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Transport of aromatic
hydrocarbons through
crosslinked nitrile rubber
membranes
a a
Asha Elizabeth Mathai & Sabu Thomas
a
School of Chemical Sciences, Mahatma Gandhi
University , Priyadarshini Hills PO, Kottayam,
686560, Kerala, India
Published online: 19 Aug 2006.

To cite this article: Asha Elizabeth Mathai & Sabu Thomas (1996) Transport of
aromatic hydrocarbons through crosslinked nitrile rubber membranes, Journal of
Macromolecular Science, Part B: Physics, 35:2, 229-253

To link to this article: http://dx.doi.org/10.1080/00222349608212383

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 J . MACROMOL. SCI. -PHYS., B35(2), 229-253 (1996)

Transport of Aromatic Hydrocarbons

Through Crosslinked Nitrile Rubber
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Membranes

ASHA ELIZABETH MATHAI and SABU THOMAS*

School of Chemical Sciences
Mahatma Gandhi University
Priyadarshini Hills PO, Kottayam - 686560
Kerala, India

ABSTRACT

The transport behavior of aromatic hydrocarbons in crosslinked

nitrile rubber (NBR) membranes has been studied in the tempera-
ture interval of 28O-7OoC. NBR was cured by different vulcanizing
techniques, viz., efficient, conventional, peroxide, and mixed. The
peroxide system showed the lowest solvent uptake; and the conven-
tional system, the highest. The effect of penetrant size on the sorp-
tion behavior of NBR was investigated. In all the systems the mech-
anism of diffusion showed an anomalous behavior. From the
sorption data, the interaction parameter, molecular weight between
crosslinks, Arrhenius activation energies, and thermodynamic
quantities such as enthalpy and entropy changes for sorption pro-
cesses were calculated. The first-order kinetic equation was used to
study the sorption kinetics. Finally, the experimental sorption data
were compared with theoretical predictions.

*To whom correspondence should be addressed.

229

Copyright 0 1996 by Marcel Dekker, Inc.

 230 MATHAI AND THOMAS

INTRODUCTION
Recently there has been a tremendous increase in the use of elastomers
as structural engineering materials. Therefore a wide knowledge about the
performance of elastomers under the influence of external forces such as
presence of solvents, temperature, etc., is essential. Elastomers have been
used in a number of barrier applications such as reverse osmosis, filtration,
separation, controlled release formulations, food packaging, encapsulation
of electronic circuits, etc. [ 11; and these have increased the interest of many
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scientists in the sorption and transport characteristics of elastomers.

Aminabhavi and coworkers [2-61 have made detailed analyses of the
diffusion process in various rubbery polymers. The transport of penetrants
through a rubbery matrix can be described by Fick’s law of diffusion.
However deviations from Fickian behavior are also reported [7]. The rate
of solvent diffusion within a polymer matrix is controlled by factors such
as polymer structure, its crosslink density, type of crosslinking, penetrant
size, presence of fillers, temperature, etc. Harogoppad and Aminabhavi
[4] investigated the swelling behavior of a series of polymer membranes
(neoprene, styrene butadiene rubber, ethylene propylene diene terpolymer,
nitrile rubber, natural rubber, etc.) in the presence of organic liquids and
its dependence on polymer structure. Barrer and Skirrow [8] studied the
effect of crosslinking density on diffusion for normal and branched alkanes
through crosslinked rubber, The effect of fillers on the sorption behavior
of elastomers was studied by Kraus [9].The influence of size and shape of
the penetrant molecule was described by Saleem et al. [lo]. Very recently,
the diffusion and transport of organic solvents through crosslinked poly-
meric membranes have been studied by our research group [ 12-15].
Nitrile rubber (NBR),a copolymer of acrylonitrile and butadiene, is
well known for its oil and chemical resistance. This elastomer offers a broad
balance of low-temperature, oil, fuel, and solvent resistance as related to
the acrylonitrile content. The oil resistance is due to the polarity of the NBR
molecule. Nitrile rubbers are highly resistant to nonpolar oils and solvents
but are swelled or dissolved by highly polar solvents. These characteristics
combined with their good abrasion- and water-resistant qualities make
them suitable for use in a wide variety of applications such as oil seals,
gaskets, hoses, etc., with these applications requiring knowledge of the
swelling of NBR in various liquids. Although these studies [16,17] are of
great research interest, no detailed investigations have been made so far on
the kinetics of diffusion and transport of organic solvents through various
crosslinked nitrile rubber membranes.
The main objectives of the present study is to investigate the effect of
mode of crosslinking systems on the phenomenon of diffusion of aromatic
 TRANSPORT OF AROMATIC HYDROCARBONS 23 1

hydrocarbons through nitrile rubber in the temperature range of 28O-7OoC.

