Application of non-isothermal dilatometry for evaluation of kinetic parameters in non-reversing reactions

The applicability of the non-isothermal dilatometric technique for the investigation of rate processes is discussed. Equations have been derived for a non-reversing reaction, which may be used to calculate the kinetic parameters from non-isothermal dilatometric curves. The main advantages of the approach are considerable economies in experimental procedure and the avoidance of experimental errors associated with the onset of reaction before isothermal conditions are attained. The position of the inflection point on the dilatometric curve and the slope at that point give the activation energy and frequency factor of the reaction. The usefulness of the new approach is demonstrated by the good agreement between values of activation energy obtained by the new equations and reported literature values for the second and third stages in the tempering reaction of a plain carbon steel.     

Effect of microstructure on thermal expansion behaviour of nanocrystalline metallic materials

Materials properties, among which thermodynamic ones, are influenced by microstructural features. This is so also in the case of nanocrystalline materials, featuring average grain size below 100 nm. A reduced grain size involves that significant fractions of atoms are localised in grain boundary regions and this has remarkable effects on the resulting thermodynamic properties, like heat capacity, transition temperatures, coefficient of thermal expansion, etc. In the present work we consider the thermal expansion behaviour of ball-milled nanocrystalline metallic powders using dilatometric measurements. High-energy ball-milling, that is capable to achieve extremely high deformation degrees, induces in the milled powders microstructural defects, like vacancies, antisites, dislocations and planar faults. Another effect of milling is the reduction of the crystallite size, that, in the long run, may reach the nanometric range. In view of the microstructural changes that can be brought about by milling and of the numerous transformations occurring during the dilatometric runs, a comparative study has been conducted on intermetallic, NiAl and Ni₃Al, and on a pure metal, nickel, powders. The results emerging from the experimental investigation are quite complex, owing to the complex defect structures that are present in the ball-milled powders. It turns out that the thermal expansion coefficient of the nanocrystalline powders increases as the average grain size is reduced. However, when the average grain size achieves very low values, the strain relaxation of the crystalline lattice and the rearrangement of grain boundary regions result in a reduction of the thermal expansion coefficient. Another aspect that emerges from the dilatometric curves is the interplay between recrystallization and reordering, i.e. the re-establishment of the long-range order in the intermetallic powders, that had been partially or fully eliminated by ball-milling.     

Stresses produced during martensitic transformation of austenite

It was shown that strains, measured when martensitic transformation curves are constructed by a dilatometric method, can be used to calculate the magnitude of structural stresses of the first kind. Structural stresses produced in three different (with respect to chemical composition) silicocalcium modified cast irons with lamellar graphite were determined.     

Q345钢奥氏体连续冷却转变曲线(CCT图)

研究了Q345钢连续冷却过程中奥氏体转变过程及转变产物的组织和性能,为制定生产工艺提供参考依据.利用膨胀法结合金相-硬度法,得到不同冷却速度连续冷却时的膨胀曲线和相应的金相组织及硬度,用DTA法及膨胀法测定其临界点Ac1、Ac3以及Ms,获得了Q345钢的连续冷却转变曲线(CCT图).由CCT图和不同冷却速度的显微组织照片可知,当冷却速度比较低时,形成较粗大的块状铁素体和珠光体,当冷却速度大于0.5℃/s时出现贝氏体,形态似针状铁素体,其形成温度在450~600℃左右,当冷却速度大于20℃/s时,发生马氏体转变,马氏体转变点约为400℃.     

Thermodynamically reversible and irreversible control on morphology of multiphase systems

Morphology and properties of polymer alloys can be controlled by thermodynamically reversible (structure freeze-in) or irreversible (structure lock-in) processes via simultaneously manipulating miscibility, mechanisms of phase separation, glass transition (structural relaxation), and cure kinetics of polymer systems. Using phase diagrams consisting of binodal and spinodal curves, the morphology of epoxy/carboxyl-terminated butadiene acrylonitrile copolymer (CTBN) systems can be controlled by the mechanism of nucleation and growth or by spinodal decomposition. We have found that the particle size of the rubber reinforcement in epoxies is affected by the mechanisms of phase separation. Phase separation by nucleation and growth gives larger rubber particles than the corresponding phase separation by spinodal decomposition. This contrast in the morphology development is the consequence of controlling phase separation through chemorheological behaviour. Modification of the phase separation kinetics in epoxy/CTBN systems was extremely effective at altering both morphology and properties of these alloys. This technique offers a means to shift the glass transition temperature of the rubber-rich phase while leaving the glass transition temperature of the epoxy-rich phase intact. Such control over morphology is the key to ultimately controlling material properties.     

