Eur. Polym. J. Vol. 24, No. 10, pp. 961-965, 1988 Printed in Great Britain.

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0014-3057/88 $3.00 +0.00 Copyright ~) 1988 Pergamon Press plc

EFFECT OF 7-MERCAPTOPROPYLTRIMETHOXYSILANE COUPLING AGENT ON tg0, TENSILE STRENGTH A N D TEAR STRENGTH OF SILICA-FILLED NR, NBR A N D SBR VULCANIZATES
M. NASIR, B. T. Port and P. S. NG School of Industrial Technology, University of Science, 11800 Minden, Penang, Malaysia
(Received 19 January 1988)
Abstract--A study has been made of the cure times (tg0), the tensile strengths and the tear strengths of

silica-filled NR, NBR and SBR, with and without the presence of 7-mercaptopropyltrimethoxysilane, (MPTS) and cured using the semi-etticient vulcanization system (semi-EV). Mixing was done using a Brabender Plasti-corder having a mixing cam attached and a two-roll mill, under approximately similar conditions. The tg0 of the Brabender mixed silica-filled NBR and NR, in the absence of MPTS display a cure retardation phenomena, while those of SBR exhibit a cure enhancement phenomenon. When MPTS is present, all Brabender mixed rubbers display a cure retardation phenomenon which can be attributed to a direct involvement of the MPTS in the sulphur vulcanization. Generally, the tensile strengths and the tear strengths of the Brabender mixed NBR and SBR are greater than those of the two-roll mill, whereas NR seems unaffected by the mixing methods. Addition of MPTS gives rise to marked improvements in the physical properties of NBR and SBR. However, the physical properties of NR are only slightly affected by the incorporation of MPTS.

INTRODUCTION

For some time, silicas and silicates of varying forms and particle sizes have been widely used as reinforcing fillers in rubbers, especially those of nonblack applications. However, their properties are usually inferior to those of carbon blacks, even when they are of comparable sizes. Furthermore, the high viscosity of a silica-filled rubber makes it more difficult to process [1, 2]. N u m e r o u s theories on filler reinforcement in rubbers habe been proposed by Smallwood [3], Guth [4], Mullins and Tobin [5] and others. Most of the mechanisms suggested to explain the reinforcement of rubber by fillers are still vague. However, the concept of rubber being occluded by a "shell" of filler, as put forward by H a r w o o d et al. [6], seems to fit most observations. Wagner [7] studied the effect of silicas having different structures in SBR vulcanizates; he concluded that silica-rubber interaction is dependent on the surface silanol content, the adsorbed water level and the surface area of silicas. The utilization of silane based coupling agents, to enhance both dynamic and mechanical properties of silica-filled rubbers, is well known and has been extensively studied by many workers such as Wagner [7,8], Dannenberg [9], Cameron et al. [10] and Fetterman [11]. Using H a r d w o o d ' s proposal of filler reinforcement, Dannenberg [9] attributed a further improvement in silica-filled rubbers, when M P T S is present, to the tightening of the shell of the occluded rubber as a consequence of coupling bonds being formed between M P T S and both the silica and the rubber phases. There is much evidence [12, 13] confirming the existence of such bonds. In all these cases, marked improvement in properties (viz. modulus, tear strength compression strength tensile strength and others) was noted [7, 11].

In order to understand further the effect of silanes on the physical properties of vulcanizates, we have studied the tg0, the tensile strength and the tear strength of N R , N B R and SBR vulcanizates, with and without an 7-mercaptopropyltrimethoxysilane coupling agent (MPTS). Brabender Plasti-corder with a mixer attached and two-roll mill mixings were utilized and the results are compared.
EXPERIMENTAL

Compounding ingredients and formulations SMR L grade natural rubber was obtained from the Rubber Research Institute of Malaysia. Nitrile-butadiene rubber (NBR) (grade Perbunun N 3307), styrene-butadience rubber (SBR), (grade 1502), precipitated silica (grade Vulcasil-S), carbon black (grade N-330) and other chemicals such as sulphur, zinc oxide, stearic acid and accelerators were all purchased from Bayer (M) Ltd. The coupling agent MPTS (grade A-169) was supplied by Union Carbide Ltd. All materials were used as supplied. Recipes used throughout the study are shown in Table 1. To allow comparison between rubbers, a semi-vulcanization system (EV) was chosen instead of the more popular conventional vulcanization system (CV). Furthermore, NR is prone to show a reversion phenomenon when the CV system is used. The amount of silane added was 2% by weight of silica. It was premixed with the silica, prior to mixing because it was reported [7, 11] that in situ addition of silane often gives rise to inferior properties of the vulcanizate. Mixing and tgo determination Mixing was separately done on the Brabender Plasticorder and the two-roll mill under approximately similar conditions. For the Brabender, the rotor speed was set at 40 RPM which is almost equivalent to the two-roll mill shear rate in which the nip size had been set at about 0.75__+0.10 me. Palmegran's method [14] was used for

