scholarly journals The Tensile Strength of Rubber and Rubber Molecule

1950 ◽  
Vol 23 (3) ◽  
pp. 581-586
Author(s):  
Chullchai Park ◽  
Usaburo Yoshida

Abstract The tensile strengths of crystallized crude rubber and vulcanized rubber are remarkably different from each other at room temperature, but are found to be almost the same at the temperature of liquid air. By assuming that the tensile strength of crystallized rubber at this low temperature is entirely due to its chain molecules, the forced needed to break a chain molecule of rubber at its weakest point is estimated.

The rotation of the CH 3 groups round the single C—C bond in ethane is associated with a threshold energy of about 3000 gcal./gmol. or 2 x 10 -13 erg/mol. (Schäfer 1938; Kistiakowsky, Lacher and Strutt 1939). In an aliphatic CH 2 chain where the carbon atoms are linked together by single bonds the corresponding energy must be of the same order and is most likely rather smaller. Supposing we consider any particular C—C bond in the chain and treat the two parts at each side of this bond as rigid rotators, then their kinetic energy would be 2 x 1/2 kT which at room temperature amounts to about one-fifth of the threshold energy. It seems very likely under these circumstances that a chain molecule of say ten to twenty carbon atoms should already at room temperature show signs of distortion due to internal rotation. If this is true, then the previously observed increase of the crystal symmetry at the melting-point of paraffins (Müller 1930, 1932) and the corresponding changes of the polarization of long-chain ketones (Müller 1937, 1938) can no longer be ascribed entirely to a rotation of the molecule in the field of the surrounding molecules but must at least partly be due to this internal distortion. It is clear that a distortion of this type tends to destroy the anisotropy of the molecule and to give an apparent isotropy to the crystal. The present experiments were made in order to obtain an estimate of the magnitude of the distortion effect. It is found to be surprisingly large.


1949 ◽  
Vol 22 (4) ◽  
pp. 1036-1044 ◽  
Author(s):  
L. Mullins

Abstract The residual extension which remains after a sample of rubber has been stretched for some period, then released and allowed to recover, is popularly called permanent set. This set, however, is far from being permanent since it continuously decreases with the period of recovery; furthermore, after the rate of recovery has become exceedingly slow and is no longer readily observable, an increase in temperature will usually result in a sharp increase in the rate of recovery. It has been usual to identify this set with irreversible plastic flow, but it will be immediately evident that this can rarely be justified for, owing to incomplete high-elastic recovery, the measured value of set is a combination of both plastic flow and high-elastic deformation which has not completely recovered. Thus before any attempt is made to discuss the interpretation of the results of set tests, a study must be made of the significance of set. Treloar has investigated this phenomenon in raw natural rubber and has shown that entanglements or cohesional linkages may form while the rubber is stretched, and these oppose recovery; further, although van der Waals forces between the long-chain molecules largely control the rate and the amount of recovery, the crystallization of rubber produced by stretching may profoundly influence the set. On the other hand Tobolsky has studied the set which results from stretching rubber vulcanizates at high temperatures ; in such cases the amount of set is controlled by two processes which take place while the rubber is stretched; one of these involves the oxidative breaking of network chains, the other the oxidative cross-linking of network chains. Although these ideas are well founded, they do not provide a completely satisfactory basis for the understanding of set, and the purpose of this work is to extend these ideas and to explain the significance of the results of normal set tests ; in these tests rubber samples were extended at room temperatures to moderate elongations for relatively short periods of time. Most of the tests performed in this investigation were made on dumbbell shaped samples, which were extended by 200 per cent of their initial length for fifteen minutes at room temperature and then allowed to recover for one hour at room temperature; the residual extension was then noted and expressed as a percentage of the initial length. These tests will be referred to as normal set tests. In some tests various periods and temperatures of extension and recovery were used.


1946 ◽  
Vol 19 (4) ◽  
pp. 956-967
Author(s):  
S. Buchan ◽  
J. R. Shanks

Abstract Although the practice of bonding rubber to metal has been in use for many years, no theories appear to have been advanced which explain adequately the mechanism of bonding. It has been stated that the brass bond between rubber and metal functions through chemical linkages, but this can only be regarded as tentative and has yet to be proved. No attempt has been made to find out how ebonite functions as a bonding medium or the more recently discovered derivatives of rubber, such as sulfonated rubber, chlorinated rubber, and rubber hydrohalides. Until it is properly elucidated just how bonding agents do act, further logical development of improved bonding media cannot be pursued. It is intended in this paper to show how the rubber-metal bond behaves at subnormal temperatures and how a low temperature technique may be used for studying the mechanism of bonding. The effect of low temperatures on the tensile strength and associated properties of vulcanized rubber, such as hardness, permanent set, flexibility, resilience and flexing, has been dealt with fairly comprehensively in the literature. Progressive reduction in temperature leads to only a moderate increase, for example, in tensile strength, until the point is reached at which the rubber stiffens and freezes, when a marked increase occurs. Examination of a brass-bonded unit at low temperatures revealed that the graph obtained for bond strength was very similar in slope and character to that for tensile strength. The similarity is illustrated by the data in Table 1 and in Figure 1.


