Mechanism of nucleation and precipitation in Li containing Al-Zn-Mg-Cu alloys

Investigations on the aging hardening behavior of four Al-Li-Zn-Mg-Cu alloys were carried out using differential scanning calorimetry, transmission electron microscopy and hardness measurement. It is shown that the addition of Li inhibits the formation of Zn-rich G.P. zones in Al-Zn-Mg-Cu alloys. The dominant aging hardening precipitates is delta'(Al3Li) phase. Coarse T ((AlZn)(49)Mg-32) phase, instead of MgZn2, precipitates primarily on grain boundaries, and provides little strengthening. The multi-stop aging involving plastic deformation introduces in the matrix a high concentration of structural defects. These defects play different role on the nucleation of Zn-rich G.P. zones in different alloys. For the Li free alloy, structural defects act as vacancy sinks and tend to suppress the homogeneous precipitation of G.P. zones, while for the Li containing alloys, these defects promote the heterogeneous nucleation of G.P. zones and metastable MgZn2. A significant aging hardening effect is attained in deformed Li containing alloys due to the extra precipitation of fine MgZn2 in the matrix combined with deformation hardening.

Influence of Forced Convection on Columnar Microstructure During Directional Solidification of Al-Ni Alloys

This paper presents a summary of cellular and dendritic morphologies resulting from the upward directional solidification of Al - Ni alloys in a cylindrical crucible. We analysed the coupling of solid-liquid interface morphology with natural and forced convection. The influence of natural convection was first analyzed as a function of growth parameters (solute concentration, growth rate and thermal gradient). In a second step, the influence of axial vibrations on solidification microstructure was investigated by varying vibration parameters (amplitude and frequency). Experimental results were compared to preliminary numerical simulations and a good agreement is found for natural convection. In this study, the critical role of the mushy zone in the interaction between fluid flow and solidification microstructure is pointed out.

Temperature Dependence of the Tribological Properties of Laser Re-Melted Al-Cu-Fe Quasicrystalline Plasma Sprayed Coatings

The aim of this study was to investigate the effect of temperature on tribological properties of plasma-sprayed Al-Cu-Fe quasicrystal (QC) coating after laser re-melting treatment. The laser treatment resulted in a more uniform, denser and harder microstructure than that of the as-sprayed coatings. Tribological experiments on the coatings were conducted under reciprocating motion at high frequency in the temperature range from 25 to 650 degreesC. Remarkable influence of temperature on the friction behavior of the coating was recorded and analyzed. Microstructural analysis indicated that the wear mechanisms of the re-melted QC coatings changed from abrasive wear at room temperature, to adhesive wear at 400 degreesC and severe adhesive wear at 650 degreesC owing to the material transfer of the counterpart ball. It was also observed that the ratio of the icosahedral (i)-phase to beta-Al-50(Fe,CU)(50) phase in the coating was higher after test at 400 'C than that at 650 'C. The variation of the ratio UP of coating and of the property of the counterpart ball and coating with the temperature are the two main factors influencing the wear mechanisms and value of the friction coefficient.

The microstructures and mechanical properties of cast Mg-Zn-Al-RE alloys

The microstructures and mechanical properties of cast Mg-Zn-Al-RE alloys with 4 wt.% RE and variable Zn and At contents were investigated. The results show that the alloys mainly consist of alpha-Mg, Al2REZn2, Al4RE and tau-Mg-32(Al,Zn)(49) phases. and a little amount of the beta-Mg17Al12 phase will also be formed with certain Zn and At contents. When increasing the Zn or At content, the distribution of the Al2REZn2 and Al4RE phases will be changed from cluster to dispersed, and the content of tau-Mg-32(Al,Zn)(49) phase increased gradually. The distribution of the Al2REZn2 and Al4RE phases, and the content of beta- or tau-phase are critical to the mechanical properties of Mg-Zn-Al-RE alloys.

