Journal of Membrane Science 202 (2002) 3554

Transport of substituted benzenes through nitrile rubber/natural rubber blend membranes

Asha Elizabeth Mathai a , R.P. Singh b , Sabu Thomas c,
c

Department of Chemistry, C.M.S. College, Kottayam, Kerala-686 001, India b National Chemical Laboratory, Pune 411 008, India School of Chemical Sciences, Mahatma Gandhi University, Priyadarshini Hills, P.O. Kottayam, Kerala 686 560, India Received 1 May 2001; accepted 4 October 2001

Abstract Diffusion and permeation properties of substituted benzenes (aromatics) through a new variety of membranes from blends of nitrile rubber and natural rubber (NR) have been investigated in the temperature interval of 2870 C to characterise the physical and chemical properties of the polymer blend. These blend membranes nd application in the dairy industry, where good mechanical properties and swelling resistance are required. The effects of blend ratio and penetrant size on the transport properties were studied. In the blends, the equilibrium solvent uptake decreases with an increase in concentration of nitrile rubber. The relationship between the transport behaviour and the morphology of the system was examined. The mechanism of diffusion shows an anomalous trend. The sorption data have been used to estimate the activation energies for diffusion and permeation. The vant Hoff relationship was used to determine the thermodynamic parameters. The afne and phantom models for chemical cross-links were used to predict the nature of cross-links. The experimental diffusion data were compared with various theoretical predictions. 2002 Elsevier Science B.V. All rights reserved.
Keywords: Nitrile rubber; Natural rubber; Morphology; Diffusion; Permeation

1. Introduction During the last few decades, the importance of polymer blends have increased, since it is possible to tailor desirable properties by simple blending of polymers. Polymer blending has already been established as an effective means for constructively altering the transport properties of polymeric materials. However, many of these polymer blends are incompatible or immiscible. They are characterised by narrow interface and weak interfacial interaction, and often exhibit
Corresponding author. Tel.: +91-481-598-303; fax: +91-481-561-190/800. E-mail addresses: sabut@md4.vsnl.net.in, sabuthom@satyam.net.in (S. Thomas).

poor mechanical properties [1]. The transport behaviour of various organic solvents and gases through polymers is of great technological importance and it plays a vital role in a variety of barrier applications [24]. Nowadays, polymer membranes are used in the preservation of food articles and vegetables [5]. For example, in a majority of high barrier food packages, copolymers containing polyvinylidene chloride and ethylenevinyl alcohol copolymer are used. Tailored nylons give a route to the fabrication of small and large containers with barrier to hydrocarbons and other types of solvents and their mixtures [6]. Xiao et al. investigated the effect of gasoline and oil contamination on the barrier properties of natural rubber (NR), nitrile rubber and bromobutyl rubber [7]. They found that oil contamination has little effect on

0376-7388/02/$ see front matter 2002 Elsevier Science B.V. All rights reserved. PII: S 0 3 7 6 - 7 3 8 8 ( 0 1 ) 0 0 7 0 0 - 1

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Nomenclature CRI D D EX h HS M Mc ML P Qt Q R S t2 t90 T V w cure rate index (min1 ) diffusion coefcient (cm2 s1 ) intrinsic diffusion coefcient (cm2 s1 ) activation energy (kJ mol1 ) initial thickness of the polymer membrane (cm) enthalpy of sorption (kJ mol1 ) mass (g) molecular weight between cross-links (g mol1 ) minimum viscosity (N m) permeability coefcient (cm2 s1 ) moles of solvent sorbed by 100 g of polymer at time t (%) moles of solvent sorbed by 100 g of polymer at equilibrium (%) universal gas constant (J K1 mol1 ) sorption coefcient (g g1 ) rheometric scorch time (min) optimum cure time (min) absolute temperature (K) molar volume (cm3 mol1 ) weight (g)

