Composites: Part B 55 (2013) 368373

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Composites: Part B
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NR/CSM/biogenic silica rubber blend composites

ija-Jovanovic a, Milena Marinovic -Cincovic b, Vojislav Jovanovic c, Suzana Samarz c,, Gordana Markovic d Jaroslava Budinski-Simendic
a

a 213, 18300 Pirot, Serbia Tigar, Nikole Paic a, Mike Petrovic a Alasa 12-14, 11000 Belgrade, Serbia University of Belgrade, Institute of Nuclear Science Vinc c Faculty of Natural Science and Mathematics, University of Pritina, Lole Ribara 29, 38220 Kosovska Mitrovica, Serbia d University of Novi Sad, Faculty of Technology, Bulevar cara Lazara 1, 21000 Novi Sad, Serbia
b

a r t i c l e

i n f o

a b s t r a c t
Biogenic silica (BSi) was added at different ratios to some polymer blends of polyisoprene rubber (NR) and chlorosulphonated polyethylene rubber (CSM) cured by conventional sulfur system. The reinforcing performance of the ller was investigated using rheometric, mechanical and swelling measurements, differential scanning calorimetry (DSC), thermogravimetric (TGA) and scanning electron microscopy (SEM) analysis. There was a remarkable decrease in the optimum cure time (tc90) and the scorch time (ts2), which was associated with an increase in the cure rate index (CRI), with ller loading up to 30 phr in the different blend ratios. The tensile strength and hardness was 45 Sh-A higher in the case for the different blend compositions, while the resistance to swelling in toluene became higher. SEM photographs show that the ller is located at the interface between the different polymers which induces compatibilization in the immiscible blends. DSC scans of the lled blends showed shifts in the glass transition temperatures Tg which can be attributed to the improve interfacial bonding between ller and NR/CSM matrix. A higher thermal stability of NR/CSM/BSi composites was detected. 2013 Elsevier Ltd. All rights reserved.

Article history: Received 9 April 2013 Received in revised form 20 May 2013 Accepted 22 June 2013 Available online 10 July 2013 Keywords: A. Particle-reinforcement B. Mechanical properties D. Thermal analysis Biogenic silica

1. Introduction Synthetic rubbers are now commonly used, especially for tire industry after blending with other rubbers and silica as an effective reinforcing agent [1]. Elastomeric materials based on polyisoprene rubber (NR) have a high strength, quite good crack resistance, wet grip and weather resistance. Chlorosulphonated polyethylene rubber (CSM) exhibits excellent ultraviolet and oxygen stability. In addition to applications for box gloves, this rubber has additional uses such as in lining and sheath materials, coatings, and adhesives [2]. The use of blends of rubber is widespread, the purpose being to obtain a balance of properties, including cost, which one elastomer alone cannot supply. Synthetic rubbers may, therefore, be added to each other as binary mixtures to improve the inferior properties of one of the components [3]. It is known that incorporation ller into a binary polymer immiscible blend can affect the phase separation due to the interaction of the individual components of the blend with the solid surface [4]. Many researchers reported the use of llers of inorganic nature for the purpose of compatibilization. The use of a mineral ller like silica served as compatibilizer for an

Corresponding author. Tel.: +381 607300105.

ija-Jovanovic ). E-mail address: vojani@sbb.rs (S. Samarz 1359-8368/$ - see front matter 2013 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.compositesb.2013.06.045

immiscible mixture of polyolen with polyacrylates and polymethacrylates [5]. Also, for polymethylmethacrylate/polyvinyl acetate blend the efciency of biogenic silica (BSi) as compatibilizer [6] is conrmed and indicated that the rate of phase separation of the lled blends became lower. Other authors [7] mentioned that the introduction of a ller surface compatible with the polymer mixture can change the position and shape of the curve of the phase separation. Explanations were put for understanding the compatibilizing effect of inorganic matter when incorporated into immiscible blends; one of these explanations is attributed to the diminished molecular mobility which prevents the phase separation of the components [6,7]. Another mechanism is proposed [8] by which large aspect ratio llers, with at least one dimension in the nanometer range, can form in situ grafts by adsorbing large amounts of polymer, which in turn are very effective at reducing the interfacial tension and inducing compatibilization in highly immiscible blends. This phenomenon appears to be mostly a function of the aspect ratio and hence widely applicable to most polymers blends irrespective of the chemical nature of the ller. The main interest was related on the effect of biogenic silica (BSi) as a ller on the deformation mechanisms and mechanical properties of composites based on the polymer matrix. Diatomaceous comes as a biogenic silica (BSi) from the word diatom, which is the single celled aquatic plant. Diatoms are living

