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Radiation Physics and Chemistry 77 (2008) 630642 www.elsevier.com/locate/radphyschem

Effect of electron beam-cross-linked gels on the rheological properties of raw natural rubber
Suman Mitraa, Santanu Chattopadhyaya, Y.K. Bharadwajb, S. Sabharwalb, Anil K. Bhowmicka,
b a Rubber Technology Centre, Indian Institute of Technology, Kharagpur, West Bengal 721302, India Radiation Technology Development Section, Bhabha Atomic Research Center, Trombay, Mumbai 400085, India

Received 7 January 2007; accepted 12 October 2007

Abstract Electron beam (EB)-cross-linked natural rubber (NR) gels were prepared from latex and characterized by various techniques. The addition of a small amount of these gels to raw NR was found to reduce the apparent shear viscosity and die swell remarkably. This effect was further enhanced with the addition of butyl acrylate as a sensitizer. The apparent shear viscosity rst decreased up to 8 phr of gel loading and then increased. However, the percent die swell value decreased steadily upon gel loading. These were explained by calculating principal normal stress difference, the activation energy of melt ow and characteristics of EB-cross-linked gels. These effects were also reected in the changes of mechanical and dynamic mechanical properties of gel-lled raw NR. Tailoring of the above properties could be done with the help of these gels. r 2007 Elsevier Ltd. All rights reserved.
Keywords: Electron beam irradiation; Gel; NR latex; Rheological properties; Tensile properties; Dynamic mechanical properties

1. Introduction Gels can be regarded as particles formed by the joining together of large polymer molecules into a cross-linked three-dimensional structure, by virtue of either chemical or physical bonding. They exhibit properties entirely different from the parent polymer chains due to their restricted mobility and interaction. In rubber industry, it is a fairly common practice to add gel to rubber to improve its processability to a marked extent. The advantages of this procedure were reported by Hofman (1964). The crosslinking of rubber latex can be performed by various methods, e.g., sulfur vulcanization and radiation curing, etc. Electron beam (EB) radiation cross-linking is a novel method of introducing cross-links into rubber matrix. There are a large number of studies on the EB cross-linking of rubber and rubber latex (Jayasuriya et al., 2001; Chirinos et al., 2003; Abad et al., 2002). Extensive work
Corresponding author. Tel.: +91 3222 283180; fax: +91 3222 220312.

E-mail address: anilkb@rtc.iitkgp.ernet.in (A.K. Bhowmick). 0969-806X/$ - see front matter r 2007 Elsevier Ltd. All rights reserved. doi:10.1016/j.radphyschem.2007.10.006

on EB cross-linking of various types of rubber was reported from our laboratory (Banik and Bhowmick, 1999; SenMajumder and Bhowmick, 1999; Chattopadhyay et al., 2001; Vijayabaskar et al., 2004). Conventional sulfur vulcanization of natural rubber (NR) latex produces a small amount of nitroso amine, which is toxic in nature. However, radiation-vulcanized rubber latex products are extremely safe due to the absence of such toxic entities. The low toxicity and fewer amounts of extractable proteins are the advantages of the EB technology (Ratnam et al., 1999). Nowadays radiation vulcanization technique of NR latex is extensively used to manufacture dipped articles like surgical gloves, balloons, etc (Chmielewski et al., 2005). In NR latex, cross-linking by EB irradiation is normally done in the presence of sensitizers, which in most cases are acrylates, namely butyl acrylate (Makuuchi and Hagiwara, 1984; Makuuchi et al., 1984). The amount of gel or crosslinks formed in the latex is dependent on the radiation dose as well as on the nature of the sensitizer and their concentration (Haque et al., 1996). The mechanism of butyl acrylate sensitization was studied in detail by

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Sabharwal et al. (1998). However, there is no literature available which describes the effect of EB-cross-linked gels on the processability of raw rubber. Several researchers have reported the effect of gel on raw rubber. The ow characteristics of raw nitrile rubber containing divinyl benzene-cross-linked gel particles were studied (Nakajima and Collins, 1978). They found that the viscosity as well as the die swell decreased with increasing gel content at intermediate and high shear rates. However, they also pointed out that there exists a crossover at lower shear rates where viscosity is markedly increased on addition of a gel in the form of discrete particles. Montes and Ponce-Velez (1983) investigated the effect of gel on the extrusion behavior of Guayule rubber. It was observed that the viscosity increased on incorporation of a gel, which was more evident at lower shear rates. Bhowmick et al. (1986) studied the inuence of gels on the crystallization, stress relaxation and orientation properties of NR. Campbell and Fuller (1984) observed that the gel produced a slight decrease in the rate of relaxation in raw NR. The effect of gel on green strength of NR was reported by Kawahara et al. (2002). Understanding the effect of various types of gel on raw rubber properties, especially on the rheological properties, is of great commercial importance, since it may lead to the advent of even superior processing grades of rubber than the existing ones. There is considerable contradiction prevailing in the current literature about the effect of gel on raw rubber viscosity as stated above. The exact nature of the inuence of gels on the raw rubber properties has not been investigated systematically in terms of the gel size, shape and degree of cross-linking of the gel till date. In addition, the improvement in various properties upon incorporation of gels shows different trends for different rubbers and is largely dependent on both the type and the size of the gel and the respective elastomers in to which they are incorporated. In our present work, NR latex was crosslinked by EB irradiation in the presence and absence of butyl acrylate to form cross-linked gelled latex. These latex gels were then mixed with raw NR latex at 2, 4, 8 and 16 phr concentrations, respectively, in the latex stage and nally dried. Their effect on raw NR properties, with particular reference to capillary rheometry, was investigated in detail.