Greek letters lattice constant polymer-solvent interaction parameter solubility parameter [(J m3 )1/2 ] volume fraction of polymer in the solvent swollen sample number of effective chains number of effective junctions 2c polymer volume fraction during cross-linking 2m polymer volume fraction at swelling equilibrium slope of the initial linear portion of the sorption curve density (g cm3 ) Subscripts p polymer (membrane) s solvent

the subsequent transport of the organic penetrants but, gasoline contamination alters the subsequent transport behaviour of the organic penetrants, depending on the nature of the rubber and the contamination conditions. Barrier properties of electron-beam-modied EPDM rubber was studied by Majumder et al. [8]. The study of diffusion, sorption and permeation in blend structures provides a valuable means for additional characterisation of polymer blends. The diffusion behaviour in polymer blends was rst reported by Cates and White [911]. They investigated the water sorption characteristics of polyacrylonitrile (PAN)/cellulose, PAN/silk and PAN/cellulose acetate blends. Dixon-Garrett et al. reported the solubility, diffusivity and permeability of ethylbenzene in poly(1-trimethylsilyl-1-propyne) (PTMSP) [12]. They found that the diffusion coefcient of ethylbenzene in PTMSP decreased with increasing concentration and decreasing temperature. Solvent sorption effects on the structure and properties of polypropylene/Rodrun (a thermotropic liquid crystal polymer) blends were also reported in [13]. The rate of sorption and desorption and the solvent content at the equilibrium were higher in the blends than in pure PP. This was attributed to microcracking in the PP matrix induced by the presence of Rodrun. Molecular transport of alkanes [14] and haloalkanes through blends of ethylenepropylene random copolymer and isotactic polypropylene has been reported by Aminabhavi et al. [15]. The sorption, desorption, resorption and redesorption characteristics were inuenced by the nature of the liquid and the temperature. Nitrile rubber (NBR) is widely used in many applications like oil seals, gaskets, etc. The performance of NBR can be improved by blending with various polymers [1619]. The blending of NBR with NR was found to improve the physical and mechanical properties of NBR [20]. The high strength of these blends has already attracted the attention of dairy industry. Such products must be capable of resistance to swelling by butter, fat, etc. and yet have the strength required by the service conditions, particularly when the use of reinforcing black llers is not practical, because of the need to meet food contact regulations. Appropriately compounded blends of NR and NBR can provide a cost-effective solution to this need. The swelling characteristics of polymeric materials can be used to understand the interaction between polymers in the

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solid state and solvent molecules. Hence, it is necessary to analyse the transport behaviour and the mechanism of transport of various organic solvents through NBR/NR blends in detail. To our knowledge, no serious attempt has been made so far to study the transport properties of these blends. The aim of the present work is to investigate the diffusion and sorption behaviour of organic solvents through cross-linked NBR/NR blends. The effects of blend composition, temperature and nature of penetrants on the diffusion process have been studied. The experimental results have been compared with theoretical predictions.

Table 2 Compounding recipe (parts per 100 parts of rubber by weight) Ingredients ZnO Stearic acid Sulphur TDQa CBSb
a b

NR 5.0 1.5 2.5 1.0 0.6

NBR 5.0 1.0 1.5 1.0

Trimethyl-dihydro-quinoline. N-cyclohexyl-2-benzothiazole-sulphenamide.

2. Experimental 2.1. Materials Nitrile rubber (Aparene-N 553 NS) with a bound acrylonitrile content of 34%, was supplied by Gujarat Apar Polymers Ltd., Mumbai, India. Indian standard natural rubber (ISNR-5) was supplied by Rubber Research Institute of India, Kottayam, India. The basic characteristics of the materials are shown in Table 1. All the rubber chemicals were of commercial grade. The mixing was done on a two-roll mixing mill (friction ratio 1:1.4) and vulcanising agents were incorporated as per ASTM procedure. The basic formulation used is given in Table 2. NBR/NR blend membranes were prepared by the masterbatch technique [21]. The blend compositions are N0 , N30 , N50 , N70 and N100 , where the subscripts denote the weight

percentage of NR. The cure characteristics of the mixes were determined on an Elastograph (Goettfert, 67.5, Rev. 1.5, Germany) at 150 C. The compounds were then compression moulded along the mill grain direction using an electrically heated hydraulic press at 150 C. 2.2. Transport experiments The circular samples of diameter 1.94-cm were cut from vulcanised sheets and immersed in test bottles, which were kept at constant temperature in an air oven. The samples were periodically removed from test bottles, the adhering solvent blotted off the surface, and the samples were weighed on an electronic balance (Shimadzu, Libror AEU-210, Japan) with an accuracy of 0.001 g and immediately replaced into the test bottles. This procedure was continued until equilibrium swelling was attained. The results of these experiments were expressed as moles of solvent uptake by 100 g