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phytoplanktons which form an important part of marine and freshwater. The silicate shell, termed frustule supports a eshy body. The fossil beds are skeletons sunk to the bed of lake or sea after as the body died and formed deposits there. Diatoms are found in a great variety of forms [9]. The skeletal remains of diatoms with sub-micron-sized hole are described as indescribable particle shape far from any simple classication [10]. The specic diatom morphology and chemical resistance could be the base of using this material as ller in composites. There is little in the literature on this subject. Adhesion between matrix and ller phases in composites is important in crack propagation and composite failure. The study of the deformation and failure process, their relation to the structure of composite and the strength of interactions between the polymer matrix and ller phases may provide useful information for the development the new composite materials with diatoms. In the present work, biogenic silica (BSi), was incorporated into some binary mixtures of polyisoprene/chlorosulphonated polyethylene (NR/CSM) rubber blends to investigate reinforcing effect of the ller. 2. Experimental 2.1. Materials Polyisoprene rubber, NR, produced by Indian Standard Natural Rubber, grade 5 (ISNR-5) Chlorosulphonated polyethylene, CSM, Hypalon-40, with 35% chlorine and 1% sulfur by weight was obtained from E. I. Du Pont de Nemours and Co., Inc., USA, 1.18 g/ cm3, Mw 5.52x105 Mw/Mn 1.97); Filler: diatomaceous earth as a biogenic silica (BSi), (DBP absorption 130 cm3/100 g) with the average size of primary particle 28 lm. The content of ller was 0, 10, 20, 30 and 40 phr. 2.2. Compounding and torque measurements The rubber compounds were prepared at different ratios of NR/ CSM, 100/0, 75/25, 50/50, 25/75 and 0/100 by using a laboratorysize two-roll mill maintained at 40 5 C. The roller speed ratio was n1/n2 = 28/22. The mixing time was 20 min. Then the ller was added in different amounts, 10, 20, 30 and 40 parts per hundred rubbers (phr), and mixed with each of the blends at room temperature. Finally, magnesium oxide (Anscor P), tetramethylthiuramdisulde (TMTD), and slow accelerator N-cyclohexyl2-benzothiazole sulfonamide (Vulcanite CZ) as curing agent were loaded. For efcient vulcanization (EV) system, the amounts of TMTD and S were 2.5 and 0.75 phr (parts per hundred), respectively. The physical and chemical characteristics of diatomaceous earth are presented in Table 1. 2.3. Characterization 2.3.1. Cure characteristics The sheeted rubber compound was conditioned at 23 2 C for 24 h prior to cure assessment on a Monsanto Moving Die Rheometer (model 100S, USA) at 160 C. The compound formulations (Table 2) expressed in part per hundred parts of rubber, phr. All test specimens were compression molded at 160 C during the respective optimum cure time (tc90) determined from the Monsanto Rheometer. The scorch time, ts2 is the time to 2 units of torque increase above minimum torque, and optimum cure time, tc90 is the time to 90% of maximum torque development calculated from the following expression:

where Mh is the maximum torque, and Mc90 a new torque reading corresponding to 90% cure in the rubber were determined from the cure traces generated at 160 2 C by oscillating disc rheometer curemeter at an angular displacement of 3 and a frequency of 1.7 Hz [11]. The cure rate index (CRI) is the measure of rate of vulcanization based on the difference between optimum cure time of vulcanization tc90 and the scorch time ts2. It can be calculated from the relation [12]:

CRI

1 100 tc90 t s2

2.3.2. Mechanical properties The sheets were cut, marked according to the time and temperature determined from the oscillating disc rheometer and vulcanized in clean polished molds in a press at 160 C. The vulcanized sheets were cut into dumbbell-shaped specimens (ve replicates from each sample) for the evaluation of the mechanical properties [13] using an electronic tensile testing machine (Zwick 1425, Germany) at speed of 500 mm/min. Samples of at least 0.12 mm in thickness with at surface were cut for hardness test. The measurement was carried out according to ASTM D 2240 using durometer of model 306L type. The unit of hardness is expressed in (Shore A). 2.3.3. Swelling measurements The swelling degree was determined on the basis of equilibrium solventswelling measurements in toluene. The samples (about 0.10.2 g) were submerged in the toluene and after the swelling equilibrium was reached, that means, no change in the weight of the swollen sample was observed, the mass of toluene was determined according to the ASTM D 471. The swollen samples were weighed and then dried in an oven to a constant weight. The last weight was taken as the correct weight of the sample free from dissolved matter. The swelling percentage (Q) of the samples was calculated as follows [14]:

