European Polymer Journal 42 (2006) 479486

EUROPEAN POLYMER JOURNAL

www.elsevier.com/locate/europolj

Roles of silane coupling agents on properties of silica-lled polychloroprene

Pongdhorn Sae-oui a,b,*, Chakrit Sirisinha b,c, Uthai Thepsuwan a, Kannika Hatthapanit a
National Metal and Materials Technology Center, 114 Thailand Science Park, Paholyothin Road, Klong 1, Klong-Luang, Pathumthani 12120, Thailand b Rubber Research Unit, Faculty of Science, Mahidol University, Salaya Campus, Phutthamonthon IV Road, Salaya, Nakhonpathom 73170, Thailand Department of Chemistry, Faculty of Science, Mahidol University, Rama VI Road, Rajdhevee, Bangkok 10400, Thailand Received 8 August 2005; received in revised form 5 September 2005; accepted 6 September 2005 Available online 18 October 2005
a

Abstract Silane coupling agent is used extensively to improve reinforcing eciency of silica. Recently, many types of silane coupling agents have been developed and their roles on reinforcing improvement have been studied in many types of rubbers. In the present study, roles of the two widely used silane coupling agents, i.e., bis-(3-triethoxysilylpropyl) tetrasulfane (Si69) and 3-thiocyanatopropyl triethoxy silane (Si-264) were studied in silica-lled polychloroprene (CR). The results reveal that the presence of Si-69 and Si-264 improves signicantly the processability of the rubber compounds. The improvement is more pronounced for Si-264 due to its lower molecular weight and, thus, viscosity. Surprisingly, the results show that Si69 and Si-264 aect cure characteristics dierently, i.e., Si-69 somewhat retards cure while Si-264 accelerates cure. However, both Si-69 and Si-264 result in an increased crosslink density of the vulcanizates. The presence of silane coupling agent also enhances the mechanical properties of the vulcanizates due to the combined eects of better ller dispersion, better rubberller interaction and increased crosslink density. A thorough look at the results also reveals that the property enhancement is obvious only at low silane loading (approximately 1.5 phr). Further increase of silane loading generally has little inuence on properties of the vulcanizates. In the case of Si-264, excessive use of silane could impair certain properties such as modulus and hardness due to the plasticizing eect. Compared with Si-264, Si-69 imparts the rubber vulcanizates with poorer aging resistance. Explanation goes to the sulfur contribution eect of Si-69. 2005 Elsevier Ltd. All rights reserved.
Keywords: Silane coupling agent; Silica; Polychloroprene; Properties

Corresponding author. Address: National Metal and Materials Technology Center, 114 Thailand Science Park, Paholyothin Road, Klong 1, Klong-Luang, Pathumthani 12120, Thailand. Tel./fax: +662 4419816 20x1159. E-mail addresses: pongdhor@mtec.or.th (P. Sae-oui), sccsr@mahidol.ac.th (C. Sirisinha), uthait@mtec.or.th (U. Thepsuwan), kannikah@mtec.or.th (K. Hatthapanit). 0014-3057/$ - see front matter 2005 Elsevier Ltd. All rights reserved. doi:10.1016/j.eurpolymj.2005.09.003

