Migration of Antioxidants and Accelerators in Natural and Synthetic Rubber II. Sulfenamide System Studies and Comparison of Age Resister Migration under Inert and Practical Conditions

1969 ◽  
Vol 42 (3) ◽  
pp. 892-902 ◽  
Author(s):  
James E. Lewis ◽  
Marvin L. Deviney ◽  
Lawrence E. Whittington

Abstract Radiochemical techniques developed for studying extender oil migration in various elastomers have been adapted for use in investigating the migration of age resisters and curatives. This paper contains basic diffusion coefficient data for nine compounds including both staining and nonstaining antioxidants and members of the sulfenamide, thiazole and thiuram accelerator series. Techniques for synthesizing these age resisters and curatives in the carbon-14 and sulfur-35 labelled form are described. Migration was studied in natural rubber, SBR, cis-polybutadiene and EPT vulcanizates. Computer techniques were used to calculate diffusion coefficients from radiochemical count data. Results from preliminary migration studies under practical curing and end-use conditions are also presented. In the case of phenyl-2-naphthylamine migration in cis-polybutadiene, a pronounced decrease in diffusivity with increasing surface area of the carbon black filler was observed.

1932 ◽  
Vol 6 (4) ◽  
pp. 398-408 ◽  
Author(s):  
George Stafford Whitby ◽  
Morris Katz

Samples of synthetic rubber prepared by the polymerization of dimethylbutadiene at room temperature and at 45 °C. respectively were subjected to vulcanization tests in comparison with natural rubber. In an accelerated gum stock containing 3% sulphur the cold polymer gave at best vulcanized products less than one-third as strong and only about one-third as extensible as natural rubber; the heat polymer gave products as extensible but only one-tenth as strong as natural rubber. The incorporation of carbon black greatly increased the strength of the synthetic rubbers, rendering both about half as strong as natural rubber in a similar stock. The vulcanized synthetic rubbers were less "snappy" than natural rubber at room temperature. Increase of temperature improved their speed of retraction, but seriously reduced their breaking strength. Products from the cold polymer showed a greatly increased stiffness and strength at 5 °C. as compared with room temperature, and at about 1 °C. were non-retractible. In general the synthetic rubbers were much more sensitive than natural rubber to change of temperature. A 50:50 mixture of the heat and cold polymers was also subjected to tests.


1977 ◽  
Vol 50 (4) ◽  
pp. 819-827 ◽  
Author(s):  
H. Y. Chen

Abstract The idea of using the radiocarbon dating technique for the differentiation of natural rubber from synthetic rubber is novel and has never been tested before experimentally. The experiments were designed to demonstrate the feasibility of the approach rather than to perfect the technique. With the limited data gathered here, it was shown that the radiocarbon dating technique furnishes results with accuracy quite satisfactory for the analysis of gum rubbers. For the cured samples, the accuracy is reduced mainly by the errors introduced from steps other than that of the radioactivity measurement. A further reduction of the accuracy results if the age of the natural rubber in the stock is not known. We conclude that the technique is feasible and yields results of an accuracy which is probably the best ever achieved by any known technique.


1938 ◽  
Vol 11 (2) ◽  
pp. 359-371 ◽  
Author(s):  
L. Frumkin ◽  
Yu Dubinker

Abstract 1. The apparatus for the determination of the coefficients of thermal conductivity which is described is satisfactory for the investigation of rubber mixtures. 2. A review of the results of the determinations of K values of various mixtures leads to the following conclusions: (a) The thermal conductivity of rubber mixtures containing synthetic rubber is greater than that of mixtures containing natural rubber. (b) The addition of zinc oxide even in considerable quantities to rubber mixtures containing a large percentage (55 per cent) of carbon black does not substantially increase thermal conductivity. (c) In the case of carcass mixtures a considerable increase in the coefficient of thermal conductivity is observed when the content of zinc oxide is increased from 7.5 to 15 per cent by weight; on further increase in the zinc oxide K increases but little. (d) The K value of carcass mixtures before vulcanization is smaller than that of the same mixtures after vulcanization by an average of 23 per cent. (e) The thermal conductivity of uncured tread mixtures is the same as that of vulcanized mixtures. (f) The coefficient of vulcanization has no effect on the K value of unloaded mixtures and mixtures containing fillers. (g) The K value of rubber mixtures increases sharply with addition up to 60 per cent by volume of fillers with good thermal conductivity (zinc oxide and graphite), but only slowly with the addition of fillers of medium thermal conductivity (carbon black). In other words, the curve of the relation between the coefficient of thermal conductivity and the percentage by volume of graphite and of zinc oxide is convex to the filler axis and is concave in the case of carbon black.


