Structural Changes in Rubber Brought about by Molecular Oxygen. II. Kinetics of Destructive Dissolution of Vulcanized Rubber

1949 ◽  
Vol 22 (1) ◽  
pp. 37-52
Author(s):  
B. Dogadkin ◽  
Z. Tarasova
Keyword(s):  
Molecular Oxygen ◽  
Structural Changes ◽  
Vulcanized Rubber ◽  
Kinetics Of

Structural Changes in Rubber Caused by the Action of Molecular Oxygen. V. Destructive Solution of Vulcanized Synthetic Rubbers

1953 ◽  
Vol 26 (4) ◽  
pp. 787-797
Author(s):  
Z. Tarasova ◽  
B. Dogadkin
Keyword(s):  
Natural Rubber ◽  
Molecular Oxygen ◽  
Structural Changes ◽  
Axial Ratio ◽  
Colloid Solution ◽  
Butadiene Rubber ◽  
Rate Of Absorption ◽  
The Mean ◽  
Kinetics Of ◽  
Butadiene Styrene

Abstract 1. Vulcanized synthetic rubbers, when heated in a hydrocarbon medium containing molecular oxygen, dissolve completely. The kinetics of destructive solution of vulcanized synthetic rubbers follows the pattern established for the destructive solution of vulcanized natural rubber. 2. The rate of destructive solution of a vulcanizate depends on the molecular structure of the rubber. Rubbers are classified in the following order according to the increase of rate of solution of their vulcanizates : Butyl rubber < sodium-butadiene rubber < butadiene-styrene rubber < polychloroprene < natural rubber. The apparent energy of activation of natural rubber is 19 kcal. per mole, for sodium-butadiene rubber 31.2 kcal. per mole, and for butadiene-styrene rubber 27.1 kcal. per mole. 3. The rate of destructive solution of vulcanized butadiene rubbers depends linearly on the extent of 1,4-structure in the rubber molecule. 4. The mechanical properties of vulcanizates do not appreciably influence the rate of their destructive solution. The type of accelerator used, however, is of essential importance; in fact, its influence corresponds to its influence on the rate of absorption of oxygen. 5. The presence of water slows down the dissolution of vulcanizates of natural and sodium-butadiene rubbers, since it retards their absorption of oxygen. 6. The rate of destructive solution of a vulcanizate in various solvents depends linearly on the coefficient of absorption of oxygen in the solvents. 7. The viscosity of a solution of decomposed vulcanized sodium-butadiene rubber depends linearly on the concentration up to 50 per cent. 8. The mean specific molecular weight, measured cryoscopically, of sodium-butadiene rubber was 2400– 3600, and the osmotic weight, 16,000. The axial ratio of the particles was 1:15. 9. The hypothesis is advanced that solutions of decomposed vulcanizates constitute a special type of colloid solution.

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
Keyword(s):  
Aromatic Amine ◽  
Structural Changes ◽  
Service Performance ◽  
Oxidation Products ◽  
Vulcanized Rubber ◽  
Autocatalytic Process ◽  
Intermediate Oxidation ◽  
Kinetics Of ◽  
Autocatalytic Oxidation ◽  
Free Sulfur

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).

Studies on the Behavior Some Paints in Electro-insulating Fluid Based on Vegetable Esters

2018 ◽  
Vol 69 (5) ◽  
pp. 1139-1144
Author(s):  
Iosif Lingvay ◽  
Adriana Mariana Bors ◽  
Livia Carmen Ungureanu ◽  
Valerica Stanoi ◽  
Traian Rus
Keyword(s):  
Structural Changes ◽  
Oxidation Processes ◽  
High Oleic ◽  
Painting Materials ◽  
Insulating Paper ◽  
Different Types ◽  
Mechanism And Kinetics ◽  
Kinetics Of ◽  
Natural Ester

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.

Biofilm Structure – An Important and Neglected Parameter in Waste Water Treatment

1989 ◽  
Vol 21 (8-9) ◽  
pp. 805-814 ◽  
Author(s):  
F. R. Christensen ◽  
G. Holm Kristensen ◽  
J. la Cour Jansen
Keyword(s):  
Wastewater Treatment ◽  
Structural Changes ◽  
Waste Water Treatment ◽  
Experimental Investigations ◽  
Biofilm Reactors ◽  
Substrate Removal ◽  
Treatment Processes ◽  
Laboratory Reactor ◽  
Biofilm Structure ◽  
Kinetics Of

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.

scholarly journals Kinetics of 1- and 2-methylallyl + O2 reaction, investigated by photoionisation using synchrotron radiation

2021 ◽  
Author(s):  
Domenik Schleier ◽  
Engelbert Reusch ◽  
Marius Gerlach ◽  
Tobias Preitschopf ◽  
Deb Pratim Mukhopadhyay ◽  
...  
Keyword(s):  
Synchrotron Radiation ◽  
Reaction Kinetics ◽  
Molecular Oxygen ◽  
Light Source ◽  
Storage Ring ◽  
Vacuum Ultraviolet ◽  
Flow Tube ◽  
Tube Reactor ◽  
Swiss Light Source ◽  
Kinetics Of

The reaction kinetics of the isomers of the methylallyl radical with molecular oxygen has been studied in a flow tube reactor at the vacuum ultraviolet (VUV) beamline of the Swiss Light Source storage ring.

scholarly journals The poly(ADP-ribose)-dependent chromatin remodeler Alc1 induces local chromatin relaxation upon DNA damage

2016 ◽  
Vol 27 (24) ◽  
pp. 3791-3799 ◽  
Author(s):  
Hafida Sellou ◽  
Théo Lebeaupin ◽  
Catherine Chapuis ◽  
Rebecca Smith ◽  
Anna Hegele ◽  
...  
Keyword(s):  
Dna Damage ◽  
Structural Changes ◽  
Cellular Responses ◽  
Dna Lesions ◽  
Fast Kinetics ◽  
Important Player ◽  
Chromatin Relaxation ◽  
Kinetics Of ◽  
Laser Microirradiation

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.

scholarly journals Combining experimental and simulation data of molecular processes via augmented Markov models

2017 ◽  
Vol 114 (31) ◽  
pp. 8265-8270 ◽  
Author(s):  
Simon Olsson ◽  
Hao Wu ◽  
Fabian Paul ◽  
Cecilia Clementi ◽  
Frank Noé
Keyword(s):  
Force Field ◽  
Structural Changes ◽  
Markov Models ◽  
Force Fields ◽  
Divide And Conquer ◽  
Simulation Data ◽  
Wide Range ◽  
Simulation And Experiment ◽  
Kinetics Of

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.

Sign in / Sign up

Export Citation Format

Share Document