58 resultados para non-isothermal kinetic


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The effect of ultrasound on the thermal decomposition behaviour of ammonium perchlorate (AP) has been investigated. It was observed that significant changes in the thermal behaviour of A-P, followed using differential thermal analysis and thermogravimetry, was observed when AP was subjected to power ultrasound in water saturated with oxygen-nitrogen mixture. The decomposition temperature of AP was found to have been lowered by nearly 25degreesC. A similar thermal sensitization was observed in AP when subjected to sonication in the presence of transition metal oxides. Kinetic parameters were calculated for AP, modified AP and catalyzed AP decomposition using non-isothermal kinetics. The activation energy for the decomposition of the sonicated AP samples were found to be lower than normal AP.

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Interpenetrating polymer networks (IPNs) of trimethylol propane triacrylate (TMPTA) and 1,6-hexane diol diacrylate (HDDA) at different weight ratios were synthesized. Temperature modulated differential scanning calorimetry (TMDSC) was used to determine whether the formation resulted in a copolymer or interpenetrating polymer network (IPN). These polymers are used as binders for microstereolithography (MSL) based ceramic microfabrication. The kinetics of thermal degradation of these polymers are important to optimize the debinding process for fabricating 3D shaped ceramic objects by MSL based rapid prototyping technique. Therefore, thermal and thermo-oxidative degradation of these IPNs have been studied by dynamic and isothermal thermogravimetry (TGA). Non-isothermal model-free kinetic methods have been adopted (isoconversional differential and KAS) to calculate the apparent activation energy (E a) as a function of conversion (α) in N 2 and air. The degradation of these polymers in N 2 atmosphere occurs via two mechanisms. Chain end scission plays a dominant role at lower temperature while the kinetics is governed by random chain scission at higher temperature. Oxidative degradation shows multiple degradation steps having higher activation energy than in N 2. Isothermal degradation was also carried out to predict the reaction model which is found to be decelerating. It was shown that the degradation of PTMPTA follows a contracting sphere reaction model in N 2. However, as the HDDA content increases in the IPNs, the degradation reaction follows Avrami-Erofeev model and diffusion governed mechanisms. The intermediate IPN compositions show both type of mechanism. Based on the above study, debinding strategy for MSL based microfabricated ceramic structure has been proposed. © 2012 Elsevier B.V.

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Transparent BaNaB9O15 (BNBO) glasses were fabricated via the conventional melt-quenching technique. X-ray powder diffraction (XRD) followed by differential scanning calorimetric (DSC) studies confirmed the amorphous and glassy nature of the as-quenched samples, respectively. The effect of seeding on the crystallization of BNBO glasses was studied by non-isothermal DSC method and was modeled using the Johnson-Mehl-Avrami and Ozawa equations. The activation energy for seeded glasses decreased with the increase in fraction of crystallization. The values for the onset of crystallization and Avrami exponent were found to be lower for seeded samples which were associated with the heterogeneous nucleation and epitaxial processes.

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Transparent glasses in the system 3BaO-3TiO2-B2O3 (BTBO) were fabricated via the conventional melt-quenching technique. The as-quenched samples were confirmed to be non-crystalline by differential thermal analysis (DTA). Thermal parameters were evaluated using non-isothermal DTA experiments. The Kauzmann temperature was found to be 759 K based on heating-rate-dependent glass transition and crystallization temperatures. A theoretical relation for the temperature-dependent viscosity is proposed for these glasses and glass-ceramics.

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The authors derive the Korteweg-de Vries equation in a multicomponent plasma that includes any number of positive and negative ions. The solitary wave solutions are also found explicitly for the case of isothermal and non-isothermal electrons.

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The thermal decomposition of methylammonium perchlorate (MAP) has been studied under isothermal and non-isothermal conditions. Differential thermal analysis of MAP showed, in addition to the exotherm due to decomposition, another exotherm at 408° which was observed for the first time. Chemical analysis and the infrared spectrum of the residue left behind after the decomposition proved it to contain NH4ClO4. The results have been explained on the basis of a methyl group transfer in addition to proton transfer in the decomposition process.

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Thixocasting requires manufacturing of billets with non-dendritic microstructure. Aluminum alloy A356 billets were produced by rheocasting in a mould placed inside a linear electromagnetic stirrer. Subsequent heat treatment was used to produce a transition from rosette to globular microstructure. The current and the duration of stirring were explored as control parameters. Simultaneous induction heating of the billet during stirring was quantified using experimentally determined thermal profiles. The effect of processing parameters on the dendrite fragmentation was discussed. Corresponding computational modeling of the process was performed using phase-field modeling of alloy solidification in order to gain insight into the process of morphological changes of a solid during this process. A non-isothermal alloy solidification model was used for simulations. The morphological evolution under such imposed thermal cycles was simulated and compared with experimentally determined one. Suitable scaling using the thermosolutal diffusion distances was used to overcome computational difficulties in quantitative comparison at system scale. The results were interpreted in the light of existing theories of microstructure refinement and globularisation.