2.2. Preparation of latex sample for irradiation NR latex was diluted to 50% by adding 1% aqueous ammonia solution and was stabilized by adding 0.2 phr of 10% KOH solution. For the preparation of the samples containing the sensitizer, 3 phr of butyl acrylate was mixed with water (1:1) and the mixture was slowly incorporated into the latex and stirred for 45 min, following an earlier reference (Haque et al., 1996). Subsequently, these latex samples were subjected to EB radiation at various irradiation doses as specied in Table 1.

2.3. Irradiation of latex samples The sensitized and sensitizer-free NR latex were taken in glass Petridishes and irradiated at an ambient temperature of 2572 1C by an EB accelerator (model ILU-6) at BARC, Mumbai, India. The ILU-6 has an energy range 0.52.0 MeV, 20 kW of beam power, a pulse current of 400900 mA and an adjusting current range 030 mA, with an acceleration voltage frequency of 100120 MHz. For the 20 kGy dose, a dose rate of 10 kGy per pass was used, while for other doses, the requisite dose was given in a single pass. An FWT-60 dosimeter based on calibration obtained from gamma-radiation was used for this EB dosimetry.

2.4. Preparation of rubber sheets from latex After the irradiation, the irradiated latex was cast on rimmed glass plates and air-dried till it became transparent and had a constant weight. The dried lms were leached in 1% ammonical water for 24 h and dried in air again until transparent. Finally the latex lms were heated in a vacuum oven at 80 1C for 2 h. These were used for the characterization of gelled rubber. For the preparation of gel-mixed rubber samples, irradiated latex was added to raw NR latex in different concentrations and stirred at a slow speed for 1 h. Then these were cast and dried following the above-mentioned procedure.

2. Experimental 2.1. Materials High ammonia centrifuged NR latex having 60% dry rubber content (DRC) was obtained from the Rubber Board, Kottayam, India. Butyl acrylate (density 896 kg m3 at 20 1C) was procured from Loba Chemie, Mumbai, India, and was used as received. All other chemicals of LR grade and doubly distilled water used were obtained from indigenous sources.

2.5. Sample designations NR latex without any sensitizer was designated as Nx/y where N stands for NR latex, and x and y denote the radiation dose in kGy and the amount of gelled latex added to the raw latex, respectively. The butyl acrylate-sensitized NR latex was given an NBx/y designation where x and y have the same notation as above. The sample designations are tabulated in Table 1. The control NR latex was designated as N0/0, while individual gels were given Nx/0 and NBx/0 designations, respectively.

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632 S. Mitra et al. / Radiation Physics and Chemistry 77 (2008) 630642 Table 1 Sample designation and irradiation dose of the samples Sample designation N0/0 N2.5/0 N5.0/0 N10.0/0 N15.0/0 N20.0/0 N2.5/2 N2.5/4 N2.5/8 N2.5/16 N5.0/2 N5.0/4 N5.0/8 N5.0/16 N10.0/2 N10.0/4 N10.0/8 N10.0/16 N15.0/2 N15.0/4 N15.0 /8 N15.0/16 N20.0/2 N20.0/4 N20.0/8 N20.0/16 Radiation dose (kGy) 0 2.5 5.0 10.0 15.0 20.0 2.5 2.5 2.5 2.5 5.0 5.0 5.0 5.0 10.0 10.0 10.0 10.0 15.0 15.0 15.0 15.0 20.0 20.0 20.0 20.0 Gel loading (phr) 0 0 0 0 0 0 2 4 8 16 2 4 8 16 2 4 8 16 2 4 8 16 2 4 8 16 Sample designation NB2.5/0 NB5.0/0 NB10.0/0 NB15.0/0 NB20.0/0 NB2.5/2 NB2.5/4 NB2.5/8 NB2.5/16 NB5.0/2 NB5.0/4 NB5.0/8 NB5.0/16 NB10.0/2 NB10.0/4 NB10.0/8 NB10.0/16 NB15.0/2 NB15.0/4 NB15.0 /8 NB15.0/16 NB20.0/2 NB20.0/4 NB20.0/8 NB20.0/16 Radiation dose (kGy) 2.5 5.0 10.0 15.0 20.0 2.5 2.5 2.5 2.5 5.0 5.0 5.0 5.0 10.0 10.0 10.0 10.0 15.0 15.0 15.0 15.0 20.0 20.0 20.0 20.0 Gel loading (phr) 0 0 0 0 0 2 4 8 16 2 4 8 16 2 4 8 16 2 4 8 16 2 4 8 16

2.6. Characterization of gelled latex samples 2.6.1. Gel fraction studies The gel fraction of the irradiated polymers was measured by immersing the samples in toluene at room temperature (2571 1C) for 48 h (equilibrium swelling time was determined from the experiments), and calculated from the weight of the samples before and after swelling as follows: Gel fraction W 2 =W 1 , (1)

Mangaraj, 1994): ur DS F f Aw r1 r , DS F f Aw r1 As r1 r s (3)

where ur, Ds, Ff, Aw, As, rr and rs are the volume fraction of rubber, the deswollen weight of the sample, fraction insoluble, sample weight, the weight of the absorbed solvent corrected for swelling increment, the density of rubber and density of the solvent, respectively. 2.6.3. Dynamic light-scattering studies For the measurement of particle size and distribution by the dynamic light-scattering (DLS) method, latex samples were diluted to a 0.1 g/l concentration level using doubly distilled water which was ltered through a Millipore Millex syringe lter (Triton free, 0.22 mm). The DLS studies were carried out in a Malvern 4800 Autosizer (Malvern Instrument, UK) using a 7132 digital collector light source Ar ion laser at 514.5 nm. 2.6.4. Mechanical properties Tensile specimens were punched out from the cast sheets, using ASTM Die-C. The tests were carried out as per the ASTM D 412-98 method in a universal testing machine Zwick Roell Z010 (Zwick Roell, Germany), at a crosshead speed of 500 mm per min at 2571 1C. The average of three tests is reported here. TestXpert II software was used for data acquisition and analysis.

