Heats of Reaction of the System Rubber-Sulfur

1935 ◽  
Vol 8 (3) ◽  
pp. 456-469
Author(s):  
Archibald T. McPherson ◽  
Norman Bekkedahl

Abstract PREVIOUS investigators have employed two methods for determining the heat effects when rubber is vulcanized. In one method the heats of vulcanization are found by subtracting the heats of combustion of vulcanized rubber—sulfur compounds from the heats of combustion of the corresponding mixtures of rubber and sulfur before vulcanization (1, 10, 11). This method is limited in precision by reason of the fact that the differences thus obtained are at most only a few per cent of the measured heath of combustion. The other method, which has been used previously, involves the determination of the temperature rise which occurs when mixtures of rubber and sulfur are vulcanized. This method has, for the most part, been used for relative measurements, but Blake (2) has recently employed it for quantitative determinations of the heats of reaction of rubber with proportions of sulfur up to about 8 per cent by weight. Recently Daynes (7) has employed a similar method for measurements over a wider range of composition. This investigation was undertaken for the purpose of measuring the heath of reaction of rubber with different percentages of sulfur over the entire range of composition in which combination takes place. The study was exploratory in character, the aim being to make the measurements by direct means with emphasis on simplicity rather than refinement of calorimetric procedure.

1935 ◽  
Vol 8 (2) ◽  
pp. 174-176
Author(s):  
Yoshio Tanaka ◽  
Shū Kambara ◽  
Hironosuke Fujita

Abstract The experiments may be summarized as follows: 1. With an increase in the time of cure, the elongation and heating elongation diminish and the Joule effect increases. 2. An increase in the vulcanization coefficient is followed by a decrease in the elongation and heating elongation and an increase in the Joule effect. The increase in the Joule effect, however, has a limit. 3. An organic accelerator reduces the elongation and heating elongation and increases the Joule effect. 4. The greater the degree of mastication the greater the elongation and the heating elongation and the less the Joule effect. 5. By exposure to ultra-violet radiation, the elongation and heating elongation are increased and the Joule effect decreased. 6. A filler increases the heating elongation and decreases the elongation and the Joule effect. Thus samples with relatively high elongations at a definite tension have relatively high heating elongations and low Joule effects. Such specimens seem to have been affected by the disaggregation and depolymerization of the rubber molecules. The effects of the time of cure, mastication, and exposure to ultra-violet radiation prove this fact. Vulcanization increases the Joule effect, but on the other hand, it is accompanied by a disaggregation and depolymerization of the rubber molecules, so the increase in the Joule effect with the progress of vulcanization has a limit. On vulcanization with an accelerator, the combination of sulfur occurs so rapidly that the increase in the Joule effect is predominant. A filler, such as carbon black, behaves only as a diluent of Joule effect. These results lead to the conclusion that the more highly polymerized rubber molecules and their sulfur compounds seem to be the chief factor in the Joule effect of vulcanized rubber.


1933 ◽  
Vol 6 (4) ◽  
pp. 512-517
Author(s):  
W. D. Guppy

Abstract 1. The method previously described for the volumetric determination of free sulfur in vulcanized rubber has been compared with the older gravimetric methods in cases where other organic compounds containing sulfur are present in the vulcanizate. 2. The volumetric method gave lower results than the methods involving oxidation of the acetone extract in the case of vulcanized rubber containing aldehydeamine condensation products of thiouram disulfide compounds. This indicated that the sulfur combined with some organic compounds was not reduced by the reagents used. 3. The results with the accelerator tetraethylthiouram disulfide showed that in some cases part of the sulfur in organic compounds was reduced under the conditions of the reaction. 4. The acetone-soluble and the acetone-insoluble portions of brown substitute contain organic sulfur compounds. Part of the sulfur in these compounds was reduced to hydrogen sulfide by the action of nascent hydrogen. 5. The sulfur compounds present in white substitute were stable toward the reducing agents used in the estimation of free sulfur. 6. The sulfur compounds formed by the vulcanization of ebonite were in part reduced to hydrogen sulfide with tin and acid. Variations in the composition of the mixing and in the vulcanizing conditions altered the amount of these reducible compounds. 7. The volumetric method previously described cannot be used for the determination of the free sulfur in ebonite, brown substitute or in vulcanized rubber containing brown substitute. In the case of vulcanized rubber containing brown substitute or of ebonite the method can be used to determine the amount of sulfur in the acetone extract. 8. The volumetric method can be employed for the determination of the free sulfur in soft vulcanized rubber containing white substitute and in reclaimed rubber.


