XRD and XPS studies on the ultra-uniform Raney-Ni catalyst prepared from the melt-quenching alloy

We present a novel method for preparing an ultra-uniform Raney-Ni catalyst, which includes melt-quenching, hydrogen treatment and leaching in an alkali solution. The resultant catalyst shows superior activity in the reaction of cyclohexanone hydrogenation. X-ray diffraction (XRD) and XPS have been employed to characterize the catalysts. As demonstrated, the pretreatment with hydrogen caused a distinct phase transfer of the Ni-Al alloys, forming more of the Ni2Al3 component. In the subsequent leaching process, the Ni2Al3 component shows high activity and the resultant catalyst exhibits high surface areas and small pores. Moreover, metallic Al in the hydrogen-pretreated alloy appeared to be leached more easily and thus the aluminium species remaining on the catalyst surface is aluminium oxide predominantly, which serves as a matrix to stabilize active Ni species on the surface. Copyright (C) 2001 John Wiley & Sons, Ltd.

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.

Fractography and Crack Initiation of Very-High-Cycle Fatigue for a High Carbon Low Alloy Steel

Very-High-Cycle Fatigue (VHCF) is the phenomenon of fatigue damage and failure of metallic materials or structures subjected to 108 cycles of fatigue loading and beyond. This paper attempts to investigate the VHCF behavior and mechanism of a high strength low alloy steel (main composition: C-1% and Cr-1.5%; quenched at 1108K and tempered at 453K). The fractography of fatigue failure was observed by optical microscopy and scanning electron microscopy. The observations reveal that, for the number of cycles to fatigue failure between 106 and 4108 cycles, fatigue cracks almost initiated in the interior of specimen and originated at non-metallic inclusions. An “optical dark area” (ODA) around initiation site is observed when fatigue initiation from interior. ODA size increases with the decrease of fatigue stress, and becomes more roundness. Fracture mechanics analysis gives the stress intensity factor of ODA, which is nearly equivalent to the corresponding fatigue threshold of the test material. The results indicate that the fatigue life of specimens with crack origin at the interior of specimen is longer than that with crack origin at specimen surface. The experimental results and the fatigue mechanism were further analyzed in terms of fracture mechanics and fracture physics, suggesting that the primary propagation of fatigue crack within the fish-eye local region is the main characteristics of VHCF.

Nonequilibrium microstructures and phase evolutions of an iron-based laser clad coating

The microstructural and compositional features of the laser-solidified microstructures and phase evolutions occurring during high temperature tempering were investigated by using analytical electron microscopy with energy dispersive X-ray analysis. The cladded alloy, a powder mixture of Fe, Cr, W, Ni and C with a weight ratio of 10:5:1:1:1, was processed with a 3 kW continuous wave CO2 laser. The cladded coating possessed the hypoeutectic microstructure of the primary dendritic gamma-austenite and interdendritic eutectic consisting of (gamma+M7C3). The gamma-austenite is a nonequilibrium phase with extended solid solution of alloying elements. And, a great deal of fine structures, i.e., a high density of dislocations, twins, and stacking faults existed in austenite phase. During high temperature aging, the precipitation of M23C6, MC and M2C in austenite and in situ transformation of M7C3(+gamma) --> M23C6 and M7C3+gamma --> M6C occurred. The laser clad coating revealed an evident secondary hardening and superior impact wear resistance.

Toughness Of Ni/Al2O3 Interfaces As Dependent On Micron-Scale Plasticity And Atomistic-Scale Separation

