Viscous behaviour of glass-forming liquids: a thermodynamic approach

The temperature dependence of the viscosity of the undercooled melts exhibits an important role in the study of nucleation, crystal growth and the glass-forming ability of materials. Several attempts have been made to study the viscous behaviour of the glass-forming melts and these investigations are mainly based on free volume theory as well as on the configurational entropy model. In the present investigation, an attempt has been made to correlate the thermodynamic parameters with the viscosity of the glass-forming melts and to study the temperature dependence of the viscosity of undercooled liquids on the basis of the free volume theory as well as on the basis of the configurational entropy model of Adam and Gibbs. The entire study is confined on the expression for thermodynamic parameters reported by the authors recently. The expression obtained has been successfully applied to study the temperature dependence of the viscosity of the metallic, molecular and oxide glass-forming liquids.     

Thermodynamic Assessment of DyCl3-MCl （M= Na, K, Rb, Cs） Systems

Using the CALPHAD （Calculation of Phase Diagram） technique, the DyCl3-MCl （M = Na, K, Rb, Cs） systems were optimized and calculated. The modified quasi-chemical model in the pair approximation for short-range ordering was used to describe the Gibbs energies of the liquid phase in these systems. From the measured phase diagram data and experimental thermodynamic properties, a series of thermodynamic functions were optimized base on an interactive computer-assisted analysis. The optimized parameters and the experimental data were thermodynamically self-consistent. The optimized results were discussed.     

中性红的光谱电化学研究

用ＦＯＳＥＣＳ研究了中性红的光谱电化学特性，测定了它的热力学函数、条件平衡常数和参加电极反应的Ｈ＾＋数，其结果与文献值一致。     

A Methionine Chemical Shift Based Order Parameter Characterizing Global Protein Dynamics

Coupling of side chain dynamics over long distances is an important component of allostery. Methionine side chains show the largest intrinsic flexibility among methyl-containing residues but the actual degree of conformational averaging depends on the proximity and mobility of neighboring residues. The ¹³C NMR chemical shifts of the methyl groups of methionine residues located at long distances in the same protein show a similar scaling with respect to the values predicted from the static X-ray structure by quantum methods. This results in a good linear correlation between calculated and observed chemical shifts. The slope is protein dependent and ranges from zero for the highly flexible calmodulin to 0.7 for the much more rigid calcineurin catalytic domain. The linear correlation is indicative of a similar level of side-chain conformational averaging over long distances, and the slope of the correlation line can be interpreted as an order parameter of the global side-chain flexibility.     

GCr15SiMn轴承钢中大尺寸TiN生成与控制

 以西宁特钢EAF→LF→VD→IC工艺路线生产GCr15SiMn轴承钢为研究背景,采用矿物解离分析仪、夹杂物自动分析系统、化学分析及X射线荧光光谱仪等检测手段与热力学计算相结合的方法,研究了铸锭中大尺寸TiN夹杂物的析出机理,分析了冶炼阶段钢液中钛含量增加的原因,并提出了相应的改进工艺。通过对轴承钢中残余钛、氮含量的热力学计算,发现大尺寸TiN主要是在凝固过程中析出和长大,降低冶炼过程中钛含量是控制TiN生成的主要途径。对原工艺冶炼过程钛含量变化进行分析,钢液中钛增量主要发生在EAF出钢→LF结束阶段,其中52%钛增量来自于炉渣。为了避免炉渣中钛进入钢液,借助于七元炉渣CaO-SiO₂-MgO-FeO-Al₂O₃-MnO-TiO₂与钢液之间平衡的钛分配比(LTi)模型,计算了铝含量和炉渣中CaO含量对LTi 的影响,预测了最佳的平衡炉渣成分。结果表明,适当降低铝含量和炉渣中CaO含量可以提高渣-钢之间的钛分配比,降低钢液的钛含量;当铝质量分数为0.015%～0.025%、CaO质量分数为50%～55%时,其他炉渣组元的最佳成分(质量分数)为18%～24% Al₂O₃和12%～17% SiO₂。此外,定量描述了不同LTi条件下EAF下渣量与LF终点钛含量的关系。最后,采用“低炉渣碱度、低铝含量以及严格控制电炉下渣量”的改进措施进行了优化试验,优化后冶炼终点钛质量分数可控制在小于0.002 0%,铸锭TiN平均数密度可由原工艺的2.09个/mm2降低至0.73个/mm2,且TiN尺寸几乎都小于10 μm。     

