基于Miedema模型和Toop模型的Al-Si-Er合金热力学参数计算

运用Miedema混合焓模型计算了Al-Er、Si-Er和Al-Si二元合金的部分热力学性质,选择Er为非对称性组元,在此基础上结合Toop模型计算出Al-Si-Er三元合金的混合焓、过剩熵与过剩自由能。结果表明,Al-Si-Er三元合金的混合焓、过剩熵与过剩自由能在整个浓度范围内均为负值,在富Er和贫Er区域各热力学参数变化趋势较大。通过计算Al、Si和Er 3种组元的偏摩尔过剩自由能得到Al-Si-Er三元合金各组元的等活度值曲线。曲线显示各组元随着摩尔分数的减少其活度值都急剧减小,在三元系成分三角形的中心部分Al、Si和Er的活度值都很小,这表明Al、Si和Er 3种组元之间存在很强的相互作用,易形成三元金属间化合物,这一结论与Al-Si-Er三元相图的实际情况相符合。     

Al-Er和Si-Er二元合金的热力学性质

以Miedema混合焓模型为基础,计算Al-Er和Si-Er二元合金的部分热力学函数,如混合焓-H,过剩熵SE以及过剩吉布斯自由能GE以及各组元的活度.结合Al-Er和Si-Er二元相图计算了Al3Er和Er5Si3相析出反应的吉布斯自由能.结果表明:Al-Er和Si-Er二元合金的混合焓、过剩自由能与过剩熵在整个浓度范围内均为负值,各组元活度计算结果相对于理想熔体有较大的负偏差,说明Er原子与Al原子和Si原子都有很强的相互作用; Al3Er和Er5Si3相反应的吉布斯自由能均为负值,且Er5Si3相的反应吉布斯自由能比Al3Er相的小,因此Er加入到Al-Si合金中会优先与Si生成Er5Si3相,过剩的Er才与Al生成Al3Er相.     

新型FeMB系纳米晶软磁材料的成分设计

运用Miedema理论,系统计算Fe,B与Cu,Mo,Ni,Cr,V,Ga,Nb,Hf和Zr等元素形成合金系时的热力学性质。运用理想溶液理论,计算1 600 K时该二元合金系的过剩Gibbs自由能、过剩熵和活度。结果表明,在FeMB体系中,Fe-Zr-B的混合焓最小;1 600 K时Fe-M-B体系的过剩Gibbs自由能与其混合焓相似,其过剩熵趋近于零,活度相对于理想溶液偏差极小,在实际应用中可忽略不计。     

MoO3—MoO2—H2O—H2系平衡及400—700℃Mo—O系相图

使用自行设计的受控气氛热重装置研究了ＭｏＯ３－ＭｏＯ２－Ｈ２Ｏ－Ｈ２系平衡，在ＰＨ２Ｏ／ＰＨ２从０．４１２至０．６０９，温度从４００至５３４℃范围内直接测定了反应：ＭｏＯ３＋Ｈ２＝ＭｏＯ２＋Ｈ２Ｏ（ｇ）的平衡常数与温度间的关系为１ｇＫｐ＝０．７０２－７３９．８／Ｔ。获得２９８．１５Ｋ下ＭｏＯ３标准生成焓及绝对熵分别为：－８４５．７５ｋＪ·ｍｏｌｅ＾－１及７８．１６Ｊ·Ｋ＾－１·ｍｏｌｅ＾－１．实验     

磷在变形IN718合金中的作用

研究了磷在变形ＩＮ７１８合金中的作用,结果表明,磷显著改善了该合金的持久性能,明显延缓蠕变进程,添加０．０２％磷可使表观蠕变激活能由６７８．６ｋＪ／ｍｏｌ提高到７４６．１Ｋｊ／ｍｏｌ,晶界扩散激活能由２７６．１ｋＪ／ｍｏｌ提高至３４９．８ｋＪ／ｍｏｌ,磷的作用起因于降低晶界能而偏聚于晶界,从而抑制晶界扩散,降低晶界结合力。     

