富钇稀土-铝合金制取的研究Study on Preparation of Yttrium-Rich RE-Al Alloys

我国江西龙南稀土矿是目前世界上储量最大的富钇稀土矿、研制具有多种用途的钇（Y）-铝（Al）或富钇混合稀土（Ymm）-铝中间合金，对于开拓我国龙南稀土矿的应用领域扩大稀土合金出口具有重要意义。基于这一背景并针对目前氟化物体系制取Ymm-Al合金时存在着电解温度高，腐蚀现象严重，电效偏低等缺点，本文系统开展了在氯化物熔盐体系中电解制取Ymm-Al合金的研究工作。本工作由三部分组成：在第一部分工作中，开展了熔盐电解所需要基本原料-无水稀土氯化物制取的工艺研究。利用化学分析和结构分析手段，弄清了干法氯化过程中YmmCl_3水解的机理，提出了减弱水解的措施，即YmmCl_3先在850-900 ℃灼烧1.5 + 0.2hr，脱掉吸附水并将碱式碳酸盐转化为氧化物，增加稀土氧化物的比表面。通过条件试验得到最佳工艺条件为：采用NH_4 Cl:Ymm_2 O_3 = 14:1（摩尔比）的配料比，每次投入氯化装置的原料量为0.26 - 0.36 kg, 在400-450 ℃氯化反应激烈开始后迅速降温至400 ℃以下，待物料粘结现象消失后，再行升温氯化。出料及后期控制温在475 ± 25 ℃。经过3.8 ± 0.2hr氯化，可制得水不溶物小于1%并符合熔盐电解要求的YmmCl_3原料。此新工艺与原有干法工艺相比，流程短，装置简单，不需密闭抽真空，成本低，适于制取任何量的优质熔盐电解所需氯化稀土原料。在第二部分工作中，利用上述YmmCl_3原料，以液态铝为阴极，在氯化物体系中进行熔盐电解，通过试验得出在小型试验规模制取Ymm-Al合金的最隹工艺条件为：电解质组成（重量比）40%YmmCl_3-1%NaF-59%等摩尔的NaCl-KCl；电解温度为790 ± 5 ℃；阴极电流密为0.7 - 0.02A/cm~2；电解电量为333 ± 5库仑/克铝，制得钇铝合金中Ymm含量为10 ± 2%。添加1%的NaF可消除阴极表面生成枝状物，减少合金中夹渣和熔盐中沉渣。在电解工作中，将方差分析应用于试验数据处理，方差分析结果表明，各种试验因素对电效有明显影响，试验数据可靠，试验误差在允许范围以内。在第三部分工作中，利用线性扫描伏安法测定了在最隹电解工艺条件下Y~（3+）和Ymm在液态铝及钼电极上的析出电位。测定结果表明：Y~（3+）和Ymm~（3+）在液态铝阴极上的析出电位比在钼阴极上偏正0.2 ～ 0.8伏，氟离子的加入要比不加氟时析出电位不有同程度的负移，但考虑到氟离了具有消渣作用，加入少量氟比物添加剂对提高电效有利。

Band crossing in isovalent semiconductor alloys with large size mismatch: First-principles calculations of the electronic structure of Bi and N incorporated GaAs

For large size- and chemical-mismatched isovalent semiconductor alloys, such as N and Bi substitution on As sites in GaAs, isovalent defect levels or defect bands are introduced. The evolution of the defect states as a function of the alloy concentration is usually described by the popular phenomenological band anticrossing (BAC) model. Using first-principles band-structure calculations we show that at the impurity limit the N-(Bi)-induced impurity level is above (below) the conduction- (valence-) band edge of GaAs. These trends reverse at high concentration, i.e., the conduction-band edge of GaAs1-xNx becomes an N-derived state and the valence-band edge of GaAs1-xBix becomes a Bi-derived state, as expected from their band characters. We show that this band crossing phenomenon cannot be described by the popular BAC model but can be naturally explained by a simple band broadening picture.

GROWTH OF WIDE-BAND GAP IMMISCIBLE II-VI ALLOYS BY METALORGANIC VAPOR-PHASE EPITAXY

Although metalorganic vapor phase epitaxy (MOVPE) is generally regarded as a non-equillibrium process, it can be assumed that a chemical equilibrium is established at the vapor-solid interface in the diffusion limited region of growth rate. In this paper, an equilibrium model was proposed to calculate the relation between vapor and solid compositions for II-VI ternary alloys. Metastable alloys in the miscibility gap may not be obtained when the growth temperature is lower than the critical temperature of the system. The influence of growth temperature, reactor pressure, input VI/II ratio, and input composition of group VI reactants has been calculated for ZnSSe, ZnSeTe and ZnSTe. The results are compared with experimental data for the ZnSSe and ZnSTe systems.

Electronic properties of zinc-blende GaN, AlN, and their alloys Ga1-xAlxN

The electronic properties of wide-energy gap zinc-blende structure GaN, A1N, and their alloys Ga(1-x)A1(x)N are investigated using the empirical pseudopotential method. Electron and hole effective mass parameters, hydrostatic and shear deformation potential constants of the valence band at Gamma and those of the conduction band at Gamma and X are obtained for GaN and AIN, respectively. The energies of Gamma, X, L conduction valleys of Ga(1-x)A1(x)N alloy versus Al fraction x are also calculated. The information will be useful for the design of lattice mismatched heterostructure optoelectronic devices based on these materials in the blue light range application. (C) 1995 American Institute of Physics.

