The Effect of Sulfur on the Oxidation of Sodium-Butadiene Rubbers

1951 ◽  
Vol 24 (4) ◽  
pp. 853-856
Author(s):  
A. S. Kuzminskii˘ ◽  
T. G. Degteva ◽  
K. A. Lapteva ◽  
N. N. Lezhnev

Abstract In the vulcanization of rubber and in the service performance of vulcanized rubber products, oxygen and free sulfur are always present. Consequently it is important to know the effect of sulfur on the oxidation of rubber. The present work is devoted to an investigation of the oxidation of a sodium-butadiene polymer in the presence of sulfur. Dogadkin and his associates established the fact that oxygen has an influence on the nature of the structural changes of rubber during vulcanization. The present authors have shown that any sulfur which is chemically combined with rubber does not appreciably affect the kinetics of its oxidation, and that free sulfur, in solution in rubber, interferes with autocatalytic oxidation. The higher the concentration of sulfur, the greater is this interference (see Figure 1). Introduction of sulfur into rubber during autocatalysis does not prevent the autocatalytic process, but hinders it noticeably (see Figure 2). The introduction of a secondary aromatic amine has been observed to arrest the process altogether. This behavior of sulfur can be explained by its ability to react with intermediate oxidation products, since the rate of combination of sulfur is practically constant (see Figure 3).

H 2 S is produced as a main end-product of anaerobic mineralization in anoxic, sulphate-rich environments by a diverse population of sulphate-reducing bacteria. The sulphate reducers can carry out an almost complete oxidation of detrital organic m atter to CO 2 . The H 2 S consequently becomes an important electron carrier from the anoxic to the oxic world. Thiobacilli and other colourless sulphur bacteria have the potential to oxidize the H 2 S at the oxic-anoxic interface in sediments or stratified waters, but their role is still poorly understood. A comparison of sulphide oxidation processes in the chemoclines of the Black Sea, the Solar Lake and in a Beggiatoa mat indicated that depth scales and retention times of coexisting O 2 and H 2 S regulate the bacterial involvement in the sulphide oxidation. The H 2 S specialists, Beggiatoa and Thiovulum, are optimally adapted to compete with the autocatalytic oxidation of H 2 S by O 2 . Microelectrode measurements show retention times of O 2 - H 2 S in the bacterial mats or veils of less than 1 s. In photic chemoclines of stratified waters or sulfureta, the phototrophic sulphur bacteria or cyanobacteria interact with the sulphide oxidation at the O 2 - H 2 S interface. Short cycles between H 2 S and intermediate oxidation products, S 0 or S 2 O 2- 3 , are created. The bacteria of the sulfuretum are highly adapted to the diurnal rhythm of light, O 2 and H 2 S.


1929 ◽  
Vol 2 (3) ◽  
pp. 341-355
Author(s):  
A. Van Rossem ◽  
P. Dekker

Abstract SINCE Kirchhof in June, 1927, gave to the first general meeting of the German Rubber Society in Essen a detailed review of work concerned with the oxidation of rubber, it seems superfluous to publish any extensive bibliography thereon. We prefer to limit ourselves, for the present, almost exclusively to a few experiments in this field. However, we may refer in a general way to the work of others. It is a notable fact that all investigations of the oxidation of vulcanized rubber have been always based on the kinetics of the oxygen combination, and, as far as isolation of the oxidation products is concerned, on a late stage of oxidation, the isolation of oxidation products during the early stages of oxidation being left out of consideration. Thus, for example, Kirchhof in his work published in 1913 studied the behavior of ground vulcanized rubber which had been heated for 100 hours in a current of air at 100° C. and thereby strongly oxidized, as indicated by the increase in weight (11–13%). Eaton and Day later in 1919 made experiments of a similar nature. Here, too, the kinetics principally were studied, and the samples were examined only after oxidation was far advanced. Again in Kirchhof's recent work already mentioned, the oxidation products were studied only after prolonged oxidation.