The temperature dependence of the diffusion coefficient and the rubber-
solvent interaction parameter have also been determined. The first-order
kinetic equation is used to analyze the sorption data. The experimental
results are compared with the theory.

EXPERIMENTAL
Materials
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Nitrile rubber used was Aparene N553NS supplied by Gujarat Apar

Polymers Ltd., Bombay. The characteristics of the NBR are given in Table
1. The penetrants -benzene, toluene, and p-xylene (Merck)- were of re-
agent grade and were distilled twice before use. All other chemicals (stearic
acid, ZnO, CBS, TMTD, DCP, sulfur) were of laboratory reagent grade.

Sample Preparation

Nitrile rubber was vulcanized by different techniques, viz., conventional

(CV), efficient (EV), peroxide (DCP), and mixed vulcanization systems.
The formulations of the mixes are given in Table 2. The mixing of NBR
with various ingredients was carried out in a two-roll (6 x 12) mixing mill
with a friction ratio (1:1.4) as per ASTM procedure. The samples were
cured up to their optimum cure time (tw) at 150OC to obtain the best
balance of properties. The rheographs are shown in Fig. 1. The cure charac-
teristics of the samples are given in Table 3.
The polymer samples were cut into circular shapes or disks (diameter
1.94 cm) by means of a sharp-edged steel die. The thickness of the samples
was measured at several points by means of a micrometer screw gauge with
an accuracy of *0.001 cm. However, the average value of the thickness of
the samples, h, was close to 2 mm in all cases.

TABLE 1
Characteristicsof NBR
Volatile matter, 070 0.130
Antioxidant, Qo 1.400
Organic acid, 070 0.250
Soap, % 0.004
Bound acrylonitrile, 070 34.000
Mooney viscosity ML( 1 + 4) 100°C 40.000
 232 MATHAI AND THOMAS

TABLE 2
Formulation of the Mixes (parts per hundred parts
of rubber by weight)

Vulcanization system
Ingredients ‘ cv EV Mixed DCP

Nitrile rubber 100.0 100.0 100.0 100.0

Stearic acid 1.o 1.o 1.o 1.o
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Zinc oxide 5.0 5.0 5.0 5.0

CBS 1.o 1.5 1.0 -
TMTD - 1.5 - -
CDP (40%) - 4.0 4.0
Sulfur 1.5 0.5 1.5 -
“CBS, N-cyclohexyl-2-benzothiazylsulfenamide; TMTD,
tetramethyl thiuram disulfide; DCP, dicumyl peroxide.

Sorption Experiments

The circular disks were immersed in about 15-20 mL of the solvent in

test bottles, which were kept at constant temperature in an air oven. The
samples were periodically removed from the test bottles, adhering solvent
was rubbed off the surface, and the samples were weighed on a highly
sensitive electronic balance with an accuracy of &0.001 g and immediately
replaced into the test bottles. The time for each weighing was kept to a
minimum of 30-40 sec in order to eliminate the error due to the escape of
solvent from the samples [ 121. This procedure was continued until no more
liquid uptake by the polymer was observed (equilibrium saturation).
The results of solvent uptake by the polymer were expressed as moles
of solvent sorbed by 100 g of the polymer material.

RESULTS AND DISCUSSION

The sorption curves, expressed as mol% uptake, Q,, of the liquid by

100 g of the polymer versus square root of time, f l ’ * , were plotted. Figure 2
shows the mol% benzene uptake of NBR with different crosslinking sys-
tems at room temperature. It is clearly seen that the solvent uptake behavior
varies in the order CV > EV > Mixed > DCP. The Qmvalues are given
in Table 4. There are two contributing factors for such a solvent uptake
behavior. The first one is associated with the flexibility of the linkages
developed during vulcanization. The different types of crosslinks formed
 TRANSPORT OF AROMATIC HYDROCARBONS 233
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0 6 12 18 24 30

TIME (min)

FIG. 1. Rheographs of the mixes.

