Application of annexation principle to the study of thermodynamic properties of Ag—Bi—In metallic melts

Based on the measured activities,the phase diagrams and the annexation principle,the calculating models of mass action concentrations for Ag-Bi and Ag-Bi-In melts have been formulated.The calculated results agree with practice and obey the mass action law,showing that the models formulated can reflect the structural characteristics of both melts.Meanwhile,it confirms that annexation principle is applicable to the Ag-Bi-In metallic melts.The melts involving eutectic which give rise to phase separation,and in which activcities exhibit positive deviation from Raoult‘s law is the basic cause of melts transforming from homogeneous to heterogeneous ones.     

Application of annexation principle to the study of thermodynamic properties of Ag-Bi-In metallic melts

Based on the measured activities, the phase diagrams and the annexation principle, the calculating models of mass action concentrations for Ag-Bi and Ag-Bi-In melts have been formulated. The calculated results agree with practice and obey the mass action law, showing that the models formulated can reflect the structural characteristics of both melts. Meanwhile, it confirms that annexation principle is applicable to the Ag-Bi-In metallic melts. The melts involving eulectic which give rise to phase separation, and in which activities exhibit positive deviation from Raoult's law is the basic cause of melts transforming from homogeneous to heterogeneous ones.     

纳米金属微粒的热力学性质研究

电子的分立能级和宇称效应是纳米颗粒的两个重要特征,它们强烈影响纳米金属颗粒的热力学性质.根据随机矩阵理论,考虑能级统计的影响,基于正则系综计算了具有奇数或偶数个电子的纳米金属颗粒的比热和自旋磁化率,并讨论了二者随温度、粒径和电子体密度的变化关系.     

五维黑弦的热力学性质和热力学几何性质

计算了五维黑弦的热容量和电容率;获得了五维黑弦的Ruppeiner几何和Weinhold几何的度规,并指出二者度规不存在共形的关系．     

Application of the annexation principle to the thermodynamic property study of ternary metallic melts In-Bi-Cu and In-Sb-Cu

Based on the phase diagrams, measured activities and the annexation principle, calculating models of mass action concentrations for In-Bi-Cu and In-Sb-Cu melts have been formulated. Calculated results not only agree well with practical values, but also obey the mass action law, showing that the deduced model can reflect the structural reality of given melts and that the annexation principle is applicable to these two ternary metallic melts. So long as there is one from three binary systems constituting the ternary melts, in which the activities of one component exhibit positive deviation relative to Raoultian behavior, heterogeous melts inevitably would form, so heterogeneous calculating model should be used to calculate their mass action concentrations. On the contrary, if all the binary melts are homogeneous and their activities exhibit negative deviation with respect to the Raoult's law, then the ternary melts formed from them will certainly be homogeneous,hence single phase model should be applied.     

Al-Zr,Al-Y和Zr-Y二元合金熔体热力学性质的计算

基于Miedema模型,利用热力学基本原理及元素的基本性质,计算Al-Zr,Al-Y和Zr-Y二元系统的混合焓、过剩熵、过剩吉布斯自由能以及各组元的活度.基于Al-Zr和Al-Y二元合金相图的数据,计算Al3Zr和Al3Y相析出反应的吉布斯自由能.研究结果表明:Al-Zr和Al-Y二元合金熔体的混合焓、过剩熵和过剩吉布斯自由能都小于0J,各组元的活度相对于理想溶液发生了较大的负偏差,而Zr-Y二元合金熔体的混合焓、过剩熵和过剩吉布斯自由能大于0J,各组元的活度相对于理想溶液发生了较大的正偏差,说明Al与Zr和Y原子有较强的相互作用,而Zr和Y原子相互作用不大.2种相析出反应的吉布斯自由能都小于0J,且Al3Y相的吉布斯自由能更小,表明过渡族元素Zr和稀土元素Y同时加入到纯Al时,更容易生成Al3Y;计算结果和实验结果相吻合,证明Miedema模型的合理性.     