Table 1 Basic characteristics of NBR and ISNR-5 Materials Nitrile rubber (Aparene N553 NS) Characteristics Volatile matter (%) Antioxidant (%) Organic acid (%) Soap (%) Mooney viscosity (ML1+4 100 C) Bound acrylonitrile (%) Intrinsic viscosity (dl g1 ) Glass transition temperature ( C) Density (kg m3 ) Solubility parameter (J m3 )1/2 Number average (mol wt.%) 0.13 1.40 0.25 4 103 40.00 34.00 1.53 72 0.92 16.2 1 106

Natural rubber (ISNR-5)

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A.E. Mathai et al. / Journal of Membrane Science 202 (2002) 3554 Table 3 Cure characteristics Cure characteristics Minimum torque (N m) Maximum torque (N m) Scorch time (min) Optimum curetime (min) CRI (min1 ) N100 0.03 0.24 2.17 5.78 27.68 N70 0.01 0.25 2.40 7.70 18.87 N50 0.02 0.30 2.93 8.03 19.62 N30 0.02 0.35 3.55 9.80 16.00 N0 0.02 0.33 8.31 20.40 8.27

of polymer sample, Qt (mol%) Qt = mass of solvent sorbed/molar mass of solvent mass of polymer 100 (1)

3. Results and discussion 3.1. Cure characteristics The rheographs of the mixes are given in Fig. 1 and cure characteristics in Table 3. In the rheograph,

torque is plotted against time. The minimum torque in the rheograph is presented as minimum viscosity value (ML ) and is a measure of the extent of mastication. The lowest value of N70 indicates its higher

Fig. 1. Rheographs of the mixes.

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39

extent of mastication during mixing. The maximum torque in the rheograph is presented as maximum viscosity. The highest value is for N30 composition. From the formulations, it can be seen that in the present study the membranes were vulcanised with conventional vulcanising system. The increase in sulphur/accelerator ratio results in predominantly polysulphidic linkages. The rheometric scorch time t2 (premature vulcanisation time) is the time taken for minimum torque value to increase by two units. It increases from N100 to N0 , i.e. the N0 composition shows maximum scorch

safety. Optimum cure time (t90 ) is the vulcanisation time to get optimum physical properties and it is the time corresponding to optimum cure torque. N0 shows maximum cure time while N100 shows minimum cure time. Cure rate index (CRI) is calculated using the equation [22] CRI = 100 t90 t2 (2)

The higher the CRI values the higher the vulcanisation rate. From Table 3, it can be seen that NR has the highest cure rate and NBR the minimum. Among the

Fig. 2. Sorption curves of homopolymers and blend compositions in toluene at 28 C.

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blend compositions, N50 has the highest cure rate. The high CRI value of NR is due to its high degrees of unsaturation. 3.2. Transport properties The effect of blend composition on the sorption behaviour of NBR/NR blend membranes in toluene is presented in Fig. 2. From Fig. 2, it is observed that the sorption behaviour varies in the order N100 > N70 > N50 > N30 > N0 , i.e. the equilibrium solvent uptake decreases with increase in volume fraction of

NBR. This is attributed to the inherent solvent resistance behaviour of NBR. The variation in equilibrium solvent uptake (Q ) with volume fraction of NR is shown in Fig. 3. The trend is in accordance with the above observation. It has already been established that the permeability of heterogeneous rubberrubber blends is intermediate between that of the component polymer [23]. The difference in Q values with blend composition can be correlated with the morphology of the system. The scanning electron micrographs of N30 , N50 and N70 blends are shown in Fig. 4. It is seen that in N70 , NBR phase is dispersed in the

Fig. 3. The variation in equilibrium toluene uptake (Q ) values with volume fraction of NR at 28 C.

