Journal of Al-Nahrain University

Vol.16 (3), September, 2013, pp.148-158

Science

The Diffusion Coefficients of Different Types of Liquid Environments

Into Binary Polymer Blend
Awham M. Hameed* and Raghad H. Helal **
*

Department of Applied Sciences, University of Technology, Baghdad-Iraq.

Department of Production Engineering and Metallurgy, University of Technology, Baghdad-Iraq.

**

Abstract
In this study, unsaturated polyester resin (UPE) and Natural rubber (NR) were used to prepared
binary polymer blend (UPE/ NR) with weight ratio (95/5) %. The present paper investigates the
diffusion behavior of three environmental groups , the first group is different types of water
included (distilled water, tap water, rain water), the second is diluted solutions with same
concentration (HCl , H2SO4, NaCl) and the third is solvents (ethanol, kerosene, benzene) and
study their effects through (UPE/NR) polymer blend. Consequently, a set of specimens were
immersed in various types of water, solutions and solvents for different periods of time. The
diffusion coefficients (Dx) of these liquids were calculated based on Fick's law. The results of a
series of experimental investigations showed that the values of (Dx) of all liquids are in the range
(3.95- 9.1 *10-12 m2/s) except benzene which behaves another behavior called (non- Fickian
diffusion) through the same time of immersion.
Keywords: polymer blends, Unsaturated polyester resin, Natural rubber, diffusion coefficient.
linked polymer; a fully interpenetrated
network can be formed by cross-linking a
second polymer within the network of a
previously cross-linked polymer [1].
The chemical resistance of a polymeric
material is its ability to withstand chemical
attack with minimal change in appearance,
dimensions, mechanical properties and weight
over a period of time [3].
Yu and Selvadurai investigated the
influence of ethanol exposure at different
concentrations on the mechanical properties
of a plasticized PVC membrane. Exposure
to pure ethanol resulted in a reduction
in flexibility, or embrittlement. The PVC
membranes exposed to a mixture of ethanol
and pure water in equal volume properties
indicate that, after more than one year of
exposure, the PVC membranes became softer
greater deformation under the same external
load. This phenomenon can be attributed to the
swelling of the PVC membrane [4].
Seo et al. [5] prepared Epoxy/
Bismaleimide (BMI) composites. The thermal
properties and water sorption behaviors of the
epoxy and BMI composites were investigated.
The diffusion coefficient and water uptake
deceased and the activation energy for water
diffusion increased with increasing BMI
content, indicating that the water sorption in
epoxy resin, which causes reliability problems

Introduction
Alloys and blends are simple mixtures of
two or more plastics; there are no chemical or
molecular links between the various polymer
molecules [1].
There are many reasons why polymer
blending is one of the most important areas in
polymer research and development. Among
these reasons, the most important is perhaps
that polymer blends offer a fast and cheap way
to obtain new polymeric materials. These
materials generally exhibit a range of
properties varies between the properties of
their components. Moreover, their properties
may be complementary and difficult to be
found together in the case of a single
component [2].
A related system of strengthening that
came into use in the mid-1980s is the
interpenetrating network (IPN): A cross
linked polymer is penetrated throughout with
another polymer such that the penetrate
becomes the matrix and the network polymer
is like a three-dimensional reinforcement of
the matrix polymer, or cross-linked polymers
can have another polymer cross-linked within
the network of the first polymer. A semiinterpenetrating network is compared with a
fully interpenetrating network in Fig.(1). Semi
IPNs are usually formed by polymerizing a
linear polymer within the network of a cross841

Awham M. Hameed

in electronic devices, can be diminished by

BMI addition.
Katoch et al.[6] studied new system of
saturated polyester and their nanocomposites
synthesized from glycolyzed PET with varied
composition. The sorption and diffusion
studies in water were investigated. The
diffusion coefficient of saturated polyester
samples decreases with an increase in
glycolyzed PET contents. The nanocomposite
samples show less diffusion coefficient than
pristine polymer and it decreases with an
increase in nano-ller up to 4 wt%. The
diffusion coefficient increases with an
increase in temperature for all the samples.
Ramesh et al.[7] prepared siliconepolyester blended coatings for corrosion
protection. The network of different
functional groups between silicone and
polyester resins was examined by FTIR
spectroscopy. Electrochemical Impedance
Spectroscopy (EIS) was used to study the
anticorrosion property of the systems by
exposing the samples to 3% NaCl solution.
EIS experimental results show that the
coatings could protect the metal surface for
the exposure to corrosive medium for more
than 30 days.
The objective of the present work is to
study the diffusivity of some liquids into
(UPE/NR) polymer blend for determining the
diffusion coefficients (DX) of them and
investigate their effects on the external
appearance nature and morphology of the
blend.

