R-curves determination of ordinary refractory ceramics assisted by digital image correlation method

As a figure-of-merit, the rising ratio of crack propagation resistance to fracture initiation resistance indicates a reduction of the brittleness and enhances the thermal shock resistance of ordinary refractory ceramics. The significant nonlinear fracture behaviour is related to the development of a fracture process zone (FPZ). The universal dimensionless load–displacement diagram method is applied as a promising graphical method for the determination of R-curves for magnesia refractories showing different brittleness. By applying digital image correlation (DIC) together with the graphical method, the problems arisen with accurate determination of the fracture initiation resistance and the crack length are overcome. Meanwhile, the R-curve is subdivided with respect to the fracture processes, viz the fracture initiation, the development of FPZ and the onset of traction free macro-crack. With the simultaneous crack lengths evaluated from DIC, the contribution of each fracture process to the crack propagation resistance at certain loading stage is quantitatively presented.     

Effect of Solute Elements and Cooling Rate on Strain in Brittle Temperature Range of Continuously Cast Strand

A micro-segregation model of solute elements in mushy zone withδ/γtransformation during solidification was established based on the regular hexagon transverse cross section of dendrite shape proposed by finite difference method under the non-equilibrium solidification condition.The model was used to calculate the non-equilibrium pseudo binary Fe-C phase diagram and the strain of steels induced by variation of temperature in brittle temperature range.On the basis of the phase diagram and the strain,the strain curve in brittle temperature range as a function of carbon content for continuously cast strand was introduced and obtained.Solute elements change the position of the strain curve.And cooling rate changes the position and the shape of the strain curve.The comprehensive formula of the strain as functions of solute elements and cooling rate in brittle temperature range has been obtained by nonlinear fitting program.     

铁素体渗氮工艺模拟

纯铁的莱勒图被广泛用于选择合金钢的渗氮工艺。本文首次采用计算热力学来确定AISI 4140钢的莱勒图。研究表明，AISI 4140钢的莱勒图与纯铁的存在明显差异。对AISI 4140钢进行了渗氮试验，目的是验证计算热力学的预测结果。扫描电镜结果显示化合物层中存在两种相，利用透射电镜对化合物层与扩散层界面的研究结果证实了γ′-Fe4N和ε-Fe2－3（C，N）相的共存。这些试验结果与用计算热力学建立的AISI 4140钢莱勒图高度吻合。     

Ni-Co-Sn三元系相平衡的实验研究

本实验通过采用电子探针显微分析和X-ray衍射分析方法实验研究了Ni-Co-Sn三元体系在700°C和1000°C时的相平衡。在这两个温度截面中均未发现三元化合物。βCo3Sn2相和Ni3Sn2（h）相形成了一个贯穿连续固溶体相。Ni-Sn侧包含Ni3Sn（l）、Ni3Sn（h）和Ni3Sn4三个化合物相，它们中Sn的固溶度是有很大区别的。700°C时，Co在Ni3Sn（l）和Ni3Sn4中的最大固溶度在分别约为6.9 at.%和25.6 at.%，在1000°C时，Co在Ni3Sn（h）中的最大固溶度约为15.5 at.%。在700℃和1000℃下，Ni-Co侧的（αCo，Ni）相为一个贯穿连续固溶体相，并且Sn在（αCo，Ni）相中的固溶度约为1 at.% ~10.5 at.%。Ni在线性化合物CoSn相中的溶解度约为15.9 at.%。     

Thermodynamic modeling and phase diagram prediction of salt lake brine systems. I. Aqueous Mg2+–Ca2+–Cl− binary and ternary systems

Salt lake brine is a complex salt-water system under natural environment. Although many models can express the thermodynamic properties and phase equilibrium of electrolyte aqueous solution, the multi-temperature characteristics and predictability are still the goals of model development. In this study, a comprehensive thermodynamic model system is re-established based on the eNRTL model and some improvements: (1) new expression of long-range electrostatic term with symmetrical reference state is proposed to handle the electrolyte solution covering entire concentration range; (2) the temperature dependence of the binary interaction parameters is formulated with a Gibbs Helmholtz expression containing three temperature coefficients, the liquid parameters, which associated with Gibbs energy, enthalpy, and heat capacity contribution; and (3) liquid parameters and solid species data are regressed from properties and solubility data at full temperature range. Together the activity coefficient model, property models and parameters of liquid and solid offer a comprehensive thermodynamic model system for the typical bittern of MgCl₂–CaCl₂–H₂O binary and ternary systems, and it shows excellent agreement with the literature data for the ternary and binary systems. The successful prediction of complete phase diagram of ternary system shows that the model has the ability to deal with high concentration and high non-ideality system, and the ability to extrapolate the temperature.     

