• Bulletin of the Korean Chemical Society
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• v.21 no.6
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• pp.628-634
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• 2000

Crosslink is the most important chemistry in a rubber vulcanizate. Degree and type of crosslinks of the vulcanizate determine its physical properties. Change of crosslink density and deformation of a rubber vulcanizate by thermal aging were studied using natural rubber (NR) vulcanizates with various cure systems (conventional, semi-EV, and EV) and different cure times (under-, optimum-, and overture). All the NR vulcanizates were deformed by the thermal aging at 60-100 $^{\circ}C.$ The higher the aging temperature is, the more degree of the deformation is. The undercured NR vulcanizates after the thermal aging were deformed more than the optimumand overcured ones. The NR vulcanizates with the EV cure system were less deformed than those with the conventional and semi-EV cure systems. The deformation of the NR vulcanizates was found to be due to change of the crosslink density of the vulcanizates. The crosslink densities of all the vulcanizates after the extraction of organic materials were also changed by the thermal ging. The sources to change the crosslink densities of the vulcanizates by the thermal aging were found to be dissociation of the existing sulfur crosslink and the formation of new crosslinks by free sulfur, reaction products of curing agents, and pendent sulfide groups.

• Macromolecular Research
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• v.16 no.6
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• pp.561-566
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• 2008

NR composites with different curing systems were aged thermally at 60, 70, 80, and $90^{\circ}C$ for 2-185 days in a convection oven, and the changes in the crosslink density were investigated as a function of the accelerated thermal aging. The overall crosslink densities increased with increasing aging time irrespective of the aging temperatures and curing systems. The changes in crosslink density were enhanced by increasing the aging temperature. The degree of the increased crosslink density was in the following order: "the conventional cure system > the semi-EV system > the EV system". For short term thermal aging, the change in crosslink density with the aging time was complicated, particularly for low temperature aging. The activation energies of the change in crosslink density with thermal aging using the conventional and semi-EV cure systems increased and then remained relatively constant with increasing aging time, whereas that of the specimen with an EV cure system tended to increase linearly. The experimental results were explained by the dissociation of the existing polysulfidic linkages and the formation of new cross links through the crosslinking-related chemicals remaining in the sample.

• Elastomers and Composites
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• v.40 no.4
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• pp.284-289
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• 2005

Changes of crosslink densities of resole-cured NR composites by thermal aging were studied. The thermal aging was performed at $50-90^{\circ}C$. The crosslink density change increased with increase of the aging temperature and then decreased. Level of the crosslink density change decreased with increase of the resole content. Increase of the crosslink density by the thermal aging was explained with the formations of new crosslinks by combination reactions of pendent groups terminated by resoles and crosslinking reactions by pendent groups having methylol or o-methylene quinone intermediate. And decrease of the crosslink density by the thermal aging was explained with the dissociations of the existing crosslinks having dimethylene ether linkages.

• Journal of Adhesion and Interface
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• v.3 no.2
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• pp.30-39
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• 2002

The effect of cure accelerator content on the change in crosslink density by thermal aging was studied for silica-filled natural rubber (NR) vulcanizates. Influence of silane coupling agent was also investigated. N-tert-Butyl-2-benzothiazole sulfenamide (TBBS) and bis-(3-(triethoxysilyl)-propyl)-tetrasulfide (TESPT) were used as a cure accelerator and a silane coupling agent, respectively. The crosslink density increased by thermal aging and the increasing level became larger as the aging temperature increased. The degree of crosslink density change of the vulcanizates without the silane coupling agent was larger than that of the vulcanizates containing the silane coupling agent. For the vulcanizates silane coupling agent, the activation energy for the crosslink density change decreased with increase of the cure accelerator content in the vulvanizate.