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1. Introduction Silica is one of the most important reinforcing llers used mainly in the production of light colored products. Compared with carbon black having similar specic surface area, silica provides lower degree of reinforcement because it contains a large number of silanol groups (OH) on the surface making it highly polar and less compatible with many non-polar rubbers such as nature rubber (NR) or styrene butadiene rubber (SBR) [1]. In addition, the presence of silanol group leads to strong llerller interaction giving rise to a high tendency for ller agglomeration in the rubber matrix and, hence, the diculty in processing [2]. These problems had limited the use of silica until the advent of silane coupling agents. Silane coupling agent is a bifunctional compound developed commercially to improve the reinforcing eciency of silica. It is composed of two functionally active end groups, i.e., the readily hydrolysable alkoxy group and the organo-functional group. The former can react chemically with the silanol groups on silica surface to form stable siloxane linkages whereas the latter, which is relatively non-polar, is more compatible with rubbers and also can participate in the sulfur vulcanization to form chemical linkages with rubbers. As a consequence, silane coupling agent could act as a bridge between silica and rubber to enhance the rubberller interaction and, thus, give a signicant improvement in properties of silica-lled compounds. Even though many attempts have been made to study the role of silane coupling agent in improving reinforcing eciency of silica, most of the published work was carried out in the non-functionally active rubbers such as NR and SBR [38]. Little attention is given to the role of silane coupling agent in a functionally active rubber such as polychloroprene (CR). Recently, it has been reported that silica and CR could form strong interaction, i.e., CR could be self-crosslinked in the sole presence of silica through the chemical interaction between allylic chlorine atoms and silanol groups [9]. It is therefore interesting to investigate the role of silane coupling agent in silica-lled CR. In the present study, two types of silane coupling agent, i.e., bis-(3-triethoxysilylpropyl) tetrasulfane (Si-69) and 3-thiocyanatopropyl triethoxy silane (Si-264), were used to study and compare their roles in improving the reinforcing eciency of silica in CR. The chemical structures of both Si-69 and Si-264 are given in Fig. 1.

C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5 C2H5

O O Si CH2 CH2 CH2 S O O O O

Si-69

S S Si CH2 CH2 CH2 S

O O Si CH2 CH2 CH2 O

Si-264

SCN

Fig. 1. Chemical structures of Si-69 and Si-264.

2. Experimental 2.1. Materials All mixing ingredients were used as received. Polychloroprene (CR, Neoprene W) was supplied by DuPont Dow Elastomers PTE Ltd. Silica (HiSil 255s with specic surface area of 175 m2/g) was manufactured by PPG-Siam Silica Co., Ltd. (Thailand). Two types of silane coupling agent, Si-69 and Si-264, were supplied by JJ-Degussa (Thailand) Co., Ltd. N-tert-butyl-2-benzothiazole sulfenamide (Santocure-TBBS) was obtained from Reliance Technochem (Flexsys) Co., Ltd. (Thailand). Stearic acid, zinc oxide (ZnO) and sulfur (S) were obtained from Chemmin Corporation (Thailand), Ltd. Ethylene thiourea (ETU 22S) and magnesium oxide (MgO) were manufactured in Japan by Kawakushi Co., Ltd. and Konoshima Chemical Co., Ltd., respectively. 2.2. Preparation and testing of rubber compounds A laboratory-sized internal mixer (Haake Rheomix 3000p) was employed to prepare the rubber compounds. The mixing conditions were set as follows: ll factor = 0.7, initial chamber temperature = 60 C, rotor speed = 40 rpm and mixing time = 12 min. The compound formulation is given in Table 1. During mixing, the mixing energy of each compound was recorded for comparison. After mixing, the compounds were sheeted out using a two-roll mill (Collin W100T). Measurement of Mooney viscosity (MS1 + 4@100 C) was carried out using the Mooney viscometer (TechPro viscTECH+). The cure characteristics, e.g., scorch time

P. Sae-oui et al. / European Polymer Journal 42 (2006) 479486 Table 1 Compound formulation Ingredient Loading (phra) 1 CR ZnO Stearic acid MgO Hi-sil 255s Si-69 Si-264 TBBS ETU S
a