超塑性本构模型材料参数识别方法研究

金泉林等提出的超塑性本构关系考虑了三种微观变形机制和晶粒生长过程,但单纯依靠实验很难准确的测定该本构关系的材料参数。应用遗传算法和Levenberg-Marquardt算法,以Ti-6Al-4V为例,识别该超塑性本构关系中的材料参数。计算结果和实验结果符合的很好。最后讨论了各种微观变形机制的体积分数与应变、应变率和晶粒尺寸之间的关系,发现在大部分情况下扩散蠕变机制对超塑变形的贡献可以忽略。     

Dilatometric study of isothermal phase tranformation in a C-Mn steel

A dilatometric study of the isothermal phase transformations in a low-alloy carbon steel is presented. The results show a TTT diagram consisting of three C shaped curves corresponding respectively to allotriomorphic ferrite-pearlite, Widmanstätten ferrite-pearlite and bainite transformations. These three temperature intervals are even better marked in a plot of total dilatation against temperature. A representation of log (ΔI/I) against logt, at each holding temperature, gives information about the transformations taking place. Hence, it is suggested that the bainitic reaction also occurs in two consecutive stages. Similarly to the other two transformations, ferrite formation in the initial stage is followed by the subsequent precipitation of cementite and further ferrite. It is concluded that the three transformations are of similar nature, controlled by carbon diffusion, the different C-curves being produced by changes either in the growth or nucleation mechanisms.     

Innovative Methode zur Partikelklassifizierung beim thermischen Spritzen

Innovative particle characterization method for thermal spray processes Coatings produced by thermal spray processes are determined by particle parameters, which can be investigated using various diagnostic systems. With the newly developed PSI (Particle Shape Imaging) four (velocity, size, shape and position) important particle parameters can be measured and evaluated. The data acquisition system consists of two separate optical setups, thus a single particle produces two pictures in the lower and upper area of an ICCD‐Camera. These pictures are evaluated by assigning specially developed shape and size parameters to the particles, which, in combination with the velocity, can be used to predict the coating quality. This instrument can be used to determine the optimum spray parameters (i.e. find the optimal distance between substrate and thermal spray system) and to survey the coating process. A newly developed, mobile PSI‐System will allow operation at industrial and research thermal spray facilities.     

Size effect and dielectric properties of NH4H2PO4 — porous glass composites

NH₄H₂PO₄ nano-composite antiferroelectric materials in porous glass have been studied by means of dielectric and dilatometric investigations. Dielectric spectroscopy measurements in a wide frequency range are reported here for the first time, for both the antiferro- and paraelectric phases of ammonium dihydrogen phosphate (ADP) embedded in a porous matrix. Low frequency relaxation processes above the phase transition temperature were shown to occur. An investigation of the thermal expansion revealed a negative volume jump at the phase transition point. It was found that the phase transition temperature in ADP crystals embedded in porous glass decreased with the decrease of the mean pore size. The experimentally observed shift of the phase transition temperature is caused by a combination of size and pressure effects.     

Emanation-Thermal Analysis of Perovskite

Structural changes in perovskite and perovskite-like ceramics in the course of thermal treatment were studied by emanation-thermal analysis (ETA) using synthetic calcium metatitanate and aluminotitanate with addition of neodymium and cerium simulating solidified radioactive wastes. The emanation was analyzed as influenced by mechanical (polishing of the surface with diamond paste), radiation (bombardment with helium and krypton ions to certain dozes), and chemical (leaching in aggressive solvents) treatments and by the atmosphere (air, argon, hydrogen) in which the thermal treatment was performed. The ETA curves exhibit characteristic peaks corresponding to regeneration and annealing of both natural structural defects and those appearing after the external treatment of the sample. The model of emanation from material involving structural transformations, which well agrees with experimental data, was proposed. The emanation-thermal analysis under the dynamic conditions allows study of the evolution in the development of the surface relief and solid-state processes proceeding in the fine near-surface layer of material in the course of thermal treatment. It was found that the perovskite-like ceramics, thanks to its high thermal, radiation, mechanical, and chemical stability, can be recommended for solidification and disposal of high-level radioactive wastes.     