Effect of substituting cerium-rich mischmetal with lanthanum on microstructure and mechanical properties of die-cast Mg-Al-RE alloys

Die-cast Mg-4Al-4RE-0.4Mn (RE = Ce-rich mischmetal) and Mg-4Al-4La-0.4Mn magnesium alloys were prepared successfully and their microstructure, tensile and creep properties have been investigated. The results show that two binary Al-RE phases, Al11RE3 and Al2RE, are formed along grain boundaries in Mg-4Al-4RE-0.4Mn alloy, while the phase compositions of Mg-4Al-4La-0.4Mn alloy mainly consist of alpha-Mg phase and Al11La3 phase. And in Mg-4Al-4La-0.4Mn alloy the Al11La3 phase occupies a large grain boundary area and grows with complicated morphologies, which is characterized by scanning electron microscopy in detail. Changing the rare earth content of the alloy from Ce-rich mischmetal to lanthanum gives a further improvement in the tensile and creep properties, and the later could be attributed to the better thermal stability of Al11La3 phase in Mg-4Al-4La-0.4Mn alloy than that of Al11RE3 phase in Mg-4Al-4RE-0.4Mn alloy.

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

Ti44Zr32Ni22Cu2 and Ti41Zr29Ni28Cu2 alloys were prepared by the melt-spinning method. The phase structure was analyzed by X-ray diffraction, and the electrochemical performances of the melt-spun alloys were investigated. The results indicated that the Ti44Zr32Ni22Cu2 alloy was composed of the icosahedral quasicrystals and amorphous phases, and the Ti41Zr29Ni28Cu2 alloy comprised icosahedral quasicrystals, amorphous, and Laves phases. The maximum discharge capacity was 141 mAh/g for the Ti44Zr32Ni22Cu2 alloy and 181 mAh/g for the Ti41Zr29Ni28Cu2 alloy, respectively. The Ti41Zr29Ni28Cu2 alloy also showed a better high-rate dischargeabifity and cycling stability. The better electrochemical properties should be ascribed to the high content of Ni, which was beneficial to the electrochemical kinetic properties and made the alloy more resistant to oxidation, as well as to the Laves phase in the Ti41Zr29Ni28Cu2 alloy, which could work as the electro-catalyst and the micro-current collector.

Metallographic Analysis of Cu-Zr-Al Bulk Amorphous Alloys with Yttrium Addition

Minor yttrium addition can improve the glass-forming ability of Cu-Zr-Al ternary alloys via suppression of the growth of eutectic clusters. Yttrium addition also makes the room temperature ductility of the alloys decrease, and both the compressive strength and elastic strain limits increase slightly.

原位生成TiC粒子在快凝Al-Fe合金中变化行为的研究

通过OM，SEM和TEM等手段研究了在常规铸态以及快速凝固Al-8wt％Fe合金中原位生成TiC粒子时棚组成及显微组织的变化。同时结合利用外加法制备的常规铸态和快速凝固Al-8wt％Fe/TiC合金的娃微组织变化，得出了原位反应TiC粒子的生成及其在合金熔体中的变化行为：在常舰铸态下生成的尺寸较大的八岍体TiC颗粒在快速凝固过程中将发生全部或部分溶解，在随后的怏冷过程中将重新析出并形成细小的TiC粒子，原位生成的TiC粒子在快速凝固过程中同样可以对α-Al起到促发形核的作用。

The mechanism of PEO process on Al–Si alloys with the bulk primary silicon

This study focuses on mechanism of ceramic coating on Al-Si alloys with bulk primary Si using plasma electrolytic oxidation (PEO) technology. Al-Si alloys with 27-32% Si in weight were used as substrates. The morphologies, composition and microstructure of PEO coatings were investigated by scanning electron microscopy (SEM) with energy dispersive X-ray system (EDX). Results showed that the PEO process had four different stages. The effect of bulk Si is greatly on the morphology and composition of coatings at first three stages. Anodic oxide films formed on Al and Si phases, respectively. When the voltage exceeded 40 V, glow appeared and concentrated on the localized zone of interface of Al and Si phase. Al-Si-O compounds formed and covered on the dendrite Si phase surface, and the coating on bulk Si, which was silicon oxide, was rougher than that on other phase. If the treatment time was long enough, the coatings with uniform surface morphologies and elements distribution will be obtained but the microstructure of inner layer is looser due to the bulk Si.

