Primary Transformation Rate Measurements Through Differential Scanning Calorimetry

The primary crystallization of molten alloy systems at high undercooling is studied by a precise quantitative analysis of the calorimetric signal obtained during the transformation in terms of the reaction rate under isothermal and continuous heating regimes. It is shown that, under specific conditions, namely, stoechiometric primary precipitates, generalized relationships for the crystallization enthalpy and the reaction rate may be obtained.     

Primary Transformation Rate Measurements Through Differential Scanning Calorimetry

Summary. The primary crystallization of molten alloy systems at high undercooling is studied by a precise quantitative analysis of the calorimetric signal obtained during the transformation in terms of the reaction rate under isothermal and continuous heating regimes. It is shown that, under specific conditions, namely, stoechiometric primary precipitates, generalized relationships for the crystallization enthalpy and the reaction rate may be obtained.     

STUDIES ON THE KINETICS OF PHASE TRANSITIONS OF A MAIN CHAIN THERMOTROPIC POLYESTER

The kinetics of phase transitions including a transition between mesophases were studied for a main-chain thermotropic polyester by means of DSC and depolarizing transmittance techniques. The isothermal process of these transitions was found to be described by the Avrami equation to high conversions. The Avrami exponents n are about 2,4, 5.3 and 2.2 for liquid crystallization, transition between mesophases and crystallization from mesophase respectively. The liquid crystallization from isotropic liquid phase occurs at very low undercoolings with high transformation rate. This behavior is explained as the results of the smaller value of the surface free energy for mesophase than that for crystallites which is evidenced by the very weak temperature dependence of liquid crystallization rate.     

Phase transformation of colloidal In2O3 nanocrystals driven by the interface nucleation mechanism: a kinetic study

The kinetics of phase transformation of colloidal In(2)O(3) nanocrystals (NCs) during their synthesis in solution was explored by a combination of structural and spectroscopic methods, including X-ray diffraction, transmission electron microscopy, and extended X-ray absorption fine structure spectroscopy. Johnson-Mehl-Avrami-Erofeyev-Kholmogorov (JMAEK) and the interface nucleation models were used to analyze the isothermal kinetic data for the phase transformation of NCs in the temperature range of 210-260 °C. The results show that NCs are initially stabilized in the metastable corundum (rh-In(2)O(3)) phase. The phase transformation occurs via nucleation of cubic bixbyite (bcc-In(2)O(3)) phase at the interface between contacting rh-In(2)O(3) NCs, and propagates rapidly throughout the NC volume. The activation energy of the phase transformation was determined from the Arrhenius expression to be 152 ± 60 kJ/mol. The interface nucleation rate is maximal at the beginning of the phase transformation process, and decreases over the course of the reaction due to a decrease in the concentration of rh-In(2)O(3) NCs in the reaction mixture. In situ high-temperature XRD patterns collected during nonisothermal treatment of In(2)O(3) NCs reveal that phase transformation of smaller NCs occurs at a faster rate and lower temperature, which is associated with their higher packing density and contact formation probability. Because NC surfaces and interfaces play a key role in phase transformation, their control through the synthesis conditions and reaction kinetics is an effective route to manipulate NC structure and properties.     

Memory effects in isothermal crystallization. I. Theory

A theoretical analysis of transient isothermal crystallization, including relaxational and athermal effects is given. The analysis is based on Kolmogoroff-Avrami-Evans transformation equation and nucleation theory of Turnbull and Fisher. The memory of previous structures manifests itself in the distribution of atomic (molecular) clusters which determines the initial number of crystal nuclei and the initial rate of thermal nucleation.     

Kinetics analysis of the isothermal crystallization of Cu55Zr45 metallic glass by differential scanning calorimetry

The crystallization kinetics of Cu₅₅Zr₄₅ (at%) glassy alloy is studied under isothermal condition using differential scanning calorimetry (DSC). The plot of correlation between the crystallized volume fraction α and annealing time t shows a sigmoid-type curve, which is steeper with higher annealing temperature. Furthermore, in isothermal crystallization condition, local activation energy E_α values, determined using the Arrhenius equation, range from 181.1 to 187.8 kJ/mol, which is nearly a constant. The local Avrami exponent n(α) values, obtained by the Johnson-Mehl-Avrami equation, which range from 2.2 to 4.0 at different annealing temeperatures, which indicates that the crystallization mechanism is diffusion-controlled transformation. Moreover, n(α) becomes greater with increasing annealing temperature, which indicates that annealing temperature can affect nucleation rate and growth type.     