481

7 100 5 1 4 30 4.5 1 0.3 2

100 100 5 5 1 1 4 4 30 30 1.5 1 1 0.3 0.3 2 2

100 100 5 5 1 1 4 4 30 30 3.0 4.5 1 1 0.3 0.3 2 2

100 100 5 5 1 1 4 4 30 30 1.5 3.0 1 1 0.3 0.3 2 2

The aging properties of the rubber vulcanizates were also studied. The specimens were aged in an aging oven at 100 C for 72 h prior to the determination of tensile properties. The degree of ller dispersion was examined using a scanning electron microscope (SEM, JEOL JSM-5410). The SEM micrographs were taken on the newly exposed surface of the rubber specimens fractured immediately after embrittling in liquid nitrogen. The specimens were then sputtered with gold to prevent charging on the surface. 3. Results and discussion Fig. 2 represents the eect of silane loading on mixing energy of the silica-lled CR compounds. Obviously, the mixing energy reduces consecutively with increasing silane loading. This is understandable because, apart from the plasticizing eect of the silane coupling agent, the alkoxy groups in silane coupling agent could react chemically with the silanol groups on silica surface, giving rise to the reduction of llerller interaction. A greater degree of silica disagglomeration is therefore achieved during mixing, leading to the reduction of compound viscosity (see also Fig. 3) and, thus, mixing energy. It can also be observed that, at a given loading, Si-264 imparts the rubber compounds with lower mixing energy and Mooney viscosity than Si-69. This is in good agreement with the work published previously [4,5]. Due to the lower molecular weight and lower viscosity of Si-264, when added into the compound, Si-264 could react with the silanol groups on silica surface more thoroughly than Si-69, leading to a greater reduction of ller ller interaction. This is further supported by the results obtained from the RPA, as shown in Fig. 4.

phr: Parts per hundred of rubber.

(ts 2) and optimum curing time (tc 90) including the minimum torque (ML) and the maximum torque (MH) were determined using a moving die rheometer (TechPro MD+) at 155 C. The cure index (ts 35 ts 5) of the compound was also investigated at 155 C using a Mooney viscometer based on ISO 289-2. The extent of llerller interaction was investigated using a rubber process analyzer (RPA 2000). The dynamic storage modulus (G 0 ) of the rubber compounds was measured at various strains (at 100 C and 1.7 Hz), i.e., from 0.98% to 200%. The dierence in G 0 at low and high strains (DG 0 ), widely known as the Payne eect, is used to represent the degree of llerller interaction [10]. 2.3. Testing of rubber vulcanizates After the preparation of standard specimens, the tensile properties were determined using a universal testing machine (Instron 4301 series) following ISO 37. The hardness was measured using a Wallace Shore A durometer according to ISO 868. The compression set was investigated according to ISO 815 (method B) at 70 C for 22 h. Crosslink density was determined using the swelling test with benzene employed as the liquid medium. The crosslink density was calculated based on the FloryRehner equation as follows [11]: h t2 i 1=3 ln1 t2 t2 v1 t2 V n t ; 1 1 2 2 2 where t2 is the volume fraction of polymer in the swollen sample, v1 is the polymersolvent interaction parameter (the interaction parameter between CR and benzene = 0.4284) [9], V1 is the molar volume of the solvent and n is the number of elastically active chains per unit volume.

4.6

Mixing energy (x10 J)

4.4 4.2 4.0 3.8 3.6 0.0

Si-69

Si-264

1.5

3.0

4.5

Silane loading (phr)

Fig. 2. Eect of silane loading on mixing energy of the silicalled CR.

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MS (1+4) at 100 C

65 60 55 50 45 0.0

Si-69

Si-264

1.5

3.0

4.5

Silane loading (phr)

Fig. 3. Eect of silane loading on Mooney viscosity of the silicalled CR.

600 500 400 300 200 0.0 Si-69 Si-264

G' (kPa)

1.5

3.0

4.5

Silane loading (phr)

Fig. 4. Eect of silane loading on the Payne eect of the silicalled CR.

As can be seen, the presence of silane coupling agent remarkably reduces the value of DG 0 and, hence, the degree of llerller interaction. The greater the amount of silane coupling agent, the lower the degree of llerller interaction. Similar observation is also found by other workers [10]. Since a close look at the results reveal that, at a given silane loading, DG 0 of Si-264 containing compound is slightly lower than that of Si-69 containing compound, it could be said that Si-264 can reduce the llerller interaction to a greater extent than Si-69. Due to the signicant reduction of llerller interaction, the addition of silane coupling agent provides better ller dispersion as can be seen from the SEM micrographs in Fig. 5. Compared to Si-69, Si-264 provides a greater degree of ller dispersion because it can wet silica surface more thoroughly and, therefore, reduce the llerller interaction to a greater extent as mentioned earlier. Fig. 6 represents the eect of silane loading on both scorch time (ts 2) and optimum curing time (tc 90) of silica-lled CR. Surprisingly, the results reveal that the two silane coupling agents aect the cure characteristics of the compounds dierently.