where W1 is the initial weight of the polymer and W2 the weight of the insoluble portion of the polymer in the gel. The results reported are the averages of three samples. 2.6.2. Determination of cross-link density Cross-link density, which is the number of network chains per unit volume, was determined from the initial weight, swollen weight and nal deswollen weight of the samples. The samples were swollen in toluene. The number of cross-link points, n per unit volume, was calculated using the FloryRehner equation (Sperling, 1992): " # 1 ln1 ur ur w1 u2 r n , (2) 1=3 2V ur ur =2 where w1 is the polymersolvent interaction parameter, V the molar volume of the solvent and ur the volume fraction of the rubber in the swollen gel. ur was calculated using the following equation (Bhowmick and

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2.6.5. Dynamic mechanical properties The dynamic mechanical properties were measured as a function of temperature using the Dynamic Mechanical Analyzer, DMA 2980 (TA Instruments, USA). The peak value of tan d curves was taken as the glass transition temperature (Tg). The measurements were performed under the tension mode in the temperature range 85 to 50 1C at a heating rate of 3 1C/min and at a frequency of 1 Hz. Thermal Advantage software was used for data acquisition and analysis. 2.7. Measurement of rheological properties 2.7.1. Melt viscosity The melt ow properties of the NR samples with and without a gel were measured by means of a Monsanto Processability Tester (MPT) (Monsanto, USA) which is a fully automated capillary rheometer with a barrel radius of 9.53 mm. The entire barrel and the capillary assembly were electrically heated with a microprocessor-based temperature controller. The capillary used had a length to diameter ratio equal to 30 (length 30.0 mm; diameter 1.0 mm). The compound entrance angles of the capillary were 451 and 601, which are known to minimize the pressure drop at the entrance. Therefore, the Bagley correction factor was assumed to be negligible and the apparent shear stress was taken as equal to the true shear stress (Shanmugharaj and Bhowmick, 2004). The preheat time for each sample was 5 min. The extrusion studies were carried out at 130 1C, at four different shear rates of 61.3, 122.5, 306.3 and 612.5 s1, respectively. The rate of shear variation was achieved by changing the speed of the plunger automatically. The pressure at the entrance of the capillary was recorded automatically with the help of a pressure transducer. The apparent shear stress (tapp), apparent shear rate (_ app ) and apparent shear viscosities (Zapp) were g calculated using the following equations (Brydson, 1981):
c DP tapp d4l c ,

The logarithmic form for Eq. (8) may be written as _ log Zapp log k n 1 log gapp . (9)

The values n and k were calculated from the initial linear region observed at a lower shear rate. 2.7.2. Measurement of die swell The die swell measurement was directly obtained from the MPT instrument through a microprocessor-controlled laser beam assembly as per the following equation: Die swell de dc 100, dc (10)

where de is the extrudate diameter and dc is the capillary diameter, respectively. 2.7.3. Maximum recoverable deformation The maximum recoverable deformation gm was calculated using the following equations (Kumar et al., 1992): r 1 4 (11) gm a 2a2 3, 2C where C 3n0 1 , 4n0 1 (12)

where a is the extrudate swell and n0 is equal to n, the ow behavior index as determined from the slope of log (apparent shear viscosity) (Zapp) vs. log (shear rate) (_ app ) g plots, following Eq. (9). 2.7.4. The principal normal stress differences The principal normal stress difference, sE, in an elastic body was calculated by using the following general equation (Vinogradov and Ya Malkin, 1979): sE 2 gm gm 2t, 21 gm (13)

(4) (5)

_ gapp

32Q , pd 3 c tapp , _ gapp

where t is the shear stress and gm the maximum recoverable deformation as mentioned earlier which is a complex function of ller loading, temperature and the nature of the uid. 2.7.5. Activation energy of melt ow The activation energy of viscous ow was calculated using the ArrheniusFrenkelEyring equation (Vinogradov and Ya Malkin, 1979), which is valid for the power law uids, as follows: Zapp BeE g =RT , (14)

Zapp

(6)

where DP is the pressure drop across the length of the capillary, dc and lc are diameter and the length of the capillary, respectively, and Q the volumetric ow rate of the material. The ow behavior index, n, and consistency index, k, were calculated by using the Power Law model tapp k_ n . gapp By denition, Zapp tapp =_ app ; therefore, g gapp Zapp k_ n1 . (8) (7)

where Eg is the activation energy of the ow at a particular shear rate, R is the universal gas constant, T is the temperature in Kelvin, B is the pre-exponential component and Zapp is the apparent viscosity in kPa s at that shear rate. The value of Eg/R was obtained from the slope of the linear plot of log viscosity vs. reciprocal of temperature (1/T), which was used to calculate the activation energy. To

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determine the activation energy, studies were carried out at three different temperatures of 120, 130 and 140 1C, respectively.

