Estimation of Gibbs free energy difference in Pd-based bulk metallic glasses

A new thermodynamic expression for Gibbs free energy difference AG between the under-cooled liquid and the corresponding crystals of bulk metallic glasses was derived. The newly proposed expression always gives results in fairly good agreement with experimental values over entire temperature range between the fusion temperature Tm and the glass transition temperature Tg of Pd40Ni40P20, Pd40Cu30Ni10P20 and Pd43Cu27Ni10P20, which possess different heat capacities. However, the TS and KN expressions cannot always provide results in good agreement with the experimental values. In addition, the deviations between the experimental values and the AG calculated by the proposed expression at Tg are smaller than those given by other expressions for all the bulk metallic glasses studied.

Thermodynamic Equilibrium of the Saturated Fluid with a Free Surface Area and the Internal Energy as a Function of the Phase-Specific Volumes and Vapor Pressure

This study is concerned with describing the thermodynamic equilibrium of the saturated fluid with and without a free surface area A. Discussion of the role of A as system variable of the interface phase and an estimate of the ratio of the respective free energies of systems with and without A show that the system variables given by Gibbs suffice to describe the volumetric properties of the fluid. The well-known Gibbsian expressions for the internal energies of the two-phase fluid, namely for the vapor and for the condensate (liquid or solid), only differ with respect to the phase-specific volumes and . The saturation temperature T, vapor presssure p, and chemical potential are intensive parameters, each of which has the same value everywhere within the fluid, and hence are phase-independent quantities. If one succeeds in representing as a function of and , then the internal energies can also be described by expressions that only differ from one another with respect to their dependence on and . Here it is shown that can be uniquely expressed by the volume function . Therefore, the internal energies can be represented explicitly as functions of the vapor pressure and volumes of the saturated vapor and condensate and are absolutely determined. The hitherto existing problem of applied thermodynamics, calculating the internal energy from the measurable quantities T, p, , and , is thus solved. The same method applies to the calculation of the entropy, chemical potential, and heat capacity.

利福霉素S的固液相平衡和溶解热力学

在288.15-323.15 K温度范围内,采用静态法测定了利福霉素S在5种纯有机溶剂(乙醇、异丙醇、正丁醇、乙酸乙酯和乙酸丁酯)中的溶解度,结果显示:利福霉素S在5种溶剂中的溶解度均随温度的升高而增大。使用修正Apelblat方程对溶解度的实验值进行了关联,并采用X射线衍射仪测定利福霉素S的晶型。在范特霍夫方程的基础上,对溶解过程中相关的热力学参数进行了估算,所得的溶解焓和吉布斯自由能均为正值,从而说明该过程是吸热的,而当溶液饱和后继续溶解是需要吸收能量的;并且分析了溶解过程中不同溶剂条件下焓与熵的贡献率。为制得纯度更高的利福霉素S,整体优化利福平合成工艺提供了理论指导。

Effects of Microalloying on Glass Forming Ability and Thermodynamic Fragility of Cu-Pr-Based Amorphous Alloys

The effects of microalloying of Ti and B on the glass formation of Cu60Pr30Ni10Al10-2xTixBx（x = 0, 0.05% （atom fraction）） amorphous alloys was investigated using differential scanning calorimetry （DSC） and X-ray diffraction （XRD）. XRD analysis showed that mieroalloying with 0.05% Ti and 0.05% B improved the glass forming ability （GFA）. The smaller difference in the Gibbs free energy between the liquid and crystalline states at the glass transition temperature （△G1-X（Tg）） and the smaller thermodynamic fragility index （△Sf/Tm, where ASf is the entropy of fusion, and Tm is the melting temperature） after mieroalloying correlated with the higher GFA.

Oxidation Kinetics of Aluminum Powders in a Gas Fluidized Bed Reactor in the Potential Application of Surge Arresting Materials

In this technical paper, the oxidation mechanism and kinetics of aluminum powders are discussed in great details. The potential applications of spherical aluminum powders after oxidation to be part of the surging arresting materials are discussed. Theoretical calculations of oxidation of spherical aluminum powders in a typical gas fluidization bed are demonstrated. Computer software written by the author is used to carry out the basic calculations of important parameters of a gas fluidization bed at different temperatures. A mathematical model of the dynamic system in a gas fluidization bed is developed and the analytical solution is obtained. The mathematical model can be used to estimate aluminum oxide thickness at a defined temperature. The mathematical model created in this study is evaluated and confirmed consistently with the experimental results on a gas fluidization bed. Detail technical discussion of the oxidation mechanism of aluminum is carried out. The mathematical deviations of the mathematical modeling have demonstrated in great details. This mathematical model developed in this study and validated with experimental results can bring a great value for the quantitative analysis of a gas fluidization bed in general from a theoretical point of view. It can be applied for the oxidation not only for aluminum spherical powders, but also for other spherical metal powders. The mathematical model developed can further enhance the applications of gas fluidization technology. In addition to the development of mathematical modeling of a gas fluidization bed reactor, the formation of oxide film through diffusion on both planar and spherical aluminum surfaces is analyzed through a thorough mathematical deviation using diffusion theory and Laplace transformation. The dominant defects and their impact to oxidation of aluminum are also discussed in detail. The well-controlled oxidation film on spherical metal powders such as aluminum and other metal spherical powders can potentially become an important part of switch devices of surge arresting materials, in general.

拟抛物面规则在氧化物陶瓷相图中的应用

运用三元系拟抛物面规则：（１）分析了氧化物三元系中热力学数据的正误；（２）判断了复杂氧化物的稳定性；（３）初步估计或预报了一些复杂氧化物的热力学数据。

热力学在无机化学“四大平衡”教学中的应用

利用化学反应吉布斯自由能变化?_rG_m~?来计算无机化学"四大平衡"的平衡常数,解释诸如沉淀-溶解平衡教学中为什么要求微溶强电解质等问题,并从化学反应等温式类推了电极反应的等温式,推导了复杂电极的标准电极电势与其简单电极的标准电极电势之间的关系,拓展了热力学在现行基础化学教学上的应用范围。

La基非晶合金的固液自由能差估计

根据热力学理论推导出了可以用于估计La基(如La55Cu15Ni5Al25,La55Cu10Ni5Al25Co5,La55Al25Ni20 and La55Cu10Ni10Al25)非晶合金固液自由能差的表达式。当La55Cu15Ni5Al25、La55Cu10Ni5Al25Co5、La55Al25Ni20和La55Cu10Ni10Al25的α值分别为0．52、0．3、0．2和0．15时,这个表达式给出的理论结果在很大的过冷区间几乎与实验测定结果重合,远远优于其它表达式给出的结果,并且其重合的最低温度可以分别达到350K(La55Al25Ni20)、450K(La55Cu10Ni5Al25Co5)、370K (La55Cu10Ni10Al25)和200K(La55Cu15Ni5Al25);另一方面,提出了用于估计非晶合金的库兹曼温度TA的表达式,即TA=Tmexp(α-1),发现此表达示估计的TA与通过实验数据计算出的吻合得很好。