Fig. 5. SEM micrographs (5000) of the CR vulcanizates: (a) without silane, (b) 4.5 phr of Si-69, and (c) 4.5 phr of Si-264.

It is found that, for Si-69, both scorch time and optimum curing time tend to increase gradually with increasing silane loading whereas, for Si-264, both scorch time and optimum curing time are found to decrease initially with increasing silane loading (up to 3.0 phr) and tend to level o afterwards. The prolonged scorch time and optimum curing time found in the presence of Si-69 are unexpected because it was previously reported by several

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20

483

tc90_Si-69
15

ts2_Si-69 ts2_Si-264

tc90_Si-264

10

0 0.0 1.5 3.0 4.5

Silane loading (phr)

Fig. 6. Dependence of cure characteristics (ts 2 and tc 90) on silane loading.

published works that both Si-69 and Si-264 would accelerate cure rate and increase state of cure for the silica-lled NR compounds [4,5]. This is simply due to the fact that the alkoxy groups of both Si-69 and Si-264 could react chemically with the silanol groups on silica surface and make the silica surface less chemically reactive. The amounts of Zn complex and other amine accelerators trapped by silica surface are therefore reduced, giving rise to faster cure rate and higher state of cure. However, for silica-lled CR, it is found that only Si-264 can accelerate cure while Si-69 somewhat retards cure. The eect of the two silane coupling agents on cure index of the silica-lled CR was also studied by the Mooney viscometer at 155 C and the results are given in Fig. 7. Obviously, the cure index tends to increase slowly with increasing Si-69 loading but, for Si264, the cure index tends to decrease with increasing Si-264 loading and tends to level o at high loading. As cure index is equal to ts 35 ts 5, the cure index is therefore inversely proportional to cure rate. The re-

sults conrm that Si-69 gives retarding eect on cure for silica-lled CR. Fig. 8 represents the relationship between torque dierence (MH ML) and silane loading. Obviously, the torque dierence is found to increase continuously with increasing silane loading for Si-69 but, for Si-264, the torque dierence is found to increase with increasing silane loading up to approximately 1.5 phr. Further increase in Si-264 loading causes very little change in the torque dierence of the compounds. As the torque dierence is directly proportional to the degree of crosslinking, the results indicate that silane coupling agent could enhance the state of cure of silica-lled CR. The increased crosslink density is thought to arise mainly from the reduction of adsorbed accelerator on silica surface in the presence of silane coupling agent. Surprisingly, the results reveal that, at the same loading, Si-69 gives higher torque dierence and, thus, higher crosslink density than Si-264, in spite of its retardation on both scorch time and optimum curing time. The torque dierence results also
20 Si-69
MH-ML (dN.m)

Time (min)

Si-264

18 16 14 12 10 0.0

1.5

3.0

4.5

Silane loading (phr)

Fig. 8. Relationship between torque dierence and silane loading.

1.8
n (x10 mol/cm )

3.8

1.6

Si-69

Si-264

Si-69 3.3 2.8 2.3 1.8 0.0 1.5 3.0

Si-264

Cure index (min)

1.4 1.2 1.0 0.8 0.6 0.0 1.5 3.0 4.5 Silane loading (phr)

-4

4.5

Silane loading (phr)

Fig. 9. Relationship between the number of elastically active chains per unit volume (n) and the silane loading.

Fig. 7. Relationship between cure index and silane loading.