氯化物熔体中电解制备Dy－Cu中间合金的研究

用循环伏安法、恒电位电解断电后的电极电位－时间曲线、电位阶跃法和Ｘ射线衍射法研究了Ｃｕ电极在ＮａＣｌ－ＫＣｌ－ＤｙＣｌ３熔体中的电化学行为，获知Ｄｙ在Ｃｕ电极上的还原过程是首先生成Ｄｙ－Ｃｕ合金，然后才析出纯金属Ｄｙ．测得Ｄｙ－Ｃｕ合金在１０７３Ｋ的标准生成自由能；在１０２３－１１４３Ｋ范围内，Ｄｙ原子在Ｄｙ－Ｃｕ合金相中的扩散系数与温度的关系式为ｌｎＤ＝－６７．１×１０３／ＲＴ－１５．８，其扩散活化能为６７．１ｋＪ·ｍｏｌ－１．用自耗阴极法制取了Ｄｙ－Ｃｕ中间合金并对其工艺条件进行了探讨。电解制取了含Ｄｙ高达９２％（质量分数）的Ｄｙ－Ｃｕ中间合金，其组成为ＤｙＣｕ和Ｄｙ，电流效率可达８０％．     

Ni47Ti44Nb9合金中各相的低温热容

采用精密自动绝热量热装置测定了Ｎｉ４７Ｔｉ４４Ｎｂ９和Ｎｂ８０Ｔｉ１４Ｎｉ６合金６０～３５０Ｋ温区的热容，并将热容实测值用最小二乘法进行了曲线拟合。在合金摩尔热容加和原则基础上，计算了Ｎｉ４７Ｔｉ４４Ｎｂ９合金中ＴｉＮｉ基体相的热容。Ｎｉ４７Ｔｉ４４Ｎｂ９合金在２１５～２６０Ｋ范围内发生的相变是ＴｉＮｉ相的热弹性马氏体相变。相变起始温度（Ａｓ）为２２２Ｋ，相变终了温度（Ａｆ）为２５５Ｋ，相变焓ΔＨ＝４１１．９±２．５Ｊｍｏｌ－１，相变熵ΔＳ＝１．７６±０．０１ＪＫ－１ｍｏｌ－１     

氯化物熔体中电解制备Dy—Cu中间合金的研究

用循环伏安法、恒电位电解断电后的电极电位－时间曲线、电位阶跃法和Ｘ射线衍射法研究了Ｃｕ电极在ＮａＣｌ－ＫＣｌ－ＤｙＣｌ３熔体中的电化学行为，获知Ｄｙ在Ｃｕ电极上的还原过程是首先生成Ｄｙ－Ｃｕ合金，然后才析出纯金属Ｄｙ．测得Ｄｙ－Ｃｕ合金在１０７３Ｋ的标准生成自由能；在１０２３－１１４３Ｋ范围内，Ｄｙ原子在Ｄｙ－Ｃｕ合金相中的扩散系数与温度的关系式为ｌｎＤ＝－６７．１×１０３／ＲＴ－１５．８，其扩散活化能为６７．１ｋＪ·ｍｏｌ－１．用自耗阴极法制取了Ｄｙ－Ｃｕ中间合金并对其工艺条件进行了探讨。电解制取了含Ｄｙ高达９２％（质量分数）的Ｄｙ－Ｃｕ中间合金，其组成为ＤｙＣｕ和Ｄｙ，电流效率可达８０％．     

T45Al10Nb附带 金全片层组织韧脆转变机制的研究

研究了应变速率和温度对Ｔｉ４５Ａｌ１０Ｎｂ合金的屈服强度和延伸率的影响。结果表明：随着应经升高,合金的屈服强度升高而延伸率下降,由此得到韧脆温度ＴＢＤＴ随应变束率升高而升工计算出Ｔｉ４５Ａｌ１０Ｎｂ合金韧脆转变的激活能为３３０ＫＪ／ｍｏｌ。这一数值与ｒ－ＴｉＡｌ合金中原子的自扩散激活能（２９０ＫＪ／ｍｏｌ）相当,说明Ｔｉ４５Ａｌ１０Ｎｂ合金韧脆转变过程受扩散控制的形迹机制,即位错攀移控制,ＴＥＭ形     