Ceramic/metal interfaces were studied that fail by atomistic separation accompanied by plastic dissipation in the metal. The macroscopic toughness of the specific Ni alloy/Al2O3 interface considered is typically on the order of ten times the atomistic work of separation in mode I and even higher if combinations of mode I and mode II act on the interface. Inputs to the computational model of interface toughness are: (i) strain gradient plasticity applied to the Ni alloy with a length parameter determined by an indentation test, and (ii) a potential characterizing mixed mode separation of the interface fit to atomistic results. The roles of the several length parameters in the strain gradient plasticity are determined for indentation and crack growth. One of the parameters is shown to be of dominant importance, thus establishing that indentation can be used to measure the relevant length parameter. Recent results for separation of Ni/Al2O3 interfaces computed by atomistic methods are reviewed, including a set of results computed for mixed mode separation. An approximate potential fit to these results is characterized by the work of separation, the peak separation stress for normal separation and the traction-displacement relation in pure shearing of the interface. With these inputs, the model for steady-state crack growth is used to compute the toughness of the interface under mode I and under the full range of mode mix. The effect of interface strength and the work of separation on macroscopic toughness is computed. Fundamental implications for plasticity-enhanced toughness emerge.

铁基激光熔覆合金设计及微观组织与性能研究

本文设计并制备了具有优良的强韧性能和高温性能的激光熔覆涂层。利用 SEM、TEMEY X－射线衍射仪等研究了涂层的化学成分、宏微观结构及其转变机制，同时研究了涂层强韧性及耐高温磨损性能及其影响机制。对激光溶覆涂层进行了合金化、微观组织、强韧化机制、加工工艺性能设计。合金系为 Fe-Cr-C-W-Ni，成分配比（质量分数），Fe:52-60%, Cr:24-30%, C:5-6%, W:4.5-7.5%, Ni:5-6%。强化机制为两相强化、亚结构强化及固溶强化，其中强化相为合金碳化物，基体相为合金元素过饱和度极高的韧性奥氏体。亚共晶及过共晶组织的领先凝固相分别为奥氏体及 M_7C_3 合金碳化物，两相共晶组织均为韧性相奥氏体和强化相 M_7C_3 合金碳化物。加工工艺控制领先凝固相的结构、组织演化及力学性能。熔覆组织在高温时效过程中形成大量新的碳化物。在过饱和奥氏体内部，可弥散析出细小的 Mc、M_2C 及 M_(23)C_6碳化物；在奥氏体与 M_7C_3 相界面，亚稳相M_7C_3发生原位转变，形成 M_(23)C_6 及 M_6C碳化物。激光熔覆合金具有较高的综合力学性能，熔覆涂层有高的显微硬度、优良的抗回火稳定性、显著的二次硬化特征、优异的抗磨粒磨损和冲击磨损性能。Fe-Cr-C-W-Ni 激光熔覆合金具有较低的裂纹形成倾向和良好的表面成形性能，这与奥氏体较高的高温韧塑性及合金的低熔点共晶特征密切相关；实验及理论分析表明，通过调整合金成分、激光工艺参数和后续热处理工艺，可获得具有不同强韧性能的熔覆涂层。

激光热处理对化学沉积Ni-P合金薄膜性能的影响

用扫描电镜(SEM)观察了化学沉积Ni-P合金薄膜/单晶硅基体的结构与颗粒度,利用X射线衍射(XRD)技术测试了其化学沉积后的残余应力,测量了激光热处理后残余应力的变化规律,分析了残余应力对磨损性能及界面结合强度的影响。实验结果表明,化学沉积Ni-P合金薄膜/硅基体的残余应力均表现为拉应力,经过激光热处理后残余应力发生了变化,由高值的拉应力变为低值的拉应力或压应力；薄膜残余应力对其磨损性能有明显的影响,其磨损量随着残余应力的减小而减小；薄膜与基体结合强度随着残余应力的增大而减小,合理地选择激光热处理参数可