熔盐电解法制备Al-Li合金的应用基础研究及其工艺初探

Al-Li合金是近年发展起来的新型航空材料，具有低密度、高强度的特点。目前世界上正就如何进一步提高其断裂韧性，使Al-Li合金尽早走出实验室，获得实际用进行广泛，深入的研究。熔盐电解法就是在这种情况下发展起来的。虽然此法现在尚处于研究的初级阶段，但已以其能够在较简单的设备上制备低Na高纯Al-Li合金的特点受到广泛的重视，是一种很有前途的发展方向。针对我国的技术、设备现状，在参考国外研究结果的基础上，采用熔盐电解法制备Al-Li母合金 → 应用合金的制备方法是可以尽快赶上世界发步伐的有效途径。因此，本文作为整个熔盐电解制备Al-Li合金系统研究的一部分，针对目前在此领域中很多应用基础问题，诸如：作为新的电解体系正在探索中的LiCl-KCl-LiF三元相图，Li在液体Al阴极中的扩散系数，利用熔盐电解法制备低Na高纯Al-Li合金的热力学基础及如何克服LiCl强烈的吸水性给电解工艺带来的种种不便等均未得到系统研究的现状，设计完成了一系列有关熔盐电化学和热力学实验，填补了本领域的一些研究空白，并为进一步系统研究工艺条件提供了重要的参考数据。1．用NH_4Cl氯化Li_2CO_3的研究 根据热力学从理论上论证了在200 ℃左右下述氯化反应：Li_2CO_3 + 2NN_4Cl = 2LiCl + 2NH_3~↑ + H_2O~↑ + CO_2~↑可以进行完全。利用DSC方法测定反应产物LiCl的纯度，并用离子色谱法分析反应产物中CO_3~=的含量，结果均证明：在Li_2CO_3:NH_4Cl = 1:4 (mol)时，Li_2CO_3可以定量转化为LiCl，剩余的NH_4Cl完全分解。根据热重分析结果推测NH_4Cl氯化Li_2CO_3的反应历程为：Li_2CO_3 + 2NH_4Cl = 2LiCl + 2NH_3~↑ + H_2O~↑ + CO_2~↑ NH_4Cl = HCl~↑ + NH_3~↑ 而并非是想像中的：NH_4Cl = HCl~↑ + NH_3~↑ 2HCl + Li_2CO_3 = 2LiCl + H2O~↑ + CO_2~↑利用X－射线衍射方法分析产物，结果亦说明氯化可以成功。将1:4（mol）= Li_2CO_3:NH_4Cl混合样品在差热分析反应炉中直接加热测定反应产物LiCl的溶点，并与纯LiCl样品熔点的测定结果相比较，二者完全一致。以上结果说明：不仅可用此氯化反应产物代替LiCl应用于熔盐电解制备Al-Li合金中，而且还可将其应用于LiCl体系的相图测定中。因Li_2CO_3，NH_4Cl均不吸水，极易处理，因此以上研究结果无论对于Al-Li合金的工艺研究还是其他有关LiCl体系的基础研究都是很有价值的。2．直接氯化法制备LiCl-KCl-LiF三元相图的研究。LiCl-KCl-LiF三元相图是研究此体系电解机制的重要基础。为将以上直接氯化法应用于差热分析中制作此三元体系相图，首先用直接氯化法测定了三个已知二元LiCl体系相图：LiCl－KCl；LiCl-LiF；LiCl-NaCl。