.20 4.26 4.36
accelerated by increasing temperature.
20 4.15 4.43 4.39 4.71 4.77 5.10
30 4.36 4.88 4.82 5.02 4.94 5.27
80 10 4.28 4.42 4.41 4.66 4.63 4.89 4. Conclusions
20 4.66 5.21 5.19 5.35 5.35 5.64
30 4.92 5.37 5.28 5.48 5.47 5.85 The effect of filler content, particle size, alkali treatment
and temperature on the sorption behavior of OPF/LDPE
composites in toluene was analyzed at three different
it lies in the range -39.39 to -41.61 J/mol/K. ΔSs in this temperatures (40, 60, and 80°C). The presence of OPF filler
studded not show any relationship to the alkali treatment, filler makes a tortuous path to the transport of solvent. As the OPF
content, and particle size. The negative entropy values indicate content in the composites increases, the hindrance for the
the orderliness of the sorbed molecule in the matrix [39]. transport of toluene increases, and hence the uptake decreases.
The swelling parameters, diffusion coefficient (D) and
3.6.Gibbs free energy of Sorption (ΔGs). permeation coefficient (P) values were found to decrease with
OPF content but with lower values for treated counterparts.
The change in ΔGs for the aromatic solvent in the The sorption coefficient values were found to exhibit a reverse
OPF/LDPE composite was obtained using the expression, order and increase with increase in filler content. The mode of
Gs  H s  TS s (16) transport of xylene into PPF/LDPE composites has been found
to be Fickian ( 0.4  n  0.5 ). The swelling parameters and
where T is the temperature in Kelvin. penetration rate have also been evaluated and were found to be
The ΔGs values were found to be positive in all cases dependent on the filler concentration and treatment. As the
indicating the non-spontaneity of the solubility of OPF/LDPE OPF content in the composite increases the change in free
composites in the toluene solvent at 313 K (Table 5). The energy (ΔGs) becomes positive, indicating the non-spontaneity
calculated ΔGs did not show any reasonable relationship to or irrespective of the nature of the organic solvent. It is found that
dependence on filler content, alkali treatment and particle size. first-order rate increase with all the parameters under study
except alkali treatment. Its temperature dependent supports
3.7.Kinetics of Diffusion high diffusion rate at high temperature.

As sorption occurs in polymeric materials, a compressive Reference

stress is developed, and sorption is controlled by the rate of
polymer expansion rather than the difference in osmotic
pressure inside and outside the polymeric materials. The stress
developed is proportional to the concentration of solvent.
Transport of toluene through the OPF/LDPE composites can
be considered as a rate controlled kinetic process which can be
studied by the first order kinetic rate equation (17)[40].
dC
 K ' (C C t ) (17)
dt
where, K’ is the first order rate constant, Ct and C∞ are the
concentrations at time t and at equilibrium respectively.
Equation 17 on integration yields
K 't
Log(C C t )  LogC 
2.303
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