ZrC的电子结构与热力学性质

运用基于密度泛函理论的超软赝势平面波方法对ZrC原胞体系的结构进行几何优化,得到了稳定体系的电子结构。利用能量与体积的函数关系得到稳定体系的晶格常数,然后利用准谐德拜模型研究了ZrC在温度为0～3 500 K和压强为0～200 GPa下的热力学性质,得到ZrC的相对体积、体胀系数、热容、熵、德拜温度和Gruneisen参数随温度与压强的变化关系。     

1,1,1,2,3,3,3-七氟丙烷的热力性质

为获得不破坏臭氧层的环保工质的热物性数据 ,对HFC- 2 2 7ea的热力学性质进行了研究 ,精确测量了 2 43～375 K的饱和蒸气压 ,使用膨胀 -定容法测量了 2 78～ 377K,压力 0 .2 6～ 2 .6 MPa的 HFC- 2 2 7ea的气相 p VT性质 ,温度和压力测量的最大不确定度分别为± 10 m K和± 5 0 0 Pa。使用测量结果关联了 HFC- 2 2 7ea的蒸气压方程 ,导出了维里系数、饱和气相密度、饱和蒸发焓 ,并关联了截断维里型的状态方程用于再现 HFC- 2 2 7ea气相区的热力性质。     

面心立方和液态Au的热力学性质

运用Debye-Grüneisen模型研究纯金属Au在温度为0~298.15 K时的低温热力学性质,实现模型修正计算得到的摩尔定压热容、焓、熵和Gibbs自由能等热力学性质与SGTE纯单质数据库在298.15 K时完全对接,对该模型的热容表达式进行修正。研究结果表明:其计算结果不仅比修正前更加符合实验数据,而且与SGTE纯单质数据库完全对接,实现了对面心立方和液态Au在温度为0~3 200 K时热力学性质的完整描述。     

紫外光谱测定电荷转移络合物的热力学参数

本文用紫外光谱技术和线性回归法编制程序,用APPle计算机计算了正已烷中硝基乙烷(A)和对二甲苯(D)形成1∶1电荷转移络合物的平衡常数,其值为0.036 L/mol(298 K),与文献报道相符。根据不同温度下的平衡常数计算了络合物的生成焓、生成自由焓和熵。     

硫化镁晶体的弹性与热力学性质的研究

利用第一性原理超软赝势平面波的方法,对MgS晶体结构进行了几何优化,得到了其晶格参数为0.522 78 nm;在优化结构的基础上计算出带隙为2.873 eV,属于间接带隙半导体;零温零压下的弹性常数为C11=134.02 GPa、C12=38.5 GPa、C44=53.9 GPa及弹性模量B0=70.3 GPa;根据德拜模型近似,由弹性常量计算了德拜温度为557.2 K,并进一步得到定容热容随温度的变化关系,在高温下,热容接近杜隆-珀蒂极限.     

硫化镁晶体的弹性与热力学性质的研究

利用第一性原理超软赝势平面波的方法,对MgS晶体结构进行了几何优化,得到了其晶格参数为0.522 78 nm;在优化结构的基础上计算出带隙为2.873 eV,属于间接带隙半导体;零温零压下的弹性常数为C11=134.02 GPa、C12=38.5 GPa、C44=53.9 GPa及弹性模量B0=70.3 GPa;根据德拜模型近似,由弹性常量计算了德拜温度为557.2 K,并进一步得到定容热容随温度的变化关系,在高温下,热容接近杜隆—珀蒂极限.     

油茶籽的吸附等温线及热力学性质

为充分了解油茶籽水分含量与水分活度、温度之间的复杂关系,运用吸附原理,通过静态调整环境湿度法,研究了油茶籽不同温度下的吸附等温线,选择5种常用数学模型进行拟合,并在此基础上分析油茶籽的热力学性质.结果表明,修正Henderson模型的拟合度最高(R2=0.999 9,RMSE=0.007 1),根据该模型获知油茶籽在20,30,40℃下的相对安全水分含量和绝对安全水分含量分别为9.48%与8.00%,8.96%与7.57%,8.51%与7.19%.热力学性质显示,油茶籽的等量吸附热、吸附结合能均随平衡含水率的增加而不断下降,当平衡含水率一定时,吸附结合能随温度的升高而增大.     

