Crosslink Formation during Aging of Natural Rubber Vulcanizates

1965 ◽  
Vol 38 (2) ◽  
pp. 374-378
Author(s):  
L. J. Maisey ◽  
J. Scanlan
Keyword(s):  
Stress Relaxation ◽  
Natural Rubber ◽  
Cross Linking ◽  
Crosslinking Reaction ◽  
Oxidative Reactions ◽  
Relaxation Measurements ◽  
Equilibrium Swelling ◽  
Form Part ◽  
The Difference ◽  
Natural Rubber Vulcanizates

Abstract The effect of antioxidant on the crosslinking reaction occurring during the oxidation of sulphur vulcanizates of natural rubber was investigated by using both continuous and intermittent stress relaxation measurements. Similarly, by means of continuous stress relaxation and equilibrium swelling measurements the cross-linking reaction in vacuum was followed. The presence of antioxidant or removal of air reduced considerably both continuous and intermittent relaxation and also the difference between them, which measures the crosslinking. The crosslink formation must therefore form part of the sequence of oxidative reactions.

Aging of Natural Rubber Vulcanizates in the Presence of Dithiocarbamates

1959 ◽  
Vol 32 (3) ◽  
pp. 739-747 ◽  
Author(s):  
J. R. Dunn ◽  
J. Scanlan
Keyword(s):  
Stress Relaxation ◽  
Natural Rubber ◽  
Protective Action ◽  
Dicumyl Peroxide ◽  
Vulcanized Rubber ◽  
Aging Properties ◽  
Photochemical Aging ◽  
Natural Rubber Vulcanizates

Abstract The thermal and photochemical aging of extracted dicumyl peroxide-, TMTD (sulfurless)- and santocure-vulcanized rubber, in presence of a number of metal and alkylammonium dithiocarbamates, has been investigated by measurements of stress relaxation. The dithiocarbamates have a considerable protective action upon the degradation of peroxide- and TMTD-vulcanizates, but they accelerate stress decay in santocure-accelerated vulcanizates. The reasons for this behavior are discussed. It is suggested that the excellent aging properties of unextracted TMTD vulcanizates are due to the presence of zinc dimethyldithiocarbamate formed during vulcanization.

Relative Contributions of Viscoelasticity and Aging to the Relaxation of Rubber Vulcanizates

1963 ◽  
Vol 36 (1) ◽  
pp. 50-58 ◽  
Author(s):  
P. Thirion ◽  
R. Chasset
Keyword(s):  
Quantitative Analysis ◽  
Natural Rubber ◽  
Time Interval ◽  
Dicumyl Peroxide ◽  
Infinite Time ◽  
Negative Power ◽  
Theoretical Assumptions ◽  
The Difference ◽  
Natural Rubber Vulcanizates ◽  
Actual Stress

Abstract Relaxation in relatively stable, gum natural rubber vulcanizates has been studied to determine the effects of viscoelasticity and aging, respectively, using a dark, air-oven. A quantitative analysis of experimental results shows that, in the case of a dicumyl peroxide vulcanizate at 100° C, relaxation is caused by aging, except in its initial stages. Stress decreases as a linear function of time, in agreement with theoretical assumptions. Conversely, at 30° C, the effect of aging is negligible. At this temperature the difference between actual stress and stress extrapolated to infinite time, is proportional to a negative power of time. At intermediate temperatures, both phenomena occur simultaneously over a time interval ranging from. 3 minutes to 150 hours.

Investigation of Un-Vulcanized Natural Rubber by Means of Temperature Scanning Stress Relaxation Measurements

2013 ◽  
Vol 718-720 ◽  
pp. 117-123 ◽  
Author(s):  
Miao Wu ◽  
Michael Heinz ◽  
Norbert Vennemann
Keyword(s):  
Mechanical Properties ◽  
Stress Relaxation ◽  
Natural Rubber ◽  
Branch Points ◽  
Relaxation Spectra ◽  
Green Strength ◽  
Testing Method ◽  
Relaxation Measurements ◽  
Different Types ◽  
Temperature Scanning

Two different types of un-vulcanized natural rubber, air dried sheets (ADS) and SVR-3L block rubber, were investigated by a new testing method and the results are compared with other mechanical properties. It was found that green strength is strongly reduced if the sample is ther­mal­ly treated before testing. Presumably, the decrease of strength is caused by a decrease of branch points, mainly composed of phospholipids, which are linked to the a - terminal groups of the rubber molecules. The existence of two different types of branch points is indicated by relaxation spectra, obtained from temperature scanning stress relaxation (TSSR) measurements.