杂多化合物的氧化还原性质、自组装和应用

1．利用电化学和现场紫外-可见-近红外光谱电化学的方法，系统研究了一系列过渡金属取代杂多化合物ZnW_(11)M(M = Cr，Mn，Fe，Co，Ni，Cu，Zn)的电化学行为。所有的这些化合物都在相近的电位处表现出四对连续的基于W中心的氧化还原反应。研究表明，ZnW_(11)M中基于W中心的氧化还原反应可能反映了它那个未知的缺位阴离子ZnW_(11)的氧化还原反应。此外，电活性过渡会属取代杂多化合物ZnW_(11)M(M = Cu，Fe，Mn)还表现了过渡金属M的氧化还原反应。例如：ZnW_(11)Cu~(11)表现出Cu的沉积和溶出，ZnW_(11)Fe~(III)在正电位处有一特殊的源于Fe的氧化还原反应，ZnW_(11)Mn则发生一个氧化反应和两个还原反应。根据实验结果我们提出了一些基本的反应机理。选取HNO_2为底物考察了这一系列过渡金属取代杂多化合物的电催化性能。通过比较电催化还原电流的大小，我们可以定性地排出这一系列过渡金属取代杂多化合物对HNO_2还原反应的电催化性能的顺序（由高到低）：ZnW_(11)Cu > ZnW_(11)Co > ZnW_(11)Cr和ZnW_(11)Fe > ZnW_(11)Zn、ZnW_(11)Mn和ZnW_(11)Ni。这一系列过渡金属取代杂多化合物的电催化性能的差别，可能主要是来自于它们分子结构中所取代的过渡金属元素的影响。实验证明ZnW_(11)M对HNO_2还原反应的电催化过程中产生NO气体。2．采用末端带有电荷的烷基硫醇首先自组装在金电极表面形成前体膜，在此前体膜上成功地沉积出杂多阴离子和一种阳离子聚合物的多层膜。利用多种技术对这种多层膜进行了表征，包括紫外可见光谱法、X射线光电子能谱法、反射-吸收红外光谱法、电化学石英晶体微天平法等。而且我们把这种修饰方法推广应用于不同结构类型、不同组成的杂多阴离子和同多阴离子中去，制备了它们的多层膜。利用原位EQCM技术研究了杂多酸分子的吸附动力学行为及电化学反应过程中的离子传输特性。实验结果表明，在修饰膜的电化学反应过程中，HSO_4~-离子的迁移在膜的电荷补偿中是必不可少的。修正并发展了依据原位EQCM技术考察迁移物种特性的方法，并基于此详细分析了HPA分子在各种修饰条件下电化学反应中正常及反常的频率响应及离子迁移行为。3．首次开发出来一种新颖的多层膜成膜方法-电化学生长法，并应用于制备含杂多化合物的多层膜中。通过多种技术表征，证明了电化学生长法比文献中通用的浸泡法更优越，可以在含有支持电解质的溶液里成膜而没有其它离子竞争吸附的缺点，制备出的自组装多层膜生长更均匀、超薄且功能良好。电化学生长法可望在制备其它种类的多层膜中会有广泛的应用。同时，我们也比较了这两种多层膜对于底物BrO_3~-和HNO_2还原反应的电催化作用。特别地，我们详细考察了多层膜厚度和最外层种类对电催化反应的影响。我们发现电催化性能随着多层膜层数（厚度）的增加而增长，这意味着我们可以通过调节多层膜的层数来达到最有效的催化性能，这一点是多层膜修饰电极优越于其它类型修饰电极最突出的优点之一。此外，我们还发现QPVP-Os最外层对催化反应有着一定的阻碍作用。这些影响作用可以从多层膜中电催化剂沉积量的多少和QPVP-Os最外层的屏蔽作用得以解释。4．尽管SiW_(l2)O_(40)~(4-)不能直接吸附在裸金电极的表面形成单层膜，我们成功地在预先自组装有半胱氨的金电极上制备出来了SiW_(12)O_(40)~(4-)单层膜。但是，这种SiW_(12)O_(40)~(4-)单层膜化学修饰电极的稳定性较差。