The Degradation of Elastomers. 2. Oxidative Degradation of Natural Rubber Vulcanizates at Different Elongations and Temperatures. II

1959 ◽  
Vol 32 (3) ◽  
pp. 759-769 ◽  
Author(s):  
Karl-Heinz Hillmer ◽  
Walter Scheele
Keyword(s):  
Activation Energy ◽  
Natural Rubber ◽  
Oxidative Degradation ◽  
Zero Order ◽  
Relaxation Rates ◽  
Good Qualitative Agreement ◽  
Kcal Mole ◽  
Pure Nitrogen ◽  
Natural Rubber Vulcanizates ◽  
Constant Activation Energy

Abstract The results of measurements of stress relaxation in natural rubber vulcanizates are reported. In the earlier work, the conditions were denned under which the drop in tension of a vulcanizate—after a pre-relaxation in pure nitrogen—follows a zero order law when tested in oxygen. The temperature dependence of the rate of relative tension relaxation was determined for 8 different vulcanizates. With a constant activation energy of about 29 kcal/mole, the vulcanizates differed in their relative relaxation rates at most by two powers of ten. Several general observations on the course of tension relaxation under different conditions were made on the grounds of experimental evidence. Good qualitative agreement was found with relations reported by Berry and Watson.

Vulcanization of Elastomers. 28. Vulcanization of Natural and Synthetic Rubbers with Sulfur in the Absence of Accelerators. I

1960 ◽  
Vol 33 (4) ◽  
pp. 1051-1061
Author(s):  
Elisabeth Echte ◽  
Walter Scheele ◽  
Sigrun Sonnenberg
Keyword(s):  
Activation Energy ◽  
Natural Rubber ◽  
Zero Order ◽  
Sulfur Concentration ◽  
Kcal Mole ◽  
Sulfur Solubility ◽  
Temperature Relation ◽  
Sulfur Vulcanization ◽  
Rate Relationship ◽  
Kinetics Of

Abstract The decrease of sulfur concentration in the reaction of sulfur with natural rubber was studied. The following was found : 1. Sulfur decrease follows the 0.6th order law independent of temperature as long as the sulfur is dissolved in the gum (temperature!). From the rate-temperature relation, an activation energy of 35 kcal/mole is calculated. 2. In an investigation of the kinetics of sulfur concentration at constant temperature but increasing starting concentration, the following two cases can be differentiated : a) As long as the sulfur is soluble in the gum, sulfur decrease still follows the 0.6th order, possibly due to autocatalysis ; the linear relationship between starting rate and starting concentration shows that the process is 1st order with respect to the concentration; this may be the consequence of a thermal, rate determining cleavage of the S8 ring. b) As the sulfur at higher concentration is only incompletely soluble in the gum, conversion curves with points of inflection are found ; this becomes more pronounced at higher concentration. At the start of the reaction one finds an autocatalytic sulfur decrease basically of zero order; in the latter part of the reaction after passing the point of inflection a 0.6th order is observed, as in the range of complete sulfur solubility. 3. A discrepancy between the time law and the concentration-rate relationship is found in pure as well as accelerated sulfur vulcanization ; these conditions are compared and discussed.

Influence of Crosslink Characteristics Induced by Aromatic-Based Antioxidants on the Swelling and Stress-Strain Behavior of Natural Rubber Vulcanizates

2003 ◽  
Vol 76 (2) ◽  
pp. 334-347 ◽  
Author(s):  
Tarek M. Madkour ◽  
Rasha A. Azzam
Keyword(s):  
Natural Rubber ◽  
Crosslinking Agent ◽  
Oxidative Degradation ◽  
Thermal Oxidative Degradation ◽  
Stress Strain ◽  
Strain Behavior ◽  
Strain Induced Crystallization ◽  
Elastomeric Chains ◽  
Natural Rubber Vulcanizates ◽  
Induced Crystallization

Abstract Stress-strain measurements were performed on dry and swollen natural rubber vulcanizates prepared using both sulfur as the crosslinking agent and aromatic-based bound antioxidants acting as a second crosslinking agent. The aromatic-based antioxidants were synthesized and analyzed spectroscopically in order to relate the final behavior of the vulcanizates to the nature of the crosslink characteristics. The anomalous upturn in the modulus values of these networks in response to the imposed stress was shown to persist in the dry as well as the swollen state. Since the swollen elastomeric chains cannot undergo a strain-induced crystallization, the abnormal upturns in the modulus values in an absence of a filler were explained on the basis of the limited extensibility of the short chains of networks prepared using two different crosslinking agents in line with earlier modeling predictions. Remarkably, the swelling experiments revealed the increase in the crosslink density of the networks in the early stages of the thermal oxidative degradation procedure indicating a post-cure of the chemically bound antioxidants to the elastomeric chains, which incidentally corresponds to a maximum in the modulus values of the networks. The rheological and other mechanical properties such as the hardness were shown not to have been affected as a result of the incorporation of the chemically bound antioxidants.