TABLE 3
Cure Characteristicsof the Mixes CV, EV, Mixed, and DCP at 15OOC
Vulcanization system

Cure characteristic cv EV Mixed DCP

Minimum torque (NM) 0.01953 0.01465 0.0173 0.0249

Maximum torque (NM) 0.328 0.322 0.363 0.260
Optimum cure time (min) 20.4 7.6 17.7 16.8
 234 MATHAI AND THOMAS

3.5
* CV *EV *MIXED 4 DCP
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I I I I I
0 10 20 30 40 50 60

FIG. 2. Sorption curves showing the mol% benzene uptake of CV, EV,
mixed, and DCP samples at 28OC.

TABLE 4
Values of Q- (mol%) at Different Temperatures

Vulcanization system

Temp. Solvent cv EV Mixed DCP

28OC Benzene 3.0048 2.8374 2.5768 2.4463
Toluene 2.1448 2.0175 1.8277 1.7609
p-Xylene 1 A223 1.3764 1.2492 1.2292
50°C Benzene 2.8255 2.6578 2.4686 2.31 14
Toluene 2.0077 1.8793 1.7321 1.6766
p-Xylene 1.356 1.3009 1.1969 1.1786
7OoC Benzene 2.7008 2.6121 2.3329 2.2907
Toluene 1.9575 1.8571 1.6992 1.6699
p-Xylene 1.3383 1.2656 1.1802 1.1607
 TRANSPORT OF AROMATIC HYDROCARBONS 235

during vulcanization are shown in Fig. 3. In the CV system, predominantly

polysulfidic linkages are present, which imparts high chain mobility. Hence
the solvent molecule can penetrate through the polymer matrix more easily,
and the liquid uptake is maximum. In the EV system, comparatively less
flexible mono- and disulfidic linkages are present. In the DCP system rigid
C-C linkages are present which hinder the penetration of solvent molecules
through the polymer matrix; hence the minimum solvent uptake. In the
mixed system, mono-, di-, and polysulfidic linkages as well as C-C link-
ages are present. Hence this system has an intermediate behavior. The same
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trend was observed for the other solvents also. The other major contribut-
ing factor is the extent of crosslinking of the various samples. This is dis-
cussed in a later section.
From the Qm values and from Fig. 4, it is observed that the benzene
uptake is maximum while the xylene uptake is minimum and toluene uptake
is intermediate; i.e., with an increase in the molecular size of the solvent
molecule, there is a decrease in the Qmvalues. Similar results were reported
earlier [10,18]. The influence of molecular weight of the solvent on the
equilibrium mol% uptake, Qm,is illustrated in Fig. 5 . It is observed that
the values of Qmdecrease linearly with increase in molecular weight of the
solvent in all systems.
Knowing that diffusion is influenced by the polymer morphology, in
addition to experimental variables, we have estimated the molar mass be-
tween crosslinks, M,, from the sorption data. The rubber-solvent interac-
tion parameter, x, which is needed for the estimation of M,, has been
calculated using the equation [7,13,19]

where V, and 6, are the molar volume and solubility parameter, respectively,
of the solvents; P is the lattice constant, whose value is normally
taken as 0.34; R is the universal gas constant; and Tis the absolute tempera-
ture. The estimated values of x for the solvents benzene, toluene, and
p-xylene are 0.3557, 0.3795, and 0.3958, respectively; i.e., the x value in-
creases with increasing molecular size of the penetrant. This result again
supports the decrease in the Qm values with increased size of the penetrant.
Using the above x values, the molar mass between crosslinks (M,) of
the network polymer was estimated from the following equation developed
from Flory-Rehner theory [3,20].
 236 MATHAI AND THOMAS

2
Predoininanlly polysulfidic linkages
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Predominantly mono or disulfidic linkages

C-C Linkages

Mixed Linkages

FIG. 3. Structure of the various crosslinks formed during vulcanization: (a)

CV system, (b) EV system, (c) DCP system, (d) mixed system.
 TRANSPORT OF AROMATIC HYDROCARBONS 237

*BENZENE *TOLUENE *pXYLENE

3-
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FIG. 4. Sorption curves showing the mol% uptake of NBR (EV system) with
different solvents at 28OC.

