Interaction between Carbon Black and Polymer in Cured Elastomers

1951 ◽  
Vol 24 (3) ◽  
pp. 597-615
Author(s):  
R. S. Stearns ◽  
B. L. Johnson

Abstract This research was initiated to determine whether the interaction at the interface between the surface of finely divided solids, such as carbon black, and cured elastomers is primarily physical or chemical in nature. Further, it was desired to correlate some physical property of the reinforced stock with the surface properties of the solid pigment. Through an examination of the thermodynamic changes accompanying the deformation of loaded stocks it is shown that physical adsorption of the van der Waals type occurring at the interface between pigment and polymer is inadequate to account for the experimental observations. However, if chemical bonding occurs at the interface between polymer and pigment, then the entropy of deformation of the stock may be correlated with the extent of this bonding. By a calorimetric method it was demonstrated that the surface of a carbon black particle contains sites that react with bromine to liberate the same amount of heat as low molecular-weight olefins. It is, therefore, proposed that a carbon black particle be considered as a disordered agglomerate of polymeric benzenoid type molecules which contain around their perimeters various functional groups. The existence of olefinic-type unsaturation on the surface of carbon blacks suggests strongly that, in the case of carbon blacks, the polymer and pigment are combined chemically through pigment-sulfur-polymer bonds into a continuous three-dimensional cross-linked matrix.

1964 ◽  
Vol 37 (4) ◽  
pp. 1006-1012 ◽  
Author(s):  
Andries Voet

Abstract It has been shown that the process of pelletization of a carbon black carried out to permit easier transportation through bulk handling, leads to irreversible changes in properties. There are strong indications that the pelletization process of carbon black involves free radical reactions, leading to chemical particle bonding. The superior physical properties of vulcanizates reinforced with unpelletized blacks indicate that chemical particle bonding is undesirable, since it reduces interaction between carbon black particle and polymer. In order to overcome chemical bonding of carbon black particles during pelletizing, carbon blacks were prepared the particles of which were covered withat least a monolayer of an oleaginous material compatible with the polymer. It was found that the product obtained could be pelletized to form predominantly physically adhering particles. These carbon black compositions disintegrate spontaneously in solvents for the oleaginous liquids, in view of the dissolution of the pellet binding material. The new carbon black compositions are ideally suited for black solvent masterbatching. In addition, they also show improved physical properties upon dry mixing with polymers in conventional dispersing equipment. Finally, they provide for a simple, rapid and efficient way to incorporate processing oils into polymers in conventional mixing equipment.


2011 ◽  
Vol 311-313 ◽  
pp. 201-204
Author(s):  
Hong Zhong Ru ◽  
Ran Ran Zhao

Electrical conductive carbon black-filled cement-based composites are significant as multifunctional structural materials. Double percolation in carbon black-filled cement-based composites involves both carbon black particle percolation and cement paste percolation, which has great effect on the resistivity of composites. Based on double percolation theory, the influences of sand-binder ratio and carbon black volume fraction on the resistivity of carbon black-filled cement-based composites are investigated. The results show that besides carbon black volume fraction, sand-binder ratio is a key factor affecting double percolation behavior in carbon black-filled cement-based composites. At a fixed carbon black content in overall mortar, with increasing sand-binder ratio, the cement paste percolation though aggregate phase increases due to high obstruction of aggregate but the carbon black particle percolation in cement paste decreases. This is because that the microstructure of aggregate is impenetrable so that the carbon black particles are limited in cement paste, that is, the carbon black content in paste is compacted and large amount of conductive paths are generated by lapped adjacent carbon black particles in paste. The double percolation in the electrical conduction in carbon black-filled cement-based composites is observed when the carbon black volume fraction is 7.5% and sand-binder ratio is 1.4, and its resistivity is only 3200 Ωcm, so that a sand-binder ratio of 1.4 and 7.5% carbon black volume fraction or more are recommended for attaining high conductivity with a compromise between workability and conductivity.