• Elastomers and Composites
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• v.46 no.3
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• pp.237-244
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• 2011

Five natural rubber (NR) composites with different reinforcing systems of unfilled, carbon black, carbon black with silane coupling agent, silica, and silica with silane coupling agent were thermally aged and change of the crosslink densities by the accelerated thermal aging was investigated. The crosslink densities on the whole increased as the aging time elapsed irrespective of the reinforcing systems. The crosslink density changes became noticeable by increasing the aging temperature. For carbon black-filled composites, the silane coupling agent made the crosslink density change to be increased. For silica-filled composites, however, the silane coupling agent made the crosslink density increment reduced at 60 and $70^{\circ}C$ and it hardly affect the degree of the crosslink density change at 80 and $90^{\circ}C$. The activation energies for the crosslink density changes of the carbon black-filled samples increased continuously in a logarithmic fashion, whereas that of the silica-filled one showed a quasi-steady state ranges at aging times of 30-150 days. The activation energy of the unfilled sample increased exponentially with the aging time. The experimental results were explained with sulfur donation from the silane coupling agent, surface modification of the filler by the silane coupling agent, adsorption of curative residues on the silica surface, and release of the adsorbed curative residues.

• Elastomers and Composites
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• v.47 no.2
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• pp.148-155
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• 2012

EPDM, IIR, and BIIR composites were thermally aged and the crosslink density changes were investigated. Crosslink densities of the EPDM composite increased with increasing the aging time and temperature, whereas those of IIR and BIIR composites for long-term aging at high temperatures tended to decrease. Activation energies for the crosslink density changes of the EPDM composite were higher than those of the BIIR one. The experimental results were explained with the number of allylic hydrogens, activation of the zinc complex, the steric hindrance effect, and oxidation of rubber chain.

• Applied Biological Chemistry
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• v.34 no.2
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• pp.86-93
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• 1991

cis-Diamminedichloroplatinum(II)(CDDP), an antitumor drug, did not generate crosslink between bluetongue virus (BTV) capsid protein at moderate concentration. Cesium chloride density gradient centrifugation study revealed that protein-RNA crosslink was not detectable in CDDP treated BTV. CDDP treated BTV ds RNA showed remarkable change in the migration pattern in polyacrylamide gel electrophoresis. These results suggest that the reduction of BTV core associated transcriptase activity is most likely by the CDDP adduction to the genomic ds RNA rather than by the protein-RNA crosslink and/or protein-protein cross-link.

• Elastomers and Composites
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• v.50 no.1
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• pp.1-6
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• 2015

Polybutadiene rubber (BR) has been well known that its physical and chemical properties are changed when it is exposed to ultraviolet light undergoing photooxidation. In this study, photooxdiation process of BR vulcanizate was investigated using a high pressure mercury lamp used as an outdoor lighting, which has high UV radiation efficiency and reasonable cost. Discoloration and crack formation of photooxdized BR vulcanite surface were examined using an image analyzer. Change of chemical functional groups of BR vulcanite surface by photooxidation was investigated using ATR-FTIR, and variation of the crosslink density with the UV irradiation time was investigated. By increasing the UV irradiation time, the crosslink density steeply increased after a period of time and did not increase any more. Formation of hydroxyl (~OH) and carbonyl (~C=O) groups on the BR vulcanizate surface increased and the1,4-cis unit was converted to the 1,4-trans unit as the photooxidation was proceeded.

• Elastomers and Composites
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• v.43 no.4
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• pp.213-220
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• 2008

In this study, the effects of curing system on the hardness of rubber materials at various temperature were investigated. NR and SBR were compounded with various sulfur or peroxide content, in order to obtain various crosslink densities. The changes of hardness and crosslink density were measured as a function of temperature and the relationship was examined. The thermal stresses were also measured in order to investigate the effect of entropy as a function of temperature. The hardness of NR and SBR compounds increased with increasing temperature above room temperature, and the measured thermal stress increased as temperature increased. However, the crosslink densities were not changed by temperature change.

• Elastomers and Composites
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• v.40 no.3
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• pp.181-187
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• 2005

Changes of physical properties or NR vulcanizates with different cure systems by thermal aging were investigated. Two sulfur cure systems and one resole cure system were employed, and total contents of the curatives were varied. For the NR vulcanizates with sulfur cure systems, hardness and modulus after the thermal aging at $90^{\circ}C$ for 3 days were increased, but elongation at break and tensile strength were decreased. For the NR vulcanizates with resloe cure system, the physical properties after the thermal aging were decreased. The change of physical properties by the thermal aging was explained with the crosslink density change. The crosslink densities or the NR vulcanizates with sulfur cure systems were increased after the thermal aging, but those with resole cure system were decreased. Influence of the migration of antidegradant on the changes of physical properties was also investigated. However, the changes of physical properties by the thermal aging were not explained sufficiently with the migration of antigradant.