where pp is the density of the polymer, V the molar volume of solvent,

and 4 the volume fraction of polymer in the fully swollen state, which is
determined by the equation [ 13,211

where w,and p1 are the weight and density of the polymer sample, respec-
tively; and w, and p 2 are the weight and density of the solvent. The esti-
mated values of M , are given in Table 5 . These values are in the order CV
> EV > Mixed > DCP, same as the order of Q.. values. As the value of
M,increases, the spacing between crosslinks increases, thereby decreasing
the number of crosslinks between polymer chains. Hence more solvent
molecules can be accommodated easily between the crosslinks. This result
supports the maximum uptake in the CV system and minimum uptake in
the DCP system, since M, is inversely proportional to crosslink density.
 238 MATHAI AND THOMAS

3.5
* CV * EV *MIXED * DCP
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I I I
70 80 90 100 110

MOLECULAR WEIGHT

FIG. 5. Dependence of maximum mol% solvent uptake on molecular weight

of the solvent.

TABLE 5
Values of Molar Mass Between Crosslinks ( M , )

Vulcanization system

Solvent cv EV Mixed DCP

Benzene 4025.62 3666.70 3137.30 2885.89

Toluene 4089.75 3695.23 3144.52 2959.95
p-Xylene 3288.19 31 15.99 2664.18 2595.27
 TRANSPORT OF AROMATIC HYDROCARBONS 239

The swelling coefficients, a,were calculated using the equation [ 121

where M , is the mass of the swollen rubber sample; M,, the initial mass of
the polymer sample; and p s , the density of the solvent. The values of swell-
ing coefficients are given in Table 6 . These values increase in the order DCP
c Mixed < EV < CV. It can be seen that these values also decrease with
increase in molecular weight of the solvent (Table 6).
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In order to investigate the type of transport mechanism, the sorption

results were fitted to the following equation [4,2,23]
log(Q,/Q,) = log k + n log t (5)
where Qt and Q, are the mol% solvent uptake at time t and at equilibrium,
respectively; and k is a constant which depends on the structural character-
istics of the polymer and its interaction with the solvent molecule. The value
of n determines the mode of diffusion mechanism. For the Fickian mode
the value of n is 0.5 and it occurs when the rate of diffusion of permeant
molecules is much less than the relaxation rate of the polymer chains.
Usually rubber polymers exhibit Fickian diffusion. If n = 1, the mode of
diffusion is non-Fickian or case 11, and this arises when the rate of diffusion
of permeant molecules is very rapid compared to the polymer relaxation
process. Glassy polymers exhibit this type of diffusion where a sharp sol-
vent front exists, which propagates into the polymer at a constant velocity.
However, values of n between 0.5 and 1.0 define the anomalous mecha-

TABLE 6
Values of Swelling Coefficient ( a )

Vulcanization system

Temp. Solvent CV EV Mixed DCP

28OC Benzene 2.67 2.52 2.29 2.17

Toluene 2.28 2.14 1.94 1.87
p-Xy1ene 1.75 1.69 1.54 1.51
50°C Benzene 2.51 2.36 2.19 2.05
Toluene 2.13 1.99 1.84 1.78
p-Xylene 1.67 1.60 1.47 1.45
7OoC Benzene 2.40 2.32 2.07 2.03
Toluene 2.08 1.97 1.80 1.77
p-Xylene 1.65 1.56 1.45 1.43
 240 MATHAI AND THOMAS

nism. Here the diffusion rate of the permeant molecules and the relaxation
rate of the polymer are similar. Plots of log(Qr/Qm) versus log t were
constructed; and using the data from the linear portions of the sorption
curves and by linear regression analysis, the values of n and k were deter-
mined. These values are given in Table 7. There is no systematic variation
in the value of n in a temperature interval of 28O-7OoC, but the values
between 0.54 and 0.66 suggest an anomalous-type transport mechanism
with the diffusion slightly deviating from the Fickian trend. This fact can
be further supported by the slight curvature of Qtversus t”’ plots shown in
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Fig. 2 and Fig. 4. However, at high temperature (7OOC) there is a tendency