与文献结果吻合很好。说明将此法应用于差热分析中制作LiCl体系相图结果是可靠的。在LiCl-KCl-LiF三元相图的测定中共做出七个垂直截面，在各截面上读出等温条件下的相界点投影到浓度三角形中，得到等温投影图。结果说明LiCl-KCl-LiF是固态完全不互溶的三元共晶体系，共有三个液－固两相区；三个液－固－固三相区；一个液－固－固－固四相区，（三元共晶平面）和一个固－固－固三相区。四相点温度为348 ℃，其组成在三相平衡线的交点处，在实验上测出近似等于：41.4KCl + 57.3LiCl + 1.3LiF (mol)。3．氯化物体系中Li~+, Na~+析出电位的比较及其去极化作用的研究。在正常电化序中，Li~+应先于Na~+析出。但在以Al作阴极电解LiCl体系时，则由于Li~+在Al上有较强的去极化作用而提前析出。这是熔盐电解法可以制备低Na，高纯Al-Li合金的基础。本文在理论上对此问题进行了较深入的研究。具体内容包括（1）。测定Li~+, Na~+在二元氯化物体系中的析出电位。通过在Al阴极，Mo阴极上二离子析出电位的比较，确认了Li~+在Al阴极上产生很强的去极化作用是能利用电解法制备低Na高纯Al-Li合金的根本原因。并为在工艺研究中选择合适的电流密度提供了参考依据。（2）．根据热力学理论推导出合金化反应产生的自由焓变化与去极化作用的关系：ΔG_x + ΔG_m = -nFΔE。揭示了产生去极化作用的原因。并根据ΔG_x（偏摩尔过剩自由焓）与合金结构的关系提出可以利用二元合金相图推测极化类型及极化大小。并根据动力学原理对温度对极化的影响提出了自己的看法。（3）．求出合金化反应的热效应，认为在一定条件下亦可利用此值作为判断去极化作用大小的标准。（4）．测定Li~+, Na~+在Al-Cu, -Al-RE合金上的析出电位。结果表明Cu，RE的存在均可加强Li~+在阴极上的去极化作用，进一步加大了Li~+, Na~+析出电位之间的差别，有利于制备更纯的Al-Li 使金。为直接生产Al-Cu-Li, Al-RE-Li三元母合金奠定了基础。（5）测定Li~+在不同组成配比的LiCl-KCl熔体中，在Al阴极上的析出电位，并求出LiCl的离子平均活度系数γ＝0.71 (T = 740 ℃), 熔体对理想状态产生负偏离。4．利用阳极计时电位法测定T＝720 ℃时Li在液体Al中的扩散系数D_(Li/Al) = 4.94 * 10~(-5)cm~2·s~(-1)，与利用Stocks-Einstan公式计算出的理论值D_(Li/Al) = 4.85 * 10~(-5)cm~2·s~(-1)吻合较好。5．在上述理论研究的基础之上进行了工艺初探，所得初步结论有：（1）．加入LiF可以提高电效。（2）．采用电流密度为1 A/cm~2时，不加搅拌亦可制备出成份均匀，含Li量为10％（w.f）的Al-Li合金。（3）．根据实验结果提出 Li在熔体中的熔解可能是影响电流效果的主要原因。