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Table 4 Values of n and k for toluene diffusion through NBR/NR blends Sample N100 N70 N50 N30 N0 n 0.64 0.60 0.60 0.60 0.63 k (g g1 minn ) 1.21 1.43 1.36 1.31 1.32

continuous NR matrix and in N30 , NR is dispersed in the continuous NBR matrix. In the N50 blend both NR and NBR form continuous phase leading to a co-continuous morphology. Because of the dispersed nature of NR phase in N30 , the continuous NBR phase acts as a tortuous path for the diffusion process of solvent and hence the uptake is less. This is schematically shown in Fig. 5. However, as the concentration of NR increases from 30 to 70 wt.%, the size of NR domain increases and it forms the continuous phase and the diffusion process is continuous through the NR phase, which leads to the high uptake in N50 and N70 . The mechanism of diffusion of NBR/NR blends was analysed using the empirical relation [24] log Qt Q = log k + n log t (3)

Fig. 4. Scanning electron micrographs of (a) N30 , (b) N50 and (c) N70 .

where Qt and Q are the mol% sorption at time t and at equilibrium, respectively, and k is a constant that depends on the structural characteristics of the polymer and gives information about the interaction between the polymer and solvents. The value of n = 0.5 indicates a Fickian mode of transport, while n = 1 indicates case II (relaxation controlled) transport. The value of n between 0.5 and 1 indicates anomalous transport behaviour. The values of n and k for NBR/NR blends is obtained by regression analysis of log (Qt /Q ) versus log t plot and the results are given in Table 4. From Table 4, it can be seen that the values of n ranges from 0.60 to 0.64, i.e. in NBR/NR blends, the mode of transport is close to Fickian. For the Fickian mode of transport, the rate of diffusion of penetrant molecules is much less than the relaxation rate of the polymer chains. The permeation of small molecules through polymers generally occurs through a solution diffusion

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Fig. 5. Schematic representation of the transport behaviour in NBR/NR blends.

mechanism, i.e. the penetrant molecules are rst sorbed by the polymer followed by diffusion through the polymer. The net transport through the polymer depends on the difference in the amount of penetrant molecules between the two surfaces. Hence, the permeability [25] P = DS where D is the diffusivity and S is the solubility. (4)

The diffusion coefcient D can be calculated using the equation [26] Qt 8 =1 2 Q

n=0

1 (D(2n + 1)2 2 t) exp (2n + 1)2 h2 (5)

where t is the time and h is the initial thickness of the polymer membrane. Although this equation can

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43

be solved readily, it is instructive to examine the short-time limiting expression as well Qt Dt =4 Q h2

1/2

Table 5 Values of sorption coefcient (S) (g g1 ) Sample Benzene 3.48 3.14 2.91 2.62 2.59 Toluene 3.45 3.03 2.65 2.32 2.01 p-Xylene 3.39 2.65 2.49 2.05 1.61

(6)

From a plot of Qt versus t1/2 , a single master curve is obtained which is initially linear. Thus D can be calculated from an equation obtained by rearranging Eq. (6) as D= h 4 Q
2

N100 N70 N50 N30 N0

(7)

where h is the sample thickness and is the slope of the initial linear portion of the sorption curves, i.e. before the attainment of 50% equilibrium solvent uptake. The value of D depends on the polymer segmental mobility. Eq. (7) holds for systems without appreciable swelling. For considerable swelling, a correction for the swelling of the polymer can be made by incorporating , the volume fraction of the polymer in the swollen mass, thus giving the intrinsic diffusion coefcient, D [27] D = D 7/3 (8)

in Fig. 7. As expected, as the size of the permeant molecule increases the solvent uptake decreases, i.e. the low molecular weight solvent benzene shows the highest uptake while xylene, the high molecular weight solvent shows lowest uptake. The permeability of a penetrant in a polymer membrane depends on the diffusivity as well as solubility or sorption of the penetrant in the polymer membrane. Therefore, the sorption coefcient that is related to the equilibrium sorption of the penetrant is calculated using the equation [29] S= Ms Mp (10)

Volume fraction of polymer in the solvent swollen sample was calculated using the equation [25] = w1 /1 (w1 /1 ) + (w2 /2 ) (9)

where w1 and 1 are the weight and density of the polymer sample, respectively; and w2 and 2 are the weight and density of the solvent. The variation in intrinsic diffusion coefcient with volume fraction of NBR in different solvents is illustrated in Fig. 6. It is observed that the D value decreases with increase in NBR content. The permeation of a penetrant into the polymer matrix depends on the polymer morphology, which controls the propagation of a molecule from one site to another. Any morphological factors that modify either the structure or the exibility of the polymer chains will be expected to change the diffusivity of the molecule [28]. Moreover, the diffusivity values decrease with increase in molecular size of the penetrant. Benzene, toluene and p-xylene were used to study the effect of penetrants. The sorption curves of N50 sample for the three solvents are exhibited

