EMPIRICAL PSEUDOPOTENTIAL BAND-STRUCTURE CALCULATION FOR ZN1-XCDXSYSE1-Y QUATERNARY ALLOY

The band structure of the Zn1-xCdxSySe1-y quaternary alloy is calculated using the empirical pseudopotential method and the virtual crystal approximation. The alloy is found to be a direct-gap semiconductor for all x and y composition. Polynomial approximation is obtained for the energy gap as a function of the composition x and y. Electron and hole effective masses are also calculated along various symmetry axes for different compositions and the results agree fairly well with available experimental values.

The effect of La or Ce on ageing response and mechanical properties of cast Mg-Gd-Zr alloys

Mg-8Gd-0.6Zr-1RE (RE = La or Ce, wt.%) alloys were prepared by casting. The microstructures, age hardening behavior and mechanical properties were investigated. The results show that the addition of 1 wt.% La or Ce to a Mg-8Gd-0.6Zr alloy reduces the dendrite arm spacing and slightly improves the mechanical properties and age hardening response.

Microstructures and mechanical properties of as-cast Mg-5Y-3Nd-Zr-xGd (x=0, 2 and 4 wt.%) alloys

Mg-5Y-3Nd-0.6Zr-xGd (x = 0, 2 and 4 wt.%) alloys were prepared by metal mould casting technique, the structures and mechanical properties were investigated. The alloys were mainly composed of alpha-Mg solid solution and beta-phase. With increasing Gd content, Mg5RE phase increased and the grain was refined. The Mg-5Y-3Nd-2Gd-0.6Zr alloy exhibited highest ultimate tensile strength and Mg-5Y-3Nd-0.6Zr alloy showed highest yield strength at room temperature. With increasing amount of Gd, the thermal resistance was improved. The Mg-5Y-3Nd-4Gd-0.6Zr alloy exhibited highest UTS and YS at 250 degrees C, they were about 1.27 times higher than those of Gd-free alloy, which was mainly attributed to the increase of the beta-phase and Mg5RE strengthening phase.

Growth of 0.55eV-GaInAsSb Quaternary Alloy Films for a Thermophotovoltaic Device by Liquid Phase Epitaxy

Lattice matched Ga_(1-x)In_xAs_ySb_(1-y) quaternary alloy films for thermophotovoltaic cells were successfully grown on n-type GaSb substrates by liquid phase epitaxy. Mirror-like surfaces for the epitaxial layers were achieved and evaluated by atomic force microscopy. The composition of the Ga_(1-x)In_xAs_ySb_(1-y) layer was characterized by energy dispersive X-ray analysis with the result that x = 0.2, y = 0.17. The absorption edges of the Ga_(1-x)In_xAs_ySb_(1-y) films were determined to be 2. 256μm at room temperature by Fourier transform infrared transmission spectrum analysis, corresponding to an energy gap of 0.55eV. Hall measurements show that the highest obtained electron mobility in the undoped p-type samples is 512cm2~/(V·s) and the carrier density is 6. 1×10~(16)cm~(-3) at room temperature. Finally, GaInAsSb based thermophotovoltaic cells in different structures with quantum efficiency values of around 60% were fabricated and the spectrum response characteristics of the cells are discussed.

Microstructure and Strengthening Mechanism of Die-Cast Mg-Gd Based Alloys

Mg-8Gd-2Y-Nd-0.3Zn (wt%) alloy was prepared by the high pressure die-cast technique. The microstructure, mechanical properties in the temperature range from room temperature to 573 K, and strengthening mechanism were investigated. It was confirmed that the Mg-Gd-based alloy with high Gd content exhibited outstanding die-cast character. The die-cast alloy was mainly composed of small cellular equiaxed dendrites and the matrix. The long lamellar-shaped stacking compound of Mg3X (X: Gd, Y, Nd, and Zn) and polygon-shaped.

Microstructure and mechanical properties of high performance Mg-Gd based alloys

The Mg-12Gd-4Y-2Nd-0.3Zn-0.6Zr (wt.%) alloy was prepared by casting technology, and the structure, age hardening behavior and mechanical properties of the alloy have been investigated. The results demonstrated that the alloy was composed of alpha-Mg matrix, a lot of dispersed Mg24RE5 (RE = Gd/Y/Nd) and Mg5RE precipitates in the as-cast and the T6 state alloys. The alloy exhibited remarkable age hardening response and excellent mechanical properties from room temperature (RT) to 300 degrees C by optimum solid solution and aging conditions. The ultimate tensile strength.