Zn—Mn和Zn—Ti二元合金热学性质

在考虑理论计算合金形成热的各种影响因素的基础上,用Miedeman二元合金生成热模型计算了彩色热镀锌用Zn-Mn和Zn-Ti二元溶液的混合焓△Hmix与添加元素的摩尔分数之间的关系,利用Tanaka近似关系式及一些基本热力学关系计算了上述两个二元体系的过剩混合熵△G^Emix及各组元的活度,结果表明,Zn-Mn和Zn-Ti两溶相对于理想溶液都有很大的负偏差。     

U基二元熔体的热力学计算

采用Miedema半经验模型计算了U-Nb、U-Ti及U-Zr二元熔体的混合热、过剩熵及过剩自由能等热力学性质,并根据热力学原理计算了组元U在不同温度的二元熔体中的活度值.结果表明,U-Nb,U-Ti和U-Zr熔体相对于拉乌尔定律均呈负偏差,U-Ti和U-Zr合金较U.Nb合金更易于形成中间化合物.计算结果与实验相图符合较好.     

第一性原理研究Re的热力学性质

基于准谐Debye-Grüneisen模型,运用第一性原理缀加投影平面波方法研究了Re的热力学性质,拟合了Re的状态方程,计算了Re不同压强下弹性模量、吉布斯自由能、焓、熵、热容和体膨胀系数随温度的变化关系。结果表明:采用八阶Birch-Murnaghan方程拟合得到的Re压强-体积曲线与实验测量结果吻合较好;计算的零压下吉布斯自由能、焓、熵、热容和体膨胀系数随温度的变化均与实验值符合较好;在零压,50、100、150和200GPa压强下,Re的弹性模量和吉布斯自由能随温度升高而减小;焓、熵随温度升高而增加;Re的电子等容热容随温度线性增加,晶格振动等容热容在低温下符合3T幂次规律并随温度增加而迅速增大,且在高温时逐渐接近Dulong-Petit极限;预测的德拜温度约为430K,与实验结果一致。     

Thermodynamic properties of liquid glass-forming Ca–Mg alloys

The complex formation model was used to investigate the thermodynamic properties of liquid Ca–Mg glassy alloys. Our expressions reproduce the thermodynamic functions such as free energy of mixing, enthalpy of mixing, entropy of mixing and activity ratio. The study of long wavelength concentration–concentration fluctuations (S_CC(0)) provides structural information about liquid glass-forming Ca–Mg alloys. Chemical short range order parameter (₁) was obtained from S_CC(0) to quantify the degree of order. The study reveals that the formation of more than one type of complex may be related to the process of glass formation.     

Determination of thermodynamic properties in full composition range of Ti-Al binary melts based on atom and molecule coexistence theory

The results of predicting thermodynamic properties in the full composition range of Ti-Al binary melts in a temperature range from 1973 to 2273 K were obtained by coupling with the developed thermodynamic model for calculating mass action concentration N_i of structural units in Ti-Al system based on the atom and molecule coexistence theory (AMCT). Temperature dependence of the activity coefficients of Ti and Al in natural logarithmic form in the infinitely dilute solution (0>x_Ti<0.01) of Ti-Al binary melts was also determined from the calculated activity coefficients of Ti and Al at temperatures of 1973, 2073, 2173, and 2273 K. The standard molar Gibbs free energy change of dissolving pure liquid element i(l) for forming 1% (mass fraction) element i in Ti-Al binary melts further was deduced. With the aid of this model, meanwhile, the determined excess thermodynamic properties, such as the excess molar mixing Gibbs free energy/entropy/enthalpy were also calculated.     

Ca、Sr和Ba掺杂Mg_2Si弹性性能和电子结构的第一性原理研究

采用第一性原理平面波赝势方法研究了合金元素X(X=Ca、Sr、Ba)掺杂Mg2Si的占位情况:(1)取代Mg原子位置;(2)取代Si原子位置;(3)间隙固溶到Mg2Si晶胞中。分析合金系Mg7Si4X,Mg8Si3X,Mg8Si4X的形成热和结合能可知,Mg7Si4X的形成热和结合能均为负值,且最小。表明Mg7Si4X更容易形成稳定化合物,具有较强的合金化能力,且Ca,Sr,Ba掺杂Mg2Si时有优先占据Mg原子的倾向。研究Mg7Si4X的弹性模量和电子结构发现:Mg7Si4Ca、Mg7Si4Sr为脆性相;Mg7Si4Ba为延性相,塑性最好;掺杂Ca,Sr,Ba使Mg2Si逐渐由脆性向韧性转变。Ca,Sr,Ba的掺入均使Mg2Si的电子态密度发生偏移,费米能级处的电荷密度增加,导电性增强,共价键作用减弱,合金系结构稳定性减弱。     

