Analysis of Vulcanized Rubbers. Influence of Accelerators on the Determination of Free Sulfur by the Copper Spiral Method

1952 ◽  
Vol 25 (4) ◽  
pp. 956-958
Author(s):  
J. Mann
Keyword(s):  
Hydrogen Sulfide ◽  
Copper Sulfide ◽  
Acetone Extract ◽  
British Standard ◽  
Standard Methods ◽  
Vulcanized Rubber ◽  
Potential Source ◽  
Source Of Error ◽  
Free Sulfur

Abstract The copper spiral method is being inserted in a revised edition of the “British Standard Methods of Testing Vulcanized Rubber”, and this raises the question of what sulfur compounds react as “free” sulfur. In this method, “free” sulfur is considered to be that part of the sulfur which is present in the acetone extract and which reacts with a copper spiral, placed in the acetone during the extraction, with the production of copper sulfide, the amount of which can be estimated after its removal from the acetone. Since most accelerators contain sulfur, it is obvious that the presence of accelerators or accelerator fragments is a potential source of error. Fourteen accelerators of various types were therefore examined, and it was found that some react with copper, producing compounds which evolve hydrogen sulfide on treatment with hydrochloric acid.

The Determination of Free Sulfur by a Volumetric Method Part II

1933 ◽  
Vol 6 (4) ◽  
pp. 512-517
Author(s):  
W. D. Guppy
Keyword(s):  
Hydrogen Sulfide ◽  
Organic Compounds ◽  
Sulfur Compounds ◽  
Acetone Extract ◽  
Volumetric Method ◽  
Organic Sulfur Compounds ◽  
Vulcanized Rubber ◽  
Volumetric Determination ◽  
Free Sulfur

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.

The Determination of Free Sulfur in Soft Vulcanized Rubber by a Volumetric Method

1932 ◽  
Vol 5 (3) ◽  
pp. 360-362 ◽  
Author(s):  
W. D. Guppy
Keyword(s):  
Hydrogen Sulfide ◽  
Sulfuric Acid ◽  
Organic Compounds ◽  
Subsequent Oxidation ◽  
Vulcanized Rubber ◽  
Elementary State ◽  
Previously Treated ◽  
Mineral Sulfides ◽  
Free Sulfur

Abstract The methods so far proposed for the determination of the free sulfur in vulcanized rubber depend upon the removal of the sulfur by extraction of the rubber with hot acetone, and subsequent oxidation to sulfuric acid of the sulfur in the extract. The extract is liable however to contain, in addition to sulfur in the elementary state, organic compounds containing sulfur derived from the rubber resins, accelerator, or antioxidant. In the subsequent oxidation this sulfur will be oxidized to sulfuric acid to an extent which depends on the method of oxidation used. In the present work, a method of analysis has been developed which is more rapid than the existing methods, and in which it is considered that the determination of the sulfur present in the elementary state is less likely to be affected by organic compounds containing sulfur. It has been found that when vulcanized rubber placed in contact with a metal, such as tin or aluminum, is boiled in hydrochloric acid, hydrogen sulfide is generated by the action of the nascent hydrogen produced. This reaction occurred with rubber which had been previously treated with acid alone to decompose metallic sulfides, but no hydrogen sulfide was obtained from rubber which had been previously extracted with acetone and was free from metallic sulfides. As these results showed that the reactions were not due to the presence of mineral sulfides, or of sulfur combined with the rubber, it was concluded that the hydrogen sulfide was formed by the reduction of the free sulfur.

Determination of Free Sulfur in Vulcanized Rubber

1941 ◽  
Vol 14 (2) ◽  
pp. 520-524
Author(s):  
J. G. Mackay ◽  
C. H. J. Avons
Keyword(s):  
Barium Chloride ◽  
American Chemical Society ◽  
Chemical Society ◽  
Acetone Extract ◽  
Vulcanized Rubber ◽  
Factory Production ◽  
Usual Manner ◽  
Physical And Chemical ◽  
Free Sulfur

Abstract In a rubber laboratory controlling uniformity of factory production by physical and chemical testing, free sulfur is perhaps the most important determination. In this investigation recently described methods for determining free sulfur have been compared. A previous examination by one of the present authors of various methods of estimating free sulfur led to the adoption of a procedure comprising oxidation of the dried acetone extract by a mixture of nitric acid, perchloric acid and bromine, followed by evaporation with sodium chloride and hydrochloric acid before precipitation of sulfate in the usual manner with barium chloride. In the Avon laboratories considerable use has also been made of the method recommended by the Rubber Division of the American Chemical Society, in which bromine alone is used to oxidize the acetone extract, and the sulfate so produced is estimated gravimetrically as the barium salt. Both methods are accurate, but they are not sufficiently quick for effective factory control. Meantime there had been published several new methods of determining free sulfur which were claimed to be quicker than the older procedures. With the aim, therefore, of finding a rapid method more suited to the requirements of a control laboratory, the following methods have been compared. Methods 1 and 2 below were included as controls. As test-samples, 22 different general rubber products selected from factory production were used. Each product contained at least one sulfur-bearing ingredient in addition to the sulfur added to effect vulcanization.