Microstructure and mechanical properties of Mg–12.3Zn–5.8Y–1.4Al alloy

Microstructure and mechanical properties of as-cast and heat-treated Mg–12.3Zn–5.8Y–1.4Al (ZYA1261) alloy were investigated. The phase compositions of the as-cast alloy are -Mg, Mg3YZn6 (I-phase), Mg3Y2Zn3 (W-phase), Mg12YZn (Z-phase), Mg24Y5, MgZn and a small quantity of Al-containing phase. The phase compositions change with various heat treatment conditions. The highest Vickers hardness is obtained in the alloy aged at 200 ◦C for 5 h, the transmission electron microscopy indicated that fine scale Z-phase precipitates in the matrix. The tensile properties of the as-cast and heat-treated alloys were reported.

Raman-forbidden mode and oxygen ordering in Bi2Sr2-xLaxCuO6+gamma single crystals annealed in oxygen

A Raman-forbidden phonon mode at about 840 cm(-1) is observed popularly on the surface of pun and La-doped Bi2Sr2-xLaxCuO6+y (0 less than or equal to x less than or equal to 0.8) single crystals annealed in oxygen. A remarkable excitation dependence of this additional line is found. Based on the properties of the structure of the Bi-O layer with excess oxygen atoms and the similarity in the appearance of the Raman-forbidden modes between RBa2Cu3Ox (R = Y, Nd, Gd, Pr) and Bi2Sr2-xLaxCuO6+y systems, we attribute the manifestation of this additional line to the ordering of the interstitial oxygen in the Bi-O layers. Our results provide Raman evidences for confirming that the ordering of the movable oxygen may exist universally in high-temperature superconductors.

耐热Mg-Gd基合金的研究和应用

本研究从二元Mg-Gd体系出发，研究了添加不同稀土元素对Mg-Gd基合金的组织、时效行为和力学性能的影响。优化出多种力学性能优异、加工性能良好和耐热性突出的新型Mg-Gd-RE-Zn-Zr系合金。在探讨Mg-Gd基合金强化机理的同时，提出了强化模型，并进行了定量分析。 在Mg-Gd二元体系中，通过对不同Gd含量的合金组织，时效行为和力学性能的研究，发现Gd不仅可以细化晶粒，还可以细化枝晶。合金中Gd的含量大于8 wt.%开始表现出时效硬化现象，Gd含量超过12wt.％时效硬化效果显著。在二元体系研究结果的基础上，选用Mg-8Gd基合金，研究了不同轻稀土元素LRE(La, Ce和Nd)和重稀土元素HRE (Y, Dy, Ho 和Er)对合金组织和性能的影响。结果表明，轻稀土中Nd的作用效果最好，其次为Ce和La。重稀土中Y和Dy的作用效果较好，其次为Ho和Er。将轻、重稀土综合考虑，在Mg-8Gd-3RE(Nd+Y)-Zr合金中，变化Nd和Y的添加量，发现Nd和Y的添加量分别为1 和2或2和1时，能够明显改善合金的综合力学性能。 研究了Mg-8Gd-2Y-1Nd-0.3Zn和Mg-8Gd-1Dy-0.3Zn压铸合金的组织和性能。研究表明，两种合金的铸造性能好，而且具有优异的抗拉性能和蠕变性能，可以满足在250℃~275℃环境下使用。进一步研究了挤压变形Mg-8Gd-2Y-1Nd-0.3Zn合金。合金成形性能好，抗拉强度和伸长率明显提高，而且改善了合金的高温抗蠕变性能，比压铸合金提高了近一个数量级。 发明了一种新型的分步固溶处理方法——振荡热处理方法，这种方法比传统的T6热处理方法更加有效，振荡热处理的主要作用是改变了凝固过程中析出相的尺寸和分布。 研究了Mg-Gd基合金凝固过程中的相析出和相转变。在合金的凝固过程中，容易生成块状的化学组成为Mg5RE（fcc结构）的共晶相；加入Zn后，凝固中容易出现片状的Mg3RE（14H型）沉淀；时效强化的主要原因是在过饱和固溶体时效过程中析出针状的50 nm~100 nm的Mg15RE3相，它与基体具有半共格的位相关系，能够有效阻止位错滑移。但随着时效时间的延长，针状析出相长大，共格关系被破坏，导致强化作用降低。而对于压铸和挤压变形合金，合金析出相的种类不变，主要的不同是挤压变形合金析出化合物的分布更加均匀，尺寸更小。 开发了高强度耐热Mg-12Gd-4Y-2Nd-0.4Zn-0.6Zr合金，这种合金经过热处理后，力学性能优良，热稳定性突出。在300 ℃的抗拉强度约为300 MPa，400 ℃的抗拉强度在100 MPa以上。本合金流动性能良好，适合于砂型铸造，在具有高温、高强度要求的镁合金制品方面极具潜力。 从金属材料强化原理出发，建立了Mg-Gd基合金的强化模型，并进行了定量分析。结果表明，析出强化是Mg-Gd基合金的主要强化方式，但实际试验值和理论值略有偏差，分析认为主要是由于β'相体积分数的变化区间较宽，且合金制备过程中不可避免地产生一些微观缺陷所致。 采用新型合金制备出了一些工业用品部件，探索了该类合金在机械、汽车和高技术等工业领域中的潜在应用