to approach the Fickian behavior. The n values of the DCP-vulcanized
samples are closest to the Fickian diffusion. The increasing values of k with
rise in temperature suggest an increase in the polymer-solvent interactions
with temperature.
From the initial linear portions of the sorption curves, the effective
diffusivity, D, of the polymer-solvent systems was calculated using the
equation [4,7,24]
D = (h8/4Q,)’ (6)
where 8 is the slope of the linear portion of the sorption curve and h is the
initial thickness of the polymer sample. The values of diffusion coefficient
are given in Table 8. The variation of the diffusion coefficient depends on
the nature of the penetrant molecule in addition to the different crosslinks
present in the polymer. However, we could not observe any systematic
trend in the values of D in terms of nature of crosslinks. The diffusion
coefficient for different crosslinking systems decreases with increasing mo-
lecular size of the penetrant. According to the free-volume theory [ 18,251
for the diffusion process in rubbery polymers, the diffusion rate of a mole-
cule depends primarily on the ease with which polymer chain segments
exchange their positions with penetrant molecules. In addition to that, the
mobility of the polymer depends on the amount of free volume in the
matrix. As the penetrant size increases, the ease of exchange becomes less,
leading to a decrease in the value of diffusion coefficient.
The diffusion coefficients for the various crosslinking systems have
been analyzed for their concentration dependencies using the model devel-
oped by Joshi and Astarita [ 2 6 ] . In this approach the model parameters
were varied incrementally over a particular range and the fit to the experi-
mental data was subjected to a linear regression analysis to get the best
values. The results of diffusion coefficient versus concentration (wtyo) at
28OC for the four different crosslinking systems in toluene and for the CV
system in the three penetrants are given in Figs. 6 and 7, respectively. All
the systems show pronounced concentration dependence of diffusivity.
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TABLE 7
Analysis of Sorption Data of NBR + Aromatic Hydrocarbons at Different Temperatures

n k x 102(g/g min")
Temp. Solvent cv EV Mixed DCP CV EV Mixed DCP

28OC Benzene 0.625 0.614 0.661 0.590 3.45 3.56 3.20 3.59
Toluene 0.621 0.622 0.590 0.581 3.60 3.51 3.92 3.65
p -X y1ene 0.625 0.609 0.576 0.585 2.81 2.92 3.19 3.52
5OoC Benzene 0.656 0.606 0.637 0.608 4.21 5.04 4.66 4.29
Toluene 0.640 0.643 0.619 0.611 4.22 4.09 4.73 4.21
p-Xylene 0.609 0.605 0.582 0.585 3.88 4.00 4.35 3.90
7OoC Benzene 0.606 0.596 0.572 0.588 5.69 5.55 6.18 5.61
Toluene 0.575 0.583 0.555 0.554 6.09 6.04 6.41 6.10
p-Xylene 0.559 0.570 0.549 0.545 5.25 5.03 5.31 4.92
 Downloaded by [University of Pennsylvania] at 15:17 20 January 2015

TABLE 8
Values of Diffusion Coefficient ( D ) ,Sorption Coefficients (S), and Permeation Coefficient (P)at 28OC

D x 107(cm2/sec) sW g ) P x 107(cm2/sec)

Solvent CV EV Mixed DCP CV EV Mixed DCP CV EV Mixed DCP

Benzene 4.05 5.15 4.50 4.62 2.34 2.21 2.01 1.91 9.48 11.38 9.04 8.82
Toluene 4.04 4.55 4.13 4.49 1.97 1.86 1.68 1.62 7.96 8.46 6.94 7.28
p-Xylene 2.59 2.68 2.72 2.73 1.51 1.46 1.32 1.30 3.91 3.92 3.60 3.57
 TRANSPORT OF AROMATIC HYDROCARBONS 243

+CV *EV *MIXED * DCP

8 ..
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3
20 30 40 50 60
CONCENTRATION ( Wt % )

FIG. 6 . Concentration dependence of diffusivity at 28OC for the different

vulcanizing systems with toluene.