液态Cu-Ni合金的超过冷与热力学性质

采用熔融玻璃净化法得到质量分数为 Cu- 2 5 % Ni,Cu- 33% Ni,Cu- 5 0 % Ni,Cu- 75 % Ni等 4种铜镍系合金的过冷度与凝固平台的关系。通过传热学分析指出凝固平台时间长度与过冷度成线性关系。在此基础上得到了这 4种成分合金的超过冷临界温度及其熔点以下液态的平均比热容。实验中 4种合金的过冷度分别达到 :381K,380 K,349K和431K。     

泡沫金属的力学性能研究综述

详细综述了泡沫金属的拉伸、压缩、能显吸收、应变率敏感性等力学性能，以及孔径、基体材料、温度、微观结构缺陷对其力学性质的影响，从而为泡沫金属的进一步的研究、开发与应用提供理论基础。     

Formation and corrosion properties of Fe-based bulk metallic glasses

Bulk metallic glass (BMG) formation was explored in the Fe-B-Si-Nb alloy system though combined use of the atomic cluster line approach and the minor alloying strategy. The basic ternary compositions in the Fe-B-Si system were determined by the intersection points of two cluster lines, namely, Fe-B cluster to Si and Fe-Si cluster to B. 3at%–4at% Nb was added to the quaternary Fe-B-Si-Nb alloy. The casting experiments revealed that good glass-forming ability (GFA) occurred at the (Fe_73.4Si_8.2B_18.4)₉₆Nb₄ composition, and 3-mm diameter BMG samples were made. The glass transition temperature (T_g), crystallization temperature (T_x), and supercooled liquid region (ΔT_x=T_x-T_g) of this BMG were measured to be 866, 889, and 23 K, respectively. The BMG shows a high Vickers hardness of about Hv 1164, a Young’s modulus of 180 GPa, and a good corrosion resistance in the solutions of 1 mol/L HCl and 3wt% NaCl.     

燃气轮机实际循环熵产分析与性能参数评价

基于热力学第二定律,引入无量纲熵产数Ns表示燃气轮机装置热力性能完善程度,对其进行热力性能熵产分析.研究了表征燃气轮机装置热力性能参数:回热度σ、温度比τ、压力比π、循环有用功系数λ等对循环性能的影响及其相互关系.结果表明,采用有回热的循环Ns相比无回热的循环Ns明显减小,且在σ较大的情况下,Ns随π增大而增大,但变化不明显,随τ增大而减小.因此可通过增大τ、增大σ(≥0.7)和适当选取π以获得较大的循环热效率ηi及较小的Ns.在较高τ的情况下,尽量提高λ,以减小Ns.     

CO2水合固化相变的热力学特性

CO2水合固化反应热的确定是实现煤体CO2水合固化防突的关键。依据ClausiusClapeyron方程和三参数对应态原理,建立CO2水合固化反应热计算模型;利用CO2水合分离实验装置,结合定温压力搜索法测定CO2水合分离相平衡参数;由CO2水合固化反应热计算模型得到实验设计体系的反应热,分析相平衡参数和SDS促进剂对CO2水合固化反应热的影响。结果表明:CO2水合固化反应具有较高反应热,且反应热的大小与相平衡参数和促进剂浓度有关。相平衡温度和相平衡压力越低,反应热越大;SDS浓度越高,反应热越低。该研究为CO2水合固化提供了技术参考。     

Thermodynamic properties and microstructural characteristics of binary Ag-Sn alloys

The liquidus and solidus temperatures and enthalpy of fusion for Ag-Sn alloys are systematically measured within the whole composition range by differential scanning calorimetry (DSC). The measured enthalpy of fusion is related to Sn content by polynomial functions, which exhibit one maximum value at 52 wt%Sn and two minimum values around 21 wt%Sn and 96.5 wt%Sn, respectively. The liquidus slope, the solidification temperature interval, the solute partition coefficient and the entropy of fusion are calculated on the basis of the measured results. The undercoolability of those liquid Ag-Sn alloys solidifying with primary (Ag) solid solution phase is stronger than the other alloys with the preferential nucleation of ζ and ε intermetallic compounds. Morphological observations reveal that peritectic reactions can rarely be completed, and the peritectic microstructures are always composed of both primary and peritectic phases.     

CaF_2晶体弹性与热力学性质的研究

利用第一性原理超软赝势平面波的方法,对CaF2晶体结构进行了几何优化,得到其晶格参数为0.548 0 nm。在优化结构的基础上计算了零温零压下的弹性常数,得到C11=154.4 GPa、C12=38.2 GPa、C44=29.9 GPa及体弹性模量B0=76.9 Gpa。根据德拜模型近似,由弹性常量计算德拜温度为489.6K,在高温下,热容接近杜隆-珀蒂极限。