• Elastomers and Composites
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• v.39 no.3
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• pp.179-185
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• 2004

Frequency dependency or electrical property stabilization during vulcanization of modified NR/IR composite materials was studied using in-situ electrical property measuring technique. Volume resistivity(p) before and after vulcanization reaction of the sample was measured as the function or frequency in the range or 1Hz to 10kHz at reaction temperatures of 130, 140, 150, and $160^{\circ}C$, respectively. A double stabilization mode of frequency dependency was observed, in which a slow stabilization process of p to a value of ca. $1.0{\times}10^7\;{\Omega}-cm$ occurred after a drastic initial decrease from ca. $9.0{\times}10^7\;{\Omega}-cm$. In addition, notable temperature dependencies of p values were also observed before and after vulcanization reaction, that is, p values at 130 and $140^{\circ}C$ after vulcanization were observed as about 1/3 of those values before vulcanization. All the observed facts were considered as the results from the interaction between the electrode and the bulk sample materials, i.e., electronic charge-discharge, and from the structure change of samples including CB rearrangement by the vulcanization.

• Elastomers and Composites
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• v.13 no.4
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• pp.277-281
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• 1978

1. A good retarder reacts fast with MBT and. forms a non-scorchy accelerator. 2. The decrease in cure rate$(k_1)$ is attributable to the slow cure rate of 2-cyclohexyldithiobenzothiazole(CDB). 3. Cyclohexyl polysulfides(CPS) and cyclohexylthioamine are believed to be also involved in the cure retardation. 4. The new retarder can stop crosslinking by intercepting the crosslink precursors. 5. Formation of cyclohexyl polysulfides and their lack of curing property may be responsible for the low state of cure when the new retarde is used. These results are schematically summarized in Figure 7.

• Elastomers and Composites
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• v.43 no.4
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• pp.281-287
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• 2008

Using solid state $^{13}C$ NMR, polybutadiene rubber vulcanizates were qualitatively and quantitatively analyzed. In the filled conventional system of BR vulcanizate accelerated with TBBS, addition to the olefinic double bond and substitution in the $\alpha$ position to the double bond occurred simultaneously. Also the latter $\alpha$ substitution reaction was faster than the former addition reaction at initial reaction time. In addition, it was suggested that double bond-addition-polysulfide structures might be modified into 5-membered and 6-membered cyclic structures in overcure time. These chain modifications were correlated with the decrease in the chemical crosslink density in overcure time.

• Elastomers and Composites
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• v.34 no.4
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• pp.321-331
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• 1999

The curing process is the final step in tire manufacturing whereby a green tire built from layers of rubber compounds is formed to the desired shape and the compounds are converted to a strong, elastic materials to meet tire performance needs under elevated pressure and temperature in a press. A numerical optimization procedure was developed to improve product quality in a tire curing process. First, a dynamic constrained optimization problem was formulated to determine the optimal condition of the supplied cure media during a curing process. The objective function is subject to an equality constraint representing the process model that describes the heat transfer and cures kinetic phenomena in a cure press and is subject to inequality constraints representing temperature limits imposed on cure media. Then, the optimization problem was solved to determine optimal condition of the supplied cure media for a tire using the complex algorithm along with a finite element model solver.

• Elastomers and Composites
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• v.46 no.2
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• pp.152-157
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• 2011

Effects of CR contents in NR/CR blends on the vulcanization kinetics and miscibility were studied by dynamic DSC and TGA, as well as the mechanical properties. While the vulcanization activation energy showed a constant value of $77.5{\pm}2.5$ kcal/mol regardless of CR contents, reaction rate, however, was observed to be somewhat lowered at increased CR contents. Partial miscibility was found between NR and CR phases at lower CR content of 3 wt%, but immiscibility was observed at higher CR content of 21 wt%. Mechanical properties were also affected by this miscibility, showing linear increase of compression set but decrease of tensile strength with CR contents in the blends.

• Elastomers and Composites
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• v.22 no.3
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• pp.213-218
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• 1987

In this study, the rheological properties of a partially valcanized black filled EPDM were investigated as a function of degree of crosslinks using capillary rheometer. In order to obtain the samples having various degree of crosslinks between 0 and 6 percent, the vulcanization kinetics was also studied by Monsanto rheometer. The results showed that the die swell ana the pressure drop at the capillary entrance and exit increase nearly linearly with the increase in degree of crosslinks. However, melt fracture occurred at a lower shear rate for the samples of higher degree of crosslinks. These results were discussed in terms of the melt elasticity produced at the entrance region of capillary by the partial vulcanization. It is also interesting to note that the fluctuation of die swell during the practical extrusion or calendering process in the factories can be caused by the partial vulcanization occurred during the process.