The permeation of a penetrant into a polymer membrane depends on

the diffusivity as well as the solubility or sorptivity of the penetrant in the
membrane. Hence sorption coefficients S, which is the maximum saturation
sorption value, has been calculated using the equation [ 131
s = M,/M, (7)
where M, is the mass of the penetrant at equilibrium swelling and Mpis the
mass of the polymer sample. The values of S are given in Table 8. It is
found that the sorption coefficient is maximum for the CV system and
minimum for the DCP system. EV and mixed systems take intermediate
positions. The maximum value for the CV system is an indication of the
better accommodation of solvent molecules in the highly flexible polymer
networks. The lowest value for the DCP system shows the least capability
to accommodate the solvent molecules in the less flexible C-C network.
The sorption coefficients are found to decrease with increasing molecular
size of the penetrant. They also decrease with increasing temperature.
The permeability coefficient p can be computed from the following
mathematical expression [ 13,27 1.
 244 MATHAI AND THOMAS

-
+BENZENE *TOLUENE * p-XYLENE

7 -

r
-
‘cn
6-

N
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8
-5
I
.
e
X
Q
4-

3-

21 I I I

CONCENTRATION ( wt. % )

FIG. 7. Concentration dependence of diffusivity at 28OC for the conventional

vulcanized system with different solvents.

p = D*S (8)
These values are also included in Table 8. It can be seen that the permeabil-
ity coefficients decrease with increasing molecular size of the solvent. The
diffusion coefficient shows the ability of the solvent molecule to move
among the polymer chains. The sorption coefficient relates to the equilib-
rium sorption of the penetrant. A higher value of S implies the tendency of
the solvent molecule to dissolve into the polymer. The permeability coeffi-
cient shows the net effect of sorption (thermodynamic) and diffusion (ki-
netic) processes.
The dependence of the diffusion process of the four vulcanizing sys-
tems on temperature was determined by conducting the experiments at 50°
and 70° in addition to 28OC. Figure 8 shows the influence of temperature
on the CV system in xylene. The initial rate of diffusion increases with
temperature but the Qm values decrease with increase in temperature. The
same trend was shown by the other systems also. This effect may be due to
the leaching out of the additives (unreacted vulcanizing agents, Table 2)
from the rubber compound [ 281.
 TRANSPORT OF AROMATIC HYDROCARBONS 245

1.e
I *28C *50% +7O0C I
1.5

3
-0
-
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E
8 0.0

0.a

0.3

(1
10 20 30 40 50 60
,F(min)

FIG. 8. Sorption curves showing the temperature dependence of mol% xylene

uptake of CV system.

From a consideration of the temperature variation of transport coeffi-

cients ( P , D,and S) we have estimated the energy of activation for the
diffusion and permeation process from the Arrhenius relationship (7).
X = X , exp (E J R T ) (9)
where X i s P,D, or S;and X o denotes Po,Do, or So, which is a constant. Ex
is the activation energy. Arrhenius plots of log D or log P versus 1/T were
constructed and from the slopes of the curves, the values of the activation
energy for diffusion ED and the activation energy for permeation Ep are
estimated by linear regression analysis. ED is found to be greater than Ep;
and from the differences between Ep and ED,the heat sorption, AHs, was
estimated. The values of Ep,ED,and AHs are compiled in Table 9. There is
no systematic variation of activation energies regarding the different types
of crosslinking systems. However, the activation energy for permeation
 246 MATHAI AND THOMAS

TABLE 9
Activation Parameters of Diffusion (ED, kJ mol -')
Permeation (Ep,kJ mol - I ) , and Heat of Sorption (AHs,kJ mol-')
for Crosslinked NBR-Solvent Systems
Vulcanization system
Solvent Property CV EV Mixed DCP

Benzene EP 3.829 -4.193 2.800 0.431

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ED 5.978 -2.527 4.863 1.795

-AH, 2.149 1.666 2.063 1.364
To1u en e EP 2,690 0.493 4.628 0.684
ED 4.590 2.216 6.141 1.785
-AH, 1.900 1.723 1.513 1.101
p-Xy lene EP 2.422 2.551 0.775 2.919
ED 3.685 4.298 1.953 4.110
- m s 1.263 1.747 1.178 1.191