NR latex at any particular dose, due to the same reason stated above. 3.1.2. DLS studies DLS studies give an idea about the particle size of the EB-irradiated latex gels. The particle sizes (Zavg diameter) of the gelled latex are in the range 290410 nm (Table 2). The particle size of the raw NR latex (N0/0) is 220 nm. Hence, on irradiation, the gel size increases and relatively higher values are observed for gels in the absence of a butyl acrylate sensitizer. However, the signicant increase in gel size is not only because of the cross-linking reaction taking place inside the latex particles, but it could also be due to partial coalescence of gel particles under high-energy radiation as the outermost protein layer surrounding the NR latex particle may get damaged. However, in the case of butyl acrylate (BA)-sensitized gel particles, the excess amount of BA present in latex serum probably provides an extra layer of protection against the high-energy EB radiation and prevents interparticle coalescence leading to a comparatively lower increase in gel sizes. 3.1.3. Tensile properties Table 2 also summarizes the tensile properties of the various EB-cross-linked latex gels used in this study. It is quite clear that the tensile strength (T.S.) of the various gelled latex increases steadily with increasing cross-link densities and is almost double at a 20 kGy irradiation dose. 3.2. Rheological behavior of gel-mixed raw NR 3.2.1. Effect of gel on raw NR viscosity Fig. 1 shows the apparent shear viscosity vs. apparent shear rate plots for the raw NR with and without gels at 130 1C. These are representative plots for gels cross-linked at 20 and 5 kGy doses with and without a butyl acrylate sensitizer. The viscosity decreases with the increase in shear rate showing the pseudoplastic or shear thinning behavior of all the systems studied. A similar behavior has been reported for all rubbers in earlier publications (Sadhu and Bhowmick, 2005; Bandyopadhyay et al., 2005). Interestingly, the viscosity of gel-lled raw rubber exhibits a

2.8. Scanning electron microscopy (SEM) The surface morphology of the extrudate prole was studied by using a JEOL JSM-5800 (JEOL, Japan) scanning electron microscope operating at an accelerating voltage of 20 kV. The samples were sputter coated with gold prior to SEM analysis.

3. Results and discussion 3.1. Characterization of EB-irradiated NR latex gel 3.1.1. Effect of radiation dose on gel content and cross-link density Table 2 presents the values of gel fraction and cross-link density, respectively, for an NR latex containing 0 and 3 phr butyl acrylate at different radiation doses. The trend of variation in gel fraction with irradiation dose is similar for both. The gel content increases with irradiation dose before displaying an almost constant value at a higher radiation dose. The butyl acrylate-sensitized latex showed a marginally higher gel content at any given dose compared to their unmodied counterpart. The increase in gel content with increasing radiation dose is due to the formation of a three-dimensional network structure. The comparatively higher gel content of butyl acrylate-sensitized latex indicates an enhancement in cross-linking in the presence of butyl acrylate. At relatively higher doses, the increase in gel content is marginal due to the lesser number of sites available for cross-linking. The variation in cross-link density with increasing radiation dose exhibits a similar behavior. In this case the cross-link density of both the unmodied and the butyl acrylate-sensitized latex increases steadily with the irradiation dose, up to 15 kGy, and then its increment slows down (Table 2). Butyl acrylate-sensitized NR latex shows considerably higher cross-link density than the unmodied
Table 2 Different types of gels and their properties Gel type N2.5/0 N5.0/0 N10.0/0 N15.0/0 N20.0/0 NB2.5/0 NB5.0/0 NB10.0/0 NB15.0/0 NB20.0/0 Gel content (%) 69.0 80.3 87.0 92.0 92.4 72.9 82.5 89.6 93.0 94.1

Crosslink density ( 105) molecm3 0.15 0.22 0.74 1.05 1.20 0.18 0.35 0.86 1.42 1.55

Gel size (Zavg dia.) (nm) 400 410 390 370 380 360 290 310 320 300

Tensile strength (MPa) 5.10 5.80 7.60 8.20 9.30 5.60 6.10 7.90 9.40 9.70

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0.6 0.5 0.4 0.3 Log app (kPa.s) 0.2 0.1 0.0 -0.1

N0/0 N20.0/2 N20.0/4 N20.0/8 N20.0/16

0.6 0.5 0.4 Log app (kPa.s) 0.3 0.2 0.1 0.0 -0.1

N0/0 N5.0/2 N5.0/4 N5.0/8 N5.0/16

-0.2 -0.2 -0.3 -0.3 -0.4 1.8 2.0 2.2 2.4 2.6 2.8 3.0 1.8 2.0 2.2 2.4 2.6 2.8 3.0 Log 0app (s-1) Log 0app (s-1)

0.6 0.5 0.4 Log app (kPa.s) 0.3 0.2 0.1 0.0 -0.1 -0.2 -0.3 -0.4 1.8 2.0 2.2 2.4

N0/0 NB20.0/2 NB20.0/4 NB20.0/8 NB20.0/16

2.6

2.8

3.0

Log 0app (s-1)

Fig. 1. Log (apparent shear viscosity) vs. log (apparent shear rate) plots for electron beam-cross-linked NR latex gel-lled raw NR for gels irradiated at: (a) 20 kGy; (b) 5 kGy; and (c) 20 kGy doses (butyl acrylate sensitized), respectively, at 130 1C.

considerably lower value especially at the lower shear rates compared to the unlled raw NR. The variation in viscosity with the gel loading is plotted in Fig. 2 for N10/y, NB10/y, N15/y and NB15/y systems. It can be seen that even with the addition of 2 phr gel, raw rubber viscosity reduces considerably and it is further decreased up to 8 phr of gel loading. After that the viscosity starts to rise sharply with the addition of gel (16 phr). It is interesting to note that the butyl acrylate-modied gels show a more pronounced effect than their unmodied counterparts. Normally, the presence of a rigid particulate ller or a gel leads to an increase in melt viscosity due to the greater resistance they offer to ow (Leblanc, 2002; Montes and Ponce-Velez, 1983; Kumar et al., 2002). However, in some cases the reverse trend is also observed (Nakajima and