• Elastomers and Composites
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• v.38 no.4
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• pp.326-333
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• 2003

Even though many studies have been reported about rubber vulcanization, it is still remained difficult to find a quantitative relationship between the final states of vulcanized rubber and initial formulation or processing conditions. Dynamic differential scanning calorimetry (DSC) method is known as a comparatively easy method to research for the rubber vulcanization in both experimental and analysis. In the present research, a study on the vulcanization reaction of NR/CB composites modified by isoprene(IR) and chloroprene(CR) rubbers is carried out using dynamic DSC method. Thermograms with several different heating rates were obtained and analyzed using the Kissinger method. Analysis showed that the vulcanization reaction was progressed through the first order reaction mechanism. In addition, the reaction temperature was severely influenced by the kinds or rubber modifiers, in this case, more influenced by CR than by IR. Those effects were clearly verified in the values of activation energy. Kinds of carbon blacks, however, could hardly influence on the reaction mechanism.

• Elastomers and Composites
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• v.35 no.4
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• pp.288-295
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• 2000

It has been tried to decrease the crosslink density of vulcanized EPDM (ethylone-propylene-diene terpolymer) rubber through a chemical devulcanization treatment. Phase transfer catalyst, alkali metal (i.e., sodium), and triphenylphosphine have been used as a chemical agent ul the devulcanization treatment. Also it has been estimated the effect of the devulcanization treatment in the case of utilization of 2-butanol as a devulcanization reaction solvent. In the devulcanization treatment using quaternary ammonium salt as a phase transfer catalyst. the devulcanization effect has been studied with the variation of catalyst molecular weight and the choice of bromide or chloride cation. In the devulcanization treatment using sodium, it has been estimated the devulcanization treatment effect depending upon the variation of reaction variables such as amount of sodium used, reaction temperature, pressure of hydrogen gas, which is used as a reaction environment. The $M_c$ value (number average molecular weight between two crosslink points) has been experimentally estimated by the equilibrium swelling method and it is quantitatively related to the crosslink density. The estimation of devulcanization effect for vulcanized EPDM rubber has been carried out by the comparison of the $M_c$ values between the untreated and the treated specimens.

• Elastomers and Composites
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• v.38 no.3
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• pp.235-242
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• 2003

A vulcanization reaction characteristics of an isoprene rubber (IR)-modified natural rubber/carbon black (NR/CB) composite was studied using in-situ electrical property measuring technique. Since the electrical conductivity of the sample composite would be changed continuously during the vulcanization reaction by rearranging of the carbon black particles within the sample, volume resistivity (${\rho}$) might be obtained as a function or reaction time. A stabilization time ($t_i$), maximum reaction speed time ($t_p$), and volume resistivity at that time(${\rho}_p$) were defined from the data for the Arrhenius analysis. Volume resistivity ${\rho}$ showed a comparatively high value of ${\sim}10^8$ order before the reaction started, and dramatically decreased to be stabilized within $1{\sim}2$ minutes as soon as the reaction started. As the more time elapsed, thereafter, ${\rho}$ decreased monotonously to a certain constant value through a peak, ${\rho}_p$ at time $t_p$, which was considered as the maximum reaction rate. As a result, while $t_i$ values were comparatively constant as $1{\sim}2$ minutes, $t_p$ values showed to become shorter and shorter as the reaction temperature.

• Elastomers and Composites
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• v.27 no.4
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• pp.275-280
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• 1992

Vulcanization reaction was studied by DSC through the comparison cure states to physical properties and the investegation of chemicals effect on vulcanization. Reaction enthalpy showed a good correlation with physical properties, increased with the increase of sulfur content, and increased with accelerator content, as well, where the ratio of MOR to sulfur was less than 1.0. Reaction temperature was decreased with increasing accelerator content and decreased also with sulfur content where the ratio of MOR to sulfur was more than 1:3. As a result, the cure state and reaction temperature could be controlled effectively with the ratio of accelerator to sulfur in the range of a third to unity.