where Ms is the mass of the solvent at equilibrium swelling and Mp is the mass of the polymer sample. These values are shown in Table 5. The sorption coefcient value decreases with increasing NBR content in the blend composition because the solvent resistance increases with increasing NBR content. The values of permeability coefcient P, which implies the net effect of sorption and diffusion, are given in Table 6. Similar trend as that of D and S is observed for P values with the change in blend composition. The effect of weight percentage of NR on intrinsic diffusion (D ) and permeation (P) coefcients is shown in Fig. 8. D and P increase regularly up to 50 wt.% of NR. Beyond that the properties increase sharply. This can be attributed
Table 6 Values of permeability coefcient (P 105 ) (cm2 s1 ) Sample N100 N70 N50 N30 N0 Benzene 14.70 8.83 6.28 4.75 3.84 Toluene 11.90 6.21 5.53 3.53 2.21 p-Xylene 11.25 5.03 3.64 1.74 0.76

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Fig. 6. Variation of intrinsic diffusion coefcient (D ) with volume fraction of NBR in different solvents at 28 C.

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Fig. 7. Sorption curves of N50 composition in different penetrants at 28 C.

to the phase inversion in the morphology of the system. In N30 , NR phase is dispersed in the continuous NBR matrix and in N50 and N70 , NR phase becomes the continuous phase. In the case of heterogeneous polymer blends, the permeability can be interpreted in terms of various theoretical models. Robesons two limiting models, namely series and parallel models, are generally used in the case of polymer blends. According to the parallel model PC = P1 1 + P2 2 (11)

and by the series model PC = P 1 P2 (1 P2 + 2 P1 ) (12)

where PC , P1 and P2 are the permeation coefcients of the blend, component I and component II, respectively, and 1 and 2 are the volume fractions of components I and II, respectively. To describe the effect of permeating component on the overall blend permeability, Maxwell suggested the

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Fig. 8. Variation of D and P with weight percentage of NR in benzene at 28 C.

following equation [30,31]: PC = Pm Pd + 2Pm 2d (Pm Pd ) Pd + 2Pm + d (Pm Pd ) (13)

expressed the equations as PC = xa P1 P2 + 2P1 22 (P1 P2 ) P2 + 2P1 + 2 (P1 P2 ) P1 + 2P2 21 (P2 P1 ) +xb P2 P1 + 2P2 + 1 (P2 P1 )

where the subscripts d and m correspond to the dispersed phase and the matrix, respectively. Robeson [31] extended Maxwells analysis to include the continuous and discontinuous characteristics of both phases at intermediate compositions and

(14)

where xa and xb are the fractional contributions to the continuous phase so that x a + x b = 1.

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Fig. 9. Theoretical modelling for the permeation coefcients of NBR/NR blends in benzene at 28 C.

Fig. 9 shows the variation of permeation coefcient with volume fraction of NBR. The experimental values are close to the Robeson model where NBR is the dispersed phase and NR is the continuous phase; beyond that it is close to the series model. In order to study the effect of temperature on the transport properties, the sorption experiments were carried out at 5070 C in addition to 28 C. Figs. 10 and 11 show the effect of temperature on mol% xylene uptake of N50 and N30 blends. As expected, the solvent uptake increases with increase in temperature. The values of transport coefcients also increase with

increase in temperature. The temperature dependence of transport properties can be used to evaluate the activation energy for the diffusion and permeation process using the Arrhenius relation [29] X = X0 exp EX RT (15)

where X represents either P or D, EX , the activation energy, R the universal gas constant, and T the absolute temperature. Arrhenius plot of log P versus 1/T for calculating the activation parameters is given in Fig. 12. Values of ED and EP are presented in Table 7.

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Fig. 10. Sorption curves of N50 in xylene at different temperatures.

Table 7 Values of activation parameter, ED , EP and Sample N100 N70 N50 N30 N0 EP (kJ mol1 ) 9.51 10.07 10.09 10.83 10.82 ED (kJ mol1 ) 7.31 8.22 8.59 10.22 10.95

The uncertainty in the values ranges from 0.001 to 0.003. It is seen that as the concentration of NBR increases both ED and EP values increase. The enthalpy of sorption is calculated from the equation
H H (kJ mol1 ) 2.20 1.85 1.50 0.61 0.13

HS = EP ED

(16)

These values are also included in Table 8. HS is a composite parameter involving the contribution from (i) Henrys law needed for the formation of a site and the dissolution of the species into that site, the formation of the site involves an endothermic

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Fig. 11. Sorption curves of N30 in xylene at different temperatures.

