中国一些河流离子组分初步研究

　　研究人类活动、全球变化对河流水质、离子化学特征及分布的影响具有重要意义。河流离子化学组成可以反映水系的区域岩性，物理化学风化特征。而对于控制河流离子化学自然因素的研究则有助于判别人类活动如农业灌溉施肥、矿山开采、工业生产等对河流的影响。同时，河流组分如NO3-、SO42-、As、Cd等的组成特征可以反映人类活动污染物输入程度。因此，河流水化学特征可以从一定程度上反映人类活动对水环境的影响。同时，研究河水离子化学特征及其分布规律也可以获得化学元素的生物地球化学循环、风化侵蚀及其在陆地—河流—海洋系统循环过程中的重要信息。此外，还有助于评价不同经济因素如人口密度等对河流离子的影响；有助于合理有效的利用河水的自净容量和环境效应，保护水资源；为水资源的开发利用、污染控制提供科学依据。 　　本文以中国南北方代表性流域—西江流域、长江中游（主要为汉水和乌江水系）、淮河上游及黄河下游流域河水为研究对象，通过对河水主要及微量金属离子的考察，结合基本水质理化参数，初步研究了我国南北方一些河流的离子化学特征及影响因素。通过此次研究，得出以下几点认识： 　　1. 西江流域河流pH均值为7.40，长江中游为8.11，黄河下游为8.34，淮河上游为7.95。西江流域河流DO含量均值为7.51 mg/l，低于黄河下游干流的8.27 mg/l；黄河下游支流DO含量显著低于干流。西江流域TDS经向分异显著，随经度增加逐渐降低。西江流域TDS平均值为152.78 mg/l，低于长江、黄河水系。 　　2. 西江流域、长江中游、淮河上游及黄河下游阴离子均以HCO3-平为主，各水系阴离子平均含量顺序均为HCO3- > SO42 -> Cl- > NO3-。研究区域水系中HCO3-平均含量以淮河上游为最高，西江流域最低；SO42 -、Cl-及NO3-平均含量则以黄河下游为最高，长江中游最低。研究区域水系阳离子均以Ca2+为主，西江流域及长江中游阳离子平均含量顺序为Ca2+ > Mg2+ > Na+ > K+，而淮河上游、黄河下游阳离子平均含量顺序则为Ca2+ > Na+ > Mg2+ > K+。 　　从长江中游到淮河上游、黄河下游，区域岩石风化是控制离子组成的主要因素，但蒸发结晶因素的贡献逐渐加强。其中，介于长江和黄河流域之间的淮河上游水系离子组成的过渡特征显著。研究区域水系中NO3-主要源于污染物排放，黄河干流污染较西江干流污染重。 　　3. 西江流域河流溶解态微量金属平均含量Zn>Cr>Cu>As>Al>Pb>Cd，其中Zn平均含量为37.72μg/l，Cd平均含量则仅为0.24μg/l。长江中游溶解态微量金属平均含量Zn>Cr>Pb>As>Cu=Al>Cd。淮河上游溶解态微量金属平均含量Zn>Cr>As>Pb>Al>Cu>Cd。黄河下游溶解态微量金属平均含量Zn>Cr>Cu>As >Al>Pb>Cd。研究区域河流中，西江流域溶解态Cu、Cr的平均含量分别为6.12μg/l和7.61μg/l，高于长江中游、淮河上游及黄河下游。长江中游溶解态Pb和Cd平均含量则高于西江流域、淮河上游及黄河下游。而研究区域中，黄河下游溶解态Al含量最高，达12.7 μg/l，淮河流域则体现出了Zn和Al的高含量特征。 　　化学风化过程在一定程度上导致了水体与风化壳之间不同化学元素的分异，使河水中溶解态Al和As相对于其它微量金属元素强烈富集，而Pb、Zn、Cu及Cr则相对亏损。河流溶解态As和Al除来源于矿物岩石风化外，也受外源输入—人类活动的影响。 　　4. 自然条件的区域差异是形成河流离子化学分异的主要因素，但人类活动对其影响逐步加深。工农业污染物输入在一定程度上改变了天然河流的离子化学组成，使河流组分NO3-、SO42-、As、Al等呈现富集趋势。化学元素在河流这一循环过程中间体中的地球化学行为越来越多地受人类活动影响。

Effect of Nb Content on the Microstructure and Mechanical Properties of Zr-Cu-Ni-Al-Nb Glass Forming Alloys

(Zr65Al10Ni10Cu15)(100-x) Nb-x glass forming alloys with Nb contents ranging from 0 to 15 at.% were prepared by water-cooled copper mould cast. The alloys with different Nb contents exhibited different microstructures and mechanical properties. Unlike the monolithic Zr65Al10Ni10Cu15 bulk metallic glass, only a few primary bee beta-Ti phase dendrites were found to distribute in the glassy matrix of the alloys with x = 5. For alloys with x = 10, more beta-phase dendrites forms, together with quasicrystalline particles densely distributed in the matrix of the alloys. For alloys with x = 15, the microstructure of the alloy is dominated by a high density of fully developed P-phase dendrites and the volume fraction of quasicrystalline particles significantly decreases. Room temperature compression tests showed that the alloys with x = 5 failed at 1793 MPa and exhibited an obvious plastic strain of 3.05%, while the other samples all failed in a brittle manner. The ultimate fracture strengths are 1793, 1975 and 1572 MPa for the alloys with x = 0, 10 and 15 at.% Nb, respectively.