电弧炉短流程冶炼石油套管钢中夹杂物的演变规律

为研究石油套管钢(34Mn6)中夹杂物的演变规律,对钙处理效果进行精准化控制,进行全流程取样分析,通过采用SEM-EDS分析夹杂物形貌和成分,同时结合Aspex夹杂物自动分析仪统计夹杂物的数量、成分和尺寸分布。研究结果表明,LF精炼具有较好的脱硫与脱氧能力;钙处理前,由于渣钢反应的进行,夹杂物数量明显减少,夹杂物成分中SiO₂含量增加;经过钙处理后,夹杂物成分发生显著变化,由MgO-Al₂O₃系转变为MgO-Al₂O₃-CaO系和SiO₂-Al₂O₃-CaO系,夹杂物形貌由尖角夹杂向球状夹杂过渡。在铸坯中,夹杂物数量减少,其成分已偏离液相区,向富CaO区域移动。对钙处理进行优化,通过利用热力学软件FactSage进行计算,得出钢液中钙的质量分数稳定在0.001 3%时对夹杂物的改性效果最佳,钢液中的夹杂物控制较好。     

FRECKLE FORMATION AND CHARACTERIZATION OF A Ni-Cr-Mo-Fe-W ALLOY

The freckle formation and their phase characterization in freckle areas were investigated by means of microstructure analysis approaches and a thermodynamic equilibrium phase calculation method in a Ni-Cr-Mo-Fe-W alloy. These results show that in freckle areas a large number of M6 C, u and P phases precipitate in grain boundaries even within grain due to the enrichment and segregation of Mo and C during solidification, which results in small grains in freckle areas. Equilibrium phase and liquid segregation calculation can give an reasonable interpretation of the freckle feature for this alloy.     

Thermodynamic study of the phase equilibria in the Sn−Ti−Zn ternary system

The Sn−Ti−Zn ternary phase diagram has been constructed using the CALPHAD technique. The Ti−Zn binary system phase boundaries were determined using differential scanning calorimetry and the solid-liquid diffusion couples method. In addition, the formation energy of some stoichiometric compounds was obtained using first-principle band energy calculations. For the ternary system, some alloys were prepared by equilibration at 600 or 700 °C, and the compositions of the precipitates were analyzed using electron probe microanalysis. Thermodynamic assessment of the Ti−Zn and Sn−Ti−Zn systems was performed based on the experimental information and by adopting reported values of the thermodynamic properties of the Sn−Zn and Sn−Ti binary systems. Microstructural observation showed that Sn₃Ti₅Zn₁₂ exists in the ternary system. Seven types of invariant reaction on the Sn-rich liquidus surface of the ternary system are predicted by the phase diagram calculations. The ternary eutectic point falls at 0,0009 mass% Ti and 8.69 mass% Zn, at T=192.40°C, which is slightly lower than the calculated eutectic point of Sn−Zn binary alloy (T=192.41°C). Based on these results, a nonequilibrium solidification process using the Scheil model was simulated. This paper was presented at the International Symposium on User Aspects of Phase Diagrams, Materials Solutions Conference and Exposition, Columbus, Ohio, 18–20 October, 2004.     

First-principles calculation of phase equilibria and phase separation of the Fe-Ni alloy system

Theoretical investigation of the phase equilibria of the Fe-Ni alloy has been performed by combining the FLAPW total energy calculations and the Cluster Variation Method through the Cluster Expansion Method. The calculations have proved the stabilization of the LIE phase at 1：3 stoichiometry, which is in agreement with the experimental result, and predicted the existence of L1 0 as a stable phase below 550 K; this L1 0 phase has been missing in the conventional phase diagram. The calculations are extended to the Fe-rich region that is characterized by a wide range phase separation and has drawn considerable attention because of the intriguing Invar property associated with a Fe concentration of 65%. To reveal the origin of the phase separation, a P-V curve in an entire concentration range is derived by the second derivative of free energy functional of the disordered phase with respect to the volume. The calculation confirmed that the phase separation is caused by the breakdown of the mechanical-stability criterion. The newly calculated phase separation line combined with the L1 0 and L12Eorder-disordered phase boundaries provides phase equilibria in the wider concentration range of the system. Furthermore, a coefficient of thermal expansion （CTE） is attempted by incorporating the thermal vibration effect through harmonic approximation of the Debye-Gruneisen model. The Invar behavior has been reproduced, and the origin of this anomalous volume change has been discussed.     

ATOMISTIC SIMULATIONS FOR Ni/Al INTERMETALLICS

ＡＴＯＭＩＳＴＩＣＳＩＭＵＬＡＴＩＯＮＳＦＯＲＮｉ／ＡｌＩＮＴＥＲＭＥＴＡＬＬＩＣＳＢＡＳＫＥＳＭ．Ｉ．（ＳａｎｄｉａＮａｔｉｏｎａｌＬａｂｏｒａｔｏｒｉｅｓ，Ｌｉｖｅｒｍｏｒｅ，Ｃａｌｉｆｏｒｍｉａ）Ａｂｓｔｒａｃｔ：ＡｌａｒｇｅｎｕｍｂｅｒｏｆＥ...