increases from benzene to p-xylene for the EV and DCP systems, and it
decreases for the CV system. In the mixed system also it shows a decreasing
trend except in toluene. The activation energy for diffusion lies between
-2.527 kJ/mol and 6.141 kJ/mol, and does not show any systematic trend
regarding the molecular size of the penetrant. The values of AHs are found
to be negative and are maximum for the CV system and minimum for the
DCP system in the solvents except in p-xylene. AH, is a composite parame-
ter involving both Henry's law and a Langmuir-type sorption mechanism.
The negative values of AHs suggest that the Langmuir-type sorption mecha-
nism predominates, in which the solvent molecules fill the holes already
existing within the polymer matrix; this gives rise to an exothermic process.
The molar equilibrium sorption coefficient (K,) is defined as [29]
No. of moles of solvent sorbed at equilibrium
K, = (10)
Mass of the polymer
These values are estimated and given in Table 10. They are in the same
order CV > EV > Mixed > DCP and are also related to the size of the
penetrant. It decreases from benzene to p-xylene. This is due to the fact
that benzene, being small in size, can be absorbed in larger amounts than
toluene and p-xylene. Thus sorption is not only governed by the differences
in solubility parameters, but also by the difference in polymer structure and
the size of the penetrant molecule. From the values of K,, the enthalpy
 TRANSPORT OF AROMATIC HYDROCARBONS 247

TABLE 10
Molar Equilibrium Sorption Constants
( K , x 10' rnol g-') at Different Temperatures

Vulcanization system
Temp.
Solvent ("C) CV EV Mixed DCP
Benzene 28 3.00 2.81 2.58 2.45
50 2.83 2.66 2.47 2.31
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70 2.70 2.61 2.33 2.29

Toluene 28 2.14 2.02 1.83 1.76
50 2.01 1.88 1.73 1.68
70 1.96 1.86 1.70 1.67
Xylene 28 1.42 1.38 1.25 1.23
50 1.36 1.30 1.20 1.18
70 1.34 1.27 1.18 1.16

(AHs)and entropy (AS)of sorption were calculated using the van't Hoff
relation [3,18].

log Ks= AS -
- u s

2.303R 2.303RT
A typical van't Hoff plot of log K,versus 1/T for the CV system with
the three solvents is shown in Fig. 9, and the computed values of MS and
AS are given in Table 11. The value of A S ranges from - 34.88 kJ/mol to
-41.43 kJ/mol and is negative in all cases, suggesting the retainment of
liquid structure in the sorbed state within the polymer matrix. The negative
values of A S increase with increasing molecular size of the penetrant, sug-
gesting the easy permeation of small molecules through the polymer matrix
and the retainment of liquid structure of larger molecules. Here also the
AHs are found to be negative, suggesting an exothermic process. It is inter-
esting to note that these values are in close agreement with those calculated
from the difference Ep - ED.It again supports the fact that the molecular
transport of aromatic hydrocarbons through crosslinked nitrile rubber is a
net effect of sorption, diffusion, and permeation processes.
We have analyzed the sorption data in terms of the first-order kinetic
model. Southern and Thomas [30] pointed out that when a sheet of rubber
vulcanizate is immersed in a solvent, the surface layer swells instantane-
ously, but that, initially, the swelling in the lateral direction is prevented by
the underlying unswollen material. Thus a two-dimensional compressive
stress is developed in the polymer surface, and this will reduce the equilib-
 248 MATHAI AND THOMAS

-1.4
* BENZENE *TOLUENE * pXYLENE

-1.6 1 I
I t

9
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- I I I I I
I

2.8 2.9 3 3.1 3.2 3.3 3.4

1/TX lo3 (K’)

FIG. 9. Van’t Hoff plots (log K , vs. 1/T) for the CV system with different
solvents.

TABLE 11
Van’t Hoff Parameters Enthalpy (AH,, kJ/mol) and
Entropy (AS, J/mol) of Sorption

Vulcanization system

Solvent Property cv EV Mixed DCP

Benzene -AH, 2.216 1.555 2.068 1.364

- AS 36.480 34.880 31.230 35.420
Toluene -AH, 1.900 1.723 1.517 1.100
-AS 38.720 38.230 38.330 37.280
p-Xylene -AHs 1.263 1 .I42 1.182 1.192
-AS 39.850 41.430 40.380 40.550
 TRANSPORT OF AROMATIC HYDROCARBONS 249

rium swelling of the surface layer. As the swelling goes on, the surface area
increases and the compressive stress decreases and finally reaches the free
unconstrained state at equilibrium swelling of the surface layer. Therefore
we can use the following first-order kinetic equation to study the transport
kinetics [ 181.
k't = 2.303 lOg[C, - C,)] (12)
where k' is the first-order rate constant; C, and C, are the mole concentra-
tion at time t and at infinite time. In order to follow the usual conventions
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in chemical kinetics, we used C , and C, instead of Qo. and Qt. Figure 10

shows the plots of log(C, - C,) versus t for all the systems in toluene at
28OC. From the slope of the graph, we estimated the values of k ' ; they are
compiled in Table 12. Except in benzene and at higher temperature, rate
constants are in the same order CV > EV > Mixed > DCP. In all cases
the DCP system has the lowest rate constant values. It decreases from
benzene to p-xylene. Moreover, in all cases the rate constant increases with

