Studies on the Characteristics of Rubber Vulcanization Exotherm by Differential Scanning Calorimetry.

Differential Scanning Calorimetry에 의(依)한 고무의 가황발열특성(加黃發熱特性)에 관(關)한 연구(硏究)

The purposes of this dissertation are to demonstrate that DSC theromoanaytical methods of vulcanization can provide useful informations on the vulcanization characteristics of industrial formulations and also provides the potential basis for a rapid and complete method of sulfur and vulcanizing accelerator analysis for quality control. The influences of those factors such as heating rate, scan temperature, vucanizing accelerator's type and concentration upon vulcanization exotherm in NR and NBR compounds in the presence of vulcanizing accelerators such as TMTD,MBTS,DPG,TMTM,CBS, and MBT were evaluated by means of DSC. In order to examine the credibility in the DSC method, the same samples which were used for DSC method were studied to compare the DSC results with the ODR (Oscillating Disk Rheometer) data. The results obtained were as follows 1. In the DSC dynamic experiments, the observed enthalpy results from vulcanization depends upon the heating rate; In the range of 2 to $20^{\circ}C/min$ of heating rate, as the heating rate was increased the enthalpy change was also increased. However, over the heating rate of $30^{\circ}C/min$ it was observed that the enthalpy change was decreased as the heating rate was further increased. Without regard to the change of enthalpy, tremendous instantaneous heat evolving was observed in the range of high heating rates. 2. For the samples which are added with various vulcanizing accelerators, the activation energies of vulcanization were as follows; 3. Regarding to the influences of vulcanizining accelerator's types upon the characteristics of vulcanization exotherm, NR and NBR compounds in the presence of thiuramsulphide compounds type accelerators such as TMTD, TMTM, were exhibited sharper and higher vulclanization exotherm than others. From the resuts of DSC thermograms which was distributed in even shape in the broad temperature range, it was clearly shown that the guanidine compounds type accelerator such as DPG acts as a delayed acting accelerator. 4. In the comparison of DSC and ODR results, the dependency of temperature in the cure rate and the observed conversions show good agreements between two results. 5. In the same curatives, by the comparison of glass transition temperatures, it was possible to predict relative values of maximum torques. Consequently, from the present studies, it is shown that the DSC thermoanalytical method can provide an alternate new method for rapid and complete quality control analysis of rubber industry.