room temperature, then after solidification, the

resulted cast of blend was put in an oven with
(Temp. = 50oC) for (1 hour) to ensure that a
full cure was achieved. According to the
standard specification (ASTM-D570), the
samples were cut in cubic shapes from the
polymer blend under study.
By using the grinding machine, the
surfaces and edges of specimens were
smoothed for minimizing surface defects and
obtaining the uniform samples.
The initial masses of prepared specimens
were obtained by using sensitive electronic
balance type (Mettler, model AE160) with
0.0001g resolution.
The samples were subjected for different
types of liquids included [(distilled water, tap
water, rain water), (HCl, H2SO4, NaCl),
(ethanol, kerosene, benzene)] at room
temperature. The dry samples were immersed
into sealed containers that contain (150ml) for
each type of water and solutions that
mentioned above.
Weight changes were monitored by
repeated weighting of the samples. The
percent weight change during immersion was
calculated using the following equation:-

w(t ) w(0)
100 ............... (1) [8,9]
w(0)
Where Wt.(%) is the percent weight
change at time (t), w(t) is the weight of the
tested specimen at time (t), and w(0) is the dry
specimen weight.
The diffusion coefficient (Dx) can be
calculated from the initial slope (mx) of the
absorption curve in region (I) using the
equation:Dx = [mx d /4 M] 2 .......................... (2) [8,9]
Where M is the equilibrium moisture
content when the slope of the curve converts to
straight line as shown in Fig.(2).
d is the initial thickness of the specimen.
The output from a diffusion experiments at
a given temperature is the percent weight gain
versus square root of time, time.
Optical
microscope
(15X)
type
(73346/digital camera, Japan) was used to
study the morphology and microstructure of
specimens after the immersion in these liquids.
Wt.(%)(t )

Experimental Part
(UPE/NR) polymer blend with weight ratio
(95/5)% was prepared by mixing Unsaturated
polyester resin (UPE) with Natural rubber
(NR). The polymers used in this work were
commercial products.
(UPE) resin was supplied by (SIR)
company, Saudi Arabia. After mixing the two
previous polymers, the hardener of (UPE) was
added to the mixture. The addition ratio of
hardener(Methyl Ethyl Ketone Peroxide
(MEKP)) is (2%) of resin. An acceleration
material of reaction (cobalt octoate in dibutyl
phthalate) was added with ratio (0.5%) of
resin.
This binary polymer was poured in a metal
mould with dimensions (14, 12, 3) cm3 at
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Journal of Al-Nahrain University

Vol.16 (3), September, 2013, pp.148-158

Science

Figs.(7-15) present the percent weight

change of samples as a function of the square
root of immersion time into different types of
liquids under study. The solid line in the same
figures shows the sigmoidal fitting for the
experiments data assuming Fickian diffusion
[8,11,12]. The absorption curves display a
pronounced linear region extending up to
about 60% of the total absorption range and
then are concave to the abscissa above the
linear portion, these results agree with
previous studies [13]. The results show a
Fickian behavior up to approximately 70 days
of all specimens (except the sample immersed
into benzene). It can be concluded that the
(UPE/NR) polymer blend has good chemical
resistance towards the corrosive solutions.
From Fig.(15), it can be seen that the
saturation case is not obtained after the
immersion into benzene solvent comparing
with other liquids at the same time of
immersion.

Results and Discussion

The kinematics of water penetration in
polymers varies with the nature of system that
is being considered and the exposure
conditions. In the simplest case, water or
solution enter the polymer without interacting
with the molecular segment network. This case
can be represented by Fick's law, which
assumes that the absorption is a diffusion
process only driven by the moisture
concentration gradient. Frequently, however,
the Fickian model does not adequately
represent the absorption process. Such cases
are called non-Fickian, or anomalous diffusion
[10].
The simplest moisture diffusion model in
this case is based on Fick's law, which is
represented mathematically by:
c/t = D (2C/x2) .................................. (3)[9]
Where c is the moisture concentration, t is the
time, x is the spatial coordinate, and D is the
diffusivity.
Table (1) lists the values of diffusion
coefficients of liquids through the polymer
blend under work at room temperature.
The diffusion coefficients of the different
types of water (distilled, tap, rain) into
(UPE/NR) polymer blend are in the range
(8-9)*10-12 m2/s, which are close to the results
obtained by other investigators.
From the definition of interpentrating
polymer networks that mentioned in
the introduction, it can be concluded that
the prepared polymer blend (UPE/NR)
is
seminterpetrating
polymer
network
(Semi IPNs) as shown in Fig.(2). Unsaturted
polyester resin is cross-linked polymer while
the Natural Rubber is linear polymer [1, 2].
Fig.(3-6) represent optical micrographs of
all prepared specimens before and after the
immersion. From these Figures, it can be seen
that there is some voids, swelling and cracks
after all the cases of immersion especially with
HCl, NaCl and ethanol. These defects may be
related to penetrate these solutions within the
structure of polymer blend more than other
liquids under work. It can be also seen
observable change in the nature and colour
(changed to dark) of the polymer blend that
immersed into benzene as shown in Fig.(5c).