Band structure parameters of zinc-blende GaN, AlN and their alloys Ga1-xAlxN

The electronic properties of wide energy gap zinc-blende structure GaN, AlN and their alloys Ga1-xAlxN are investigated using the empirical pseudopotential method. Electron and hole Effective mass parameters, hydrostatic and shear deformation potential constants of the valence band at Gamma and those of the conduction band at Gamma and X are obtained. The energies of Gamma, X, L conduction valleys of Ga1-xAlxN alloy versus Al fraction x are also calculated. The information will be useful for the design of lattice mismatched heterostructure optoelectronic devices in the blue light range.

Optical properties of AIInGaN quaternary alloys

Carrier recombination dynamics in AlInGaN alloy has been studied by photoluminescence (PL) and time-resolved photoluminescence (TRPL). The fast redshift of PL peak energy is observed and well fitted by a physical model considering the thermal activation and transfer processes. This result provides evidence for the exciton localization in the quantum dot (QD)-like potentials in our AlInGaN alloy. The TRPL signals are found to be described by a stretched exponential function of exp[(-t/tau)(beta)], indicating the presence of a significant disorder in the material. The disorder is attributed to a randomly distributed quantum dots or clusters caused by indium fluctuations. By studying the dependence of the dispersive exponent 8 on the temperature and emission energy, we suggest that the exciton hopping dominate the diffusion of carriers localized in the disordered quantum dots. Furthermore, the localized states are found to have OD density of states up to 250 K, since the radiative lifetime remains almost unchanged with increasing temperature.

The SPER and characteristics of Si1-yCy alloys

\Si1-yCy alloys with carbon composition of 0.5 at.% were successfully grown on n-Si(100) substrate by solid phase epitaxy recraystallization. The result was presented in this paper. With the help of the SiO2 capping layer, rather uniform carbon profile in amorphous Si layer was obtained by dual-energy implantation. Since ion-flow was small and implantation time was long enough, the emergency of beta-SiC was avoided and the dynamic annealing effect was depressed. The pre-amorphization of the Si substrate increased the fraction of the substitutions carbon and the two-step annealing reduced point defects. As a result, Si1-yCy alloys with high quality was recrystallized on Si substrate.

Pressure behavior of deep centers in ZnSxTe1-x alloys

We have measured photoluminescence of ZnSxTe1-x alloys (x > 0.7) at 300 K and under hydrostatic pressure up to 7 GPa. The spectra contain only a broad emission band under excitation of the 406.7 nm line. Its pressure coefficients are 47, 62 and 45 meV/GPa for x = 0.98, 0.92 and 0.79 samples, which are about 26%, 7% and 38% smaller than that of the band gap in the corresponding alloys. The Stokes shifts between emission and absorption of the bands were calculated by fitting the pressure dependence of the emission intensity, being 0.29, 0.48 and 0.13 eV for the three samples, respectively. The small pressure coefficient and large Stokes shift indicate that the emission band observed in our samples may correspond to the Te isoelectronic center in the ZnSxTe1-x alloy.

K-shell ionization cross section of aluminium induced by low-energy highly charged argon ions

Al K-shell X-ray yields are measured with highly charged Arq+ ions (q = 12-16) bombarding against aluminium. The energy range of the Ar ions is from 180 to 380 keV. K-shell ionization cross sections of aluminium are also obtained from the yields data. The experimental data is explained within the framework of 2p pi-2p sigma s rotational coupling. When Ar ions with 2p-shell vacancies are incident on aluminium, the vacancies begin to reduce. Meanwhile, collisions against Al atoms lead to the production of new 2p-shell vacancies of Ar ions. These Ar 2p-shell vacancies will transfer to the 1s orbit of an Al atom via 2p pi-2p sigma s rotational coupling leading to the emission of a K-shell X-ray of aluminiun. A model is constructed based on the base of the above physical scenario. The calculation results of the model are in agreement with the experimental results.

Effects of rare earth on the structure and properties of Mg–6Zn–5Al–4Gd–1RE (RE = Ce or Y) alloys

The microstructures and mechanical properties of Mg-6Zn-5Al-4Gd-1RE (RE = Ce or Y) alloys were investigated. The addition of Ce or Y obviously refines the grain size for the Mg-6Zn-5Al-4Gd-based alloy, while the Y element has a better refining effect. The Ce and Y show different grain-refining mechanisms: Ce addition mostly promotes the growth of secondary dendrite, while Y addition mainly increases the heterogeneous nucleation sites.

Crystallographic and electrochemical characteristics of melt-spun Ti–Zr–Ni–Y alloys

Ti45Zr30Ni25Yx (x = 1, 3, 5 and 7) alloys were prepared by melt-spinning at wheel velocity of 20 m s(-1). The effect of additive Y on phase structure and electrochemical performance of melt-spun alloys was investigated. Ti45Zr30Ni25Yx melt-spun alloys were composed of I-phase and amorphous phase. T