基于同阳离子聚合物QPVP-Os的静电相互作用，我们成功地制备了均匀的SiW_(l2)O_(40)~(4-)多层膜。SiW_(l2)O_(40)~(4-)多层膜CMEs对BrO_3~-，H_2O_2和HNO_2的还原表现出显著的催化效应。对HNO，还原的催化效应随着层数由l到3的增加而增强，而这种催化效应的增强却随着层数由3到7而趋于平缓。由于多层膜结构是建立在同QPVP-Os的强烈的静电作用上的，因此SiW_(12)O_(40)~(4-)多层膜CMEs比单层膜CMEs有更好的稳定性。我们主要利用电化学方法（循环伏安法，CV）、紫外可见光谱法(UV-vis)、X-射线光电子能谱法(XPS)、X-射线反射法(XR)和电化学交流阻抗法(EIS)，对这种杂多阴离子自组装多层膜的成膜过程、多层膜结构和组成进行了进一步地表征。5．通过氨阳离子自由基修饰方法，把4-氨基苯甲酸修饰到玻碳电极表面。研究了该单层膜对多种电活性分子的影响，膜的阻滞行为主要是由于静电相互作用所导致的。利用循环伏安和电化学交流阻抗法考察了4-氨基苯甲酸修饰电极对不同酸度条件下铁氰化钾的电子传递情况，并测得了它的表面pKa值大约为3.1。以修饰在玻碳电极表面的4-氨基苯甲酸单层膜为前体膜，成功地静电沉积了阳离 子聚合物QPVP-Os和多种杂多化合物组成的多层膜。采用循环伏安法详细研究了这种杂多化合物单层膜和多层膜的电化学行为，并且考察了这种复合膜对三种底物BrO_3~-,HNO_2及H_2O_2的还原反应的电催化性能。6．类似地，在4-氨基苯甲酸修饰的玻碳电极表面上，我们也成功地制备了SiW_(12)的多层膜。循环伏安、X-射线光电子能谱和X-射线反射的实验结果证明多层膜的生长非常均匀而且稳定。X-射线反射实验测定了多层膜中每个SiW_(12)/QPVP-Os双层的平均厚度为30.3A。这种复合膜对Br0_3~-，HNO_2和H_2O_2还原有明显的催化活性，并且在较大的浓度范围内催化电流与浓度具有良好的线性关系。更有意义的是，随着SiW_(12)多层膜层数的增加（固定在多层膜中催化剂量的增加），多层膜的催化能力具较大程度地提高。因此，我们可以通过合理地控制多层膜的厚度来改善其催化活性及分析测定的灵敏度，从而达到最佳的催化效能和优化出最适宜的实验条件。由于电极的稳定性较好，期望可以实际用于Br0_3~-，HNO_2和H_20_2的检测。7．采用电化学生长方法在4-氨基硫酚自组装膜修饰的金电极上，制备了包含杂多阴离子（SiMo_(11)VO_(40)~(5-)和Pr(SiMo_7W_4)O_(40)~(5-)）和阳离子聚合物PDDA的多层膜修饰电极。用循环伏安法研究了多层膜修饰电极的电化学行为。在多层膜生长过程中，我们发现Mo的第三个氧化还原峰随多层膜层数的增加显著增长，而前两个氧化还原峰增长缓慢甚至不增长，这可能是由于PDDA对Mo的前两个还原峰有一定的阻碍作用所导致的。多层膜修饰电极的峰电位随pH的增加而线性负移，表明有氢离子参与到杂多阴离子的氧化还原反应中。多层膜修饰电极对BrO_3~-和HNO_2的还原反应有良好的电催化作用，Mo的第三个还原峰峰电流与BrO_3~-的浓度都有良好的线性关系，并且催化电流随着多层膜层数的增加而增长。8．我们考察了首先通过静电沉积技术（离子键组装）成膜，然后经过后续光化学反应来制备一类含聚苯胺的基于共价键结合的多层膜。通过紫外光的辐照，膜的交联结构可由离子键型转变为共价键型。溶剂刻蚀的结果表明此种共价键合多层膜有更好的稳定性。电化学实验表明，以此种方式组装在多层膜中的聚苯胺仍保留了其电化学性质。