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M, NASIR et al. Table 1. Formulations of NR, SBR and NBR )'rubber 100; ZnO 2.0; stearic acid 1.5; sulphur Base recipes: .~. 1.6; CBSa 1.9; TMTD b 0.9; IPPD c 2.0 Silica (phr rubber) 5 10 20 40 Silane (phr silica) 0.I 0.2 0.4 0.8 PEG d (phr silica) 1.9 2.8 5.6 11.2 aN-Cyclohexyl-2-benzothiazole-2-sulphenamide. bTetramethylthiuram disulphide. CN-Isopropyl-N-phenylenediamine. dpolyethylene glycol. 60 70 1.2 1.4 17.3 20.6 80 1.6 22.4

Table 2. Cure times (t~0) of silica-filledBrabender-mixed rubber vulcanizates with and without silane coupling agent, measured at 140 (a) Silica without MPTS Silica (phr) 0 5 10 20 40 60 70 80 NR 10 3.5 3.5 4.0 4.0 4.0 4.0 4.0 SBR 19 9.5 9.0 8.5 8.0 8.0 8.0 8.0 NBR 6.0 5.8 6.0 8.0 8.5 8.5 8.5 8.5 (b) Silica with MPTS NR 10 5.0 4.5 4.5 4.5 3.5 3.5 3.0 SBR 19 10 10 8.5 8.0 8.0 7.5 6.0 NBR 6.0 6.0 6.0 5.0 5.0 4.0 4.0 3.5

estimating the shear rates of the mixing equipment. The respective cure times, as measured by tg0, were then determined using the Monsanto Rheometer. Only those of systems with silica are shown in Table 2.

Measurements of tensile and tear strengths The various recipes were compression moulded at 140, according to their respective tgo, into sheets of 1 and 2 mm, thickness. Dumbell and trouser test pieces were cut out o1 the sheets. Tests were then carried out on the Instron Universal Testing Machine according to BS 903, at 50 and 100mmmin -~ cross-head speeds for tensile and tear strengths respectively.
RESULTS AND DISCUSSION

the rubber phases. The presence of such bonds has been confirmed by evidence previously noted [ 12, 13]. Wagner [7, 8] observed that mercaptosilanes generally enhance the scorch and cure time to varying extents, depending on accelerator system and type of elastomer. It was further suggested that the silane participates in the vulcanization by activating the accelerators.

Cure characteristics (tgo)

Only tg0 of the Brabender mixed rubber vulcanizates are given (Table 2). The t90 for both N R and N B R exhibit a cure retardation phenomenon, whereas SBR shows retardation with increasing silica content. The cure retardation phenomenon can be attributed to a silica-rubber interaction, in which the silica reacts with zinc oxide and subsequently reduces the zinc reactivity, so slowing down the sulphur reaction. Fetterman [11], studying the influence of silica on cure behaviour of rubbers, concluded that the effect upon cure retardation is directly proportional to the total surface area of silica present and the functionality of sulphur is dependent on both the particle size and the total content of silica. Similar observations were made by others [9, 15]; it was found that the cure effect is also dependent on the accelerator system and the type of elastomer. This can perhaps explain why SBR displays the cure enhancement phenomenon, instead of cure retardation like N R and N B R . When M P T S is present, all rubbers exhibit a cure enhancement phenomenon. In fact, for SBR t90 is further shortened, showing an improvement of cure behaviour. The enhancement can be associated, perhaps, to direct involvement of the silane in the vulcanization mechanism, resulting in coupling bond formation between the silane and both the silica and

Tensile and tear strengths in the absence of M P T S Tensile strengths of silica-filled N R , N B R and SBR are shown in Figs 1 and 2. Both mixing methods exhibit similar trends; increasing the silica content results in a rise of tensile strengths until maximum levels are reached. Further increase in silica content reduces the tensile strengths. As expected, N R gives the highest tensile strength, followed by N B R and then SBR. However, beyond 50 phr, the Brabender mixed N B R is higher than the N R counterpart. Brabender mixed N B R and SBR show higher tensile strengths than their two-roU mill counterparts,

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Fig. 1. The tensile strengths of the Brabender-mixed silicafilled rubbers ([:], NR; O, NBR; A, SBR).