FIG. 10. Dependence of log(C, - C,) versus t for the different vulcanizing
systems in toluene at 28OC.
 250 MATHAI AND THOMAS

TABLE 12
Rate Constants (K' x lo3min -') for
NBR-Solvent Systems at Different Temperatures

Vulcanization system
Temp.
Solvent ("C) CV EV Mixed DCP

Benzene 28 10.6 10.3 11.5 8.8

50 13.8 14.1 14.6 12.2
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I0 16.6 14.1 17.0 14.9

Toluene 28 10.6 10.3 10.1 8.1
50 14.5 14.7 16.5 12.6
70 16.1 17.6 16.8 14.7
p-Xylene 28 7.0 6.4 5.7 4.6
50 10.9 11.4 11.1 9.1
70 13.5 14.0 13.2 10.5

1.2
--THEORETICAL *EXPERIMENTAL

0 5 10 15 20 25 30 35 40 45 50
JT(rnin)
FIG. 11. Sorption curve showing the comparison between experimental and
theoretical curve for the EV system in toluene at 28OC.
 TRANSPORT OF AROMATIC HYDROCARBONS 25 1

1.2
-THEORETICAL *EXPERIMENTAL

’I
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I I I I I I I I I I
0 5 10 15 20 25 30 35 40 45 50
J(min)

FIG. 12. Sorption curve showing the comparison between experimental and
theoretical curves for the DCP system in toluene at 28OC.

increasing temperature, supporting the fact that the rate of diffusion in-
creases with increasing temperature.
The diffusion coefficients as calculated from Eq. (3) have been fitted
to the following equation, which describes the Fickian diffusion model, to
generate the theoretical sorption curves [311.

c 1/(2n + l)’exp[-D(2n
cn

-
Qt - 1 - -8i + 1)2?r2t/h2] (13)
Qo. n=O

Q,,Qm, D, t, h, etc., have the same meaning as before. These sorption curves
are compared in Figs. 11 and 12 with the experimental profile for the EV and
DCP systems in toluene at 28OC. The total agreement is fairly good. A similar
trend was shown by the other systems and other solvents also.

CONCLUSIONS

In the present study, diffusivity, sorptivity, and permeability of three

aromatic hydrocarbons through crosslinked nitrile rubber membranes are
 252 MATHAI AND THOMAS

investigated, and it is found that the nature of crosslinking system has

an important role in the transport process. The uptake is highest for the
conventional system, and lowest for the peroxide system. The mixed and
the EV systems show intermediate behavior. This has been explained based
on the flexibility of the polymeric chains as well as the molecular weight
between crosslinks. In the conventional system, highly flexible polysulfidic
linkages are present which can accommodate more solvent molecules within
the polymer matrix. Hence the solvent uptake is maximum. As the pene-
trant size increases the maximum solvent uptake decreases. The values of n
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suggest slight deviation from the normal Fickian behavior and the mecha-
nism is anomalous. It is found that temperature activates the diffusion
process, which is supported by the increasing rate constant values. The
Arrhenius parameters were estimated. The van’t Hoff relationship was used
to compute the entropy and enthalpy of sorption, and the first-order rate
equation was fit for the crosslinked NBR-solvent systems. The rubber-
solvent interaction parameter was estimated and it was found that benzene
has the maximum interaction with crosslinked NBR. Theoretical and exper-
imental results were in good agreement in all systems and solvents. Finally,
it is important to mention that a knowledge of these parameters should be
highly helpful for the widespread application of nitrile rubber membranes.

ACKNOWLEDGMENT

One of the authors (A.E.M.) is thankful to Mr. George Varghese,

Managing Director, and the staff of the R&D Centre of Midas Rubber [PI
Ltd., Kottayam, for providing experimental facilities and valuable help.

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Received May 15, 1995

Revised August 11, 1995
Accepted September 5, 1995