The Determination of Network Chain Density and the Chemical Stress Relaxation of Crosslinked Polymers

1973 ◽  
Vol 46 (2) ◽  
pp. 477-482
Author(s):  
Saburo Tamura ◽  
Kenkichi Murakami
Keyword(s):  
Stress Relaxation ◽  
Natural Rubber ◽  
Main Chain ◽  
Chemical Stress ◽  
Dicumyl Peroxide ◽  
Constant Independent ◽  
Crosslinked Polymers ◽  
Network Chain ◽  
The Difference ◽  
Entanglement Network

Abstract Both initial network chain densities nM(0) and nS(0) of dicumyl peroxide- cured natural rubbers were determined from the tensile stress and swelling method, respectively. The difference between nM(0) and nS(0) was usually constant, independent of the magnitude of network chain density. That is, it was found that the number of entanglement network chains in the crosslinked natural rubber was usually constant, independent of network chain density. The entanglement network chain density nII(0) was 0.7×10−4 mole/cc. This led to the supposition that the molecular weight between entanglement points Me would be about 9000. Although this value is far from exact, it does not differ too greatly from the value found for noncrosslinked natural rubber. Next, in order to calculate the number of main-chain scissions of crosslinked polymers from their chemical stress relaxation, we proposed our modification of Tobolsky's equation. Using our equation, it was found that the scission of dicumyl peroxide-cured natural rubber occurred in the main chain only. Furthermore, this value agreed with the one obtained from the oxidation of toluene solution of noncrosslinked rubber under the same conditions.

Simultaneous Measurements of Stress and Infrared Dichroism on Polymers I. Stress Relaxation of Vulcanized Natural Rubber

1967 ◽  
Vol 40 (2) ◽  
pp. 663-672
Author(s):  
Rempei Gotoh ◽  
Tohru Takenaka ◽  
Naomi Hayama
Keyword(s):  
Stress Relaxation ◽  
Absorption Band ◽  
Natural Rubber ◽  
Reference Beam ◽  
Simple Relationship ◽  
Absorption Bands ◽  
Simultaneous Measurements ◽  
Double Beam ◽  
The Difference ◽  
Infrared Dichroism

Abstract A method for simultaneous measurements of stress and infrared dichroism as time-dependent behavior of polymer films was devised using a double beam infrared spectrometer. The film sample held between clamps of a stretching device was placed just in front of the entrance slit of the spectrometer where the sample and reference beams came alternately. Two polarizers were used, one in the sample beam and the other in the reference beam. Thus the sample and reference beams were polarized to have the electric vectors parallel and perpendicular to the stretching direction of the sample, respectively. With this arrangement the spectrometer responded only to the difference in the transmittance of the two beams. Setting the spectrometer at one of the wavenumbers of the absorption band maxima, we could record continuously the change in its dichroism during mechanical treatments which gave rise to molecular orientation in the sample. The stress was recorded automatically by means of a pair of strain gauges pasted on the cantilever beam of the stretching device. By theoretical considerations, a simple relationship was found to exist between the quantity recorded on the spectrometer by this method and the orientation function of transition moment of a vibrational absorption band with respect to the stretching direction. The method was applied to the stress relaxation experiments of vulcanized natural rubber carried out at different elongations less than 600 per cent and at room temperature. Changes of infrared dichroism were measured for five absorption bands at 1664, 1380, 1361, 1129, and 844 cm−1, of which the last one is a crystalline band. From the results of this study, the stress relaxation observed was ascribed mainly to the amorphous orientation rather than to the crystalline orientation, which was completed almost immediately after elongation.