ms m0 100 m0

where ms and mo represent the weights of the samples after swelling and free from dissolved matter respectively. All these tests were
Table 1 The physical and chemical characteristics of biogenic silica (BSi) (diatomaceous earth). Physical properties Specication grade Appearance Description Specic gravity Moisture Loss on ignition PH PH slurry Bulk density Median particle size range Retained on 325 mesh Water absorption by weight Oil absorption by weight Refraction rate White ne powder Flux-calcined 2.3 g/cm3 61.0% 63.8% 810 9.2010.20 0.380.45 g/ cm3 325 Mesh 624% 6180 100150 (%) 1.421.55 Chemical properties SiO2 Al2O3 Fe2O3 CaO MgO Others Pb, mg/kg Water difuence Arsenite Heavy metal NaOH solubility HCI solubility Precipitating speed Refractory degree P90.1% 64% 61.5% 60.6% 60.5% 60.8% <0.3 <25 mg/l <4 ppm <0.005% 4575% 3.06.0% 63555 (ml/h) 900 1380 C

M c90 M h M l 0:9 Ml

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Table 2 Effect of biogenic silica (BSi) content on the cure characteristic of NR/CSM rubber blends. NR/CSM (phr) 100/0 BSi (phr) 0 10 20 30 40 0 10 20 30 40 0 10 20 30 40 0 10 20 30 40 0 10 20 30 40 Ml (dNm) 5 6 6 6 6 7 7 7 7 7 7 7 7 7 7 8 8 8 9 9 9 9 9 9 9 Mh (dNm) 25 26 26 27 28 27 27 28 28 29 28 28 28 29 29 28 28 28 30 29 29 30 30 32 32

DM (dNm)
20 20 20 21 22 20 20 21 22 22 21 21 21 22 22 20 20 20 21 20 20 21 21 22 22

ts2 (min) 7 8 8 8 7 8 9 10 9 8 7 8 8 7 6 8 9 9 8 7 10 8 8 8 7

tc90 (min) 10 9 9 9 8 12 11 11 10 9 15 14 14 13 13 16 16 15 15 14 19 18 18 17 17

CRI (min1) 33 100 100 100 100 25 50 100 100 100 12.5 16.7 16.7 16.7 14.3 12.5 14.3 16.7 14.3 14.3 11.1 10 10 11.1 10

af
0 0 0.05 0.1 0 0.05 0.1 0.1 0 0 0.05 0.05 0 0 0.05 0 0.05 0.05 0.1 0.1

75/25

50/50

25/75

tions, however, a signicant increase in the maximum torque, Mh, resulted from increasing the biogenic silica (BSi) to 30 phr and started to decrease upon further increase in the ller loading (30 phr). The difference between Mh and Ml is a rough measure of the crosslink density of the samples and usually known as DM. It can be seen that, DM increases with increasing biogenic silica concentrations except for (30 phr silica) there is a slightly decrease in DM due to the highly increase of the llerller interagglomeration formation of biogenic silica remarked with the high value of Ml. The table also shows that the incorporation of the biogenic silica (BSi) signicantly decreases the optimum cure time (tc90) and increases the scorch time (ts2), while the cure rate index (CRI) is nearly constant may be due to strong interfacial rubberller interaction. The changes in rheometric torque with ller loading can be used to characterize the ller-matrix interaction or reinforcement. The reinforcement factor af can calculated from the rheographs [16] and is given by:

af

DM filled DM unfilled DM unfilled

0/100

performed at room temperature (25 C) for 24 h, and the reported results were averaged from a minimum of ve specimens. 2.3.4. Thermogravimetric analysis The measurements were made at a heating rate 10 C min1, at a temperature range 0800 C, using Perkin Elmer TGS-2 Thermo gravimetric system. The experiments were done in nitrogen atmosphere. About 58 mg of the sample was used for the analysis. 2.3.5. Differential scanning calorimetry (DSC) The differential scanning calorimetry (DSC) was performed on a DSC 2910 (DuPont instrument) for the determination of the glass transition temperatures. 2.3.6. Scanning electron microscopy (SEM) The scanning electron microscopy images of the rubber blends fractured surfaces were taken by a JEOL JSM-5400 model of the microscope. The samples were sputter coated with gold for 3 min under high vacuum with image magnications of 2000 and 7500X, respectively. 3. Results and discussion 3.1. Cure characteristics In the case of biogenic silica, however, strong ller/ ller interactions resulting from polar surface functional groups such as siloxane [15] are believed to be primarily responsible for the increases recorded. It is interesting that measured the Mooney viscosities of some silica lled rubber compounds, and likewise observed large increases, particularly at high loading of the ller, with some of their results. These workers ascribed the increases to strong ller/ller interaction of silica. The cure characteristics of the different blends are shown in Table 2. The minimum torque, Ml was slightly affected with increase of the biogenic silica (BSi) loading for the different blend composi-

where DMlled and DMunlled are the changes in max torque during vulcanization for the lled and unlled compounds respectively. From af values listed in Table 2 it is clear that the values of af for NR/CSM/BSi are continuously increasing with the addition of biogenic silica including the pure NR and CSM, which indicates afnity of the biogenic silica (BSi) for both phases. 30 phr seems to be the optimum loading of the biogenic silica (BSi), further increase (40 phr) was associated with a re-increase in the tc90 and scorch time ts2 or a decrease in the CRI, which can be explained by the agglomeration of the ller particles. 3.2. Mechanical properties It is well known that the smaller particle size ller has a larger surface area and thus there is greater interaction between ller and polymer matrix. The degree of reinforcement depends on the extent of polymer and ller interaction. Generally, mechanical properties increase is a result of the additional reinforcement of the polymer phase. Also, the mechanical properties of the pure NR and CSM components are weak in the absence of reinforcing ller, and consequently the mechanical properties of their blends are also inferior and this originates principally from the incompatibility of both components with each other in view of the fact that NR has less polarity than the CSM. Tensile strength is mainly related to the stress distribution within rubber and the effective increase in the rupture path. From the Table 3, tensile modulus is improvement as a ller loading increase up to 30 phr. With further increase in the loading of the ller, the tensile strength reduced. The lowest tensile strength observed is due to large mean agglomerate particles size of biogenic silica and weak interaction between ller and polymer matrix. It is well known that interaction between ller and ller is dominant in the case of silica lled polymer blends. These observations indicate that the mean agglomerate particles size play an important role in affecting the mechanical properties of NR/CSM blends. However, they were still much better in comparison with the equivalent blends without ller, particularly in the case of tensile strength (45 MPa). It is worthy to note that the tensile strength was also enhanced, especially in the case of NR/CSM, (50/50) and (25/75) blends, which indicate the lubricating effect of the diatomaceous earth and the lack of weak spots or inhomogeneities in the lled blends [17]. The surface activity is an important factor, indicating the extent of polymer-ller interaction. With good polymerller interaction,

 et al. / Composites: Part B 55 (2013) 368373 G. Markovic Table 3 Effect of biogenic silica (BSi) content on the mechanical and swelling properties of NR/ CSM rubber blends. NR/ CSM (phr) 100/0 BSi (phr) 0 10 20 30 40 0 10 20 30 40 0 10 20 30 40 0 10 20 30 40 0 10 20 30 40 Tensile strength (MPa) 10 12 13 14 14 11 13 14 14 15 12 12 14 17 15 14 15 16 17 17 15 16 16 17 17 Elongation at break (%) 350 340 330 300 370 340 330 330 320 310 330 320 300 280 270 340 330 320 320 320 320 300 290 250 230 Hardness (Sh-A) 40 42 44 45 45 45 46 47 48 48 47 48 49 54 50 48 49 49 50 52 51 53 54 54 54 Equilibrium swelling (%) 68 64 62 58 58 64 60 59 57 56 55 51 40 38 37 50 48 47 45 40 48 47 46 45 45