Silica-filled NR, NBR and SBR vulcanizates

963

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o ~: 2o

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30 40 .50 60 SiLica Loading (phr)

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Fig. 2. The tensile strengths of the two-roll mill mixed silica-filled rubbers ([~, NR; , NBR; /~, SBR). whereas NR seems unaffected by either mixing methods. Furthermore, regardless of mixing method, both NBR and SBR have larger loading capacities than NR, about 60 and 25 phr, respectively. This can be due perhaps to the nature of the rubbers, NBR and SBR being amorphous while NR is crystalline. Similar observations have been reported by others [7, 11], even though lower tensile strengths were obtained here. This is as expected since a semi-EV system was used here, instead of the more popular CV system used by others. In fact, it is well known [16, 17] that a vulcanizate cured using a CV system, by virtue of its polysulphidic network crosslinks, would generally exhibit a tensile strength superior to that of a semi-EV system, which is predominantly monosulphidic in nature. It must be reiterated that the semi-EV system was specifically chosen for the purpose of comparing the three rubbers. The overall tensile strengths of the silica-filled rubbers are found to be inferior to those of carbon blacks, although both fillers have comparable particle sizes. Dan-

nenberg [9] attributed the inferior reinforcing effect of silicas to several reasons, including, the weak bonds and interactions of silica with hydrocarbon rubber phases, the difficult and poorer dispersion and also the cure retardation phenomenon. Somewhat similar trends were observed with tear strengths (Figs 3 and 4) with NR having the highest tear strength, followed by NBR and then SBR. Again, NR is unaffected by the mixing method; for the others, the Brabender mixing is more effective than the two-roll mill. Generally, both mixing techniques and all rubbers show higher loading capacities in tear strengths than those of tensile strengths. In fact, the loading capacities of the two-roll mill mixed NBR and SBR exceed 80 phr. These anomalies are unexpected and unexplained since they were not observed with tensile strengths, and therefore, cannot be attributed to better mixing. Hewitt [1] also obtained higher loading capacities with tear strengths when compared with tensile strengths.
Tensile and tear strengths with M P T S

The tensile strengths of the rubber vulcanizates with the presence of MPTS are shown in Figs 5 and 6. No distinctive differences, relative to those without silane, were observed for all rubbers. However, marked property improvements were noticed with NBR and SBR; a slight increase was seen with NR. Comparing the mixing methods, the Brabender mixed NBR and SBR are greater than those of the two-roll mill but NR seems unaffected by mixing method, as for those without silanes which were discussed previously. When a silane is present, the enhancement in silica reinforcement can be attributed to better wetting and dispersion, hence, coupling bonds being formed between the "shell" of silica and the occluded rubber phases. The results show that silane efficiency is very much dependent on the mixing methods, especially for NBR and SBR and also the type of elastomer. Compared to carbon blacks, silica-filled NBR and SBR, especially at higher loadings, exhibit slightly higher tensile

40

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~: 2o

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I0

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30 40 50 60 SiLico Loading (phr)

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Fig. 3. The tear strengths of the Brabender-mixed silicafilled rubbers (rq, NR; O, NBR; A, SBR).

Fig. 4. The tear strengths o f the two-roll mill mixed silica-filled rubbers (F3, NR; O , N B R ; /k, SBR).

964
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M. NASlRet al.
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SiLica toading (phr)

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Fig. 5. The effect of silanes on the tensile strengths of the Brabender-mixed silica-filled rubber ([1, NR; C), NBR;/x, SBR). 30-

I I I I 30 40 50 60 SiLica Loading (phr)

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Fig. 8. The effect of silanes on the tear strengths of the roll-mill mixed rubbers ([i], NR; (i), NBR; A, SBR).

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SiLica Loading (phr)

Fig. 6. The effect of silanes on the tensile strengths of the two-roU mill mixed silica-filled rubber ([i], NR; O, NBR; z~, SBR).
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strengths than those of the carbon blacks. However, this phenomenon is not observed for NR. Similar observations of silica improvement when silanes are present, have been reported by many workers [7, 11]. Wagner [7], using the same type of silane and by varying the amount of silane and sulphur in silica-filled SBR, found that reinforcement in properties (viz. heat build-up, stress at 300%, Pica Abrasion Index etc.), is dependent of the network structure and the coupling bonds. It was further proposed that any particular property change can be attained by either altering the curative level or adding a silane. Edwards and Sato [18], comparing the various properties of 50phr silica-filled funtionalized SBR vulcanizates with and without the same type of silane, also noticed a large increase in modulus, lower tensile set and heat build-up and better ageing resistance. Dannenberg [9] however reported that better silane efficiency is obtainable

30

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Tear strength (x103 Nm-2 )

Fig. 7. The effect of silanes on the tear strengths of the two-roll mill mixed rubbers (O, NR; C), NBR; /X, SBR).