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correspond well with the results of crosslink density obtained from calculation using the FloryRehner equation as shown in Fig. 9. As can be seen, the crosslink density, represented by the number of elastically active chains per unit volume (n), is increased continuously with increasing silane loading for Si-69 but, for Si-264, the crosslink density is found to increase with increasing silane loading up to 1.5 phr. Further increase of Si-264 loading has no signicant eect on crosslink density. Results also reveal that, at a given loading, Si-69 imparts greater degree of crosslinking than Si-264. This is possibly attributed to the fact that Si-69 contains 4 sulfur atoms on its molecule and these sulfur atoms can be contributed to the rubber matrix during vulcanization. This phenomenon is widely known as sulfur contribution eect [1]. Si-264, on the other hand, possesses only one sulfur atom on its molecule and, therefore, cannot contribute sulfur to the rubber matrix. The inuence of Si-264 on crosslink density of the vulcanizate is therefore less pronounced compared to Si69. The eects of silane coupling agent on hardness and tensile properties of the silica-lled CR vulcanizates were also investigated and the results are given in Table 2. Although the addition of silane coupling agent could enhance the tensile strength of the vulcanizate, such enhancement is relatively small compared to that found in most non-polar rubbers such as NR or SBR. It is widely known that silica contains a large number of silanol groups on its surface and, when added into CR, the silanol groups could form strong interaction with chlorine atoms in CR. The interaction between silica and CR is therefore relatively high, compared to that between silica and non-polar rubbers. This explains why the presence of silane coupling agent has little inuence on tensile strength of the CR vulcanizates. The small improvement of tensile strength in the

presence of silane coupling agent is thought to arise mainly from the better ller dispersion. As it is widely known that both modulus and hardness of the rubber vulcanizate are directly proportional to crosslink density, the results of 100% modulus and hardness therefore follow the same trend as the crosslink density results. Generally, both 100% modulus and hardness tend to increase with increasing silane loading. Exception is found in the vulcanizates containing high loading of Si264 (P3.0 phr) in which their moduli and hardness are reduced with increasing silane loading. The reduction of modulus and hardness at high loadings of Si-264 is attributed to the plasticizing eect of excessive silane. Compared with Si-264 at the same loading, Si-69 gives the rubber vulcanizates with higher 100% modulus and hardness due to the greater degree of crosslinking. Corresponding to the crosslink density results (Fig. 9), the elongation at break of the rubber vulcanizate is continuously reduced with increasing Si-69 loading. This is simply due to the increased crosslink density with increasing Si-69 loading. However, for Si-264, the elongation at break is found to decrease initially with increasing silane loading up to 1.5 phr. Further increase of Si-264 loading results in an increase of elongation at break. Again, the explanation is given by the plasticizing eect of excessive silane. Fig. 10 represents the inuence of silane coupling agents on abrasion resistance of the silica-lled CR. Obviously, the presence of silane coupling agent improves signicantly the abrasion resistance of the vulcanizates. However, it could be observed that the improvement is pronounced only at low silane loadings (61.5 phr). At higher silane loadings, no signicant improvement is observed. Possible explanation for such improvement goes to the combined eect of better ller dispersion, higher state of cure and better rubberller interaction.

Table 2 Eect of silane coupling agent on hardness and tensile properties of the silica-lled CR vulcanizates Silane type Si-69 Loading (phr) 0.0 1.5 3.0 4.5 0.0 1.5 3.0 4.5 Hardness (shore A) 63.0 0.4 63.6 0.9 65.6 1.0 66.7 0.5 63.0 0.4 63.3 0.5 61.8 0.6 61.6 0.5 Tensile strength (MPa) 25.0 0.6 25.9 0.3 26.5 0.8 26.4 0.5 25.0 0.6 26.0 1.1 26.6 1.0 26.0 0.5 100% Modulus (MPa) 1.61 0.12 2.15 0.24 2.33 0.13 2.48 0.16 1.61 0.12 1.77 0.10 1.72 0.07 1.64 0.04 Elongation at break (%) 902 33 853 10 845 21 771 29 902 33 882 35 890 25 902 20

Si-264

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485

Volume loss (x10 cm )

16 14 12 10 8 6 0.0 1.5 3.0 4.5 Silane loading (phr) Si-69 Si-264

Fig. 10. Eect of silane coupling agent on abrasion resistance of the silica-lled CR vulcanizates.

-2

Fig. 12. Eect of silane coupling agent on relative tensile strength of the silica-lled CR vulcanizates.

50

Compression set (%)

47 44 41 38 35 0.0

Si-69

Si-264

1.5

3.0

4.5

Silane loading (phr)

Fig. 11. Relationship between compression set at elevated temperature (70 C) and silane loading.