1941 ◽  
Vol 14 (4) ◽  
pp. 786-798
Author(s):  
A. Kusov

Abstract 1. A method of measuring the tear resistance of rubber compounds was developed. This method has a number of advantages over other methods (Goodrich, Heidensohn, Goodyear, etc.), including the following. (a) The symmetrical shape and the large surface of tearing (20 sq. cm.). This excludes the possibility of short, accidental tears, and enables better observation of the nature of the tear. (b) Owing to the small size of the clamped portion of the specimen compared to the size of the tearing surface, “end effects” are largely eliminated. (c) Tearing forces are registered periodically (every 10 seconds), and it is possible in this way to determine the total energy expended on tearing, and the nature of its changes. (d) The experiments are easy to perform, and the apparatus is simple. 2. The addition of carbon black (10–100 per cent) to synthetic rubber compounds increases considerably the tear resistances of the vulcanized products. The best results are obtained with compounds containing between 50 and 75 per cent of carbon black. 3. A zinc oxide content of between 8 and 14 per cent improves the tear resistances of compounds of both synthetic and natural rubbers. 4. Compounds with increased fibrous structure show increased abrasion resistance when the fiber direction is parallel to the movement of the abrading surface. 5. Compounds cured for short times only show low tear resistances when made of synthetic rubbers of both low (0.31) and high (0.87) plasticity. The best results are obtained with compounds made of synthetic rubber of medium plasticity (0.53 and 0.40) (see Figure 4). 6. When comparing tear resistances, it is of the utmost importance to maintain the thickness of test-specimens within narrow limits. It is desirable to keep variations within 10–15 per cent. 7. The weakening of the uncut portion of a test-specimen with increase in depth of cut is less pronounced with compounds of synthetic rubber than it is with natural rubber compounds, particularly in the case of overcured samples. With synthetic compounds, this weakening effect varies 2–3 times; with natural rubber compounds it is 3.5–6.5 times. The relation between tear resistance and depth of cut is shown in Figure 5 and Table VI. 8. Carbon black compounds of both synthetic and natural rubbers exhibit various structural forms of tearing. Synthetic rubber compounds with low tear resistances show simple and smooth tearing surfaces, usually in the prolongation of the cut, or at a slight angle to it (Figure 1, type A or intermediate between A and B). Synthetic compounds with high tear resistances show complicated tearing surfaces (Figures 6 and 7, types C, D, E and F).


1932 ◽  
Vol 5 (4) ◽  
pp. 566-575
Author(s):  
George Stafford Whitby ◽  
Morris Katz

Abstract Samples of synthetic rubber prepared by the polymerization of dimethylbutadiene at room temperature and at 45° C., respectively, were subjected to vulcanization tests in comparison with natural rubber. In an accelerated gum stock containing 3% sulfur the cold polymer gave at best vulcanized products less than one-third as strong and only about one-third as extensible as natural rubber; the heat polymer gave products as extensible but only one-tenth as strong as natural rubber. The incorporation of carbon black greatly increased the strength of the synthetic rubbers, rendering both about one-half as strong as natural rubber in a similar stock. The vulcanized synthetic rubbers were less “snappy” than natural rubber at room temperature. Increase of temperature improved their speed of retraction, but seriously reduced their breaking strength. Products from the cold polymer showed a greatly increased stiffness and strength at 5° C. as compared with room temperature, and at about 1° C. were non-retractible. In general the synthetic rubbers were much more sensitive than natural rubber to change of temperature. A 50:50 mixture of the heat and cold polymers was also subjected to tests.


1971 ◽  
Vol 44 (5) ◽  
pp. 1307-1315 ◽  
Author(s):  
M. Mozisek

Abstract The object of measurement was the diffusion of elemental sulfur labeled with the radioisotope S in representative types of rubber. The highest values of diffusion coefficient were found in cis-1,4 polybutadiene. The lowest measured value was found for butyl rubber. The activation energy, expressing the temperature dependence of the diffusion coefficients, ranges from 4 to 10 kcal mol-1. For some rubbers studied, the activation energy is to a certain degree dependent upon temperature. The values of the diffusion coefficients and the characteristic constants for their temperature dependence are related to the mobility of the macromolecular segments.