Crystallographic and electrochemical characteristics of Ti45Zr35Ni13Pd7 melt-spun alloys

Ti45Zr35Ni13Pd7 alloys are prepared by melt spinning at different cooling rates (v). The phase structure and electrochemical hydrogen storage performance are investigated. When U is 10 m/s, the alloy consists of icosahedral quasicrystalline phase (I-phase), C14 Laves phase and a little amorphous phase. When v increases to 20 or 30 m/s, a mixed structure of I-phase and amorphous phase is formed. Maximum discharge capacity of alloy electrode decreases from 156 mAh/g (v = 10 m/s) to 139 mAh/g (v = 30 m/s) with increasing v. High-rate discharge ability at the discharge current density of 240 mA/g decreases monotonically from 61.2% (v = 10 m/s) to 56.8% (v = 30 m/s).

Microstructures, mechanical properties and corrosion behavior of high-pressure die-cast Mg-4Al-0.4Mn-xPr (x=1, 2, 4, 6) alloys

Mg-4Al-0.4Mn-xPr (x = 1, 2, 4 and 6 wt.%) magnesium alloys were prepared successfully by the high-pressure die-casting technique. The microstructures, mechanical properties, corrosion behavior as well as strengthening mechanism were investigated. The die-cast alloys were mainly composed of small equiaxed dendrites and the matrix. The fine rigid skin region was related to the high cooling rate and the aggregation of alloying elements, such as Pr. With the Pr content increasing, the alpha-Mg grain sizes were reduced gradually and the amounts of the Al2Pr phase and All, Pr-3 phase which mainly concentrated along the grain boundaries were increased and the relative volume ratio of above two phases was changed. Considering the performance-price ratio, the Pr content added around 4 wt.% was suitable to obtain the optimal mechanical properties which can keep well until 200 degrees C as well as good corrosion resistance. The outstanding mechanical properties were mainly attributed to the rigid casting surface layer, grain refinement, grain boundary strengthening obtained by an amount of precipitates as well as solid solution strengthening.

Catalytic reduction of NO, by CO on hydrotalcites-derived mixed oxides CoAlM and MgAlM (M = Cr, Mn, Fe, Co, Ni, Cu)

Two series of mixed oxides, CoAlM and MgAlM (M = Cr, Mn, Fe, Co, Ni, Cu), were prepared by calcining their corresponding hydrotalcite-like compounds (HTLc). The ratio of Mg: Al: M (or Co: Al: hi) was 3:1:1. The catalytic activity of all samples for the reaction of NO + CO was investigated. The results showed that the activity of CoAlM was much higher than that of MgAlM. The structure and the property of redox were characterized by XRD and H-2-TPR. The results indicated that only MgO phase was observed after calcining MgAlM hydrotalcites, and the transition metals became more stable. The spinel-like phase appeared in all of CoAlM samples after the calcination, and the transition metals were changed to be more active, and easily reduced. The activities of three series of mixed oxides CoAlCu obtained from different preparation methods, different ratio of Co:Al: Cu and at different calcination temperatures, were studied in detail for proposing the mechanism of reaction. The ability of adsorption of NO and CO were investigated respectively for supporting the mechanism.

Shear Localization In Dynamic Deformation: Microstructural Evolution

Investigations made by the authors and collaborators into the microstructural aspects of adiabatic shear localization are critically reviewed. The materials analyzed are low-carbon steels, 304 stainless steel, monocrystalline Fe-Ni-Cr, Ti and its alloys, Al-Li alloys, Zircaloy, copper, and Al/SiCp composites. The principal findings are the following: (a) there is a strain-rate-dependent critical strain for the development of shear bands; (b) deformed bands and white-etching bands correspond to different stages of deformation; (c) different slip activities occur in different stages of band development; (d) grain refinement and amorphization occur in shear bands; (e) loss of stress-carrying capability is more closely associated with microdefects rather than with localization of strain; (f) both crystalline rotation and slip play important roles; and (g) band development and band structures are material dependent. Additionally, avenues for new research directions are suggested.

铸态铝硅合金在磷酸盐电解液中表面陶瓷化行为及结构特征

采用等离子体电解氧化技术在铝硅合金表面制备了陶瓷层,电解液为磷酸盐系列。利用轮廓仪、SEM和XRD对陶瓷层的粗糙度、形貌和相组成进行了研究。结果表明,PEO处理过程可分为4个典型阶段。随处理时间延长,陶瓷层的厚度近似线性增长,表面缺陷增大增多,粗糙度显著增加,达到9.5μm。PEO处理初期只生成γ-Al_2O_3,一定时间后α-Al_2O_3出现,其相对含量逐渐增多.