1. Heat treatment of carbon black-rubber mixtures is a method of “in process” polymer grafting which gives a definite improvement in the dynamic properties of vulcanizates. 2. The heat treatment process can be more effective if chemical promoters are used. These chemical promoters function as coupling agents between filler surface and rubber. 3. With very unreactive butyl rubber an effective interaction is produced both by the addition of chemical promoters and by the use of specially active surface-modified carbon black. 4. In normal unsaturated rubbers, surface modifications of carbon black with a wide variety of groups has shown only minimal effects on rubber-reinforcing ability. Halogenated blacks have a pronounced effect on vulcanization kinetics, giving cured vulcanizates of high crosslink density. 5. Carbon black surfaces can be deactivated by calcining at high temperatures. The loss of surface-bound hydrogen may not account for this loss in surface activity. 6. Grafting of polymers to the surface of carbon black is a new method for surface deactivation. 7. Activation of carbon black surfaces by polymer grafting or other types of surface modification has not as yet been demonstrated for normal hydrocarbon rubbers.
The first description of the bound rubber phenomenon was by Twiss in 1925, who made the observation that the resistance of carbon black-natural rubber mixes to solvents was related to improved mechanical properties. Boiry studied many of the factors influencing the insolubilization of NR by fillers including type and amount of fillers, and mixing and testing variables. In 1937 J. H. Fielding of Goodyear developed a so-called “bound rubber” test because of his interest in the possibility of chemical bond formation between fillers and rubber. During the start of the U.S. synthetic rubber program, Baker and Walker reported in 1945 an insolubilization of SBR when mixed with carbon black significantly greater than the amount of normal gel in the unfilled elastomer. They were also the first to report that the amount of gel increased with increasing molecular weight and that a selective adsorption of high molecular weight material occurred. Since that time, many investigations have confirmed these findings with other elastomers, and theories of “bound rubber” formation have been based on these observations. The early concept that “bound rubber” is a gel of carbon black particles held together in a three-dimensional lattice by longer interparticle polymer molecules is still valid. The nature of the segmental attachments of the polymer molecules to the filler surfaces now appears to be both physical and chemical, depending upon filler surface activity and chemical functionality, and the chemical composition and functionality of the elastomer. Regardless of the type of interaction, the bonding is essentially permanent and can only be disrupted by extraction with good solvents at high temperatures.
The interaction between fumed silica and silicone elastomer after various treatments of the silica surface has been investigated. The effect of the treatments was determined by measuring bound rubber, an interaction coefficient by means of the oscillating disk rheometer, the mechanical properties of the vulcanizates, the morphology of the silica aggregates, and the use of an hydroxyl-terminated silicone rubber. The results indicated that the interaction is much more intensive than in carbon black-hydrocarbon rubber systems. This is demonstrated by much higher bound rubber values (by a factor of 2–3) and a higher interaction coefficient. It is shown that the major effect on this interaction coefficient is the specific interaction by hydrogen bonding, between silica surface silanol groups and the polydimethylsiloxane chain. In this bonding the isolated hydroxyl groups should play the major part. Partial inactivation of these isolated silanol groups leads to improved strength but lower modulus. Maximum inactivation of the surface hydroxyl groups leads to soft compounds with lower tensile strengths and moduli, as well as very low bound rubber. Replacement of surface hydroxyl groups by vinyldimethylsilyl groups did not have the expected activating effect. Apparently the attached vinyldimethylsilyl groups do not form crosslinks with the elastomer chains, so that the overall result of the presence of these groups on the silica surface is a weakening of the interaction with the silicone rubber chains, although to a lesser degree than in the case of trimethylsilyl groups. The interaction between filler surface and polysiloxane can be maximizedby the use of a hydroxyl-terminated elastomer. The terminal groups will react with the silica surface so strongly that the particles act as crosslinks after proper heat treatment and a crosslinked polymer is obtained with a tensile strength of the same level as a peroxide-crosslinked vulcanizate but with higher compression set. At the temperature of the compression set test (175°C) the bonds apparently rearrange so that the permanent deformation is practically 100%. Quantitative data have been presented which prove that breakdown of silica aggregates does occur during mixing in silicone rubber on a two-roll mill.
Stress softening of vulcanizates of SBR 1500 containing different blacks possessing the same “structure” but varying in surface activity, and effects of different black loadings, of black structure levels, and of particle size, were investigated. It was concluded: 1. Strain-energy loss can be used as a quantitative measure of stress softening, and initial strain-energy input as a measure of prestress severity. 2. The effects of carbon black and polymer variables can be normalized in a single general relationship by plotting per cent strain-energy loss as a function of initial strain-energy input for filled vulcanizates. 3. With the exception of natural rubber, gum vulcanizates studied showed no stress softening. The stress softening of natural rubber gum vulcanizates is attributed mainly to stress-crystallization. 4. Stress-softening of filled vulcanizates is not a completely reversible process. Rates of stress recovery are reasonably rapid. 5. The degree of stress softening can be predicted from the initial stress—strain curve, the prestress severity desired, and the general correlation based on strain-energy considerations found in this study. 6. Prestressing reduces abrasion resistance as measured in the laboratory.
A wide variety of inorganic fillers are produced for the rubber industry. The most important are the clays, precipitated silicas and silicates, and the ground and precipitated calcium carbonates. The silicas and silicates provide the broadest particle size range falling into the carbon black range from FEF (N550) to finer than SAF (N110). The clays and calcium carbonates are in the larger carbon black particle size range from coarser than thermal black (N990) to FEF (N550). if particle size were the only important parameter determining the usefulness of rubber fillers, these products would meet the requirements presently served by carbon black. Their failure to be interchangeable with the carbon blacks is due to their lower modulus and reinforcement performance. These deficiencies are caused by the nature of their surfaces, which are generally more polar and hydrated than carbon black. This makes them more difficult to adhere to and interact with the rubber phase. In order to improve the surface interaction of inorganic fillers with hydrocarbon rubbers, a number of new polymer-reactive, surface-treated products have been introduced. The addition of silane coupling agents during mixing has also been recommended. Silane treated clays and talc, and polymer-grafted clay and calcium carbonate are commercially available. These products are better than their base materials. For some applications, they have been suggested as alternatives to the lower reinforcing grades of carbon black. For the higher reinforcing carbon blacks, only the precipitated silicas with silane additives can be considered as alternatives. However, in tire tread applications, the performance of these combinations has not been clearly defined, and the high cost of the silanes makes their use with silica prohibitive. A more economic method for coupling may result from recent research on functionalized polymers capable of reacting with the surface silanol groups of silica. This survey also includes two finely divided carbonaceous fillers made from coal and petroleum coke. Blends of these materials with more reinforcing carbon blacks and other fillers have been recommended as alternatives to the carbon blacks in the thermal to SRF range. A number of commercial fillers have been suggested as alternatives to the lower reinforcing grades of carbon black for some applications. There are no satisfactory substitute products for the medium to high reinforcing grades of carbon black.
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