Microstructure and mechanical properties of Zr-Cu-Al bulk metallic glasses

Zr49Cu46Al5 and Zr48.5Cu46.5Al5 bulk metallic glasses(BMGs) with diameter of 5 mm were prepared through water-cooled copper mold casting. The phase structures of the two alloys were identified by X-ray diffractometry(XRD). The thermal stability was examined by differential scanning calorimetry(DSC). Zr49Cu46Al5 alloy shows a glass transition temperature, T, of about 689 K, an crystallization temperature, T-x, of about 736 K. The Zr48.5Cu46.5Al5 alloy shows no obvious exothermic peak. The microstructure of the as-cast alloys was analyzed by transmission electron microscopy(TEM). The aggregations of CuZr and CuZr2 nanocrystals with grain size of about 20 nm are observed in Zr49Cu46Al5 nanocrystalline composite, while the Zr48.5Cu46.5Al5 alloy containing many CuZr martensite plates is crystallized seriously. Mechanical properties of bulk Zr49Cu46Al5 nanocrystalline composite and Zr48.5Cu46.5Al5 alloy measured by compression tests at room temperature show that the work hardening ability of Zr48.5Cu46.5Al5 alloy is larger than that of Zr48.5Cu46.5Al5 alloy.

Atomistic investigation of the effects of temperature and surface roughness on diffusion bonding between Cu and Al

Molecular dynamics (MD) simulations are carried out to analyze the diffusion bonding at Cu/Al interfaces. The results indicate that the thickness of the interfacial layer is temperature-dependent, with higher temperatures yielding larger thicknesses. At temperatures below 750 K, the interface thickness is found to increase in a stepwise manner as a function of time. At temperatures above 750 K, the thickness increases rapidly and smoothly. When surface roughness is present, the bonding process consists of three stages. In the first stage, surfaces deform under stress, resulting in increased contact areas. The second stage involves significant plastic deformation at the interface as temperature increases, resulting in the disappearance of interstices and full contact of the surface pair. The last stage entails the diffusion of atoms under constant temperature. The bonded specimens show tensile strengths reaching 88% of the ideal Cu/Al contact strength. (c) 2007 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

A Thermodynamic Constitutive Model for Stress Induced Phase Transformation in Shape Memory Alloys

In this paper a thermodynamic constitutive model is developed for stress induced phase transformation in single crystalline and polycrystalline shape memory alloys (SMAs). Volume fractions of different martensite variants are chosen as internal variables to describe the evolution of microstructure state in the material. This model is then used in prediction the transformation behavior of a SMA (Cu-Al-Zn-Mn) under complex thermomechanical load (including complete and incomplete transformation in mechanical cycling, and proportional/non-proportional loading). (C) 2002 Elsevier Science Ltd. All rights reserved.

氮化铝基板与Cu和Al的接合及其表面改质效果

对AlN陶瓷基板进行了减压直流等离子体喷涂镀Al，在基板表面形成厚度约２μｍ的金属Al薄层，实现了Al与AlN中的良好接合。

Comparative Study Of The Influence Of Natural Convection On Directional Solidification Of Al-3.5 Wt% Ni And Al-7 Wt% Si Alloys

We present numerical simulations of thermosolutal convection for directional solidification of Al-3.5 wt% Ni and Al-7 wt% Si. Numerical results predict that fragmentation of dendrite arms resulting from dissolution could be favored in Al-7 wt% Si, but not in Al-3.5 wt% Ni. Corresponding experiments are in qualitative agreement with the numerical predictions. Distinguishing the two fragmentation mechanisms, namely dissolution and remelting, is critical during experiments on earth, when fluid flow is dominant. (C) 2007 COSPAR. Published by Elsevier Ltd. All rights reserved.

Theory Of Phase Transformation And Reorientation In Single Crystalline Shape Memory Alloys

A constitutive model, based on an (n + 1)-phase mixture of the Mori-Tanaka average theory, has been developed for stress-induced martensitic transformation and reorientation in single crystalline shape memory alloys. Volume fractions of different martensite lattice correspondence variants are chosen as internal variables to describe microstructural evolution. Macroscopic Gibbs free energy for the phase transformation is derived with thermodynamics principles and the ensemble average method of micro-mechanics. The critical condition and the evolution equation are proposed for both the phase transition and reorientation. This model can also simulate interior hysteresis loops during loading/unloading by switching the critical driving forces when an opposite transition takes place.

The growth of high-Al-content InAlGaN quaternary alloys by RF-MBE

High-Al-content InxAlyGa1-x-yN (x = 1-10%, y = 34-45%) quaternary alloys were grown on sapphire by radio-frequency plasma-excited molecular beam epitaxy. Rutherford back-scattering spectrometry, high resolution x-ray diffraction and cathodoluminescence were used to characterize the InAlGaN alloys. The experimental results show that InAlGaN with an appropriate Al/In ratio (near 4.7, which is a lattice-match to the GaN under-layer) has better crystal and optical quality than the InAlGaN alloys whose Al/In ratios are far from 4.7. Some cracks and V-defects occur in high-Al/In-ratio InAlGaN alloys. In the CL image, the cracks and V-defect regions are the emission-enhanced regions.

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。