1946 ◽  
Vol 19 (3) ◽  
pp. 525-533
Author(s):  
Kurt H. Meter ◽  
A. J. A. Van Der Wyk

Abstract It has been demonstrated that the elastic force of a moderately vulcanized rubber kept at a constant stress is proportional to the absolute temperature, T, in the region of medium elongations. In this respect, rubber behaves somewhat like an ideal gas, the pressure of which at constant volume is also proportional to T. By applying the first and second laws of thermodynamics, it can be shown that the internal energy of isothermally stretched rubber changes as little as that of an ideal gas if its volume is increased or decreased isothermally. In both cases, however, the entropy of the system changes. Meyer, Susich, and Valkó, Karrer, and Busse explain this behavior in the following way. All rubberlike substances consist of long, flexible, chain molecules whose links are thermally mobile. In the undeformed amorphous rubber, the molecules represent randomly coiled chains ; as a result of the deformation their shape is changed, e.g., partly stretched by elongation. Thus a thermo-dynamically less probable shape is forced on them ; the thermal agitation tends to eliminate it ; because of the reciprocal felting and intertwining of the molecules, a return to the thermodynamically more probable state is possible only if the deformation can be reversed. The thermally mobile chain links are referred to as kinetic units or chain segments. In the present paper, we shall discuss the molecular processes taking place in the course of deformation, in particular such questions as: “How is the deforming force transferred to an individual chain molecule and its segment?” “How does the molecule react to this force?” After having discussed these questions, we shall examine how far the requirements are complied with for a quantitative theory such as the derivation of an equation to calculate the modulus of elasticity from structural data. We shall also discuss the attempts known to have been made in this direction so far.


1943 ◽  
Vol 16 (2) ◽  
pp. 318-341
Author(s):  
J. W. Van Dalfsen

Abstract Patents granted to Schidrowitz show that when latex is vulcanized and then dried at room temperature, the product has the properties of vulcanized rubber. Films produced in this way show tensile strengths and elasticity which correspond to those of latex films vulcanized in the dry state. It is apparent, however, that when fresh latex is vulcanized under certain definite conditions, the product has fair tensile strength and elasticity only at a relative humidity of zero, but which under ordinary atmospheric conditions is brittle, seems to be overcured, and is practically without tensile strength. This tensile strength, however, is increased by additional dry vulcanization, so there can be no question of overcure. Just as soon as vulcanization has proceeded to a point where brittle films without tensile strength are obtained, the latex, when treated with acid, does not coagulate, but merely flocculates. Nor can such vulcanized fresh latex at this stage be made to coagulate coherently by other means. This form of latex is not sticky. The flocculate referred to can be obtained only by vulcanizing fresh latex in the presence of zinc oxide, and under conditions such that hydrolysis of the nonrubber substances is a minimum. It is, therefore, desirable to have recourse to ultra-accelerators and to be sure that the vulcanization temperature is not too high. By keeping fresh latex alkaline, or by purifying it, it will not flocculate. Latex that has been purified or aged may occasionally, under similar conditions, give a brittle and incoherent coagulum, whereas in other cases a normally coherent but somewhat brittle coagulum results. The nature of the coagulum is governed by the degree of purification and hydrolysis of the nonrubber substances; hence all transition stages between a flocculate and a completely coherent coagulum may occur. By adding serum from fresh latex to purified latex, the behavior of such purified latex changes in the sense that it behaves more like fresh latex. In studying experimentally the difference in behavior of fresh latex and purified latex, the first thing considered was the combination of sulfur. It was found that sulfur first dissolves in the serum, after which it dissolves in the rubber itself. Only then does vulcanization take place. This became evident from the definite acceleration of the combination of sulfur in the latex stage, when before vulcanization, latex was heated with sulfur alone. By this preparatory treatment too, dry vulcanization at room temperature was accelerated, but there was no noticeable effect on dry vulcanization at 80° and 110° C. At 30° C, about 1 per cent of the sulfur dissolved in the rubber particles, in the form of free sulfur. From this it was concluded that it is not possible to remove by mechanical means (as by clarification) excess free sulfur from vulcanized latex. No essential difference could be found between the combined sulfur of fresh latex and that of purified old latex.


