Thomas-Fermi模型含外电场作用的铝镁合金熵能的计算

本文基于Thomas-Fermi（TF）模型，提出外势场与原子内势场的作用，确定外势场对体系势场边界条件的影响，建立了外电场作用下的原子势场外边界条件。应用体积相加法，把单原子TF模型推广到化合物和固溶体。并以Al，Mg，Li等元素的单原子，Al-Mg固溶体，Mg5Al8化合物为例，计算和分析了电场作用对体系的熵能的影响。结果表明：熵能在整个电场区域内呈先减小后增大的变化趋势，并且边界势下和极板电压下的整体变化趋势一致，但零点处熵能的变化趋势不同。     

电场作用下Al6CuMg4准晶相自由能的计算

基于Thomas—Fermi模型，系统定量地计算研究了在电场作用下Al6CuMg4准晶相对于Al-Cu-Mg固溶体及普通化合物的自由能和吉氏自由能的变化趋势。结果表明：Al6CuMg。准晶相、Al2CuMg及Al-Cu-Mg固溶体的自由能与吉氏自由能，均随着电场强度的增大而升高。正电场作用要高于负电场作用，但差距不大。Al6CuMg。准晶相的自由能与吉氏自由能相对于固溶体对电场的变化更为敏感，随着电场的升高，Al6CuMg4与固溶体间的自由能与吉氏自由能的差值迅速增加。电场作用使得准晶相的不稳定性增加，Al2CuMg的稳定性显著高于Al6CuMg4的电场稳定性。对于Al-Cu-Mg固溶体，随着Mg含量的增加，合金对电场的敏感性增强，但增大幅度要远远小于化合物与准晶相的增大幅度。     

外势场作用对Al-Cu-Fe准晶自由能影响的计算

基于Thomas-Fermi模型,计算研究了电场作用下Al-Cu-Fe系合金及其Al62.5 Cu25 Fe12.5,准晶相的自由能和吉氏自由能的变化趋势.结果表明:固溶温度下Al62.5,Cu12.5,准晶的电场稳定性最低,其次是化合物Al7Cu2Fe,二元化合物Al2Cu的稳定性要远高于前两者,但比固溶体的电场稳定性要低.正、负边界势和极板电压作用下,准晶、化合物、固溶体的自由能与吉氏自由能随边界势和极板电压的升高而升高,且近似零点对称,但正边界势和正极板电压的作用要比负边界势和负极板电压的作用强.     

Sb、Bi合金化提高Mg-Al系合金抗蠕变性能的机理

采用基于密度泛函理论的Dmol 4.1程序,从合金形成热、结合能、热力学性能和态密度等方面,研究Sb、Bi合金化提高Mg-Al系合金抗蠕变性能的影响机理。结果表明：Sb、Bi分别置换Mg-Al系合金Mg17Al12相中Mg（Ⅰ）,Mg（Ⅱ）,Mg（Ⅲ）和Al原子时,仅Sb置换Mg17Al12相中Mg（Ⅰ）,Mg（Ⅱ）原子,Bi置换Mg17Al12相中Mg（Ⅰ）原子能形成稳定的Mg17Al12固溶体结构,这表明Sb、Bi在Mg17Al12中固溶量有限。进一步比较合金化形成稳定的固溶体结构,发现Sb、Bi合金化后,固溶体结构的稳定性比未合金化时增强,其中,Sb置换Mg17Al12相中Mg（Ⅱ）原子时,其结构稳定性最高,其次Sb置换Mg17Al12相中Mg（Ⅰ）原子,再次Bi置换Mg17Al12相中Mg（Ⅰ）原子;而析出金属间化合物Mg3Bi2和Mg3Sb2,比相应合金化Mg17Al12固溶体的结构更稳定。不同温度下热力学性能的计算发现,合金体系中形成了结构稳定性高的Sb、Bi合金化Mg17Al12固溶体以及金属间化合物Mg3Sb2和Mg3Bi2,这些相高的结构稳定性并不因温度的升高而消失,其结构稳定性仍比Mg17Al12相高,因此Sb、Bi合金化提高了Mg-Al系合金的抗蠕变性能。电子态密度的分析结果进一步表明,Mg-Al系合金中相结构稳定性提高的主要原因在于：Sb、Bi合金化后,体系费米能级以下低能级区成键电子数的增多,其来源主要是Mg（s）、Mg（p）、Al（p）、Bi（d）和Sb（d）的价电子。     