Calorimetric study of Cr-Ge alloys

The molar integral enthalpy of formation of Cr–Ge alloys was determined with respect to concentration at three temperatures (1305, 1273 and 1226 K) by direct reaction calorimetry (drop method) with the help of a high-temperature Tian–Calvet calorimeter. The measurements were performed on the Ge-rich side and extrapolated in the whole range of concentration. The enthalpy of formation is negative at any concentration and shows a minimum around x_Ge=0.35, in agreement with the results of Shlapak et al. (Ukr. Khim. Zh. 1979; 45; 670) at 1773 K. The minimum (extrapolated) decreases when temperature increases, showing negative excess heat capacity in the concentrated range. We observed the opposite behaviour in the Ge-rich part in agreement with the values of the partial enthalpies of the components at infinite dilution).     

玻璃纤维滤膜基纳米钛酸锶钡的制备及其对Cd2+吸附行为

采用柠檬酸络合溶胶-凝胶法制备玻璃纤维滤膜基纳米钛酸锶钡(BBST),用X射线衍射(XRD)、扫描电镜(SEM)和傅里叶变换红外光谱(FTIR)进行表征.并系统地研究玻璃纤维滤膜基钛酸锶钡对水中Cd~(2+)吸附行为.结果表明,纳米钛酸锶钡通过Si-O-Ti和B-O-Ti键与玻璃纤维滤膜结合,成为新型多孔块体吸附剂.当介质的pH值为4～8时,该吸附剂对水中的Cd~(2+)具有很强的吸附能力,吸附容量为9.8 mg·g~(-1);其吸附行为符合Freundlich吸附等温模型和HO准二级动力学方程式,吸附过程焓变(△H)为17.241 kJ·mol~(-1),各温度下的自由能变(△G)均小于零,熵变(△S)均为正值,该吸附过程是自发的吸热物理过程.     

Prediction of structure and elastic properties of AlCrFeNiTi system high entropy alloys

The effect of alloy compositions on structure and elastic properties of single-phase AlCrFeNiTi and AlCrFeNiTiX (X = V, Mn, Co, Zn, Zr, Nb, Mo and La) high entropy alloys was investigated by calculating solid solution characteristics of alloys combining with the first principles method. The obtained formation enthalpy, cohesive energy and mechanical stability indicated AlCrFeNiTi and AlCrFeNiTiX (X = V, Mn, Co, Nb and Mo) HEAs adopt the body centered cubic structure instead of face centered cubic structure. There is a rather good agreement between theoretical structure predictions and the classic criteria of valence electron concentration VEC. A detailed investigation on electronic structure of AlCrFeNiTi and AlCrFeNiTiX alloys revealed the bonding behavior of alloys. In addition, the calculated results of polycrystalline elastic parameters confirmed the ductility of AlCrFeNiTiX alloys would weaken with increasing mixing enthalpy ΔH_mix (or decreasing atomic size difference δ), and the increase in ΔH_mix is predicted to decrease the elastic anisotropy. Furthermore, we predicted that the present high entropy alloys should be more elastically isotropic when the corresponding the mixing enthalpy ΔH_mix has a larger value.     

In对Pd氢化的影响

本文使用超微高压天平装置，在压力为０．００１－３．５ＭＰａ，温度为３８１－６２１Ｋ范围内测得纯Ｐｄ和４种成分Ｐｄ－Ｉｎ合金的吸放氢等温线。结果表明：价电子浓度低于０．５，晶格膨胀占主导作用，氢的溶解度随Ｉｎ含量增加而升高；价电子浓度高于０．５，费米能升高占主导作用，氢溶解度随Ｉｎ含量增加而降低。这同对Ｐｄ－Ａｇ，Ｐｄ－Ｓｎ合金中Ａｇ，Ｓｎ的作用解释相似，即它们在合金中对氢的溶解度确有上述两种相反的影响。