Table 8 Comparison of network structure System N100 N70 N50 N30 N0 Mc (expt) (g mol1 ) 8108 5788 3603 3207 3288 Mc (aff) (g mol1 ) 7581 5433 3390 3026 3114 Mc (ph) (g mol1 ) 3790 2716 1695 1513 1557

contribution and (ii) Langmuirs (hole lling) type sorption mechanism, in which case the site already exists in the polymer matrix and sorption by hole lling gives exothermic heat of sorption. The positive HS values for NR and the blends suggest a Henrys type sorption and the negative HS value for NBR suggests a Langmuir type sorption. 3.3. Determination of the network structure The investigation of swelling equilibrium can help to elucidate the structure of the polymer network.

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Fig. 12. Arrhenius plot of log P vs. 1/T.

Diffusion into solid polymers depends on the availability of appropriate molecular size holes in the network, in addition to the attractive forces between the penetrant molecules and the polymer. From the structure and morphology of the polymer, the presence of holes is determined in terms of chain entanglement densities and its dependence on swelling. In order to gain further insight into the sorption process in relation to the morphological characteristics of the polymer, the molecular weight between cross-links (Mc ) has been estimated by using the equation

[32,33] Mc = p Vs 1/3 ln(1 ) + + 2 (17)

where p is the density of the polymer, Vs the molar volume of the solvent, the volume fraction of the polymer in the fully swollen state and is the polymerpenetrant interaction parameter which is calculated from the equation [34] Vs =+ (s p )2 (18) RT

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where s and p are the solubility parameters of the solvent and the polymer, the lattice constant whose value is taken as 0.34, R is the universal gas constant and T is the absolute temperature. Whenever a polymer is immersed in an organic liquid, its molecules will diffuse into the solid polymer lm to produce a swollen gel. Dissolution is prevented if the attraction between neighbouring polymer molecules is sufciently great, perhaps due to cross-linking. Swelling equilibrium is approached when the chemical potential of the solvent inside the swollen polymer becomes equal to that of the outside phase. The estimated values

of Mc are given in Table 8. These values are in the order N100 > N70 > N50 > N30 > N0 , supporting the solvent uptake behaviour in the blends and the component polymers. 3.4. Model tting Flory and Rehner [35] developed the afne model for a network deforming afnely, where the components of each chain vector transform linearly with macroscopic deformation and the junction points are assumed to be embedded in the network without

Fig. 13. Comparison of experimental and theoretical diffusion curves of N50 in toluene at 28 C.

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uctuations. Then the molecular weight between cross-links (Mc ) for the afne limit of the model [Mc (aff)] was calculated using the formula [35,36] Mc (aff ) = Vs 2c 2m (1 /2m )
2 ] [ln(1 2m ) + 2m + 2m 2/3 1/3 1/3

(19)

where Vs is the molar volume of the solvent, and are called the number of effective chains and junctions, 2m , the polymer volume fraction at swelling equilibrium, 2c , the polymer volume fraction during cross-linking, and is the polymer density.

The phantom network model was proposed by James and Guth [37], where the chains may move freely through one another. The junction points uctuate over time around their mean position without being hindered by the presence of the neighbouring chains and are independent of deformation. The molecular weight between cross-links for the phantom limit of the model [Mc (ph)] was calculated by [36,38] Mc (ph) = (1 2/)Vs 2c 2m
2/3 1/3 2 ] [ln(1 2m ) + 2m + 2m

(20)

where is the junction functionality.

Fig. 14. Comparison of experimental and theoretical diffusion curves of N30 in toluene at 28 C.

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Mc (aff) and Mc (ph) were compared with Mc (expt) and these values are also given in Table 8. It is observed that Mc values are close to Mc (aff). This suggests that in the highly swollen state, the chains in the blends and in the component polymers deform afnely, i.e. the chains in the network are freely moving without uctuating the junction points. 3.5. Comparison with theory The experimental diffusion results were compared with theoretical predictions using the relation [39] Qt =1 Q
x =0

lie close to the afne model. Theoretical and experimental diffusion results were in good agreement in all the blend compositions.