HXNBR Coating for Improving Aging Resistance of Natural Rubber Products

2006 ◽  
Vol 79 (4) ◽  
pp. 553-560 ◽  
Author(s):  
Rani Joseph
Keyword(s):  
Mechanical Properties ◽  
Natural Rubber ◽  
Room Temperature ◽  
Oxidative Degradation ◽  
Thin Coating ◽  
Oil Resistance ◽  
Aging Resistance ◽  
Natural Rubber Vulcanizates ◽  
Good Heat ◽  
Accelerator System

Abstract HXNBR (Hydrogenated Carboxylated Nitrile Rubber) has very good heat ageing resistance and oil resistance. A novel accelerator system is designed to bring about the vulcanization of HXNBR at room temperature. The room temperature cured samples showed good mechanical properties equivalent to those of high (150 °C) temperature cured samples. Natural rubber vulcanizates are highly prone to oxidative and ozone degradation. The oil resistance of natural rubber vulcanizates is also very low. The oil resistance, ozone and oxidative degradation resistance of natural rubber vulcanizates are considerably improved by placing a thin coating of HXNBR over it.

Chemical Vapor Deposition of SiO2 from Ozone-Organosilane Mixtures near Atmospheric Pressure

1992 ◽  
Vol 282 ◽  
Author(s):  
K. V. Guinn ◽  
J. A. Mucha
Keyword(s):  
Activation Energy ◽  
Chemical Vapor Deposition ◽  
Vapor Deposition ◽  
Atmospheric Pressure ◽  
Chemical Vapor ◽  
Zero Order ◽  
Kcal Mole ◽  
Consumption Ratio ◽  
Zero Order Kinetics ◽  
Kinetics Of

ABSTRACTThe kinetics of deposition of SiO2 by the reaction of tetramethylsilane (TMS) with ozone (O3) has been studied over the temperature range 180 – 380° C and compared with available data for the same process using tetraethoxysilane (TEOS). Both processes exhibit the same activation energy (17 kcal/mole) below 300 ° C which falls-off at higher temperatures due to transport limitations. Transition from first- to zero-order kinetics occurs with increasing concentrations of TMS and O3, which gives an overall O3/TMS consumption ratio of 10 at 258° C and5 at 325° C. TEOS is estimated to be 5 times more reactive than TMS above 300° C and over 10 times more reactive in the kinetically-limited regime below 300° C. Results suggest that O3-induced SiO2 deposition proceeds via surface reactions and is limited by heterogeneous decomposition of ozone.

The Oxidative Aging of a Compounded Natural Rubber Vulcanizate

1978 ◽  
Vol 51 (1) ◽  
pp. 1-6 ◽  
Author(s):  
R. A. Pett ◽  
R. J. Tabar
Keyword(s):  
Natural Rubber ◽  
Reaction Rate ◽  
Oxidative Degradation ◽  
Accelerated Aging ◽  
Zero Order ◽  
Elongation At Break ◽  
Oxidative Aging ◽  
Zero Order Reaction ◽  
The Impact

Abstract For the type of natural rubber compound used in the impact absorbing bumper system, it has been shown that an apparent zero order reaction rate is valid for the degradation of tensile strength, elongation at break and tear strength during oven aging. The zero order rate applies to aging times beyond an induction period and prior to the onset of hardening. Since the rates follow the Arrhenius equation for rate-temperature dependence, accelerated aging can be readily applied to the prediction of long term changes in properties (within the temperature range of 82–171°C). The magnitude of the activation energy determined from losses in mechanical properties indicates the dominance of oxidative degradation as the mechanism of the losses in properties.

Vulcanization of Elastomers. 40. Vulcanization of Natural Rubber and Synthetic Rubber with Sulfur in Presence of Sulfenamides. III

1965 ◽  
Vol 38 (1) ◽  
pp. 189-203 ◽  
Author(s):  
W. Scheele ◽  
J. Helberg
Keyword(s):  
Activation Energy ◽  
Reaction Mechanism ◽  
Natural Rubber ◽  
Rate Constants ◽  
Sulfur Concentration ◽  
Kcal Mole ◽  
Synthetic Rubber ◽  
Chemical Constitution ◽  
Induction Times ◽  
Kinetics Of

Abstract Vulcanization of natural rubber with sulfur was studied in presence of six sulfenamides, to determine the effect of the chemical constitution of the sulfenamide on sulfur decrease and on crosslinking. The results can be condensed as follows: (1) The kinetics of sulfur disappearance is in every respect qualitatively independent of the chemical constitution of the sulfenamide. (2) For the sulfenamides investigated, the smallest and largest rate constants for sulfur decrease differed only by a factor of two. (3) Greater differences are encountered in the induction times for sulfur decrease and for crosslinking. The latter are notably longer than those for sulfur disappearance. (4) The same activation energy, 23 kcal/mole, is derived from the temperature dependence of the induction times for all the sulfenamides. (5) The dissociation of sulfenamides in solution and their reaction with mercaptobenzothiazole were investigated further. The results provide the basis for a proposed reaction mechanism, which is presented in detail and can account for a number of the features typical of sulfenamide-accelerated vulcanization. (6) The drop in sulfur concentration goes at practically the same rate, if one introduces, instead of N, N-dicyclohexyl-2-benzothiazolesulfenamide, the corresponding ammonium mercaptide in equimolar concentration.

