The strength of highly elastic materials

Under repeated stressing, cracks in a specimen of vulcanized rubber may propagate and lead to failure. It has been found, however, that below a critical severity of strain no propagation occurs in the absence of chemical corrosion. This severity defines a fatigue limit for repeated stressing below which the life can be virtually indefinite. It can be expressed as the energy per unit area required to produce new surface ( T 0 ), and is about 5 x 10 4 erg/cm 2 . In contrast with gross strength properties such as tear and tensile strength, T 0 does not correlate with the viscoelastic behaviour of the material and varies only relatively slightly with chemical structure. It is shown that T 0 can be calculated approximately by considering the energy required to rupture the polymer chains lying across the path of the crack. This energy is calculated from the strengths of the chemical bonds, secondary forces being ignored. Theory and experiment agree within a factor of 2. Reasons why T 0 and the gross strength properties are influenced by different aspects of the structure of the material are discussed.

1960 ◽  
Vol 33 (4) ◽  
pp. 946-952
Author(s):  
E. V. Reztsova ◽  
B. G. Lipkina ◽  
G. L. Slonimskiĭ

Abstract 1. The substantial effect of inhibitors and initiators of chain radical processes on the change in the properties of rubbers in milling, as well as on the resistance of vulcanizates to fatigue, has been shown. This indicates a mechanochemical mechanism of the processes occurring in processing polymers and of the fatigue of highly elastic materials (e.g., rubber vulcanizates). The act of mechanical scission of chemical bonds, with the formation of free radicals which initiate the secondary chain processes, rests on these processes. 2. The possibility has been shown of regulating the properties of polymers in the course of their industrial processing, and also of increasing the dynamic fatigue resistance of vulcanizates by incorporating small quantities of additives active in regard to free radicals.


1951 ◽  
Vol 24 (3) ◽  
pp. 638-639
Author(s):  
Jean Le Bras ◽  
Jacques Le Foll

Abstract One of the present authors has already offered evidence which indicates the existence of a deactivating effect, whereby vulcanized rubber is protected against deterioration by oxygen. This effect is evident with such compounds as mercaptobenzimidazole (I), mercaptobenzoxazole, and ethylene-bis (N,N′-phenylthiourea) (II), and the phenomenon seems to be connected in some way with the presence in the molecule of a thiol group united to a nitrogen atom under such conditions that the possible tautomerism between the thion and thiol forms (III) is probably displaced toward the thiol form. We have completed these earlier experiments by a more systematic study, which has included an examination of the influence of cyclization, the nature of the ring, and hetero atoms.


1939 ◽  
Vol 12 (1) ◽  
pp. 43-55
Author(s):  
J. R. Brown ◽  
E. A. Hauser

Abstract A CENTURY ago, Charles Goodyear in America and Th. Hancock in England found that the properties of crude rubber could be greatly improved by heating it with sulfur. The product resulting was more elastic, more resistant to tear and abrasion, less affected by solvents, and decidedly less thermoplastic. The treatment of rubber to give these desired properties is known generally as vulcanization and must be considered as the basis for the enormous growth of the rubber industry and the extensive use of rubber products in our everyday life. Broadly speaking, vulcanization involves the reaction, in some fashion, of sulfur with rubber. Extensive investigation has revealed other substances, such as benzoyl peroxide or polynitrobenzenes, which can transform rubber into a “vulcanized” condition. Experience has also shown that metallic salts of zinc or lead and especially certain organic compounds called “accelerators” greatly affect the rate of vulcanization, and these are favorably employed in practice. A vast amount of empirical knowledge has been gained which has greatly improved the practical application of vulcanization and the quality of rubber products, but which has failed as yet to reveal a complete picture of the true nature of the process.


1953 ◽  
Vol 26 (4) ◽  
pp. 759-763 ◽  
Author(s):  
B. Dogadkin ◽  
Z. Tarasova

Abstract According to the hypotheses developed by the authors, vulcanized rubber is a system in which the molecular chains are united by local molecular and chemical bonds of varying intensity. The concentration, distribution, and strength of these bonds determine the principal physical and mechanical properties of the vulcanizates. Consequently the study of the structure of the vulcanizate is of primary practical value. The explanation of the nature of the bonds in a vulcanizate by chemical methods is very difficult, mainly because of the impossibility of distinguishing the specific chemical groups which enter into the composition of the different molecular chains from those bonds between the chains which are responsible for the development of spatial structures. From this view point, the thermo-mechanical method described below, which is based on the study of stress relaxation at different temperatures, is of great significance. As was shown by Dogadkin and Reznikovskii˘, the delayed stress relaxation in a vulcanizate at temperatures up to 70° C is caused by rupture of the local intermolecular bonds and the regrouping of the structural elements of the polymeric chains without destruction of the chemical bonds between them. Accordingly, after some time at these temperatures, a practically balanced stress is established, which depends on the number of the stronger bonds remaining. At temperatures above 70° C, rupture of the chemical bonds between the chains takes place; its speed increases with decrease of the energy activating the rupture of the given type of bond. Particularly in the case of sulfur vulcanizates, we can assume that the following types of bonds exist between the chains of the rubber: (1) —C—C—, which develop as a result of the polymerizationprocesses; (2) —C—S—C— monosulfide; (3) —C—S—S—C— disulfide, and (4) —C—Sn—C— polysulfide, formed as a result of the direct participation of the vulcanizing agent, sulfur, in the process of joining of the molecular chains. The energy of these chains can be estimated as 62.7 kcal, per mole for C—C, 54.5 kcal. per mole for C—S, and 27.5 kcal. per mole for the —S—S bond. Naturally, the heat stability of a vulcanizate will depend on which of the indicated types of bonds predominates.