Acknowledgements One of the authors (A.E. Mathai) is grateful to Council of Scientic and Industrial Research, New Delhi for the award of Senior Research Fellowship. References
[1] D.R. Paul (Ed.), Polymer blends, Vol. II, Academic Press, New York. NY, 1976 (Chapter 12). [2] Y.M. Lee, D. Bourgeois, G. Belfort, Sorption, diffusion and pervaporation of organics in polymer membranes, J. Membr. Sci. 44 (1989) 161. [3] T.M. Aminabhavi, U.S. Aithal, Molecular transport of oxygen and nitrogen through polymer lms, J. Macromol. Sci. Rev. Macromol. Chem. Phys. C 31 (2/3) (1991) 117. [4] W.J. Koros, Barrier polymers and structures: overview, in: W.J. Koros (Ed.), Barrier Polymers and Structures, ACS Symposium Series, Washington, DC, 1990, pp. 121. [5] R.J. Ashley, Plastic Materials. Illiffe, London, 1966 (Chapter 7). [6] P.M. Subramanian, Polymer blendsmorphology and solvent barriers, in: W.J. Koros (Ed.), Barrier Polymers and Structures, ACS Symposium Series, Washington, DC, 1990. [7] S. Xiao, D. DeKee, J. Bovenkamp, Effect of gasoline contamination on the permeation of organic liquids through rubber membranes, Rubber Chem. Technol. 72 (1999) 758. [8] P.S. Majumder, A.K. Bhowmick, A.B. Majali, V.K. Tikku, Barrier properties of electron-beam-modied EPDM rubber, J. Appl. Polym. Sci. 75 (2000) 784. [9] D.M. Cates, H.J. White Jr., Preparation and properties of bers containing mixed polymers. Part I. Polyacrylonitrilecellulose acetate bers, J. Polym. Sci. 20 (1956) 155. [10] D.M. Cates, H.J. White Jr., Preparation and properties of bers containing mixed polymers. Part II. Polyacrylonitrilecellulose bers, J. Polym. Sci. 20 (1956) 181. [11] D.M. Cates, H.J. White Jr., Preparation and properties of bers containing mixed polymers. Part III. Polyacrylonitrilesilk bers, J. Polym. Sci. 21 (1956) 125. [12] S.V. Dixon-Garrett, K. Nagai, B.D. Freeman, Sorption, diffusion, and permeation of ethyl benzene in poly(1-trimethylsilyl-1-propyne), J. Polym. Sci. B: Phys. 38 (2000) 1078. [13] G. Guerrica-Echevarria, J.I. Eguiazabal, J. Nazabal, Solvent sorption effects on the structure and properties of PP/Rodrun blends, J. Polym. Sci. B: Phys. 38 (2000) 1090. [14] T.M. Aminabhavi, H.T.S. Phayde, Molecular transport of alkanes through thermoplastic miscible blends of ethylene propylene random copolymer and isotactic polypropylene, J. Appl. Polym. Sci. 55 (1995) 1335.

8 2 2 2 e(2x +1) (Dt/ h ) (21) (2x + 1)2 2

where Qt and Q are the mass of mole percent solvent uptake at time t and at equilibrium and h is the initial thickness of the polymer sample. This equation represents a Fickian mode of transport. The experimentally determined values of diffusion coefcient (D) for N50 and N30 were substituted in the equation and the curves obtained are given in Figs. 13 and 14. The total agreement is fairly good. The blend N70 also shows a similar trend.

4. Conclusion The diffusion of organic solvents, namely, benzene, toluene and p-xylene through cross-linked NBR/NR blend membranes has been studied. The inuence of blend composition, penetrant size and temperature on the diffusion process has been analysed. The maximum solvent uptake decreases with increase in concentration of NBR due to the inherent solvent resistance behaviour of NBR. The mode of diffusion was close to the Fickian behaviour. The transport behaviour of the blends was correlated with the morphology of the system. The intrinsic diffusion coefcient was found to decrease with increase in NBR content. The diffusivity values decrease with increase in molecular size of the penetrant. The transport coefcients increase with increase in temperature. Activation energy for diffusion and permeation was determined using Arrhenius relationship. Chemical cross-links were determined using afne and phantom models and it was found that the experimental values

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