Collins, 1978). Kumar et al. (1992) have reported a decrease in the shear viscosity of a silica and carbon black-lled compound up to 10 phr of ller loading in NR. The addition of both unmodied and modied nanoclays to styrene butadiene rubber, polybutadiene rubber and acrylonitrile butadiene rubber decreases the shear viscosity of the nanocomposites compared to the gum rubber (Sadhu and Bhowmick, 2005). In the present case probably the large polymer chains rollover or slip past the comparatively rigid quasi nanogel particles leading to a substantial decrease in the melt viscosity at an intermediate shear rate. This can be attributed to the relatively largesized ow unit of the uncross-linked polymer chains compared to the near-nano-sized gel particles (Nakajima and Collins, 1978). As the gel loading increases beyond

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636 S. Mitra et al. / Radiation Physics and Chemistry 77 (2008) 630642 Table 3 Flow behavior index (n0 ) and consistency index (k) at 130 1C Sample N0/0 N2.5/2 N2.5/4 N2.5/8 N2.5/16 N5.0/2 N5.0/4 N5.0/8 N5.0/16 N10.0/2 N10.0/4 N10.0/8 N10.0/16 N15.0/2 N15.0/4 N15.0 /8 N15.0/16 N20.0/2 N20.0/4 N20.0/8 N20.0/16 k ( 103 kPa sn) 60.67 52.20 48.73 46.81 44.26 42.28 39.81 36.34 38.22 40.18 38.28 36.75 46.77 33.11 28.91 26.65 36.56 37.67 34.36 21.28 37.93 n0 0.30 0.34 0.35 0.35 0.34 0.34 0.37 0.36 0.36 0.36 0.36 0.33 0.34 0.37 0.37 0.33 0.36 0.33 0.34 0.32 0.33 Sample NB2.5/2 NB2.5/4 NB2.5/8 NB2.5/16 NB5.0/2 NB5.0/4 NB5.0/8 NB5.0/16 NB10.0/2 NB10.0/4 NB10.0/8 NB10.0/16 NB15.0/2 NB15.0/4 NB15.0 /8 NB15.0/16 NB20.0/2 NB20.0/4 NB20.0/8 NB20.0/16 k ( 103 kPa sn) 50.15 49.10 43.34 47.21 39.81 37.35 35.54 37.34 36.22 31.55 30.48 37.07 33.25 26.42 25.82 33.88 28.05 24.66 22.70 34.38 n0 0.34 0.37 0.36 0.33 0.37 0.38 0.37 0.36 0.34 0.36 0.36 0.34 0.31 0.36 0.35 0.36 0.33 0.34 0.34 0.35
N10/y N15/y NB10/y at 130C and 122.5 s-1 shear rate

0.35

0.30 Log app (kPa.s)

NB15/y

0.25

0.20

0.15

8 10 12 Gel loading (phr)

14

16

18

Fig. 2. Variation in the apparent shear viscosity of N10.0/y, N15.0/y, NB10.0/y and NB15.0/y systems with gel loading, at 130 1C and 122.5 s1 shear rate.

0.30
at 130C and

0.28 0.26 Log app (kPa.s) 0.24 0.22 0.20

-1 122.5 s shear rate

Nx type gel NBx type gel

N2.5 / 8

N5.0 / 8

NB2.5 / 8

N10.0 / 8 N15.0 / 8 N20.0 / 8

0.18 0.16 0.14 0.12 0.0 0.2 0.4 0.6 0.8 1.0
NB5.0 / 8 NB10.0 / 8

NB15.0 / 8

NB20.0 / 8

1.2

1.4

1.6

Crosslink density (X 10-5, mole/cc)

Fig. 3. Effect of cross-link density on apparent shear viscosity for unmodied and butyl acrylate-modied electron beam-cross-linked gelmixed systems.

inuence of diminishing particle size of the gels in reducing the viscosity cannot be ruled out. In fact, it seems more probable that increasing cross-linking density with decreasing particle size of the gels are mutually responsible for the drop in the viscosity of the gel-lled rubber. The ow behavior of raw NR and all the gel-lled raw NR systems is quite well represented by the power law model. The power law constants, the ow behavior index n0 and the consistency index k are calculated from the linear t of the viscosity vs. shear rate curves for all the systems and are tabulated in Table 3. The k values decrease with the increase in gel loading up to 8 phr; after that it increases, indicating that the resistance to ow for the gel-lled raw rubber system is much less than the unlled raw rubber and the 16 phr gel-loaded samples. The variation in ow behavior index n0 is marginal and it shows pseudoplastic behavior (n0 o1) for raw NR and gel-lled raw NR systems. The value lies between 0.30 and 0.38 and there is no particular trend. 3.2.2. Effect of gel on die swell of raw rubber The die or extrudate swell is a fairly common phenomenon observed in high molecular-weight polymeric materials especially in rubbers under high shear stress, which is due to the relaxation of the normal tensile stress generated while the material ows through the channel (Brydson, 1981). Fig. 4 exhibits the variation in die swell with the experimental shear rates at 130 1C for various representative systems irradiated at 10 and 2.5 kGy doses. Because of the unlled and raw nature of the NR and its highmolecular weight, all the systems including the raw NR show large values of die swell. The die swell increases almost linearly within the experimental shear rate.