皂化环烷酸串级萃取体系计算机模拟的研究

溶剂萃取法是目前国内外广泛采用的分离提纯和富集稀土元素的方法之一，与其它方法相比较，具有许多优点，为了改变稀土萃取分离工艺的研究方法还比较落后的状态，研究和解决这个问题已令人瞩目。计算机的数学模拟法就是其中较为先进的方法之一。本论文用计算机的数学模拟法对皂化环烷酸分离钇和镧系元素的串级萃取体系进行了初步的研究。在分析皂化环烷酸和皂化P507串级萃取体系特点的基础上，提出了皂化环烷酸分离钇(Y)和镧系元素(Nd,Er)串级萃取体系的静态数学模型，对模型参数及其求法做了较为详细的讨论，分别用矩辄法和逐级计算法解算，并将计算结果与实验结果进行比较，发现矩阵法的计算精度较逐级计算法为好。可以得出：所提出的模型对氨化环烷酸分离钆和镧系元素的串级萃取体系是基本适用的，并且预计，对皂化弱酸类萃取剂分离金属离子的串级萃取体系也将具有一定的通用性；初步尝试了一种实验方法，对皂化的串级萃取体系，根据串级条件，只做单级实验就可以用电子计算机模拟地计算出各组份的逐级浓度，实验结果表明，这种方法对氨化环烷酸萃取体系是可行的。对皂化环烷酸分离钇(Y)和镧系元素(Nd)的串级萃取体系进行了改变工艺条件的计算。所建立的模型为非线性方程组，用改进牛顿法解非线性方程组，对解的初值要求较为严格，为了方便并且较快地找到一组初值，首先用逐级计算法解算，其结果就作为矩法的初值，并对端级模型作了简化，对工艺参数改变（洗液的酸度、料液的总浓度、料液的组成以及级数）进行了相应条件下的单级实验，求得了各模型参数，然后进行模拟计算，得到了与萃取规律相符的计算结果，又进行了常级模拟实验加以比较，计算值与实际串级萃取体系的实验值相比较，端级结果比较一致，中间各级有时误差较大，我们希望能够能过对计算结果的比较，从而对工艺条件加以筛选，这方面的工作还需要进行较为深入的研究，模型和计算方法都有待于进一步的完善。论文中，还对近年来李涵等提出的单一稀土线性规则进行了进一步探讨，结果表明对非稀土元素如Cu(Ⅱ)，Co(Ⅱ)，Ni(Ⅱ)等单一元素的萃取，该线性规则仍然成立。