1950 ◽  
Vol 23 (2) ◽  
pp. 338-346 ◽  
Author(s):  
B. S. T. T. Boonstra

Abstract It is necessary to determine the physical properties of rubbers at relatively high temperatures when products made from them are to be used at such temperatures in actual service. The term heat aging is used when the vulcanizate is tested at room temperature, exposed to elevated temperatures for given periods of time, and then tested again at room temperature. The term high-temperature strength is proposed for values obtained when the vulcanizates are tested at the actual higher service temperatures. Effective comparison of natural and synthetic rubbers is best obtained by determining tensile product values, which are the result of the combining of tensile strength and elongation values. In the evaluating of vulcanizates of tire compounds of various rubbers, another factor must be taken into account. Synthetic-rubber tires develop more heat in service than do natural-rubber tires, and the former therefore generally operate at higher temperatures than do the latter. Synthetic-rubber tires therefore require a greater high temperature strength than do natural rubber tires, but, as has been shown, synthetic rubbers actually have a lower high-temperature strength. The part played by carbon black with respect to the tensile properties of some synthetic rubbers is considered that of a substitute for crystallization in natural and other synthetic rubbers, which substitute does not, however, possess the same favorable features. Carbon black even in noncrystallizing rubbers does not increase strength; it merely shifts the optimum strength value to a higher temperature so that this temperature is in the room temperature range. The temperature coefficient of strength for Butyl and Neoprene rubbers is so large at room temperature that a few degrees' difference in temperature causes large changes in strength. The tensile strength and elongation at break of these two rubbers decrease sharply between 20 and 40° C.


1967 ◽  
Vol 40 (5) ◽  
pp. 1570-1584 ◽  
Author(s):  
James E. Lewis ◽  
Marvin L. Deviney

Abstract The migration of oil, and in particular, the migration of extender oils in rubber is being studied through the use of radioactive isotopes. Techniques have been developed for uniform carbon-14 labelling of the aromatic-polar fractions of extender oils by Friedel-Crafts reaction and for the uniform labelling of the paraffinic fraction by methylene diradicals generated during photolysis of diazomethane-C14. These techniques formed the basis for a comparative study of the diffusion rates of aromatic and polar, and paraffinic, fractions of a highly aromatic and a paraffinic extender oil in several rubbers which represent a wide range in type of polymeric structure. Faster diffusion rates of both aromatic and polar, and paraffinic fractions, were observed in polybutadiene and natural rubber than in SBR, EPT, and polychloroprene. In most rubbers, paraffinic materials migrated appreciably faster than aromatic and polar fractions. Experiments using Firestone flex blocks indicated that oil migration rates are higher under simulated working conditions than when the sample is subjected to heat treatment alone. Diffusion coefficients for the migrating fractions were calculated from an appropriate solution of the basic differential equation of diffusion using modern computer techniques. The methods which have been developed are suitable for fundamental studies to gain more insight into the mechanisms of diffusion. These experimental methods are also suitable for use in practical studies of oil migration under actual or simulated working and environmental conditions. Ultimately sufficient information should be obtained to permit an accurate prediction of the performance of an extender oil in selected rubbers on the basis of the physical properties of the oil and a quantitative knowledge of the major molecular types present in the oil.


1946 ◽  
Vol 19 (1) ◽  
pp. 100-122 ◽  
Author(s):  
D. Parkinson

Abstract The importance of different types of colloidal carbon as reinforcing agents for the butadiene-styrene copolymer, GR-S, has been stressed in recent papers. It has been shown that, to a first approximation, the effect of carbon blacks in this type of synthetic rubber is similar to that in natural rubber, but it has been shown also that the extremely low tensile strength and poor tearing properties of uncompounded vulcanized GR-S necessitates the addition of some form of carbon black to almost all types of compounds. The present paper considers the influence of carbon blacks in vulcanized GR-S compounds. Earlier papers have discussed the effect of carbon blacks in natural rubber.


Author(s):  
P. Sadhukhan ◽  
J. B. Zimmerman

Rubber stocks, specially tires, are composed of natural rubber and synthetic polymers and also of several compounding ingredients, such as carbon black, silica, zinc oxide etc. These are generally mixed and vulcanized with additional curing agents, mainly organic in nature, to achieve certain “designing properties” including wear, traction, rolling resistance and handling of tires. Considerable importance is, therefore, attached both by the manufacturers and their competitors to be able to extract, identify and characterize various types of fillers and pigments. Several analytical procedures have been in use to extract, preferentially, these fillers and pigments and subsequently identify and characterize them under a transmission electron microscope.Rubber stocks and tire sections are subjected to heat under nitrogen atmosphere to 550°C for one hour and then cooled under nitrogen to remove polymers, leaving behind carbon black, silica and zinc oxide and 650°C to eliminate carbon blacks, leaving only silica and zinc oxide.


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