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[22]. Presence of these stiff llers and entanglement of polymer chains renders the rubber composites harder than the respective unlled polymer [23]. These results are well agreed with the encountered increase in the cross-link density. 3.3. Swelling properties Table 3 shows the effect of blend compositions on the swelling degree of NR/CSM/BSi rubber blends composites. CSM rubber has excellent resistance to most chemicals and this explains why percentage of swelling of BSi lled NR/CSM rubber blend matrix is low. The swelling ratio Q is gradually decreased with increasing silica. This is a result for the formation of more cross-links in the vicinity of the llers owing to the chain segments and facilitates the cross-link formation [24] consequently an increase in the llerrubber interaction will be constructed. Incorporating the ller into the blend caused a decrease in the equilibrium swelling in toluene. The decrease reached 58% in the case of NR/CSM (100/0) blend lled with 30 phr, while in the case of NR/CSM (0/100) blend with the same ller loading the ratio rise to 45%. This proves that the ller increased the polarity of the overall system due to the presence of hydroxyl groups on its surface and this lowers the interactions with toluene. Additional evidence for this explanation is the re-increase in the equilibrium swelling in toluene above 30 phr loading which means agglomeration of the ller particles due to the interaction of the hydroxyl groups with each other. It was expected that these interactions at 30 phr should be shifted to higher or lower concentrations of the ller with varying the composition of the blend, however, this was not the case. 3.4. Thermogravimetric analysis The thermal stability of the NR/CSM/BSi rubber blend composites as a function of blend compositions was investigated using thermo-gravimetric analysis. (Table 4 and Fig. 1a and b). One region of NR/CSM/BSi rubber blends degradation is observed. The degradation occurs in the temperature region 350400 C. The degradation started at 60 C and was completed at 800 C. The degradation is due to the elimination of chlorine from the CSM chain is due to the main chain scission. The total mass loss observed at 814.5 C was 70.4%. It has been reported that the thermal stability of polymer blend can be improved by the incorporation of biogenic silica (BSi). In the case of NR/CSM/BSi rubber blends, the degradation starts at a higher temperature than that for NR/CSM rubber blend and NR and CSM rubber alone and unlled. T0.5 indicates the initial decomposition temperature (IDT) (5% mass loss) whereas T10 and T30 show the higher degradation rate of the polymer blends composites. It can be seen that according to the IDT biogenic silica lled NR/CSM compounds are more stable than unlled compounds. In the next step (at 10% mass loss) with 30 phr of biogenic silica lled NR/CSM rubber composites have higher temperature values (309.1 C) than other samples. At 30% mass loss, the NR/CSM rubber blends lled with 30 phr biogenic silica are the most stability (394 C) also, than other compounds. As shown in Fig. 1a and b, the incorporation of the ller resulted in all samples improvement of thermal stability. Ash residue content increased with higher ller loading. The higher content of ash residue in degradation process depends on the initial CSM plus added experimentally. The large exible polysuldic linkages undergo chain scission and convert into monosuldic and disuldic linkages [25]. Synthetic rubber decomposes by random-chain scission with intramolecular hydrogen transfer. The shift of values of the DTG peaks to a high temperature indicating increased thermal stability with 30 phr content of biogenic silica lled rubber blend composites.

75/25

50/50

25/75

0/100

there would be increases in modulus as well as mechanical properties. Based on this concept, biogenic silica has very high surface activity, which is provide greater reinforcement. The probability for the formation of a ller network enhanced with further increase in loading which is caused by a closer distance between aggregates in the rubber system and a better ller ller interaction [18]. The further loaded biogenic silica could stiffen rubber by replacing the polymer with rigid and non deformable particles, which yielded higher modulus which is noticed clearly from Table 3. In the Table 3 the effect of ller loading on elongation-at-break are shown. It indicates that elongation-at break (%) decreases gradually with increasing ller loading. The reduction of elongation-at-break is due to stiffening of the polymer matrix by the ller. Further increase in ller loading causes the molecular mobility decrease due to extensive formation of physical bond between the ller particles and the polymer chain that stiffen the matrix [19]. When the biogenic silica is ller increase, the polymer matrix progressively is becoming reinforced and hence lowering elongationat-break at any ller loading. The hardness which depends on the distribution of the rigid ller in the host matrix is increased with increasing the ller content. It is well known that incorporation of the ller particles in the soft matrix reduces the elasticity of the polymer chains resulting in more rigid composites [20]. From Table 3 one can see that the addition of the biogenic silica showed a marked increase in hardness, which reects an improved stiffness for the rubberller composites. This result is expected because as more ller is incorporated in the rubber matrix, the plasticity of the rubber chain is reduced resulting in more rigid composites [21]. The hardness is increased because the ller particles have relatively higher modulus than that of rubber matrix. It is well known that the addition of the ller in rubber compounding leads to a linear increase in materials hardness; moreover the international rubber hardness degree is correlated with the elastic modulus