The eect of silane coupling agent on compression set at elevated temperature is illustrated in Fig. 11. Regardless of the silane type, the compression set is noticeably reduced when 1.5 phr of silane coupling agent is added and it remains unchanged at higher loadings. The improvement in compression set in the presence of silane coupling agent is thought to arise mainly from the better ller dispersion and the higher degree of crosslinking. Compared with Si-264, Si-69 provides rubber vulcanizate with poorer compression set at elevated temperature. Again, the explanation mainly goes to the sulfur contribution eect of Si-69. As Si-69 can contribute sulfur to the rubber matrix, it can be expected that the linkages between rubber molecules are likely to take place through polysuldic bonds rather than mono or disuldic bonds because higher amount of sulfur is available for sulfur vulcanization reaction. Si-69 therefore gives the vulcanizate with poorer thermal aging resistance and, thus, poorer compression set at elevated temperature, compared to Si-264. The eect of silane loading on aging properties of the silica-lled CR vulcanizate was also studied. The

Fig. 13. Eects of silane coupling agent on relative 100% modulus of the silica-lled CR vulcanizates.

results are represented in terms of the relative tensile strength and the relative 100% modulus as shown in Figs. 12 and 13, respectively. As can be seen, the thermal aging causes the reduction of tensile strength of the vulcanizates. Si-264 seems to have little inuence on the relative tensile strength whereas Si-69 aects the relative tensile strength to a greater extent, i.e., the relative tensile strength decreases noticeably with increasing Si-69 loading. Again, the poor aging resistance of the vulcanizates containing Si-69 arises from the sulfur contribution eect of Si-69 as mentioned previously. It can also be observed from Fig. 13 that, without silane coupling agent, the thermal aging remarkably increases the modulus of the vulcanizates (the relative 100% modulus > 2). This is ascribed to the increased crosslink density after thermal aging which is generally known as post curing eect. This eect is often found in silica-lled CR because, when subjected to high temperature, the silanol groups on silica surface could form primary chemical bonds with allylic chlorine atoms in CR leading to an increase in

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crosslink density. It is also obvious that the relative 100% modulus is further increased in the presence of silane coupling agent. The higher the silane loading, the greater the relative 100% modulus. The results imply that silane coupling agent could greatly enhance the post curing eect. Apart from the post curing eect, it is thought that the evaporation of excessive silane during the thermal aging also contributes to the signicant increase in relative 100% modulus at high silane loadings. 4. Conclusions Similar to the eect in most non-polar rubbers, the presence of silane coupling agent in silica-lled CR improves signicantly the processability of the compounds by reducing the mixing energy, the compound viscosity as well as the llerller interaction. The higher the silane loading, the better the compound processability. Due to the lower molecular weight and lower viscosity, Si-264 gives better compound processability than Si-69. Interestingly, results reveal that the two silanes aect the cure characteristics dierently, i.e., Si-69 retards cure whereas Si-264 accelerates cure. However, the presence of both Si-69 and Si-264 enhances the state of cure. For Si-69, crosslink density is increased continuously with increasing silane loading whereas, for Si-264, the increase in crosslink density is found only at low loading. Apart from the processability, the addition of silane coupling agent also improves the mechanical properties such as tensile strength, modulus, abrasion resistance including compression set. Generally, the improvement of such properties is pronounced at low silane loading (1.5 phr). Excessive use of silane coupling agent should be avoided because silane coupling agent is expensive and the excessive silane could cause negative eect on certain properties such as modulus and hardness due to the plasticizing eect (particularly obvious in Si-264). The aging properties of the vulcanizate are also aected when silane coupling agent is added. Although Si-264 seems to have little inuence on the relative tensile strength, it noticeably aects

the relative 100% modulus, i.e., the higher the Si264 loading, the greater the relative 100% modulus. The post curing enhancement and the evaporation of excessive silane are the possible explanations. The Si-69, on the other hand, aects the relative 100% modulus to a smaller extent than Si-264, but its inuence on the relative tensile strength is more obvious. The relative tensile strength tends to decrease with increasing Si-69 loading. Explanation is given by the sulfur contribution eect of Si-69. References
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