Inverse gas chromatography in the study of polymer degradation. Part 2. Oxidation of sulphurated squalene as a model for the oxidative degradation of natural rubber vulcanizates

1978 ◽  
Vol 11 (6) ◽  
pp. 311-315 ◽  
Author(s):  
M. B. Evans ◽  
R. Newton
2003 ◽  
Vol 76 (2) ◽  
pp. 334-347 ◽  
Author(s):  
Tarek M. Madkour ◽  
Rasha A. Azzam

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.


2006 ◽  
Vol 79 (4) ◽  
pp. 553-560 ◽  
Author(s):  
Rani Joseph

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.


1959 ◽  
Vol 32 (3) ◽  
pp. 759-769 ◽  
Author(s):  
Karl-Heinz Hillmer ◽  
Walter Scheele

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.


1966 ◽  
Vol 39 (5) ◽  
pp. 1577-1583
Author(s):  
C. L. M. Bell

Abstract The effect of high strain on the oxidative stress relaxation of several natural rubber vulcanizates has been investigated. In peroxide and CBS accelerated vulcanizates, the rate of stress relaxation increases with increasing strain, and this increase appears to be due to an increase in the rate of oxidation of the network. TMTD and MBT vulcanizates showed marked premature failure at high strains and no oxidative stress relaxation measurement could be made. The tensile strength of a TMTD vulcanizate was at least 20 per cent higher in vacuum than in oxygen, due, it is believed, to stress-induced oxidative degradation at the tip of surface flaws in the rubber.


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