8 phr, the viscosity again starts to rise indicating additional resistance to ow due to the additional contribution of the viscoelastic relaxation of quasi nanogel agglomerates. The dependence of viscosity on the cross-link densities of the added gels is shown in Fig. 3. The reduction in viscosity seems to be dependent on the cross-link density of the respective gels, with the higher cross-link density gel showing a greater effect. This could explain the greater efciency of butyl acrylate-sensitized gels compared to unsensitized ones in reducing the viscosity of the raw rubber. This may be due to the higher number of crosslinks (less number of labile chain ends) which leads to lesser number of polymergel interactions. As a result, less energy is required to upset the microstructure. However, the

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140 125 135 120 115 Die Swell (%) 110 105
N0/0 N0/0 NB10.0/2 NB10.0/4 NB10.0/8 NB10.0/16

130 125 Die Swell (%) 2.8 3.0 120 115 110 105 100 95 90 1.8

100 95 90 1.8 2.0 2.2 2.4 2.6

N10.0/2 N10.0/4 N10.0/8 N10.0/16

2.0

2.2

2.4

2.6

2.8

3.0

Log 0app (s-1)

Log 0app (s-1)

125 120 115 110 105 100 95 1.8 2.0 2.2 2.4 2.6
N0/0 N2.5/2 N2.5/4 N2.5/8 N2.5/16

Die Swell (%)

2.8

3.0

Log 0 app (s-1)

Fig. 4. Die swell vs. apparent shear rate plots for EB-cross-linked NR latex gel-lled raw NR for gels irradiated at 10 kGy: (a) without a sensitizer; (b) with a butyl acrylate sensitizer; and (c) without a sensitizer at 2.5 kGy, respectively.

However, as expected the introduction of cross-linked gel into the raw NR matrix reduces the die swell to a great extent. Unlike the viscosity, the die swell decreases steadily with the increase in gel loading within the experimental range (Fig. 5). The higher the radiation dose, the larger the decrease. It has been clearly demonstrated here that both die swell and viscosity can be monitored and manipulated by variation of structure of the gel. The decrease in die swell is more indicative of the viscous nature of the material, whereas the higher value of the same represents the contribution of the elastic component. The predominant viscous or elastic effect within the experimental shear rate is fully inuenced by the nature of the polymer, as it controls the level of normal stress generated within the barrel and the die region of the processing instrument.

In order to understand the elastic effect within these systems more distinctively, the rst normal stress difference is calculated within the experimental shear rates using Eq. (13) at 130 1C. The logarithmic value of the normal stress difference when plotted against log (apparent shear stress) gives a straight line according to Eq. (16) (Kumar et al., 1992). These representative plots are presented for NB10.0/y systems in Fig. 6 sE Itapp m or log sE log I m log tapp . (16) (15)

The slope (m) and intercept [log(I)] values calculated by using the best-t line (with 97% condence limit) are

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120
at 130C and 122.5 s
-1

N2.5/y N5.0/y N10.0/y N15.0/y N20.0/y

115

110 Die Swell (%)

105

100

95

90 0 4 8 Gel loading (phr)

Fig. 5. Variation in die swell (%) with gel concentration for unmodied electron beam-cross-linked NR latex gel-lled raw NR systems at 130 1C and 122.5 s1 shear rate.

12

16

tabulated in Table 4. The slope increases and the intercept value decreases at 130 1C, for EB-cross-linked gel-lled raw NRs compared to the control raw NR sample. This is primarily due to the incorporation of cross-linked gel particle in to raw rubber which decreases the elastic (memory) effect in raw rubber by enhancing the viscous nature of the raw rubber matrix. At the same time due to the roll-over or slip effect of these gels, gel-lled polymer chains experience less amount of elastic strain energy compared to their unlled counterpart which facilitates a decrease in the die swell value. This lowering of elastic strain energy (Rosen and Rodriguez, 1965) contributes to the overall improvement in raw NRs processability. One interesting point to note at this stage is that compared to the conventionally cross-linked gels (Nakajima and Collins, 1978), EB-cross-linked gels drastically reduce the viscosity and die swell of raw NR at a much lower gel loading. 3.2.3. Effect of temperature on die swell With a progressive increase in temperature, the die swell of both raw NR and gel-lled raw NR systems reduces to a great extent (Fig. 7). The reduction in die swell is more in the case of raw NR than the gel-lled systems at the representative shear rate of 122.5 s1. The decrease is more evident at a higher temperature (140 1C). Unlled raw NR can store more elastic energy due to the higher chain entanglements. This effect decreases sharply with an increase in the temperature. This is due to the greater mobility imparted to the polymer chains at a higher thermal energy, which leads to a progressive reduction in the maximum relaxation time for ow. In the case of the gel-lled raw NR systems, the more viscous nature of the cross-linked gels (evident from Fig. 6) probably restricts the extensive chain de-coiling during the ow through the capillary and as a result gives lower die swell values.
125 120
N0/0 NB15.0/2 NB15.0/4 NB15.0/8 NB15.0/16

N0/0

at 130C

4.6

NB10.0/2 NB10.0/4 NB10.0/8 NB10.0/16

Log E (kPa)

4.5

4.4

4.3 2.2 2.3 2.4 Log app (kPa) 2.5 2.6

Fig. 6. Plot of log (normal stress difference) vs. log (apparent shear stress) for control NR and NB10/y gel systems.

115 Die Swell (%) 110 105 100 95 90 85 120 125 130 135 Temperature (C)

Table 4 Slope (m) and intercept (I) of the raw NR and gel-lled NR samples at 130 1C calculated using Eq. (16) Sample N0/0 N10.0/2 N10.0/4 N10.0/8 N10.0/16 NB10.0/2 NB10.0/4 NB10.0/8 NB10.0/16 Slope (m) 0.43 0.38 0.40 0.44 0.49 0.39 0.44 0.52 0.53 Intercept [log (I)] 3.54 3.52 3.46 3.35 3.27 3.44 3.28 3.05 3.01

140

Fig. 7. Variation in die swell (%) of butyl acrylate-modied electron beam-cross-linked NR latex gel (15 kGy dose)-lled raw NR systems with temperature at a 122.5 s1 shear rate.

