• Elastomers and Composites
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• 제50권3호
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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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• 제54권3호
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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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• 제16권6호
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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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• 제21권6호
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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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• 제27권9호
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• pp.1473-1476
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• 2006

• Elastomers and Composites
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• 제40권4호
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• pp.284-289
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• 2005

레졸로 가교된 NR 복합체의 열노화에 의한 가교밀도변화를 연구하였다. 노화 온도는 $50-90^{\circ}C$였다. 가교밀도 변화는 노화 온도가 올라감에 따라 증가하다 감소하였다. 가교밀도 변화 정도는 레졸 함량이 증가함에 따라 감소하였다. 열노화에 의한 가교밀도의 증가는 레졸로 마감된 매달린 작용기들의 결합 반응과 메틸올이나 메틸렌 퀴논 중간체를 갖는 매달린 작용기의 가교 반응으로 설명하였다. 그리고 열노화에 의한 가교밀도의 감소는 디메틸렌 에테르 연결을 갖는 기존 레졸 가교의 분해로 설명하였다.

• Elastomers and Composites
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• 제57권4호
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• pp.222-230
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• 2022

In this study, a low-heat additive with a crosslink structure was dispersed in asphalt to simultaneously lower the production temperature of, and to modify the asphalt binder. This low-heat additive was prepared by different feeding ratios of styrene-butadiene-styrene (SBS) and polyvinylchloride (PVC) as polymer modifiers, and ZnO as a crosslinking agent. In order to confirm the crosslinking density and compatibility of the crosslink structured low-heat additive with asphalt, surface free energy, swelling ratio, differential scanning calorimetry (DSC), and scanning electron microscope (SEM) parameters were carefully investigated to examine this relationship, and the role of the crosslink structured low-heat additive. In addition, by measuring the penetration and softening point of the asphalt binder, it was confirmed that it corresponds to PG 64-22. With increasing ZnO in the crosslink structured low-heat additive, the swelling ratio decreased, leading to an increase in crosslinking density. The crosslink structured low-heat additive and the asphalt binder were found to be compatible with each other by DSC and SEM analysis.

• Elastomers and Composites
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• 제55권3호
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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.

• Bulletin of the Korean Chemical Society
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• 제31권9호
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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.

• 접착 및 계면
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• 제3권2호
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• pp.30-39
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• 2002

실리카로 보강된 천연고무 가황물에서 가황촉진제의 양이 열노화에 의한 가교밀도의 변화에 미치는 영향에 대해 연구하였다. 또한 실란커플링제의 영향도 조사하였다. 가황촉진제로는 N-tert-butyl-2-benzothiazole sulfenamide(TBBS)를 실란 커플링제로는 bis-(3-(triethoxysilyl)-propyl)-tetrasulfide(TESPT)를 사용하였다. 가황물을 열노화 시키면 가교밀도는 증가하였고 노화 온도가 높을수록 그 변화 정도는 컸다. 실란 커플링제가 포함되지 않은 가황물의 가교밀도 변화가 실란 커플링제를 포함한 것에 비해 더 크게 나타났다. 실란 커플링제가 포함되지 않은 가황물의 경우에는 가교밀도의 변화에 대한 활성화 에너지가 가황촉진제의 함량이 증가할수록 순차적으로 낮아지는 경향을 보였다.