数学模拟法优化设计氨化体系稀土分离工艺

应用数学模拟法对氨化环烷酸体系分离钇与镧系元素的萃到过程及氨化P_(507)体系分离稀土元素的萃取过程分别进行了优化工艺设计。采用复合形优化法，在进料浓度和进料量一定的情况下，选取 Q = (N · Zo · VOE)/(x(1, 1)·VAE)为目标函数。选取N、NF、Zo、VOE、Hw和VAW为六个优化参数，选取二出口产品的纯度和收率为约束条件。首先对氨化环烷酸体系分离Y与镧系元素（Nd）的串级萃取过程进行了优化工艺设计。优化设计中所用的串级计算采用了占计算机内存较小的求解稀疏矩阵的方法。在满足出口产品Y的纯度不小于99.98%的情况下，得到了一组优化工艺参数和该优化工艺条件下的各级二相数据。并与已有实验结果进行了对比，论证了其合理性。其次，将逐级计算法引入了优化设计过程，对氨化环烷酸体系分离Y与Nd的过程再次进行了计算，并与矩阵法结果作了对比，认为逐级计算法可以与优化方法结合设计工艺。用此方法对氨化环烷酸体系分离Y与Nd，Er的串级萃取过程进行了优化工艺设计，在满足出口产品Y纯度≥99.99%的情况下，得到了一组优化工艺参数，同时给出了优化工艺条件下的各级二相数据，对比已有实验，结果比较满意。利用所提出的方法对文献报道的从江西矿分离高纯Y的实际过程进行了计算，所得的结果与串级理论设计出的结果比较接近。由于文献已进行了实验验证，故可以认为本文所得的结果基本可靠。最后，在分析了氨化P_(507)体系萃取稀土元素的特点以后，提出了逐级计算法与复合优化法相结合来优化工艺参数。在水相出口级、进料级、有机相出口级建立单级分配模型，采用所建立的模型和方法对氨化P_(507)体系分离Nd, Sm的串级萃取过程进行了优化工艺设计，得到了一组优化参数及优化工艺下的二相各级各组分浓度，并在优化的工艺条件下做了验证实验，实验结果与计算结果基本吻合。

对金属稀土金属有机配合物的合成、结构及催化性质研究

合成出三类18种双金属稀土金属有机配合物：第一类：Ln-Li双金属π－烯丙基稀土配合物－LiLn(π-C_3H_5)_4 nD(Ln=La、Tb, n=3; Ln=Y、Dy, n=2.5; Ln=Ce、Pr、Nd、Sm、Gd、Er, n=2; D=二氧六环）。第二类：Ln-Mg双金属π－烯丙基稀土配合物-(π-C_3H_5)_2CnCl_5Mg_2(tmed)_2 (Ln=Ce、Nd)和(π-C_4H_7)_2LnCl_5Mg_2(tmed)_2 (Ln=La、Ce、Nd; C_4H_7=i-C_4H_7)。第三类：Ln-Al双金属配合物－[(CF_3CO_2)_3LnHAlR_2·2THF]_2 (Ln=Y、Nd, R=i-Bu; Ln=Eu, R=Et)。用四园X－ray衍射仪在低温下测定了LiCe(π-C_3H_5)_4·4D、[(CF_3CO_2)_3YHAl(i-Bu)_2 2THF]_2、[(CF_3CO_2)_3NdHAl(i-Bu)_2 2THF]_2和[(CF_3CO_2)_3EuHAlEt_2·2THF]_2的晶体结构。对[(CF_3CO_2)_3YHAl(i-Bu)_2·2THF]_2和LiLn(π-C_3H_5)_4 nD类配合物进行了较详细的NMR研究。二维C－H相关NMR谱表明在[(CF_3CO_2)_3YHAl(i-Bu)_2·2THF]_2配合物中6个CF_3CO_2~-有2个羰基的C与H成键，该结果解释了Ln-Al双金属配合物中相应羰基的非平面结构现象。研究表明LiLn(π-CC_3H_5)_4·nD可催化异戊二烯和苯乙烯均聚合；不同配合物中均以Y配合物的活性为最高。(π-C_3H_5)_2CeCl_5Mg_2(tmed)_2对异戊二烯、丁二烯、苯乙烯以及甲基丙烯酸甲酯（MMA）的聚合有较低的催化活性；(π-C_4H_7)_2LnCl_5Mg_2(tmed)_2也对苯乙烯和异戊二烯的聚合有一定的催化活性。分别以LiCe(π-C_3H_5)_4·4D和(π-C_3H_5)_2CeCl_5Mg_2(tmed)_2作为稀土配位催化剂的模型配合物，研究了其催化所得聚异戊二烯的端基结构。表明聚合物均具有烯丙基端基(-CH_2-CH=CH_2)。证明单体在Ce~(3+)和π－烯丙基之间发生了插入反应，聚合按π－烯丙基机理进行。该结果首次为稀土配位催化共轭双烯烃聚合的活性链端π－烯丙基机理提供了直接的实验证据。(π-C_3H_5)_2CeCl_5Mg_2(tmed)_2-Al(i-Bu)_3(Al/Ce(摩尔比)=4))体系对异戊二烯的聚合具有较高的催化活性，所得聚合物仍具有－CH_3-CH=CH_2端基，而没有i-Bu端基。该结果又一次为上述π-烯丙基机理提供了直接的实验证据。发现Ln(CF_3CO_2)_3-AlEt_3体系可催化THF开环聚合。首次实现稀土催化THF开环聚合。研究了Y(CF_3CO_2)_3-HAl(i-Bu)_2-ECH（环氧氯丙烷）体系催化THF开环聚合法性及聚合机理。讨论了各种聚合条件对该体系催化活性的影响。研究了[(CF_3Co_2)YHAl(i-Bu)_2·2THF]_2在ECH存在下催化THF聚合活性并认为该双金属配合物为Y(CF_3CO_2)_3-HAl(i-Bu)_2-ECH体系的活性体。[(CF_3CO_2)_3YHA(i-Bu)_2·2THF]_2和[(CF_3CO_2)_3EuHAlEt_2·2THF]_2均可催化ECH和MMA聚合，所得PMMA的间同(rr)含量可达76.5％。