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3.2.4. Effect of gel on extrudate roughness Fig. 8 shows the SEM photographs of raw NR extrudate and NR containing a butyl acrylate-sensitized 20 kGy EBcross-linked gel at 35 magnication. It is quite clear from the SEM photos that as the concentration of gel in the raw rubber increases, its surface roughness improves tremendously. The raw NR shows the maximum amount of die swell and yields a very rough, irregular and rippled extrudate surface, which is due to the elastic effect or melt fracture observed in various high-molecular-weight polymers. Melt fracture is the manifestation of the normal stress generated during extrusion through the capillary. Compared to N0/0, NB20/2 and NB20/4 exhibit much reduced surface roughness; however, NB20/8 and NB20/16 show a much smoother extrudate surface with almost no sign of any melt fracture. Similar trends are observed in all

the different systems. For any given system, extrudate roughness increases with the increasing shear rate, indicating a higher elastic memory. Incorporation of a crosslinked gel into raw rubber reduces the rst normal stress difference values (as given in Table 4) which leads to the lowering of die swell values and consequently a smoother extrudate surface. 3.2.5. Activation energy of melt ow Fig. 9 shows the dependence of activation energy on the shear rates for butyl acrylate-modied EB-cross-linked gellled raw NR systems. In all the cases, as expected the activation energy decreases with an increase in the shear rate within the experimental range of shear rates. It is very interesting to note that the activation energy of raw NR at any particular shear rate is actually higher than that of gel-

Fig. 8. SEM micrographs of extrudates at 35 magnication for: (a) control N0/0; (b) NB20/2; (c) NB20/4; (d) NB20/8; and (e) NB20/16 systems at a shear rate of 122.5 s1 and at 130 1C.

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lled raw NR as shown here for the NB15.0/y-type gel system (Fig. 9). The activation energy decreases with the gel loading to 8 phr, and then again starts to increase. This observation is in line with the trend of apparent viscosity variation with gel loading as stated earlier and therefore can be explained with a similar reasoning. Here also, both the cross-linking density as well as the particle size of the gels are the determining factors for the reduction in activation energy. For all the cases, the drop in the activation energy value at lower shear rates is very sharp, which tends to level off at comparatively higher shear rates.

22 20 18 Activation energy (kJ/mol) 16 14 12 10 8 6 4 2 0 100 200 300 400 500 600 700
N0/0 NB15.0/2 NB15.0/4 NB15.0/8 NB15.0/16

3.3. Effect of gel on the mechanical properties of raw NR The effect of modied and unmodied gels on the tensile properties of the raw NR has been studied by measuring the T.S., modulus at 5% elongation and elongation at break (Eb). The values are tabulated in Table 5. It is quite clear that the incorporation of cross-linked gel in the raw rubber matrix increases the T.S. and the modulus with an accompanying decrease in the Eb. As the cross-linked gels having a higher T.S. and modulus are introduced into the raw rubber, the T.S. and modulus of the mixed systems rise depending on the tensile properties of the respective gels. For example, gels having a higher cross-linked density produce a greater strength in the mixed system, N20.0/16 cf. N2.5/16. T.S. vs. gel loading is plotted in Fig. 10, which shows that T.S. increases steadily with gel loading. The moderate decrease in elongation at break with the increase in gel loading is due to the restricted mobility of the chains under tensile forces in the presence of the cross-linked gels. The 5% modulus values are very important to understand the effect of gel on the tensile properties of raw rubber. 5% modulus increases steadily with increasing gel loading. This is due to the comparatively higher resistance to tensile deformation provided by the cross-link network structure of the gels, which is very pronounced at a low strain level. The low strain modulus value apparently follows the opposite trend as compared to the decreasing trend of viscosity with gel loading. 3.4. Effect of gel on the dynamic mechanical properties of raw NR The dynamic mechanical thermal analysis (DMTA) plots, i.e., the storage modulus and the tan d vs. temperature plots for the representative samples, i.e., N0/0, NB20.0/4

Shear rate (s-1)

Fig. 9. Plot of activation energy with shear rate for butyl acrylatemodied electron beam-cross-linked NR latex gel-lled raw NR systems. Table 5 Tensile properties of different gel-lled raw NR samples Sample Tensile strength (MPa) 1.8570.05 1.9570.03 2.0370.03 2.2170.04 2.3970.04 2.0070.02 2.1270.05 2.3470.03 2.7070.03 2.0670.02 2.3270.02 2.5070.05 3.0070.07 2.1270.02 2.5670.03 2.7070.05 3.2570.04 2.2070.02 2.6170.03 2.8570.06 3.4070.08 Elongation at break (%) 1400710 1390710 1370710 133075 1300710 1360710 133075 129075 127075 1370710 1310710 1280710 126075 1350710 129075 124075 125075 1340710 1300710 126075 125075 Modulus at 5% elongation (MPa) 0.0470.01 0.0570.01 0.0670.01 0.0670.01 0.0770.01 0.0570.01 0.0670.01 0.0770.01 0.0870.01 0.0670.01 0.0770.01 0.087001 0.0970.01 0.0570.01 0.0770.01 0.0870.01 0.1070.01 0.0670.01 0.0770.01 0.0970.01 0.1070.01