T91铁素体耐热钢过冷奥氏体转变过程中临界冷却速度的研究

利用DIL805A/D高精度差分膨胀仪,通过线膨胀行为测量与微观组织分析,获得T91铁素体耐热钢连续冷却转变过程中相关动力学信息,结合冷却后T91钢组织特征,确定了T91钢过冷奥氏体转变过程中的临界冷却速度.研究表明:T91钢过冷奥氏体连续冷却过程中只存在铁素体和马氏体转变区,而不出现贝氏体和珠光体转变.在冷却速度为10K/min时该钢获得完全板条马氏体组织,9K/min时组织中开始出现铁素体,即10K/min可以定为T91钢奥氏体向马氏体转变的上临界冷却速度;当冷却速度介于3～9K/min时为马氏体和铁素体的混合组织,冷却速度为2K/min时T91钢中不存在马氏体转变,室温组织为铁素体,即2K/min可以定为T91钢奥氏体向马氏体转变的下临界冷却速度.     

Synthesis and thermal expansion hysteresis of Ca<Subscript>1-x</Subscript>Sr<Subscript>x</Subscript>Zr<Subscript>4</Subscript>P<Subscript>6</Subscript>O<Subscript>24</Subscript>

The low thermal expansion ceramic system, Ca_1-xSr{x}Zr₄P₆O₂₄, for the compositions with x = 0, 0.25, 0.50, 0.75 and 1 was synthesized by solid-state reaction. The sintering characteristics were ascertained by bulk density measurements. The fracture surface microstructure examined by scanning electron microscopy showed the average grain size of 2.47 μm for all the compositions. The thermal expansion data for these ceramic systems over the temperature range 25–800°C is reported. The sinterability of various solid solutions and the hysteresis in dilatometric behaviour are shown to be related to the crystallographic thermal expansion anisotropy. A steady increase in the amount of porosity and critical grain size with increase in x is suggested to explain the observed decrease in the hysteresis.     

The physical interpretation of the parameters measured during the tensile testing of materials at elevated temperatures

Hot tensile (or compression) testing, where the stress developed in a material is measured under an imposed strain rate, is often used as an alternative to conventional creep testing. The advantages of the hot tensile test are that its duration can be more closely controlled by the experimenter and also that the technique is more convenient, since high precision testing machines are available. These factors can be particularly important when extensive testing programmes of radioactive samples are involved. The main disadvantage is that the interpretation of results is more complex. Confusion can easily arise when attempts are made to extend the use of parameters which satisfactorily categorize behaviour at lower temperatures, into regimes where concurrent thermal recovery can occur. The present paper relates the parameters which are measured in hot tensile tests, to physical processes which occur in materials deforming by a variety of mechanisms. For cases where no significant structural changes occur, as in viscous or superplastic flow, analytical expressions are derived which relate the stresses measured in these tests to material constants. When deformation is controlled by recovery processes, account has to be taken of the structural changes which occur concurrently. A wide variety of behaviour may then be exhibited which depends on the initial dislocation density, the presence of second-phase particles and the relative values of the recovery rate parameters and the velocity imposed by the testing machine. Numerical examples are provided for simple recovery models.     

Solid state reactions of cordierite precursor oxides and effect of CaO doping on the thermal expansion behaviour of cordierite honeycomb structures

The extruded cordierite honeycomb structure from a stoichiometric formulation of talc, kaolinite, and alumina was subjected to TGA-DSC, dilatometric and XRD investigations. The experimental observations were made to identify the phase transformation sequence in order to understand the solid state reactions involved in the cordierite formation. A maximum cordierite content of 90% was achieved for the samples sintered at 1693 K with a soaking time of 4 h, corresponding to a lowest coefficient of thermal expansion (CTE) of 0.74 × 10^–6/K (along the direction of extrusion) was observed. Attempts were made to establish correlations with cordierite content, processing temperature and CTE of the samples. A few mechanisms are proposed to explain our observations. Attempts are also made to rationalize the low CTE observed along the direction of extrusion on the basis of orientation of anisotropic cordierite crystals as revealed by the transverse I-ratio calculated from the XRD patterns. Effect of CaO doping on CTE of cordierite has been studied in the present work. It was observed that though there is an increase in bulk thermal expansion of cordierite honeycombs on CaO doping due to the absence of micro-cracks as reveled by thermal cycling hysteresis, axial anisotropy was found to be reduced significantly.     