Phase equilibria of Co−Mo−Zn ternary system

To experimentally determine the isothermal sections of Co−Mo−Zn ternary system at 600 and 450 °C, the equilibrated alloy and diffusion couple methods were adopted by using scanning electron microscopy coupled with energy-dispersive spectrometry, X-ray diffractometry and electron probe microanalysis. Experimental results show that there are six three-phase regions on the Co−Mo−Zn isothermal section at 600 °C and nine three-phase regions on the Co−Mo−Zn isothermal section at 450 °C. No ternary compound is found in these two isothermal sections. Both the maximum solubilities of Mo in the Co−Zn compounds (γ-Co₅Zn₂₁, γ₁-CoZn₇, γ₂-CoZn₁₃ and β₁-CoZn) and that of Zn in ε-Co₃Mo are no more than 1.5 at.%. The maximum solubilities of Zn in μ-Co₇Mo₆ are determined to be 2.1 at.% and 2.7 at.% at 600 and 450 °C, respectively. In addition, the maximum solubilities of Co in MoZn₇ and MoZn₂₂ are 0.5 at.% and 4.7 at.% at 450 °C, respectively.     

Phase diagram of the Li2SO4–Na2SO4 system

The thermal analysis and X-ray powder diffraction studies of the Li₂SO₄–Na₂SO₄ system, including the high-temperature X-ray diffraction technique, have elucidated four phases of variable composition: three solid solutions based on the α-Li₂SO₄, α-Na₂SO₄, and α-LiNaSO₄ high-temperature polymorphs, and a low-temperature β-LiNaSO₄ phase. α-Na₂SO₄-Base solid solution disintegrates into two phases via a monotectoid phase transformation. It is quite probable that the monotectoid process is related to the conversion of the second-order phase transition to the first-order phase transition.     

Phase equilibria in CaNaPO4-CaKPO4 system and their influence on formation of bioceramics based on mixed Ca-K-Na phosphates

An investigation of the two-component phase diagram of the CaNaPO₄- CaKPO₄system performed using various analysis techniques is reported. The continuous solid solution series of α-CaMPO₄ existing above 700 °C undergoes eutectoid decomposition during cooling to β-CaMPO₄-based solid solutions enriched with Na and K, and to an intermediate nonstoichiometric compound with an ideal composition of CaK_0.6Na_0.4PO₄. All three compounds exhibit significant volumetric effects associated with first-order phase transitions, with positive volume changes under cooling for the intermediate compound. Increased K content in ceramics based on CaK_yNa_1-yPO₄ compositions enhances the strength properties of those ceramics, including their fracture toughness, which is associated with increased density. Increased K content also has a smaller effect of inducing phase transformations accompanied by strong volume changes.     

Feasibility of high performance in p-type Ge1−xBixTe materials for thermoelectric modules

GeTe is a promising candidate for the fabrication of high-temperature segments for p-type thermoelectric (TE) legs. The main restriction for the widespread use of this material in TE devices is high carrier concentration (up to ∼ 10²¹ cm⁻³), which causes the low Seebeck coefficient and high electronic component of thermal conductivity. In this work, the band structure diagram and phase equilibria data have been effectively used to attune the carrier concentration and to obtain the high TE performance. The Ge_1−xBi_xTe (x = 0.04) material prepared by the Spark plasma sintering (SPS) technique demonstrates a high power factor accompanied by moderate thermal conductivity. As a result, a significantly higher dimensionless TE figure of merit ZT = 2.0 has been obtained at ∼ 800 K. Moreover, we are the first to propose that application of the developed Ge_1−xBi_xTe (x = 0.04) material in the TE unicouple should be accompanied by SnTe and CoGe₂ transition layers. Only such a unique solution for the TE unicouple makes it possible to prevent the negative effects of high contact resistance and chemical diffusion between the segments at high temperatures.     

Trace element distributions between matte and slag in direct nickel matte smelting

ABSTRACT

Behaviour of trace elements in the nickel matte smelting was studied at 1673 K (1400°C) by equilibration-quenching techniques followed by direct phase analyses using electron probe X-ray microanalysis and laser ablation-inductively coupled plasma-mass spectrometry. The matte-slag samples at silica saturation were equilibrated with SO₂-CO-CO₂-Ar mixtures of fixed p_SO2, p_S2 and p_O2 in order to obtain a pre-determined oxidation degree for the sulphide matte, and thus to generate a targeted iron concentration of the nickel-copper–iron sulphide matte (Ni:Cu = 5, w/w), depending on the slag chemistry. The slag composition was varied from 0 to 2 wt-% K₂O and 0–10 wt-% MgO in silica saturation. The studied trace elements were Co, Ge, Pb, Se and Sn, but also the matte-to-slag distributions of the slag forming fluxing components Mg (MgO) and Si (SiO₂) were determined experimentally. Selenium was the only trace element studied which strongly enriched in the low-iron nickel mattes, and the deportment became larger when the sulphide matte depleted with iron. All the other trace elements behaved in the opposite way.