Fig. 9. The composite plot of tensile strength and tear strength of silica-filled NR ( 0 , silica/two-roll mill; O, silica/Brabrender; A, silica/silane/two-roll mill; A, silica/silane/Brabrender).

Silica-filled NR, NBR and SBR vulcanizates 30

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Tear strength ( x 103 Nm -2 )

observed. Hewitt [1] and Dannenberg [9] also reported similar silane influence on tear strengths. The composite plots between tensile strengths and tear strengths of NR, N B R and SBR are shown in Figs 9, 10 and 1t respectively. The properties of silica-filled, with and without silane, for each rubber and both mixing methods are separately combined in each figures. For NR, a nonlinear relationship with a correlation factor of only 0.46 was obtained; in fact, a curve can be drawn, instead of a straight line. Hence a further increase of the silica filled N R tensile strength is not linearly linked to an expected increase in the tear strength. For NBR and SBR, a linear relationship can be drawn, with correlation factors estimated to be 0.87 and 0.75 respectively. The nonlinear relation in N R is not unexpected since Mullins et aL [16] and Bueche [19] reported similar behaviour in NR, although with gum vulcanizates. CONCLUSIONS The use of ~-mercaptopropyltrimethoxysilane in small quantities results in tensile strength and the tear strength enhancements in silica-filled NR, N B R and SBR vuicanizates; N B R shows the greatest increase, followed by SBR and then NR. Brabender mixings, due to better controllable conditions, give rise to overall better properties in N B R and SBR; for NR, the effect seems to be independent of the mixing method. N B R and SBR show better correlations between tensile strengths and tear strengths while N R displays a completely non-linear relationship.
REFERENCES

Fig. 10. The composite plot of tensile strength and tear strength of silica-filled NBR ( 0 , silica/two-roll mill; O, silica/Brabrender; A, silica/silane/two-roll mill; A, silica/silane/Brabrender). with polar rubbers like N B R and CR, but not in nonpolar rubbers like N R and SBR. The influences of silane on tear strengths are shown in Figs 7 and 8. Like tensile strengths, a slight improvement occurs with N R but marked improvements are found with N B R and SBR. Again, N R has the highest tear strength. The Brabender mixing gives overall better tear strength than the two-roll mill in N B R and SBR; in the case of NR, it seems to be unaffected by the mixing methods. Higher silica loadings than those of tensile strengths were also
30-

1. 2. 3. 4. 5. 6.

e 20
_=
A

7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18. 19.

1o

I 10

I 20

I 30

I 4O

Tear strength (x103 Nm -2)

Fig. 11. The composite plot of tensile strength and tear strength of silica-filled SBR (O, silica/two-roll mill; Q, silica/Brabrender; A, silica/silane/two-roll mill; A, silica/silane/Brabrender).

N. L. Hewitt. Elastomerics 113, 33 (1981). H. P. Wagner. Elastomerics 113, 40 (1981). W. M. Smallwood. J. appl. Phys. 15, 758 (1941). E. Guth. J. appl. Phys. 16, 20 (1945). L Mullins and N. R. Tobin. J. appl. Polym. Sci. 9, 2993 (1965). J. C. Harwood, A. R. Payne and R. E. Whittaker. J. Macromolec. Sci. Phys. 5, 473 (1971). H. P. Wagner. Rubber Chem. Techn. 49, 704 (1976). H. P. Wagner. Rubber World 164, 46 (1971). E. M. Dannenberg. Elastomerics 113, 30 (1981). G. M. Cameron, M. W. Ranney and K. J. Sollman. Eur. Polym. J. 156, 37 (1974). M. Q. Fetterman. Rubber Chem. Techn. 46, 927 (1973). M. Hertl. J. Phys. Chem. 2, 3993 (1968). A. N. Gent and E. S. Hsu. Macromolecules 7, 933 (1974). H. Palmegran. Eur. Polym. J. 156, 70 (1974). M. Q. Fetterman. Elastomerics 116, 18 (1984). L. Bateman, L. Mullins, J. J. Cunnen, L. G. Moore and A. G. Thomas. The Chemistry and Physics of Rubberlike Substances, p. 715. Maclaren, London (1963). C. M. Kok and V. H. Yee. Eur. Polym. J. 22, 341 (1986). D. C. Edwards and K. Sato. Rubber Chem. Techn. 55, 16 (1980). F. Bueche. Physical Properties of Polymers, p. 329. Interscience, New York (1962).

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