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Abstract  

Over 90% of the cumene hydroperoxide (CHP) produced in the world is applied in the production of phenol and acetone. The additional applications were used as a catalyst, a curing agent, and as an initiator for polymerization. Many previous studies from open literature have verified and employed various aspects of the thermal decomposition and thermokinetics of CHP reactions. An isothermal microcalorimeter (thermal activity monitor III, TAM III), and a thermal dynamic calorimetry (differential scanning calorimetry, DSC) were used to resolve the exothermic behaviors, such as exothermic onset temperature (T 0), heat power, heat of decomposition (ΔH d), self-heating rate, peak temperature of reaction system, time to maximum rate (TMR), etc. Furthermore, Fourier transform infrared (FT-IR) spectrometry was used to analyze the CHP products with its derivatives at 150 °C. This study will assess and validate the thermal hazards of CHP and incompatible reactions of CHP mixed with its derivatives, such as acetonphenone (AP), and dimethylphenyl carbinol (DMPC), that are essential to process safety design.

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Abstract  

Cumene hydroperoxide (CHP) being catalyzed by acid is one of the crucial processes for producing phenol and acetone globally. However, it is thermally unstable to the runaway reaction readily. In this study, various concentrations of phenol and acetone were added into CHP for determination of thermal hazards. Differential scanning calorimetry (DSC) tests were used to obtain the parameters of exothermic behaviors under dynamic screening. The parameters included exothermic onset temperature (T 0), heat of decomposition (ΔH d), and exothermic peak temperature (T p). Vent sizing package 2 (VSP2) was employed to receive the maximum pressure (P max), the maximum temperature (T max), the self-heating rate (dT/dt), maximum pressure rise rate ((dP/dt)max), and adiabatic time to maximum rate ((TMR)ad) under the worst case. Finally, a procedure for predicting thermal hazard data was developed. The results revealed that phenol and acetone sharply caused a exothermic reaction of CHP. As a result, phenol and acetone are important indicators that may cause a thermal hazard in the manufacturing process.

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Abstract  

Hydrogen peroxide (H2O2) is popularly employed as a reaction reagent in cleaning processes for the chemical industry and semiconductor plants. By using differential scanning calorimetry (DSC) and vent sizing package 2 (VSP2), this study focused on the thermal decomposition reaction of H2O2 mixed with sulfuric acid (H2SO4) with low (0.1, 0.5 and 1.0 N), and high concentrations of 96 mass%, respectively. Thermokinetic data, such as exothermic onset temperature (T 0), heat of decomposition (ΔH d), pressure rise rate (dP/dt), and self-heating rate (dT/dt), were obtained and assessed by the DSC and VSP2 experiments. From the thermal decomposition reaction on various concentrations of H2SO4, the experimental data of T 0, ΔH, dP/dt, and dT/dt were obtained. Comparisons of the reactivity for H2O2 and H2O2 mixed with H2SO4 (lower and higher concentrations) were evaluated to corroborate the decomposition reaction in these systems.

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Abstract  

This work refers to a study of the thermal decomposition of octahydro-1,3,5,7-tetranitro-1,3,5,7 tetrazocine (HMX) by differential scanning calorimetry (DSC) in non-isothermal conditions, with heating rates from1 to 25C min−1. The influence of the heating rate, the particle and the sample size were verified. The activation energy was calculated using the peak temperature shift method, proposed by Ozawa and a significant variation in the results was observed according to the range of the used heating rates. As the heating rate was increased, different conversions and self-heating effects were observed at the respective DSC peaks, indicating that the use of this method was inadequate and it may lead to incorrect results, which, in turn, could explain the wide range of activation energy values published in literature. At lower heating rates HMX decomposition occurs on the solid state and at higher ones decomposition occurs after melting practically at the same temperature, which does not depend on the heating rate.