1970 ◽  
Vol 43 (5) ◽  
pp. 973-980 ◽  
Author(s):  
A. K. Sircar ◽  
A. Voet

Abstract Determinations have been made of the amount of elastomer unextractable from unvulcanized masticated mixes with carbon black by a given solvent at boil, expressed as immobilized elastomer. Saturated and unsaturated elastomers varying in molecular weights from 2000 to 325,000, were used, while solvents of greatly differing boiling points and solvent power were employed. It could be shown that the bonding between elastomers and carbon black is not a simple adsorption, but involves a higher energy interaction, defined as chemisorption. At successively higher temperatures elastomer is increasingly removed from the carbon black surface. The temperature Tm, obtained by extrapolation of the linear relationship between amounts immobilized and temperature of extraction, represents the temperature theoretically required to eliminate all bonds between carbon black and elastomer and is therefore indicative of the bond strength. Data suggest the existence of a bonding energy spectrum. Upon graphitization, blacks show a considerable decline in high energy bonding ability for elastomers. Saturated elastomers show less bonding than unsaturated elastomers with the same furnace black. “Bound rubber” represents the sum total of physically adsorbed, mechanically entangled, and chemisorbed elastomer. The actual values are greatly dependent upon the procedure used. “Immobilized rubber”, indicating chemisorbed elastomer, is easily determined, is not influenced by the method, and is more significant as an indicator of reinforcement.


1995 ◽  
Vol 269 (6) ◽  
pp. H2124-H2140 ◽  
Author(s):  
B. M. Fu ◽  
F. E. Curry ◽  
S. Weinbaum

We developed a time-dependent diffusion model for analyzing the concentration profiles of low-molecular-weight tracers in the interendothelial clefts of the capillary wall that takes into account the three-dimensional time-dependent filling of the surrounding tissue space. The model provides a connecting link between two methods to investigate transvascular exchange: electron-microscopic experiments to study the time-dependent wake formed by low-molecular-weight tracers (such as lanthanum nitrate) on the tissue side of the junction strand discontinuities in the interendothelial cleft of frog mesentery capillaries (R. H. Adamson and C. C. Michel. J. Physiol. Lond. 466: 303-327, 1993) and confocal-microscopic experiments to measure the spread of low-molecular-weight fluorescent tracers in the tissue space surrounding these microvessels (R. H. Adamson, J. F. Lenz, and F. E. Curry, Microcirculation 1: 251-265, 1994). We show that the interpretation of the presence of tracer as an all-or-none indication of a pathway across the junctional strand is likely to be incorrect for small solutes. Large-pore pathways, in which the local tracer flux densities are high, reach a threshold concentration for detection and are likely to be detected after relatively short perfusion times, whereas distributed small-pore pathways may not be detected until the tissue concentrations surrounding the entire vessel approach threshold concentrations. The analysis using this approach supports the hypothesis advanced by Fu et al. (J. Biomech. Eng. 116: 502-513, 1994) that the principal pathways for water and solutes of < 1.0 nm diameter across the interendothelial cleft may be different and suggests new experiments to test this hypothesis.


1958 ◽  
Vol 31 (1) ◽  
pp. 82-85
Author(s):  
D. Barnard

Abstract The preparation of graft and block interpolymers of natural rubber and synthetic polymers has made it desirable that the number and size of polymer chains attached to rubber be readily determinate. The degradation of unsaturated polymers with tert-butyl hydroperoxide in the presence of osmium tet oxide has been used for the determination of free polystyrene in SBR and carbon black in several elastomers, and has recently been applied to the present problem. The accurate determination of the rubber content of interpolymers by quantitative ozonolysis essentially according to the method of Boer and Kooyman suggested that this might be made the basis of isolation of the attached polymer, the rubber being degraded into fragments of low molecular weight, from which the polymer could be separated by conventional techniques. The method should be applicable to any interpolymer, or mixture, of a polyunsaturated and a saturated polymer and is illustrated with reference to interpolymers of natural rubber (NR)-polymethyl methacrylate (PMM) and NR-polystyrene (PS).


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