1935 ◽  
Vol 8 (4) ◽  
pp. 554-570 ◽  
Author(s):  
P. A. Gibbons

Abstract Hitherto two products of the reaction between sulfur and rubber have been studied and used commercially, soft rubber and ebonite. Few publications have appeared concerning the products obtained by vulcanization of proportions between 5 and 30 parts of sulfur with 100 parts of rubber. Before the introduction of organic accelerators of vulcanization the coefficient of vulcanization was considered a satisfactory criterion of the quality of soft vulcanized rubber. Mixes of rubber and sulfur vulcanized to a coefficient of more than 3.5 to 4 were usually considered overvulcanized in that experience showed that the optimum properties as regards tensile strength and elongation at rupture occurred at this degree of vulcanization. Semi-ebonites differ from soft rubber and ebonite in as much as they are extremely sensitive to small changes in the time of vulcanization. Their plasticity is such that the velocity of plastic flow just prior to break is relatively great, and thus they may experience a large elongation at constant load. Their plasticity decreases with further vulcanization, in fact, with advance in vulcanization they become almost rigid at room temperature. The decrease in plastic flow is accompanied by an increase in hardness and brittleness and the ultimate stage in the rubber-sulfur reaction, ebonite, is reached.


2015 ◽  
Vol 44 (3) ◽  
pp. 20140208 ◽  
Author(s):  
E. A. S. Marques ◽  
M. D. Banea ◽  
Lucas F. M. da Silva ◽  
R. J. C. Carbas ◽  
C. Sato

1943 ◽  
Vol 16 (4) ◽  
pp. 924-925
Author(s):  
J. R. Scott

Abstract The work described below was carried out as a first step in determining whether an oxygen-bomb test at room temperature could be used as an accelerated aging test for unvulcanized rubber compositions, e.g., as used on surgical and adhesive plasters and for combining shoe fabrics, because a high-temperature test is unsatisfactory in such cases, owing to the melting of the compositions. The only infallible way of assessing the value of an accelerated test for such compositions is by comparison with natural aging, but as this is a very lengthy process and as the deterioration is difficult to measure quantitatively, it was decided to make preliminary tests on the effect of high oxygen concentration at room temperature by using vulcanized rubber. Although the results proved to be negative so far as the original purpose of the work was concerned, it is considered of interest to place them on record in view of the prominence given in some papers on aging to the relationship between oxygen concentration and rate of oxidation and deterioration of rubber. A mix composed of rubber 100, sulfur 3, zinc oxide 5, stearic acid 1, and diphenylguanidine 0.75, was vulcanized for 30 minutes at 153° C. Tensile tests, using standard ring-specimens and the Schopper machine, were made on unaged specimens and on specimens that had been aged (1) in an oxygen bomb at 300 lb. per sq. in. oxygen pressure and at room temperature (about 10° C), (2) in a Geer oven at 70° C. Four rings were used for each test, the tensile strength and breaking elongation figures quoted being the average for the two rings giving the highest tensile strength, and the figures for the elongations at constant loads the average of all four rings.


1944 ◽  
Vol 17 (1) ◽  
pp. 221-226
Author(s):  
E. C. B. Bott ◽  
L. D. Gill

Abstract The deterioration of vulcanized rubber containing increasing percentages of copper and manganese compounds and the extent of the protection given to the stocks by a secondary naphthylamine have been investigated. Jones and Craig showed that the addition of copper stearate made no difference to the type of aging of stocks containing various percentages of antioxidant when measured by decrease in tensile strength, and the results of Taylor and Jones indicate that the decrease is proportional to the time of aging in the Geer oven. Preliminary work.—Experiments were made on the base mix to determine its suitability and its optimum cure. The optimum cures of the base mix plus copper or manganese compounds after storage for six weeks in the dark at normal room temperature and of the base mix plus sym. di-β-naphthyl-p-phenylenediamine also were obtained. The following compounds A, B, C and D were mixed on a laboratory mill having 12 × 6 in. rolls.


2004 ◽  
Vol 52 (4) ◽  
pp. 479-487 ◽  
Author(s):  
Cs. Pribenszky ◽  
M. Molnár ◽  
S. Cseh ◽  
L. Solti

Cryoinjuries are almost inevitable during the freezing of embryos. The present study examines the possibility of using high hydrostatic pressure to reduce substantially the freezing point of the embryo-holding solution, in order to preserve embryos at subzero temperatures, thus avoiding all the disadvantages of freezing. The pressure of 210 MPa lowers the phase transition temperature of water to -21°C. According to the results of this study, embryos can survive in high hydrostatic pressure environment at room temperature; the time embryos spend under pressure without significant loss in their survival could be lengthened by gradual decompression. Pressurisation at 0°C significantly reduced the survival capacity of the embryos; gradual decompression had no beneficial effect on survival at that stage. Based on the findings, the use of the phenomena is not applicable in this form, since pressure and low temperature together proved to be lethal to the embryos in these experiments. The application of hydrostatic pressure in embryo cryopreservation requires more detailed research, although the experience gained in this study can be applied usefully in different circumstances.


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