1933 ◽  
Vol 6 (1) ◽  
pp. 46-55 ◽  
Author(s):  
A. D. Cummings

Abstract This paper presents the results of measurements of the evolution of hydrogen sulfide from rubber-sulfur compounds heated at various temperatures. Determination of the amount of hydrogen sulfide produced under different conditions was used to measure the degree of decomposition of the rubber. Two types of experiments were carried out: (1) Samples of vulcanized rubber containing 8 to 32 per cent sulfur were heated for 8-hour intervals at 13 temperatures between 105° and 265° C., and (2) samples having sulfur contents of 4, 10, 18, and 32 per cent were maintained for about 200 hours at constant temperature, one set of specimens at 136° and another group at 220° C. These measurements of deterioration were undertaken in connection with an investigation on the electrical properties of vulcanized rubber at relatively high temperatures. During these experiments, samples of rubber-sulfur compounds had been subjected to a wide range of temperatures. Time of exposure to each temperature had been about eight hours. The purpose of the present work was to determine when the sulfur content of a specimen had changed sufficiently to affect its dielectric constant and power factor by a measurable amount. In order to approximate the conditions under which the electrical tests were made, it was necessary to determine the amount of decomposition when rubber vulcanized with 8 to 32 per cent sulfur was heated for successive intervals of eight hours each at temperatures changed in unequal steps from 105° to 265° C. To make this information more complete and to obtain additional data which could be compared with previous investigations, the work was extended to include determinations of the loss of hydrogen sulfide from vulcanized rubber heated for a long time at constant temperature. The electrical properties of the whole series of rubber-sulfur compounds is the subject of a separate investigation at this bureau, and will be reported in another paper.


Data on the heats of combustion of nitrous oxide and of oxygen in carbon monoxide are not only of thermo-chemical importance in themselves but they also afford a basis for evaluating the heat of formation of nitrous oxide from its elements. The present paper is concerned with the measurement of these two heats of combustion by the constant pressure method. The reaction was brought about by the continuous burning of one of the reacting gases in an excess atmosphere of the other. The heat evolution was obtained by measuring the temperature rise of the water in a calorimeter, and the weight of gas involved in the reaction was determined by absorbing and weighing the carbon dioxide produced.


Author(s):  
D.R. Rasmussen ◽  
N.-H. Cho ◽  
C.B. Carter

Domains in GaAs can exist which are related to one another by the inversion symmetry, i.e., the sites of gallium and arsenic in one domain are interchanged in the other domain. The boundary between these two different domains is known as an antiphase boundary [1], In the terminology used to describe grain boundaries, the grains on either side of this boundary can be regarded as being Σ=1-related. For the {110} interface plane, in particular, there are equal numbers of GaGa and As-As anti-site bonds across the interface. The equilibrium distance between two atoms of the same kind crossing the boundary is expected to be different from the length of normal GaAs bonds in the bulk. Therefore, the relative position of each grain on either side of an APB may be translated such that the boundary can have a lower energy situation. This translation does not affect the perfect Σ=1 coincidence site relationship. Such a lattice translation is expected for all high-angle grain boundaries as a way of relaxation of the boundary structure.


Author(s):  
Y. Ishida ◽  
H. Ishida ◽  
K. Kohra ◽  
H. Ichinose

IntroductionA simple and accurate technique to determine the Burgers vector of a dislocation has become feasible with the advent of HVEM. The conventional image vanishing technique(1) using Bragg conditions with the diffraction vector perpendicular to the Burgers vector suffers from various drawbacks; The dislocation image appears even when the g.b = 0 criterion is satisfied, if the edge component of the dislocation is large. On the other hand, the image disappears for certain high order diffractions even when g.b ≠ 0. Furthermore, the determination of the magnitude of the Burgers vector is not easy with the criterion. Recent image simulation technique is free from the ambiguities but require too many parameters for the computation. The weak-beam “fringe counting” technique investigated in the present study is immune from the problems. Even the magnitude of the Burgers vector is determined from the number of the terminating thickness fringes at the exit of the dislocation in wedge shaped foil surfaces.


1962 ◽  
Vol 08 (03) ◽  
pp. 434-441 ◽  
Author(s):  
Edmond R Cole ◽  
Ewa Marciniak ◽  
Walter H Seegers

SummaryTwo quantitative procedures for autoprothrombin C are described. In one of these purified prothrombin is used as a substrate, and the activity of autoprothrombin C can be measured even if thrombin is in the preparation. In this procedure a reaction mixture is used wherein the thrombin titer which develops in 20 minutes is proportional to the autoprothrombin C in the reaction mixture. A unit is defined as the amount which will generate 70 units of thrombin in the standardized reaction mixture. In the other method thrombin interferes with the result, because a standard bovine plasma sample is recalcified and the clotting time is noted. Autoprothrombin C shortens the clotting time, and the extent of this is a quantitative measure of autoprothrombin C activity.


1983 ◽  
Vol 50 (02) ◽  
pp. 563-566 ◽  
Author(s):  
P Hellstern ◽  
K Schilz ◽  
G von Blohn ◽  
E Wenzel

SummaryAn assay for rapid factor XIII activity measurement has been developed based on the determination of the ammonium released during fibrin stabilization. Factor XIII was activated by thrombin and calcium. Ammonium was measured by an ammonium-sensitive electrode. It was demonstrated that the assay procedure yields accurate and precise results and that factor XIII-catalyzed fibrin stabilization can be measured kinetically. The amount of ammonium released during the first 90 min of fibrin stabilization was found to be 7.8 ± 0.5 moles per mole fibrinogen, which is in agreement with the findings of other authors. In 15 normal subjects and in 15 patients suffering from diseases with suspected factor XIII deficiency there was a satisfactory correlation between the results obtained by the “ammonium-release-method”, Bohn’s method, and the immunological assay (r1 = 0.65; r2= 0.70; p<0.01). In 3 of 5 patients with paraproteinemias the values of factor XIII activity determined by the ammonium-release method were markedly lower than those estimated by the other methods. It could be shown that inhibitor mechanisms were responsible for these discrepancies.


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