Conclusions
After carrying out the current study, it can
be concluded that there is some changes in the
colour of the prepared polymer blend after
the immersion into kerosene and benzene
for (70) days. It is clear that the changes
associated with immersion were due to the
plasticization case of material specimens
rather than hydrolysis. The diffusion behavior
of benzene through the polymer blend is
different comparing with other liquids under
study at the same time of immersion so that
it can be say that (UPE/NR) polymer blend
has chemical resistance towards these
environments (except benzene) at this time of
immersion.

851

Awham M. Hameed

Table (1)
Values of the diffusions coefficients (Dx) of liquids into polymer blends
(UPE/NR) at room temperature.
Immersion type

Dx *10-12 m2/s

M (%)

Distilled water

9.098

1.326

Tap water (pH=7.1)

8.07

1.46

Rain water (pH=7.7)

8.88

1.491

HCl (0.25N)

8.607

1.358

H2SO4 (0.25N)

3.955

1.109

NaCl (0.25N)

8.442

0.901

Ethanol

7.115

1.39

kerosene

6.444

1.084

benzene

* The behavior is different after the immersion in benzene, there is no saturation, and the mechanism of
diffusion is anomalous when it is compared with other liquids.

Fig.(1) Formation of interpenetrating networks formed by interpenetrating

cross-linking of different polymers [1].

Fig.(2) Schematic absorption curve for a two phase resin system showing absorption into both
the dense and less dense phases (region I) and the dense phase alone (region II)[11].
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Journal of Al-Nahrain University

Vol.16 (3), September, 2013, pp.148-158

Fig.(3) Optical micrograph of (UPE/NR) polymer blend before immersion(15X).

(a)

(b)

(c)
Fig.(4) Optical micrograph of (UPE/NR) polymer blend after immersion into
(a) distilled water, (b) tap water, and (c) rain water(15X).
851

Science

Awham M. Hameed

(a)

(b)

(c)
Fig.(5) Optical micrograph of (UPE/NR) polymer blend after immersion into
(a) HCl, (b) H2SO4, and (c) NaCl (15X).

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Journal of Al-Nahrain University

Vol.16 (3), September, 2013, pp.148-158

(a)

(b)

(C)
Fig.(6) Optical micrograph of (UPE/NR) polymer blend after immersion into
(a) ethanol, (b) kerosene, and (c) benzene (15X).
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Science

Awham M. Hameed

weight gain %

1.75
1.5
1.25
1
0.75
0.5
0.25
0
0

5
0.5

Time

10

0.5

(day)

Fig.(7) Weight gain% of (UPE/NR) polymer blend with square

root of immersion time in distilled water.
2

weight gain %

1.75
1.5
1.25
1
0.75
0.5
0.25
0
0

4
Time

5
0.5

10

0.5

(day)

Fig.(8) Weight gain% of (UPE/NR) polymer blend with square

root of immersion time in tap water.
2

weight gain %

1.75
1.5
1.25
1
0.75
0.5
0.25
0
0

Time 0.5 (day)0.5

Fig.(9) Weight gain% of (UPE/NR) polymer blend with square

root of immersion time in rain water.

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Journal of Al-Nahrain University

Vol.16 (3), September, 2013, pp.148-158

Science

1.75

weight gain %

1.5
1.25
1
0.75
0.5
0.25
0
0

10

Time 0.5 (day)0.5

Fig.(10) Weight gain% of (UPE/NR) polymer blend with square

root of immersion time in HCl acid.
1.75

weight gain %

1.5
1.25
1
0.75
0.5
0.25
0
0

10

Time 0.5 (day)0.5

Fig.(11) Weight gain% of (UPE/NR) polymer blend with square

root of immersion time in H2SO4 acid.
1.5

Weight gain (%)

1.25
1
0.75
0.5
0.25
0
0

4
Time

5
(0.5)

(0.5)

day

Fig.(12) Weight gain% of (UPE/NR) polymer blend with square

root of immersion time in NaCl salt.
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Awham M. Hameed

1.6

Weight gain (%)

1.4
1.2
1
0.8
0.6
0.4
0.2
0
0

Time

0.5

10

0.5

(day)

Fig.(13) Weight gain% of (UPE/NR) polymer blend with square

root of immersion time in ethanol .
1.5

Weight gain (%)

1.25
1
0.75
0.5
0.25
0
0

4
Time

5
0.5

10

0.5

(day)

Fig.(14) Weight gain% of (UPE/NR) polymer blend with square

root of immersion time in kerosene.
2

Weight gain (%)

1.75
1.5
1.25
1
0.75
0.5
0.25
0
0

4
Time

5
0.5

0.5

(day)

Fig.(15) Weight gain% of (UPE/NR) polymer blend with square

root of immersion time in Benzene .
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Journal of Al-Nahrain University

Vol.16 (3), September, 2013, pp.148-158

Science

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) NR( ) ( UPE(
.% )95/5( ( UPE/ NR)

) (
) HCl , H2SO4, NaCl(
) (
.)UPE/NR(

) Dx( ( .
.

( Dx( (

) 3.95-9.1*10-12)m2/s.

.)non- Fickian diffusion(

851