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The metallic glass Vitrovac 4040 with the composition Fe39Ni39Mo4Si6B12 crystallizes in the order alpha-Fe, hexagonal Ni5Si2 and gamma-(Fe,Ni,Mo) by primary, secondary and polymorphic modes, respectively. The activation energies determined from the non-isothermal kinetics using Kissinger method turn out to be 490, 550 and 449 kJ.mol-1 for the above crystallization reactions. It has been observed that alpha transforms to gamma during annealing. Further, the bct (Fe1-xNix)3B phase has been identified when the glass is annealed above 1023 K.

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The flow and heat transfer over an upstream moving non-isothermal wall with a parallel free stream have been considered. The magnetic field has been applied in the free stream parallel to the wall and the effect of induced magnetic field has been included in the analysis. The boundary layer equations governing the steady incompressible electrically conducting fluid flow have been solved numerically using a shooting method. This problem is interesting because a solution exists only when the ratio of the wall velocity does not exceed a certain critical value and this critical value depends on the magnetic field and magnetic Prandtl number. Also dual solutions exist for a certain range of wall velocity.

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The present investigation of ion-acoustic waves is based on the study of the nonlinearity of plasma waves in a dispersive medium. Here the authors study ion-acoustic solitary waves in a warm ion plasma with non-isothermal electrons and then the results for solitary waves in a plasma with isothermal electrons are obtained. Incorporating the previous results obtained from the solitary wave solutions, the authors generalize the effect of negative ions on ion-acoustic waves in plasmas consisting of either a warm or cold ion species. A reflection phenomenon of ions in these waves is also studied. These results can be generalized, but the discussion is limited to a particular model of the plasma.

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The basic principles of operation of gas sensors based on solid-state galvanic cells are described. The polarisation of the electrodes can be minimised by the use of point electrodes made of the solid electrolyte, the use of a reference system with chemical potential close to that of the sample system and the use of graded condensed phase reference electrodes. Factors affecting the speed of response of galvanic sensors in equilibrium and non-equilibrium gas mixtures are considered with reference to products of combustion of fossil fuels. An expression for the emf of non-isothermal galvanic sensors and the criterion for the design of temperature compensated reference electrodes for non-isothermal galvanic sensors are briefly outlined. Non-isothermal sensors are useful for the continuous monitoring of concentrations or chemical potentials in reactive systems at high temperatures. Sensors for oxygen, carbon, and alloying elements (Zn and Si) in liquid metals and alloys are discussed. The use of auxiliary electrodes permits the detection of chemical species in the gas phase which are not mobile in the solid electrolyte. Finally, the cause of common errors in galvanic measurements, and tests for correct functioning of galvanic sensors are given. 60 ref.--AA

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Differential scanning calorimetry (DSC) can be used for obtaining various non-isothermal properties of glassy materials. The thermal properties of the Si-As-Te glass system are discussed in relation to the interesting information obtained on the local ordering in these glasses.

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The kinetics of the oxidation of electrodeposited boron powder and the boron powder produced by the reduction process were studied using thermogravimetry (TG). The oxidation was carried out by heating boron powder in a stream of oxygen. Both isothermal and non-isothermal methods were used to study the kinetics. Model-free isoconversional method was used to derive the kinetics parameters. A two step oxidation reaction (exothermic) was observed. The oxidation reaction could not be completed due to the formation of glassy layer of boric oxide on the surface of boron powder which acts as a barrier for further diffusion of oxygen into the particle. The activation energy obtained using model-free method for electrodeposited boron is 122 +/- 7 kJ mol(-1) whereas a value of 205 +/- 9 kJ mol(-1) was obtained for boron produced by the reduction process (commercially procured boron). Mechanistic interpretation of the oxidation reaction was done using model based method. The activation energy was found to depend on the size distribution of the particles and specific surface area of the powder. (C) 2010 Elsevier B.V. All rights reserved.

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Glasses of the composition 2TeO(2)-V2O5 were fabricated via the conventional melt-quenching technique. The amorphous and the glassy nature of the as-quenched samples were confirmed by X-ray powder diffraction (XRD) and differential scanning calorimetry (DSC), respectively. The glass transition and crystallization parameters were evaluated under non-isothermal conditions using DSC. X-ray diffraction studies confirmed the presence of partially oriented crystallites in the heat-treated glasses. Kauzmann temperature (lower bound for the kinetically observed glass transition) was deduced from the heating rate dependent glass transition and crystallization temperatures.

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In this present paper, the effects of non-isothermal rolling temperature and reduction in thickness followed by annealing on microstructure and mechanical properties of ZM21 magnesium alloy were investigated. The alloy rolled at four different temperatures 250 degrees C, 300 degrees C, 350 degrees C and 400 degrees C with reductions of 25%, 50% and 75%. Non-isothermal rolling resulted in grain refinement, introduction of shear bands and twins in the matrix alloy. Partial to full recrystallization was observed when the rolling temperature was above recrystallization temperature. Rolling and subsequent annealing resulted in strain-free equiaxed grains and complete disappearance of shear bands and twins. Maximum ultimate strength (345 MPa) with good ductility (14%) observed in the sample rolled at 250 degrees C with 75% reduction in thickness followed by short annealing. Recrystallization during warm/hot rolling was sluggish, but post-roll treatment gives distinct views about dynamic and static recrystallization. (C) 2011 Elsevier B.V. All rights reserved.