The Determination of Free Sulfur in Vulcanizates by a Polarographic Method

1952 ◽  
Vol 25 (1) ◽  
pp. 161-166 ◽  
Author(s):  
F. C. J. Poulton ◽  
L. Tarrant
Keyword(s):  
Quantitative Determination ◽  
Acetone Extract ◽  
Polarographic Method ◽  
The Common ◽  
Free Sulfur ◽  
Working Processes

Abstract The polarographic method offers a rapid and accurate means of determining the “true” free sulfur in vulcanizates. In the case of single estimations, the test takes approximately as long as the copper-spiral method, but for multiple or replicate testing it is much quicker. Since the determination is made directly on the acetone extract, it was necessary to examine at some length the possibility of interference from other ingredients of the extract. It is shown that most of the common accelerators and antioxidants are not likely to interfere, and promising methods of determining certain of these substances were revealed. Thus MBT, MBTS, TCA, A11, ONV, ZDC, TMT, TET, Ureka, and some of the Nonox series of antioxidants give regular Polarographic waves readily distinguishable from that of sulfur, and the development of working processes for their determination should not present any great difficulties. Other accelerators and antioxidants, notably ZIX, some Nonox antioxidants and Agerite White, while showing Polarographic activity, give poor curves in the pyridine electrolyte. No doubt in other base solutions the form of curve could be improved, and their quantitative determination would then follow.

Investigations of the Reversion of Vulcanized Rubber under Heat

1952 ◽  
Vol 25 (2) ◽  
pp. 241-250 ◽  
Author(s):  
Uma Shankar
Keyword(s):  
Free Energy ◽  
Hydrogen Sulfide ◽  
Methyl Iodide ◽  
Energy Of Activation ◽  
Cross Linking ◽  
Molar Free Energy ◽  
Vulcanized Rubber ◽  
Free Energy Of Activation ◽  
Equilibrium Swelling ◽  
Free Sulfur

Abstract (1) During reversion of a vulcanizate, the breakdown of cross-linkages, including those of polysulfides, predominates over any simultaneous reformation of cross-linkages. (2) The reverting modulus falls exponentially with time. (3) The calculated molar free energy of activation is 33.3 ± 1.7 kcal., irrespective of the temperature or the atmosphere of cure or the composition of the mix, and is sufficient to rupture an —S—S— bond. (4) The degree of cross-linking, estimated from the equilibrium swelling measurements in benzene, falls during reversion. (5) The exclusion of oxygen during curing does not prevent reversion if the temperature is high enough to supply the energy needed to break up the cross-linkages. (6) During reversion in nitrogen, hydrogen sulfide is freely evolved, and the C/H ratio rises above the value for C5H8. (7) Evidence for the formation and breakdown of polysulfides during reversion is provided by an increase in free sulfur and a decrease in combined sulfur during a given cure, and the methyl iodide reaction of the reverted vulcanizates.

Studies of Hard Rubber Reactions. VI. Liberation of So-Called Free Sulfur and Changes in the Acetone Extract of Vulcanized Rubber by Repeated Extraction and Heating

1940 ◽  
Vol 13 (3) ◽  
pp. 598-603 ◽  
Author(s):  
Seiiti Numaziri
Keyword(s):  
Sulfur Compound ◽  
Acetone Extract ◽  
Acetone Extraction ◽  
Vulcanized Rubber ◽  
Rubber Product ◽  
Free Sulfur

Abstract 1. True Free Sulfur.—In the case of the pure rubber-sulfur compound, as shown in the graph, the quantity of true free sulfur liberated from the thermally active hard rubber product by 120 minutes' cure was generally a little greater than that from the thermally nonactive sample with 300 minutes' cure. During the whole course of the extraction and heating, there occurs a lowest point in the true free sulfur curve, which increases again. In view of this fact, liberation of free sulfur can not be attributed to the insufficiency of the acetone extraction but is probably attributable to depolymerization of the vulcanizate or the like. 2. Acetone Extract.—Although purified rubber was used, the corrected acetone extract due to the formation of resinous substances from the depolymerized or aged hard rubber product showed relatively high values at the beginning of extraction and heating. To some extent, the change in acetone followed a course similar to that of the true free sulfur.

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