Critical examination of Ga2Se3 phase equilibria

The Ga₂Se₃ phase equilibria were examined by DTA, X-ray diffractometry, visual observation, and isothermal crystal growth to resolve discrepancies in the reported binary phase diagrams. The Se-rich solid solubility extends to less than 60.5 at. % Se. There is no peritectic transformation at 880°C, nor is there a liquid immiscibility from 75 to 85 at. % Se. The rate of crystal growth influences the incorporation of lattice defects and thus determines which polymorphic form of Ga₂Se₃ crystallizes from the melt. The preferred liquidus curve from 60 to 100 at. % Se is presented and compared to those reported in the literature.     

Der Mechanismus der Umwandlung von γ- zu α-Eisensesquioxid [1]

The rate of the isothermal transformation of γ into α Fe₂O₃ and the increase of the crystallites of α Fe₂O₃ during the transformation were measured using X-ray methods.     

Transformation of dynamic DSC results into isothermal data for the curing kinetics study of the resol resins

Kinetics of thermosetting polymers curing is difficult to study by isothermal methods based on the differential scanning calorimetry (DSC) technique. The difficulty is due to the low sensitivity of the equipment for total reaction heat measurements during high temperature process. The aim of this paper is to display the equivalence between a dynamic model, the Ozawa method, and an isothermal isoconversional fit, which allows predicting the isothermal behavior of the resol resins cure through dynamic runs by DSC. In this work, lignin–phenol–formaldehyde and commercial phenol–formaldehyde resol resins were employed. In addition, the isothermal kinetic parameters for both resins were performed by means of transformation of the data obtained from the dynamic Ozawa method.     

The using of thermal analysis methods for the construction of isothermal transformation diagrams of thermosets

The article reviews the using of thermal analysis methods and mathematic modeling of kinetics of chemical processes for the creation of isothermal transformation diagrams of thermosetting binders. Differential scanning calorimetry (DSC), temperature modulated DSC, gel-timer and thermogravimetry are used for the construction of isothermal transformation diagrams with vitrification and gelation curves, areas of thermal stability and post-curing. The Time-Temperature-Transformation diagrams obtained can be used for optimization of time-temperature schedules for polymer matrix composites fabrication at the laboratory scale.     

Temperature programmed retention indices: Calculation from isothermal data. Part 1: Theory

Direct conversion of isothermal to temperature programmed indices is not possible. In this work it is shown that linear temperature programmed retention indices can only be calculated from isothermal retention data if the temperature dependence of both the distribution coefficients and the column dead time are taken into account. Procedures are described which allow calculation of retention temperatures and from these, accurate programmed retention indices. Within certain limits the initial oven temperature and programming rate can be chosen freely. The prerequisite for this calculation is the availability of reliable isothermal retention data (retention times, retention factors, relative retention times, or retention indices) at two different temperatures for one column. The use of compiled isothermal retention indices at two different temperatures for the calculation of retention temperatures and thus temperature programmed indices is demonstrated. For the column for which programmed retention indices have to be determined, the isothermal retention times of the n-alkanes and the column dead time as a function of temperature have to be known in addition to the compiled data for a given stationary phase. Once the programmed retention indices have been calculated for a given column the concept allows the calculation of temperature programmed indices for columns with different specifications. The characteristics which can be varied are: column length, column inner diameter, phase-ratio, initial oven temperature, and programming rate.     

Isothermal crystallization kinetics of Fe<Subscript>75</Subscript>Cr<Subscript>5</Subscript>P<Subscript>9</Subscript>B<Subscript>4</Subscript>C<Subscript>7</Subscript> metallic glass with cost-effectiveness and desirable merits

In this work, the isothermal crystallization kinetics of cost-effective Fe₇₅Cr₅P₉B₄C₇ metallic glass with a combination of desired merits synthesized by industrial ferro-alloys without high-purity materials was evaluated by Johnson–Mehl–Avrami approach using differential scanning calorimeter. The Avrami exponents at all isothermal annealing temperatures range from about 2.93 to 4.61, indicating a three-dimensional diffusion-controlled growth with an increasing nucleation rate during the isothermal crystallization. Meanwhile, the Avrami exponent firstly increases from 2.93 at the initial time to a maximum value of 4.61 and then decreases to 4.09 with the increment of the isothermal annealing temperature, which can be attributed to the atomic diffusion in the alloy. Additionally, the trend of the local Avrami exponent variations at different isothermal annealing temperatures reflects a variable crystallization mechanism during the crystallization process. Moreover, the local activation energy determined by Arrhenius equation gradually decreases from about 412 to 383 kJ mol^?1 during the present isothermal crystallization, further revealing that the process is dominated by a three-dimensional diffusion-controlled growth with an increasing nucleation rate, which provides useful insights into the formation of the present alloy.     