Sample

Tensile strength (MPa) 1.9770.02 2.0670.03 2.2670.03 2.5170.06 2.0570.04 2.1670.02 2.3970.05 2.9070.06 2.1570.03 2.4570.04 2.7070.05 3.3070.10 2.2270.04 2.6670.04 2.9070.05 3.4670.11 2.3170.03 2.6370.02 2.9670.05 3.5370.10

Elongation at break (%) 1360710 1340710 132075 127075 1340710 1330710 1300710 129075 1340710 1320710 128075 125075 1310710 1300710 125075 122075 1320710 129075 127075 124075

Modulus at 5% elongation (MPa) 0.0570.01 0.0670.01 0.0770.01 0.0870.01 0.0570.01 0.0570.01 0.0670.01 0.0770.01 0.0670.01 0.0770.01 0.0870.01 0.1070.01 0.0670.01 0.0870.01 0.0970.01 0.1070.01 0.0770.01 0.0970.01 0.1070.01 0.1170.01

N0/0 N2.5/2 N2.5/4 N2.5/8 N2.5/16 N5.0/2 N5.0/4 N5.0/8 N5.0/16 N10.0/2 N10.0/4 N10.0/8 N10.0/16 N15.0/2 N15.0/4 N15.0 /8 N15.0/16 N20.0/2 N20.0/4 N20.0/8 N20.0/16

NB2.5/2 NB2.5/4 NB2.5/8 NB2.5/16 NB5.0/2 NB5.0/4 NB5.0/8 NB5.0/16 NB10.0/2 NB10.0/4 NB10.0/8 NB10.0/16 NB15.0/2 NB15.0/4 NB15.0 /8 NB15.0/16 NB20.0/2 NB20.0/4 NB20.0/8 NB20.0/16

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NB2.5/y

3.5

NB5.0/y NB10.0/y NB15.0/y

Tensile strength (MPa)

NB20.0/y

3.0

2.5

2.0

(Fig. 11, inset). The tan d curve is also broadened and its peak height reduces gradually with the addition of 4 and 16 phr of gel in the raw NR matrix. If we compare the tan d values, especially the maxima of the tan d curves, the gellled systems exhibit a marginal increase toward a higher temperature (50.7 1C in N0/0 to 48.5 1C in NB20.0/16). The shift in the Tg to a higher temperature in the case of the gel-lled system is due to the restricted mobility imparted by the cross-linked gel particles. The presence of cross-links in the raw NR matrix hinders the segmental motions of the polymer chains and, therefore, Tg is shifted to a higher temperature. Similarly, the increase in storage modulus upon gel loading is manifested due to the restricted chain loading. 4. Conclusions

8 12 Gel loading (phr)

16

Fig. 10. Variation of tensile strength with gel loading for butyl acrylatesensitized NR gel-lled systems.

In the present investigation, EB-cross-linked gels were prepared by EB irradiation of an NR latex with and without a butyl acrylate sensitizer. They were characterized by various methods. The rheological, mechanical and dynamic mechanical properties of the raw NR and NR containing unmodied and modied EB-cross-linked gels were investigated. From the above study, the following conclusions are drawn: 1. The apparent shear viscosity decreases with increasing shear rate for the raw NR and raw NR containing the unmodied and the butyl acrylate-modied EB-crosslinked gels showing the pseudoplastic or shear thinning nature of the systems examined. 2. The EB-cross-linked gels drastically reduce the apparent shear viscosity of the gel-lled raw NR up to 8 phr of gel loading, compared to unlled raw NR, and then rises again. The decrease in shear viscosity is more evident at comparatively low shear rates. The reduction in viscosity seems to be dependent on the degree of crosslinking and the nature of cross-linking used and the size of the gels. 3. The EB-cross-linked gels also improve the die swell of the raw NR to a great extent. It decreases steadily with an increase in gel loading. This is explained by calculating the normal stress difference for all the systems. The rst normal stress difference values decrease steadily with the gel loading. The reduction in die swell is also due to the lesser amount of elastic strain experienced by the polymer chains. 4. With the increase in EB-cross-linked gel loading, the extrudate surface smoothness becomes progressively better as evident from the SEM pictures of the extrudate. 5. The tensile properties of the gel-mixed system are dependent on the cross-link density of the gel used. T.S. and 5% modulus increase while Eb decreases with the increase in gel loading. It has been found that higher EB dose-cross-linked gels give higher value of T.S. and modulus in the lled systems. The dynamic mechanical property of the gel-lled systems also corroborates this.

Fig. 11. Temperature variation of log (storage modulus) for control, 4 and 16 phr butyl acrylate-sensitized NR gel-loaded systems and the temperature variation of tan d for the same systems (inset).

and NB20.0/16 systems are shown in Fig. 11. The raw NR (N0/0) has a storage modulus value of 325 MPa at 85 1C whereas it is 1870 MPa for 16 phr of a butyl acrylatemodied 20 kGy EB-cross-linked gel containing raw NR (NB20.0/16). The storage modulus increases with increasing gel content. This follows the same trend of low strain static modulus as described earlier. Similar results are obtained for the other systems also at various concentrations of gel. As the temperature is increased, the modulus decreases sharply near the glass transition temperature, beyond which it remains almost constant. However, as the gel loading in the matrix increases, the tan dmax value decreases

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The maxima of the tan d curve shift towards a higher temperature with gel loading.

Acknowledgments We would like to acknowledge the nancial assistance provided by DAE, BRNS, Mumbai vide Sanction no. 2005/35/4/BRNS/516 dated 08-06-2005. We are also thankful to Dr. K.S. Sharma and Mr. M. Asaddulla, RTDS, BARC, for their help in carrying out electron beam irradiation. References
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