单侧变截面辊弯成形系统的运动分析

对直线电机驱动的单侧变截面辊弯成形系统进行了运动分析。应用正解法分析了末端轧辊的位移、速度、加速度等受直线电机相关参数的影响,并列出了相关的运动方程。应用Matlab语言描绘出了末端轧辊的运动参数的变化曲线,通过曲线对比,分析了直线电机的各个运动参数的变化对末端轧辊速度、加速度等影响;分析并探讨了有关的结构参数的变化对末端轧辊的位移、速度、加速度的影响。     

Effective Thermal Conductivity and Heat Transfer Characteristics of a Series of Ceramic Triply Periodic Minimal Surface Lattice Structure

Triply periodic minimal surface (TPMS) structures with high surface area, high porosity, complex pore channels, and pore size distribution have great potential for application in thermal metamaterials and thermal engineering applications. To demonstrate the possibility of the use of TPMS structures as thermal metamaterials, the thermal insulation properties and heat transfer mechanisms of TPMS structures are investigated in detail. The results show that modulation of the volume fraction to within 15% by a rational geometric design indicates the possibility to obtain excellent lightweight properties. The effective thermal conductivity is within 0.25 W m⁻¹ K⁻¹, which is much lower than this component, indicating that the TPMS structure is designed to reduce the effective thermal conductivity and provide a lightweight design. However, in a high-temperature environment, reasonable structural parameters can shield the cavity radiation in the TPMS structure and play an effective role to provide high-temperature thermal insulation. Finally, based on the relationship between structural parameters and thermal insulation performance, a dynamic density TPMS-graded structure is proposed, which exhibits a better thermal insulation performance than the conventional TPMS structure both at room temperature and at high temperature.     

Application of inert radioactive gases in the study of solids

Two methods based on the release of inert radioactive gases were used to study processes taking place on heating of solids: the classical emanation method and the surface labelling method. The results obtained with the use of these methods are compared for the study of (a) substances which do not change chemically when being heated in the temperature range studied (e.g. -Fe₂O₃), (b) substances in which dehydration and thermal decomposition takes place (e.g. Th(C₂O₄).6H₂O).For substances which exhibit chemical and structural changes when being heated, results of investigation by means of the two above mentioned radiochemical methods are compared with DTA and dilatometric data, obtained under identical experimental conditions. Apparatus permitting simultaneous measurement of the release of two radioactive gases, DTA and dilatometric measurement is described.From the substances which do not change when being heated, values of the activation energy of diffusion of inert gases incorporated by different ways are discussed. The advantages of the emanation and surface labelling methods over other physico-chemical methods are given and the possibilities of their application for the study of processes taking place in solids on heating, are described.The experimental part of this study was carried out during the author's stay at the Radiochemistry Dept, Moscow State University.     

Kinetics and dilatometric behaviour of non-isothermal ferrite–austenite transformation

Abstract

A model that describes the ferrite–austenite transformation during continuous heating in Armco iron and three very low carbon, low manganese steels with a fully ferritic initial microstructure is presented. This model allows calculation of the volume fractions of austenite and ferrite during transformation as a function of temperature, and hence knowledge of the austenite formation kinetics under non-isothermal conditions in fully ferritic steels. Moreover, since dilatometric analysis is a technique very often used to study phase transformations in steels, a second model, which describes the dilatometric behaviour of the material and calculates the relative change in length that occurs during the ferrite–austenite transformation, has also been developed. Both kinetics and dilatometric models have been validated by comparison of theoretical and experimental dilatometric heating curves. Predicted and experimental results are in satisfactory agreement.     

近场地震下隔震结构基底发生碰撞的鲁棒易损性曲线计算

用凸集模型模拟隔震结构参数(如刚度、质量、支座的屈服力和屈服后刚度等)的不确定性,而用随机模型模拟地震动输入的不确定性,提出了计算近场地震作用下在考虑双不确定性因素时隔震结构基底发生碰撞的易损性曲线计算新方法;提出了鲁棒易损性曲线的新概念,计算结果将给隔震支座力学参数的设计以及基底与限位墙之间空隙宽度的选取提供参考;通过计算实例中基底最大位移敏感度分析发现,上部结构的质量和隔震支座的力学参数(如屈服力、屈服后刚度等)对基底最大位移影响较大,而上部结构的刚度对其影响不大;此外,该文的研究内容也为考虑结构参数和输入地震动双不确定性因素的情况下,计算各类结构地震易损性曲线提供了一种新的思路和途径。     

65Mn钢奥氏体连续冷却转变曲线(CCT图)

利用膨胀法结合金相--硬度法,在Gleeble-1500热模拟机上测定了65Mn钢的临界点Ar1、Ar3、Ac1和Ac3以及Ms;测定了该钢在不同冷却速度下连续冷却时的膨胀曲线,获得了该钢的连续冷却转变曲线(CCT曲线);研究了65Mn钢连续冷却过程中奥氏体转变过程及转变产物的组织和性能,大致确定了避免网状铁素体、贝氏体以及魏氏组织铁素体的冷却速度,找出了生产65Mn钢盘条的控冷速度范围,为生产实践和新工艺的制定提供了参考依据.