1973 ◽  
Vol 7 (1) ◽  
pp. 115-120
Author(s):  
G. M. Bartenev ◽  
V. V. Lavrent'ev ◽  
V. S. Voevodskii

1950 ◽  
Vol 23 (1) ◽  
pp. 67-88
Author(s):  
Fritz Rössler

Abstract A more extended investigation was made of the surprising flow phenomena which were found in an earlier study of rubber at low temperatures. The tensile apparatus was reconstructed so that a dead-weight load could be applied to the rubber test-specimen. Determinations of the dependence of the rate of flow on time of stressing, initial elongation, magnitude of the stress, and temperature showed that a simple law can be derived for expressing the flow phenomena. Yield point, change in color, and deterioration in physical properties, as well as the reversibility of these phenomena were investigated and are discussed. The phenomena of flow at room temperature are expressed by the same constants as at lower temperatures. Only the effective stress increases at low temperatures and only by this change does flow become perceptible. Different types of rubber were compared, and all showed approximately the same value for the flow constant. The essential characteristics of the flow phenomenon can be explained, on a basis of the theory of highly elastic materials, by their microliquid state of aggregation. This applies to the high degree of dependence of the mechanical properties of rubber on the temperature.


1962 ◽  
Vol 35 (5) ◽  
pp. 1308-1341 ◽  
Author(s):  
Jean LeBras

Abstract According to the partial conclusions drawn from the results given in each of the three chapters of this review, one can say that the question of reinforcement by resins, if it has not yet attained the aims sought for, has accumulated a great deal of useful information and now seems in a position to make rapid progress. The most significant point that seems to emerge is the necessity for the establishment of strong chemical bonds between the resin particle and the elastomer. This is undoubtedly not sufficient, and other characteristics of the particle must also intervene; but we have said above that one could now imagine a systematic study of the influence of these characteristics, and we need not return to it here. Many questions are still posed and the investigator will have the task of answering them. We consider it important to insist, however, in this conclusion, on some very recent results which it seemed preferable to us to mention here rather than to incorporate them in the text. In fact, they will either bring a confirmation on the influence of chemical bonds or show the possibility of preparing rubbers which should lend themselves remarkably well to this kind of reinforcement. In studying the crosslinking phenomena that involve the well known hardening of dry natural rubber on storage, Sekhar has shown that reactive groups are present as in integral part of the polyisoprene chain when it leaves the tree. These reactive groups have the characteristic property of carbonyl groups or, more specifically, aldehyde groups. They are responsible for crosslinking of the rubber molecules, and reactive monofunctional amines or other carbonyl reagents are capable of inhibiting this crosslinking effectively. From the critical concentration of reagent required to inhibit hardening, one has to postulate the presence of 9 to 29 aldehyde groups per polyisoprene molecule, assuming a molecular weight of 1,000,000). Because of the presence of these aldehyde groups on the chain of the rubber hydrocarbon, one was led logically to suppose that molecules of aminoplast resins formed in the latex might be fixed chemically on the rubber through the aid of these groups. This is what Sekhar and Angove realized with hydrazine-formalde-hyde resins. At a concentration of 5% and less of resin based on rubber, the latex remained fluid with no tendency to gel. Films and foam rubbers prepared from such resin latex showed considerable reinforcement: thus for a 3% resin content, for example, the tensile strength of a latex film passes from 285 kg/cm2 for the control to 362 kg/cm2 (the elongation in both cases being 925%), the 600% modulus from 32 to 75 kg/cm2, the tear resistance from 64 to 100 kg/cm. It is therefore with the greatest interest that one should consider such reinforcement results obtained with such a small proportion of resin; they emphasize the very important part that must be played by a strong chemical bond between the filler particle and the elastomer. It is evident, however, that the small proportion of aldehyde groups present on the rubber molecule limits the possibilities of such a fixation and must not permit to obtain the maximal reinforcing effects. That is why it seems necessary to pay a great attention to the reaction of glyoxal on rubber, which is endowing this latter with aldehyde-α alcohol side groups and gives it the reactivity toward the resins that seems to be desirable. We may therefore think that the years to come will bring into this field new and useful results, with a view toward the improvement of the characteristics of vulcanized rubber and ever-widening development of its application.


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