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Table 4 The temperature values of 0.5%,mass loss (T0.5), 10% mass loss (T10) and 30% mass loss (T30) and the nal decomposition temperature of NR, CSM, NR/CSM (50/50) and NR/ CSM/BSi (50/50/30) rubber blend composites. NR DTG peak (C) Mass loss (%) Total mass loss (%) 283.3 31.9 71.8 CSM 354.5 444.8 26.3 50.1 70.9 NR/CSM 319.6 452.2 25.3 53 68.2 19.9 255.2 333.3 718.5 NR/CSM/BSi 405.6 34.3 70.4 63.9 309.1 394 814.5

Temperature values for selected mass loss T0.5% (C) 59.9 127.2 T10% (C) 226.8 303.6 T30%(C) 279.4 361.7 800.7 803 Tend(C)

Fig. 2. DSC scans of NR/CSM (100/0), NR/CSM (0/100), NR/CSM (50/50) and NR/ CSM/BSi (50/50/30) rubber blend composites.

in a small increase of their segmental mobility. The presence of biogenic silica, change Tg of rubber blend (Fig. 2) due to the restriction on the segmental motion of the polymeric chain by the addition of cross-linking. The separation of polymer macromolecules under the inuence of this biogenic silica is compensated in this case by the polymerller interactions. 3.6. Morphological study According to Sadhu and Bhowmick [27], SEM is an important tool for observing the surface morphology of crack initiation and

Fig. 1. TG (a) and DTG (b) curve of NR/CSM (100/0), NR/CSM (0/100), NR/CSM (50/ 50) and NR/CSM/BSi (50/50/30) rubber blend composites.

3.5. DSC measurement DSC scans for the individual components NR and CSM rubber, unlled NR/CSM rubber blend (50/50) and 30 phr biogenic silica lled NR /CSM/BSi (50/50/30) rubber blend are represented in Fig. 2. The Tg of the individual components of the blends were found to be 76 and 49 C for NR and CSM, respectively. For the unlled blends, the Tg is shifted to high temperature for 54 and 33 C and this was explained [26], as due to interactions between the different phases at the boundaries forming a third phase, whose presence causes the polymer chains to draw aside resulting

Fig. 3. SEM of unlled NR/CSM (50/50) (a) and biogenic silica lled NR/CSM (50/50/ 30) rubber blends (b).

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the failure process in composite materials. Figs. 3 show the SEM photograph of the fracture surfaces of tensile test specimen of the composites studied. The fracture surface of NR/CSM rubber blend composite without biogenic silica (BSi) (composite A) in Fig. 3a exhibits brittle fracture. However, the presence of BSi changes the failure pattern which indicates the presence of bonded BSi as a result of ller-rubber interaction and adhesion. The stronger BSi/rubber adhesion in Fig. 3a and b causes low breakage in the rubber matrix leading to the reduction of tensile properties as tensile strength and elongation at break. This observation is supported by the swelling measurement data shown in Table 3. Since the lower the Q, values, the higher will be the extent of interaction between the ller and the rubber matrix [27], it can be concluded that the higher BSi/rubber adhesion in the composites obtained. 4. Conclusions Biogenic silica (BSi) was used as a reinforcing ller at different ratios in polyisoprene/chlorosulphonated polyethylene (NR/CSM) rubber blends. A decrease in the optimum cure time (tc90) and scorch time (ts2) was observed and this was associated with an increase in the cure rate index (CRI) with ller loading up to 30 phr. The tensile strength for 45 MPa higher in the case of the lled blends; also the toughness increased with the use of the ller which indicates the lubricating effect of the ller. Furthermore, the resistance to swelling in toluene became higher. Induced compatibilization can be obtained from the location of the ller at the interface between the immiscible blends as can be evidenced from the SEM pictures. The Tg of lled rubber blends is shifted to high temperature. Also, thermal stability increase with ller content increases. Biogenic silica (BSi) has a potential to be used as ecological ller in the rubber industry. Acknowledgements Financial support for this study was granted by the Ministry of Science and Technological Development of the Republic of Serbia (Projects Numbers 45022 and 45020). References
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