2018 ◽  
Vol 69 (5) ◽  
pp. 1139-1144
Author(s):  
Iosif Lingvay ◽  
Adriana Mariana Bors ◽  
Livia Carmen Ungureanu ◽  
Valerica Stanoi ◽  
Traian Rus

For the purpose of using three different types of painting materials for the inner protection of the transformer vats, their behavior was studied under actual conditions of operation in the transformer (thermal stress in electro-insulating fluid based on the natural ester in contact with copper for electro-technical use and electro-insulating paper). By comparing determination of the content in furans products (HPLC technique) and gases formed (by gas-chromatography) in the electro-insulating fluid (natural ester with high oleic content) thermally aged at 130 �C to 1000 hours in closed glass vessels, it have been found that the presence the investigated painting materials lead to a change in the mechanism and kinetics of the thermo-oxidation processes. These changes are supported by oxygen dissolved in oil, what leads to decrease both to gases formation CO2, CO, H2, CH4, C2H4 and C2H6) and furans products (5-HMF, 2-FOL, 2 -FAL and 2-ACF). The painting materials investigated during the heat treatment applied did not suffer any remarkable structural changes affecting their functionality in the electro-insulating fluid based on vegetable esters.


1989 ◽  
Vol 21 (8-9) ◽  
pp. 805-814 ◽  
Author(s):  
F. R. Christensen ◽  
G. Holm Kristensen ◽  
J. la Cour Jansen

Experimental investigations on the kinetics of wastewater treatment processes in biofilms were performed in a laboratory reactor. Parallel with the kinetic experiments, the influence of the biofilm kinetics on the biofilm structure was studied at macroscopic and microscopic levels. The close interrelationship between biofilm kinetics and structural changes caused by the kinetics is illustrated by several examples. From the study, it is evident that the traditional modelling of wastewater treatment processes in biofilm reactors based on substrate removal kinetics alone will fail in many cases, due to the inevitable changes in the biofilm structure not taken into consideration. Therefore design rules for substrate removal in biofilms used for wastewater treatment must include correlations between the removal kinetics and the structure and development of the biological film.


2016 ◽  
Vol 27 (24) ◽  
pp. 3791-3799 ◽  
Author(s):  
Hafida Sellou ◽  
Théo Lebeaupin ◽  
Catherine Chapuis ◽  
Rebecca Smith ◽  
Anna Hegele ◽  
...  

Chromatin relaxation is one of the earliest cellular responses to DNA damage. However, what determines these structural changes, including their ATP requirement, is not well understood. Using live-cell imaging and laser microirradiation to induce DNA lesions, we show that the local chromatin relaxation at DNA damage sites is regulated by PARP1 enzymatic activity. We also report that H1 is mobilized at DNA damage sites, but, since this mobilization is largely independent of poly(ADP-ribosyl)ation, it cannot solely explain the chromatin relaxation. Finally, we demonstrate the involvement of Alc1, a poly(ADP-ribose)- and ATP-dependent remodeler, in the chromatin-relaxation process. Deletion of Alc1 impairs chromatin relaxation after DNA damage, while its overexpression strongly enhances relaxation. Altogether our results identify Alc1 as an important player in the fast kinetics of the NAD+- and ATP-dependent chromatin relaxation upon DNA damage in vivo.


2017 ◽  
Vol 114 (31) ◽  
pp. 8265-8270 ◽  
Author(s):  
Simon Olsson ◽  
Hao Wu ◽  
Fabian Paul ◽  
Cecilia Clementi ◽  
Frank Noé

Accurate mechanistic description of structural changes in biomolecules is an increasingly important topic in structural and chemical biology. Markov models have emerged as a powerful way to approximate the molecular kinetics of large biomolecules while keeping full structural resolution in a divide-and-conquer fashion. However, the accuracy of these models is limited by that of the force fields used to generate the underlying molecular dynamics (MD) simulation data. Whereas the quality of classical MD force fields has improved significantly in recent years, remaining errors in the Boltzmann weights are still on the order of a few kT, which may lead to significant discrepancies when comparing to experimentally measured rates or state populations. Here we take the view that simulations using a sufficiently good force-field sample conformations that are valid but have inaccurate weights, yet these weights may be made accurate by incorporating experimental data a posteriori. To do so, we propose augmented Markov models (AMMs), an approach that combines concepts from probability theory and information theory to consistently treat systematic force-field error and statistical errors in simulation and experiment. Our results demonstrate that AMMs can reconcile conflicting results for protein mechanisms obtained by different force fields and correct for a wide range of stationary and dynamical observables even when only equilibrium measurements are incorporated into the estimation process. This approach constitutes a unique avenue to combine experiment and computation into integrative models of biomolecular structure and dynamics.


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