脱晶蒽油改质煤焦油沥青的研究——中间相非等温动力学

在热转化装置上,对宝钢Ⅰ期焦油沥青（简称I－CTP）及其添加18％、30％脱晶蒽油（简称DCAO）制成的软沥青进行了中间相转化非等温动力学研究,采用积分法求得了有关动力学参数。结果表明,沥青中间相形成过程可以用一级反应来描述。宝钢Ⅰ期焦油沥青活化能为180.02kJ/mol。添加80％脱晶蒽油则提高了原料沥青的反应性,活化能为147.89kJ/mol,不利于优质中间相的形成。     

Development and applications of sample controlled thermomicroscopy

Sample controlled thermal analysis techniques such as constant rate transformation analysis or stepwise isothermal analysis, where the transformation rate of the sample itself is used to control the experiment, are becoming increasingly important [1]. The measurements are normally carried out using changes in the sample mass, sample dimensions or in the evolved gas, as the property used to control the experiment, and enable reactions to be studied in greater detail than is possible using linear heating techniques. A new approach is described here where a thermomicroscopy system has been developed to enable the intensity of the light reflected or transmitted by the sample to be used as the controlling signal [2]. This revised version was published online in July 2006 with corrections to the Cover Date.     

A comparative study on the single-scan and multiple-scan techniques in differential scanning calorimetry: Application to the crystallization of the semiconducting Ge0.13Sb0.23Se0.64 alloy

A method has been developed for analysing the evolution with time of the volume fraction transformed and for calculating the kinetic parameters at non-isothermal reactions in materials involving formation and growth of nuclei. By considering the assumptions of extended volume and random nucleation, a general expression of the fraction transformed as a function of time has been obtained in isothermal crystallization processes. Considering the mutual interference of regions growing from separate nuclei the Johnson–Mehl–Avrami equation has been deduced as a particular case. The application of the transformation rate equation to the non-isothermal processes has been carried out under the restriction of a nucleation which takes place early in the transformation and the nucleation frequency is zero thereafter. Under these conditions, the kinetic parameters have been deduced by using the techniques of data analysis of single-scan and multiple-scan. The theoretical method developed has been applied to the glass-crystal transformation kinetics of the semiconducting Ge_0.13Sb_0.23Se_0.64 alloy. The kinetic parameters obtained according to both techniques differ by only about 2.5%, which confirms the reliability and accuracy of the single-scan technique when calculating the above-mentioned parameters in non-isothermal transformation processes. The phases at which the above-mentioned semiconducting glass crystallizes after the thermal process have been identified by X-ray diffraction. The diffractogram of the transformed material shows that microcrystallites of Sb₂Se₃ and GeSe are associated with the crystallization process, remaining a residual amorphous matrix.     

Some demonstrations of the effect of the heating rate on thermoanalytical curves

Thermoanalytical curves of two parallel competitive reaction systems and of two systems in which two mutually independent reactions occur concurrently are made by simulation, as well as isothermal curves of the systems. From these curves, an effect of heating rate is illustratively shown; one peak is observed in a derivative thermoanalytical curve at one heating rate, while a shoulder or two peaks appear in another derivative curve of the same reaction system at another heating rate. An advantage of thermal analysis over isothermal experiments, and its limitations, are discussed.     

Precipitation sequence during ageing in β1 phase of Cu–Al–Ni shape memory alloy

The shape memory alloys based on the ternary system Cu–Al–Ni are able to produce a memory effect at high temperatures. However, if the material undergoes an accidental overheating, a transformation process leads to progressive loss of its characteristics. In this study, the effect of ageing on the metastable β₁ (austenite) phase of a Cu–13.3 %Al–4 %Ni shape memory alloy was investigated. In addition, the effects of heating rate between 450 and 580 °C on the structural transformations of austenite after cooling to room temperature were studied. Observation by transmission electron microscopy of the structure that has undergone an isothermal ageing shows that the precipitation process depends on the maximum ageing temperature. Furthermore, calorimetric analysis shows that precipitates dissolution is possible when rapid heating between 450 and 580 °C. This behaviour is observed on the cooling diagram which shows a martensitic transformation.     

Aerobic oxidation of primary alcohols under mild aqueous conditions promoted by a dinuclear copper(II) complex

A sugar-discriminating dinuclear copper(II) complex was investigated for its ability to promote aerobic oxidation of primary benzylic alcohols in the presence of TEMPO and base. The transformation of benzyl alcohol to benzaldehyde was chosen as exploratory model reaction. The constitution of the catalytically active species was deducted from isothermal titration calorimetry and kinetic experiments, and the catalytic reaction was characterized both in aqueous organic and aqueous solution. The dinuclear complex is found to selectively oxidize primary over secondary alcohols in aqueous solution at ambient temperature with a turnover rate of 9 h⁻¹. A mechanism for the catalytic cycle is proposed.