• Elastomers and Composites
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• v.50 no.3
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• pp.196-204
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• 2015

Crosslink density of a rubber vulcanizate determines the chemical and physical properties, while bound rubber is an important factor to estimate reinforcement of a filled rubber compound. Extender oil is added to a raw rubber with very high molecular weight for improving processability of a rubber composite. Influence of extender oil on crosslink density, bound rubber formation, and physical properties of solution styrene-butadiene rubber (SSBR) composites with differing microstructures was investigated. Crosslink densities of non-oil-extended SSBR (NO-SSBR) vulcanizates were higher than those of oil-extended SSBR (OE-SSBR) ones. Bound rubber contents of NO-SSBR compounds were also greater than those of OE-SSBR ones. The experimental results could be explained by interfering of extender oil. The OE-SSBR vulcanizates had low modulus but long elongation at break, whereas the NO-SSBR ones had high modulus but short elongation at break. It was found that the crosslink densities affected the physical properties more than the bound rubber contents. The moduli increased with increase in the crosslink density irrespective of extender oil, while the elongation at break decreased. Each variation of the tensile strengths of NO-SSBR and OE-SSBR vulcanizates with the crosslink density showed a decreasing trend. Tear strength of the OE-SSBR vulcanizate increased with increase in the crosslink density, whereas variation of the tear strength of NO-SSBR vulcanizate with the crosslink density showed a weak decreasing trend.

• Elastomers and Composites
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• v.54 no.3
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• pp.209-219
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• 2019

It is important to analyze crosslink densities of rubber articles because the physical properties are dependent on the crosslink densities. In this paper, analytical techniques for the measurement of crosslink densities of rubber vulcanizates are described. The most widely used method to measure the crosslink density is a swelling method combined with the Flory-Rehner equation. Application of the interaction parameter (${\chi}$) of rubber and swelling solvent is critical because the crosslink density is absolutely dependent on the ${\chi}$ value. Methods for obtaining ${\chi}$ employ not only solubility parameters of the polymer and swelling solvent but also inverse gas chromatography (IGC). The solubilities of rubbers can be obtained using micro differential scanning calorimetry (${\mu}DSC$), intrinsic viscosity measurement, and UV-visible spectroscopy. Nuclear magnetic resonance (NMR) spectroscopy has been also used for the measurement of the crosslink density using the $T_2$ relaxation time, which is determined by spin-spin relaxation in solid-state NMR. For sulfur-cured rubber vulcanizates, crosslink densities according to the crosslink types of mono-, di-, and polysulfides are measured by treating the rubber samples with a chemical probe composed of thiol and amine compounds. Measurement methods of physical crosslinking by filler, crystallization, and ionic bonding have also been introduced.

• 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.

• 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.

• Bulletin of the Korean Chemical Society
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• v.27 no.9
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• pp.1473-1476
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• 2006

• Bulletin of the Korean Chemical Society
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• v.31 no.9
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• pp.2613-2617
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• 2010

Chloroprene is a chlorine substituent of 1,3-butadiene. Butadiene rubber (BR) and chloroprene rubber (CR) composites were thermally aged at 60, 70, 80, and $90^{\circ}C$ for 2 - 185 days in a convection oven and changes of the crosslink densities by the accelerated thermal aging were investigated. The crosslink densities increased as the aging time elapsed and as the aging temperature became higher. Degrees of the crosslink density changes of the BR composite were on the whole larger than those of the CR one except the short-term thermal aging at 60 and $70^{\circ}C$. The crosslink densities abnormally increased after themal aging at high temperatures for a long time. Activation energies for the crosslink density changes of the rubber composites tended to increase with increase of the aging time and the variation showed a local minimum. The activation energies of the CR composite were lower than those of the BR one. The experimental results were explained with a role of ligand of chlorine atom of CR in a zinc complex, steric hindrance by chlorine atom of CR, and oxidation of rubber chain.

• 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.

• Elastomers and Composites
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• v.55 no.3
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• pp.229-234
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• 2020

Automobile wiper blades are generally treated with chlorine to lower their friction coefficient with the windshield surface. This treatment could affect the crosslink density measurement of rubber vulcanizates, a material used in windshield wipers, which would consequently alter its chemical and physical properties. Therefore, this study evaluated the influence of chlorination on crosslink density measurements of natural rubber (NR) vulcanizates using a vehicle wiper blade. A method for determining the degree of chlorination was developed where the interaction parameter between the rubber and the swelling solvent was corrected. A decrease in the rubber sample swelling ratio was observed upon chlorination, and the chlorination penetrated less than 1% of the sample thickness. The chlorinated NR was assumed to be chloroprene rubber (CR), which was used to correct the interaction parameter. The results showed the CR contributed approximately 7% to the parameter.

• 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.

• Composites Research
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• v.22 no.3
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• pp.35-43
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• 2009

In this study, for a radiator hose made of carbon black filled EPDM(ethylene-propylene diene monomer) rubber, a measuring method of crosslink density was established to analyze the aging behaviors under thermo-oxidative stresses. At $125^{\circ}C$, the crosslink density of the rubber specimens decreased slightly in the initial stage, but increased with increasing the aging time. Such variation in crosslink density was similar to that of tensile strength. This might be due to the formation of sulphoxide crosslinks as well as to additional crosslinks made by the reaction of unvalcunized sulfurs. A high temperature aging of rubber specimens at $180^{\circ}C$ caused a slight increase in crosslink density while it did a large decrease in tensile strength and elongation. With aging at high temperature, the formation of carbonyl groups in EPDM molecule chain and formation of sulphoxide crosslink, rather than the crosslink density variation itself, had a large influence on such changes in mechanical property.