微量Ag，Mg对Al-Cu-Li合金时效特性和显微组织的影响

研究了微量Ag，Mg对Al—Cu—Li合金显微组织和时效特性的影响。结果表明：单独加Ag对Al—Cu—Li系2197合金的固溶强化效果很小，但有较强的时效强化作用，Ag含量不同，时效强化效果也不同；Ag，Mg共同加入提高了Tl相（Al2CuLi）的析出速率和析出密度，使合金具有较大的固溶强化效果及最强烈的时效响应和时效强化效果。Ag，Mg的添加对合金的不同影响可通过溶质原子与空位、溶质原子与溶质原子之间的相互作用来解释。     

多组元Alx（TiVCrMnFeCoNiCu）100-x高熵合金系微观组织研究

制备了一族多组元A1x（TiVCrMnFeCoNiCu）10-x（x=0，11．1，20，40）（x为原子百分数，下同）伪二元高熵合金，研究了该新型合金系的显微组织。结果表明：Al含量为零时，合金为fcc，bcc，σ相和非晶相等多相共存；随着Al含量的增加，合金微观组织趋于简单，当x=20时，合金中只有bee简单固溶体；但当Al含量继续增加到x=40时，合金中开始出现Al，Ti等金属间化合物；多组元合金的高混合熵效应能够有效抑制金属间化合物等复杂相的析出，有助于简单固溶体的形成。使该合金系的相数低于由Gibbs相律所定的最大平衡相数。     

Mg-Li-Al合金的力学性能和阻尼性能

研究了不同锂含量的Mg Li Al合金的力学性能和阻尼性能。结果表明 ,随锂含量的增加 ,Mg Li Al合金的密度和抗拉强度降低、塑性明显提高 ;而Mg Li Al合金的阻尼性能随锂含量的增多和温度的提高而明显增高 ,其中Mg 8Li 1Al合金的室温延伸率为 35% ,室温阻尼性能高达 0 .0 1。Mg 8Li 1Al合金的阻尼明显大于Mg 4Li 1Al合金的阻尼 ,是由于Mg 8Li 1Al合金具有α β双相共晶混合组织 ,α和β相的相界面在循环载荷下产生微滑移 ,而形成相界阻尼 ;而Mg 4Li 1Al合金中只存在α单相组织。     

Al-Li-Mg(Ti)合金形成焓的EAM研究

采用普适分析型的嵌入原子模型,通过拟合纯元素的晶格常数、空位形成能、结合能和体积弹性模量等,确定了Al、Li、Mg和Ti 4个元素的嵌入原子模型参数.不同元素之间的相互作用势的参数由拟合实验或第一原理计算结果确定.用确定的嵌入原子模型分别计算了由Al,Li、Mg和Ti元素构成的二元系以及三元系中的有序合金化合物的形成焓,计算结果与已有的实验结果和第一原理计算结果符合得比较好.     

Al-Li合金时效初期的价键分析

运用固体经验电子理论(EET),对Al-Li合金时效初期的若干偏聚晶胞的价电子结构进行了计算.计算结果表明:不包含空位的偏聚晶胞的键络最强键为Al-Al键,其中Al原子的共价半径较Li原子的共价半径要大;而含空位的偏聚晶胞的最强键为Al-Li键,Al原子的共价半径要比Li原子的共价半径要小;在空位存在的情况下,由于Al原子与Li原子的电负性相差明显,促使Al和Li原子结合,倾向形成Al-Li短程序结构偏聚区,这种含空位的短程序结构很可能就是δ′(Al3Li)亚稳相的前兆结构和生长胚胎;由于Al-Li-空位有序偏聚晶胞的Al-Li键络比基体键络要强许多,因此,淬火过程中合金生成的Al-Li-空位偏聚晶胞对合金过饱和固溶体起主要强化作用;后续析出的δ′(Al3Li)亚稳相键络各项异性显著,键络强度明显提高;由于Al3Li与基体共格,其大量均匀弥散析出起到提升基体整体键络强度,同样对合金产生强化作用.     

两种Al-Mg合金超塑性能的对比研究

对Al－Mg－Li－Zr（01420）合金和Al－Mg－Mn－Zr（LF6）合金超塑性能进行了对比研究，发现Li元素的加入可以显著提高Al-Mg合金的超塑性能。     

Calculation of electric field effects on the Gibbs free energy of the Al-Li-Mg alloy

Based on the Thomas-Fermi model,the calculation methods of the monatomic Gibbs free energy were found. The interior potential boundary condition under electric field was defined. The calculation methods of Gibbs free energy for the monatomic,compound,and solid solution with electric field were set up. Under the influence of electric field,the Gibbs free energy of Al is the most sensitive,followed by those of Li and Mg. At the solution temperature the Gibbs free energies of Al3Li and its elements under electric field are not symmetrical about the zero point of electric field,whereas at the aging temperature their values are symmetrical about the zero point of electric field. At the solution temperature near the zero point of electric field,the Gibbs free energy of Al3Li is higher than that of Al-2.14%Li. And at 460 K the Gibbs free energy of Al3Li is lower than that of Al-2.14wt.%Li under electric field. The Gibbs free energy of 1420 alloy decreases from both sides of electric field to the zero point at the aging temperature.     