Microstructure and mechanical properties of Mg-4.5Zn-xNd (x=0, 1 and 2, wt%) alloys

Microstructure and mechanical properties of Mg-4.5Zn-xNd (x = 0, 1 and 2, wt%) alloys heat-treated at 603 K for 2 It have been investigated. T-phase (an Mg-Zn-Nd ternary phase) was observed in the Nd containing alloys. The optimal mechanical properties were obtained in the Mg-4.5Zn-1Nd alloy, and the ultimate tensile strength and yield strength were 228 and 79 MPa, respectively. Through comparing with the Mg-4.5Zn alloy, the increments of ultimate tensile strength and yield strength were 51 and 17 MPa.

Investigation of Chemical Bond Characteristics, Thermal Expansion Coefficients and Bulk Moduli of alpha-R2MoO6 and R2Mo2O7 (R = rare earths) by Using a Dielectric Chemical Bond Method

Theoretical researches are performed on the alpha-R2MoO6 (R = Y, Gd, Tb Dy, Ho, Er, Tm and Yb) and pyrochlore-type R2Mo2O7 (R = Y, Nd, Sm, Gd, Tb and Dy) rare earth molybdates by using chemical bond theory of dielectric description. The chemical bonding characteristics and their relationship with thermal expansion property and compressibility are explored. The calculated values of linear thermal expansion coefficient (LTEC) and bulk modulus agree well with the available experimental values. The calculations reveal that the LTECs and the bulk moduli do have linear relationship with the ionic radii of the lanthanides: the LTEC decreases from 6.80 to 6.62 10(-6)/K and the bulk modulus increases from 141 to 154 GPa when R goes in the order Gd, Tb Dy, Ho, Er, Tm, and Yb in the alpha-R2MoO6 series; while in the R2Mo2O7 series, the LTEC ranges from 6.80 to 6.61 10(-6)/K and the bulk modulus ranges from 147 to 163 GPa when R varies in the order Nd, Sm, Gd, Tb and Dy.

Serrated Plastic Flow During Nanoindentation in Nd-Based Bulk Metallic Glasses

The microstructure of Nd_{60}Al_{10}Ni_{10}Cu_{20-x}Fex (x = 0, 5, 7, 10, 15, 20) alloys can change from homogeneous phase to a composite structure consisting of amorphous phase plus clusters or nanocrystals by adjusting the Fe content. The effect of microstructure on the plastic deformation behavior in this alloy system is studied by using nanoindentation. The alloys with homogeneous amorphous structure exhibit pronounced flow serrations during the loading process of nanoindentation. The addition of Fe changes the plastic deformation behavior remarkablely. No flow serration is observed in the alloys with high Fe content for the indentation depth of 500 nm. The mechanism for the change of plastic serrated flow behavior is discussed.