Stress Relaxation during the Photoxidation of Peroxide Crosslinked Rubber

1960 ◽  
Vol 33 (2) ◽  
pp. 433-444
Author(s):  
J. R. Dunn ◽  
J. Scanlan ◽  
W. F. Watson
Keyword(s):  
Stress Relaxation ◽  
Natural Rubber ◽  
Physical Properties ◽  
Chemical Reactions ◽  
Small Extent ◽  
Organic Peroxides ◽  
Physical Measurement ◽  
Crosslinked Networks ◽  
Photochemical Aging ◽  
Natural Rubber Vulcanizates

Abstract The chemical reactions involved in the thermal and photochemical aging of natural rubber vulcanizates are largely unknown. Experimental difficulties have precluded direct chemical investigation owing to the insolubility of the crosslinked networks and the small extent of reaction required for a great deterioration in physical properties. Accordingly recourse has been made to physical measurement. Tobolsky et al. (e.g. Ref. (1)) have shown that the relaxation in stress on holding a rubber strip at constant extension during aging is a convenient experimental measure capable of interpretation in terms of network breakdown. In photochemical studies the opacity of conventional sulfur vulcanizates provides a further complication. In the present work, the stress relaxation technique has been used in a study of the degradation by 365 mµ radiation of the comparatively transparent and chemically simple rubber networks obtained after crosslinking by organic peroxides.

Thermomechanical Effects Associated With Crystallization of Rubber Under Stretch and During Slow Extension

1997 ◽  
Vol 119 (3) ◽  
pp. 298-304 ◽  
Author(s):  
Mehrdad Negahban
Keyword(s):  
Stress Relaxation ◽  
Natural Rubber ◽  
Thermodynamic Model ◽  
The Other ◽  
Equilibrium Stress ◽  
Rubber Sample ◽  
Other Hand ◽  
The Difference ◽  
Thermomechanical Effects

A natural rubber sample which crystallizes after stretching normally shows stress relaxation associated with this crystallization and normally ends up at a stress lower than that of the fully amorphous rubber before crystallization. On the other hand, a natural rubber sample which crystallizes during stretching becomes more rigid as a result of the crystallization and the stress required to extend it to a given stretch increases substantially above the stress needed to extend the fully amorphous rubber to the same elongation. Even though the former effect has been modeled and studied by the likes of Flory (1947), the latter effect has not yet been properly modeled or studied. The difference between crystallization during or after stretching will be studied in this article based on a thermodynamic model developed by the author to capture the thermomechanical effects of crystallization in natural rubber. The two limit cases of very rapid and very slow extension to a given stretch are singled out for comparison of the equilibrium stress.

Stress Relaxation during the Thermal Oxidation of Vulcanized Natural Rubber

1960 ◽  
Vol 33 (2) ◽  
pp. 423-432
Author(s):  
J. R. Dunn ◽  
J. Scanlan ◽  
W. F. Watson
Keyword(s):  
Free Radical ◽  
Stress Relaxation ◽  
Natural Rubber ◽  
Thermal Aging ◽  
Elevated Temperatures ◽  
The Other ◽  
Tetramethylthiuram Disulfide ◽  
Oxidative Aging ◽  
Relaxation Measurements ◽  
Cross Links

Abstract The photoinitiated oxidative aging of peroxide vulcanized natural rubber (which contains only carbon-carbon cross-links) was found by stress relaxation measurements to be autocatalytic and to be sensitive to the presence of free radical retarders and catalysts. Similar behavior would be expected in thermal aging. However, earlier work in these laboratories indicated that the thermal aging of peroxide vulcanizates was not autocatalytic. Because of this discrepancy the stress relaxation of peroxide vulcanizates at elevated temperatures has now been reinvestigated and the study has been extended to include also the aging of the other types of networks which are produced on vulcanization by tetramethylthiuram disulfide in the absence of sulfur, by sulfenamide-sulfur, and by sulfur alone.

Cross Linking in Natural Rubber Vulcanizates

1953 ◽  
Vol 45 (7) ◽  
pp. 1539-1546 ◽  
Author(s):  
H. E. Adams ◽  
B. L. Johnson
Keyword(s):  
Natural Rubber ◽  
Cross Linking ◽  
Natural Rubber Vulcanizates
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