Calculation of free energy of Al-Cu-Li alloy under electric field

Based on Thomas-Fermi model, the interior potential boundary condition with the effect of electric field was defined, the calculation method of free energy for atom cluster under electric field was established. The change of free energy of Al-Cu-Li alloy under the effect of electric field was calculated quantitatively. It is shown that： near the zero electric field and the side of positive electric field, the free energy of Cu4LiAl7 compound at aging temperature 460 K is higher than that of free energy at solid solution temperature 725 K, but once the negative electric field increases to certain degree there will be opposite result. Under the effect of electric field, at 725 K the free energy of Cu4LiAl7 is higher than that of Al-1.0%Li-4.0%Cu, and at 460 K the free energy of compound is lower than that of solid solution. When the copper content in the Al-Li-Cu solid solution is below 5%, under the effect of electric field the free energy of solid solution increases gradually with the increasing of copper content, but the increasing amplitude reduces with the increasing of copper content. The free energy of binary solid solution increases with the addition of lithium, and with the increasing of electric field intensity the free energy margin of two kinds of solid solution becomes bigger.     

Hydrogen absorption characteristics of Pd1−xLix (x = 0.055 and 0.072) alloys and ordered Pd7Li

Thermodynamic quantities were determined for the absorption of hydrogen in Pd-5.5at.%Li and Pd-7.2at.%Li alloys, the latter alloy being in the two-phase field of saturated -Pd(Li,s) solid solution and the ordered Pd₇Li phase. Data were also determined for the Pd-10.6at.%Li alloy which consists only of the ordered Pd₇Li phase. The data were determined from measurements of pressure-composition isotherms at temperatures between 273 K and 463 K and hydrogen pressures up to 1000 Torr. The Pd---Li alloys dissolve considerable amounts of hydrogen and form a more stable hydride phase than Pd despite the lattice contraction which occurs on alloying Pd with Li. The hydrogen solubility in the ordered Pd₇Li phase alone is a little smaller than that in the two-phase mixture. The large hydrogen absorption of Pd---Li alloys, which does not depend on the presence of ordered Pd₇Li, may be attributed to (i) an attractive H---Li pair interaction, (ii) a decrease in the strain energies necessary for hydrogen occupation of the interstices, because of the similar lattice parameters of the -Pd(Li,s) and ordered Pd₇Li phases, and the large compressibility of Pd---Li alloys, and (iii) the valence of 1 of Li in Pd compared with 3 for, for example, Y in Pd.     

常压及高压凝固Al-Mg及Al-Mg-Zn合金中Al相的固溶体结构

采用X射线衍射仪、能谱仪和透射电镜分别对Al-9.6%Mg合金、Al-11Mg-4.5Zn合金和Al-17Zn-1.5Mg合金常压及6 GPa高压凝固后Al相的固溶体结构进行研究。结果表明:6GPa高压凝固后,Al-9.6%Mg合金中Mg在Al相中的固溶度显著增大;在Al-11Mg-4.5Zn合金和Al-17Zn-1.5Mg合金中,Mg、Zn溶质在Al相中的固溶度均增大,但Zn比Mg固溶的比例要大得多。在常压凝固条件下,与纯铝相比,3种合金中Al相的晶格常数均增大。与常压凝固相比,高压凝固Al-9.6Mg合金和Al-11Mg-4.5Zn中Al相晶格常数分别增大了1.178%和0.220%;在Al-17Zn-1.5Mg合金中,Al相晶格常数变化很小。此外,在Al-Mg-Zn合金中,原子半径较大的Mg固溶到Al相中,导致其晶格常数增大,原子半径较小的Zn固溶到Al相中,导致其晶格常数减小,且高压凝固后,溶质的原子半径越小,在Al相中固溶的比例越大。     