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Journal of Thermal Analysis and Calorimetry
Authors: B. Roduit, Ch. Borgeat, B. Berger, P. Folly, B. Alonso, and J. N. Aebischer

Summary An advanced study on the thermal behaviour of double base (boost and sustain propellant) rocket motor used in a ground to air missile has been carried out by differential scanning calorimetry (DSC). The presence of two propellants as well as the different experimental conditions (open vs. closed crucibles) influence the relative thermal stability of the energetic materials. Several methods have been presented for predictions of the reaction progress of exothermic reactions under adiabatic conditions. However, because decomposition reactions usually have a multi-step nature, the accurate determination of the kinetic characteristics strongly influences the ability to correctly describe the progress of the reaction. For self-heating reactions, incorrect kinetic description of the process is usually the main source of serious errors for the determination of the time to maximum rate under adiabatic conditions (TMRad). It is hazardous to develop safety predictive models that are based on simplified kinetics determined by thermoanalytical methods. Applications of finite element analysis (FEA) and accurate kinetic description allow determination of the effect of scale, geometry, heat transfer, thermal conductivity and ambient temperature on the heat accumulation conditions. Due to limited thermal conductivity, a progressive temperature increase in the sample can easily take place resulting in a thermal explosion. Use of both, kinetics and FEA [1], enables the determination of the reaction progress and temperature profiles in storage containers. The reaction progress and temperature can be determined quantitatively at every point in time and in space. This information is essential for the design of containers of self-reactive chemicals, cooling systems and the measures to be taken in the event of a cooling failure.

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Metastable effects on martensitic transformation in SMA

Part VIII. Temperature effects on cycling

Journal of Thermal Analysis and Calorimetry
Authors: V. Torra, C. Auguet, A. Isalgue, F. Lovey, A. Sepulveda, and H. Soul

Abstract  

The use of Shape Memory Alloys (SMA) in technical applications as damping in civil engineering structures requires the characterization of the alloy for each specific application. This involves the evolution of the mechanical properties and damping capacity with the number of cycles, frequency, maximum deformation, applied stresses, and the evolution of the alloy with aging time and temperature. In particular, the temperature effects associated to self-heating need to be evaluated. In continuous cycling the effects of latent heat, the associated dissipation induced by the hysteresis, the heat flow to surroundings and the cycling frequency induce different states of temperature in the specimen, which in turn produces changes in the transformation-retransformation stresses. In this article, the temperature effects associated to cycling are outlined for different cycling frequencies. The results show that, for relatively faster frequency the temperature arrives at an oscillatory state superimposed to an exponential increase. For lower frequencies, some parts of the sample attain temperatures below room temperature. The experimental results are represented with an elementary model (the 1-body model or the Tian equation used in calorimetric representation) of heat transfer. For the higher fracture where life requirements are associated to damping in stayed cables for bridges, the results show (for the NiTi alloy) a reduction of the hysteresis width as the frequency increases for deformations up to 8%. For reduced deformation, under 2% appears an asymptotic behavior where the frictional area is practically independent of the cycling frequency (up to 20 Hz). In addition, it is shown that more than 4 million of working cycles can be attained if the maximum applied stress is kept below a threshold of about 200 MPa. Although under this condition the deformation must remain lower than 2% a reasonable damping capacity can still be obtained.

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Decomposition of urea nitrate in an initially evacuated system gave sigmoidal pressurevs. time curves. The experimental kinetic data fit the growing nuclei model with a measured enthalpy of activation of 142±12.5 kJ/mole as compared to 115±11.3 kJ/mole obtained thermogravimetrically. This higher value ofΔH is explained on the basis of two factors: 1) the inhibitory effect of the product gases and 2) self heating, whose extent increasedΔH by about 12.5 kJ/mole.

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tended to be dominant and the heat flow decreased with the time. ARC measurement The reaction temperature, self-heating rate, and pressure data may be collected during the exothermic processes with ARC. It is effective

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of self-heating leading to thermal runaway, etc., still persist. Yuhai and Shilin [ 2 ] investigated the preparation technology and the safety analysis of the production process of smokeless fireworks made by the expired single base propellant

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Journal of Thermal Analysis and Calorimetry
Authors: Sheng-Hung Wu, Hung-Cheng Chou, Ryh-Nan Pan, Yi-Hao Huang, Jao-Jia Horng, Jen-Hao Chi, and Chi-Min Shu

. When the maximum self-heating rate compared with the time constant is the same in the system, then the temperature will rise to T NR [ 8 ]. The E a and A is developed from Arrhenius equation that is displayed in Eq. 3 . The E a calculation

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