The Vulcanization of Elastomers. XI. The Vulcanization of Natural Rubber with Sulfur in the Presence of Mercaptobenzothiazole. I

1957 ◽  
Vol 30 (3) ◽  
pp. 911-927 ◽  
Author(s):  
Otto Lorenz ◽  
Elisabeth Echte
Keyword(s):  
Activation Energy ◽  
Zinc Oxide ◽  
Natural Rubber ◽  
Kinetic Analysis ◽  
Rate Constants ◽  
Network Formation ◽  
Zinc Salt ◽  
Kcal Mole ◽  
Minimum Quantity ◽  
First Order

Abstract 1. The decrease of free sulfur occurs according to the first order law during the vulcanization of natural rubber accelerated by mercaptobenzothiazole in the presence of zinc oxide. The activating energy for this reaction amounts to 30.5 kcal./mole. 2. If zinc benzothiazolylmercaptide is used as an accelerator, one obtains the same rate constants for the sulfur decrease as in the presence of mercaptobenzothiazole. These seem to be equivalent as regards their effectiveness of acceleration. 3. A kinetic analysis of the reciprocal swelling, which represents a measure of network formation, indicates that the reaction is first order. Sulfur decrease and reciprocal swelling prove to be equal processes as regards rate. This is true where vulcanization is accelerated with mercaptobenzothiazole or with the zinc salt. 4. During vulcanization there occurs a decrease of accelerator concentration. This is dependent upon the temperature and is tied in with the combination sulfur with rubber. 5. If the quantity of the accelerator added is changed, the rate constants for sulfur decrease and for reciprocal swelling do not change, provided that a minimum quantity of accelerator is present. 6. In vulcanization accelerated with zinc benzothiazolylmercaptide, zinc oxide being absent, sulfur decrease again occurs according to the first order law but considerably faster, without thereby changing the activation energy. These investigations are being continued and the results will be discussed in detail in relation to other published contributions in this field.

Investigations in the Field of Rubber Vulcanization. VII. Influence of Organic Accelerators on the Kinetics of Vulcanization and the Properties of Natural-Rubber Vulcanizates

1950 ◽  
Vol 23 (3) ◽  
pp. 563-575
Author(s):  
B. Dogadkin ◽  
B. Karmin ◽  
A. Dobromyslova ◽  
L. Sapozhkova
Keyword(s):  
Activation Energy ◽  
Natural Rubber ◽  
Oxidative Destruction ◽  
Tetramethylthiuram Disulfide ◽  
Vulcanization Kinetics ◽  
Strength Curve ◽  
Increasing Temperature ◽  
Low Sulfur ◽  
Natural Rubber Vulcanizates ◽  
Kinetics Of

Abstract 1. Vulcanization accelerators change all parameters of the kinetic strength curve during the vulcanization of natural-rubber mixtures with low sulfur contents. 2. Calculation of the kinetic constants of the fundamental vulcanization equation proposed by Dogadkin, Karmin, and Gol'berg shows that vulcanization accelerators affect both the kinetics of the interaction of rubber with sulfur and the kinetics of the interaction of rubber with oxygen. 3. Direct experiments on the oxidation of rubber have shown that tetramethylthiuram disulfide and diphenylguanidine retard the process of addition of oxygen to rubber, while mercaptobenzothiazole accelerates this process. 4. Data on the rate of plasticization and change in viscosity of rubber solutions during oxidation indicate that tetramethylthiuram disulfide and diphenylguanidine promote the disintegration of molecular chains of rubber during the oxidative destruction of the latter. 5. The activation energy of the process of oxidation of rubber in the presence of mercaptobenzothiazole corresponds to the activation energy calculated from the fundamental vulcanization reaction for the process of oxidative destruction. This provides additional proof of the participation of oxygen in the vulcanization process. 6. It has been established with the aid of the methyl iodide reaction that accelerators increase the bridge-sulfur content of the vulcanizate, which is present in the form of monosulfides, with one sulfur atom connected to an allyl type radical. 7. With increasing temperature, the tensile strength at the vulcanization optimum increases in mixtures containing tetramethylthiuram disulfide, decreases in mixtures containing mercaptobenzothiazole, and remains unchanged in mixtures containing diphenylguanidine. The limiting strength decreases in all cases with increasing temperature. This phenomenon is explained on the basis of the proposed concepts of the character of vulcanization kinetics and of the nature of the vulcanization optimum.

Sign in / Sign up

Export Citation Format

Share Document