超轻双相镁锂合金的超塑性、显微组织演变与变形机理

采用熔铸、大变形轧制(加工率大于92%)和硝酸盐浴退火方法制备Mg-7.83%Li 合金与Mg-8.42%Li合金细晶板材,研究合金的超塑性、显微组织、空洞与断裂形貌和变形机制.计算α相(5.7%Li)和β相(11%Li)的扩散系数和Gibbs自由能,讨论573 K时超塑性晶粒长大的原因.结果表明:Mg-7.83Li和Mg-8.42Li合金分别获得850%和920%的最大超塑性;Mg-7.83Li合金在573 K时发生了显著的超塑性晶粒长大;在573 K和1.67×10~(-3) s~(-1)条件下制备的Mg-8.42Li合金中的空洞较少,且在变形区中随机而孤立地分布.断裂形貌观察发现Mg-8.42Li合金在573 K和5×10~(-4) s~(-1)条件下发生穿晶断裂;Mg-7.83Li合金在573 K和1.67×10~(-3) s~(-1)条件下发生沿晶界韧窝断裂.归一化实验数据与考虑位错数量的变形机制图对比表明合金超塑性变形机制为晶格扩散控制的位错调节的晶界滑移.     

Experimental and modelling assessment of precipitation kinetics in an Al-Li-Mg alloy

The precipitation behaviour in an Al-5 wt.% Mg-1.8 wt.% Li alloy has been systematically investigated for both isothermal and non-isothermal heat treatments, using atom probe tomography, transmission electron microscopy and in situ small-angle X-ray scattering. In the investigated temperature range, the δ′ phase is shown to form, with a Mg content similar to that of the alloy, and a Li content of 18.5 at.%. The quantitative data on isothermal and non-isothermal kinetics from the in situ experiments are compared to the outcome of a precipitation class model adapted to the case of high volume fractions. The model parameters suggest that the main effect of Mg on the precipitation of the δ′ phase in Al is to lower the solubility of Li in the α-Al solid solution, with little effect on the interfacial energy of the precipitates or on the Li diffusivity in Al.     

焊接温度对Mg/Al扩散焊接头微观组织和性能的影响

采用真空扩散焊在不同焊接温度下对AZ31B镁合金和6061铝合金进行连接。利用光学显微镜（OM）、扫描电镜（SEM）和能谱（EDX）观察Mg/Al异种金属接头的显微组织。结果表明：随着焊接温度的升高,扩散区各层的厚度增加,且组织发生明显变化。440°C时扩散层由Mg2Al3层和Mg17Al12层组成;460和480°C时由Mg2Al3层、Mg17Al12层和Mg17Al12与镁基固溶体的共晶层组成。随着加热温度的升高,高硬度区域显著增多,区域内不同位置的硬度存在明显差别。当焊接温度为440°C时接头的最大抗拉强度为37MPa,脆性断裂发生在Mg17Al12层。     

Li对纯Al在酸性NaCl水溶液中腐蚀行为的影响

真空熔炼制备1wt%和2wt%Li的Al-Li二元模型合金,研究Li含量对其在0.1MNaCl+0.01MH2SO4酸性水溶液中电化学腐蚀行为的影响。采用自腐蚀电位和电化学阻抗（EIS）评价纯Al、Al-1Li和Al-2Li合金的耐蚀性能,结合X射线光电子能谱（XPS）和Mott-Schottky（M-S）曲线对三种试样表面腐蚀产物膜成分和半导体特征进行分析。结果表明1wt%和2wt%Li使纯Al自腐蚀电位负移的同时,耐蚀性有所提高。合金元素Li参与腐蚀产物膜的形成,以Li2O的形式掺杂于Al2O3为主要成分的腐蚀产物膜中,没有改变腐蚀产物膜的n型半导体特征;但Li2O掺杂引起膜内氧空位浓度的降低,是Li提高纯Al耐蚀性的主要原因。     

Determination of interfacial energies for solid al solution in equilibrium with Al-Cu-Ag liquid

The equilibrated grain boundary groove shapes of a solid Al solution in equilibrium with Al-Cu-Ag liquid were observed from a quenched sample using a radial heat flow apparatus. The Gibbs-Thomson coefficient, solid-liquid interfacial energy, and grain boundary energy of the solid Al solution were determined from the observed grain boundary groove shapes. The thermal conductivity of the solid phase for Al-16.42 at.% Ag-4.97 at.% Cu and Al-16.57 at.% Ag-11.87 at.% Cu alloys and the thermal conductivity ratio of the liquid phase to the solid phase for Al-16.57 at.% Ag-11.87 at.% Cu alloy at the melting temperature were also measured with a radial heat flow apparatus and a Bridgman-type growth apparatus, respectively.