内标法提高ICP-AES法测定精度和准确度-铜合金分析

电感耦合等离子体发射光谱（ICP-AES）已有20多年的历史，经过20年来的发展，ICP-AES已成为世界各地分析化学实验室制备的分析手段之一。目前ICP-AES已经应用于生物样品、地质样品，合金等各种样品的分析中。虽然ICP-AES已成为溶液分析最理想、最有效的方法之一，但由于样品组成的复杂性，也使分析化学工作者面临着许多困难。如在钢铁及合金分析中，样品主成份的分析需准确度要好于1%，精密度≤0.3%，采用ICP-AES法的非内标法通常是达不到要求的。对于一些较纯的水溶液样品，一般可以采用简单的水样标准化，而含有复杂的、可变的基体成份就不适合于基体匹配。为了使冶金样品主成份分析的精度小于0.3%，准确度好于1%，我们将ICP摄谱法广泛应用的内标法应用到光电直读光谱仪中。内标法的作用达到了这一目的。使用内标法，就是要使内标元素能起到在等离子体激发过程中变动的补偿作用同时，还能起到在样品引入过程中，对样品喷雾量和提升率变动的补偿作用以提高分析方法精度和准确度。在初步的试验中，我们考察了28种元素谱线强度随等离子体操作参数变化的情况。（a）谱线强度与正向功率的关系；（b）谱线强度与观察高度的关系；（c）谱线强度与载气流速的关系。这样各元素在等离子体中的行为就因所给定的条件不同而异。根据上述28种元素在等离子体中的行为进行分类，为选择合适的内标元素奠定了基础。我们还对等离子体的正向功率、载气流量、观察高度、酸度等实验条件做了研究。发现，当各操作参数等主要条件改变时，谱线强度往往改变较大，但选择的内标元素谱线亦有类似的变化。因此，在采用内标法后，可以使这种变动得到一定的补偿，从而提高了分析结果的精度。本工作选用的折衷工作条件为：正向功率：1.30KW；载气流量：0.75 l/min; 观察高度：17 mm; 酸度：10% HNO_3(v/v)。研究了单一酸对分析元素谱线强度的影响。结果表明，单一酸的酸度在20%（v/v）以内，对分析元素与内标元素的谱线净强度的比值无影响。在折衷工作条件下，我们用合成水溶液体系研究了共存元素引起的物理干扰对分析元素谱线强度的影响。实验结果表明，随着试液中共存元素（Cu）浓度的增加，粘度明显增加，并导致提升量的急剧降低，谱线强度相应下降。但是当气溶胶导入量发生变化的时候，同时也引起内标元素和分析元素的原子或离子在等离子体中浓度分布的发迹内标元素与分析元素严格一致，可以较正共存元素引起的物理干扰。当共存元素达到一定的浓度时，由于内标元素与分析元素不严格一致，内标法失去作用。我们又考察了内标元素的浓度对分析元素的影响，内标元素的加入量从5～500μg/ml变化。当内标元素的浓度为200μg/ml时，对Mo, Ni, Pb, Ti及Mg略有影响，对其它元素无影响。我们选定内标元素的浓度为10 PPm。在折衷工作条件下，我们绘制了含有Y作内标的一套工作曲线及相应的不含Y的工作曲线，并分析了BMn40-1.5锰白铜样品。结果表明，当含量大于0.3%时，测定精度均低于0.3%，并得出以下结论：（1）各种元素在等离子体中的行为依测定条件而异，因此内标元素的选择最好是从在等离子体中行为相似的一组内选择。（2）在光电直流光谱仪中动用内标法可以提高样品中主成份元素的精度和准确度。（3）内标法在SBR较高的情况下可以起到较好的效果，但当SBR较小时，内标法就会失去作用。样品分解是样品分析的关键步骤。在现有的分解方法中，常用的有干灰化法和湿灰化法等。然而这些方法各有其缺点。因此，我们试图寻找一种快速的湿法消解技术，微波炉快速样品溶解似乎很具有吸引力。我们利用国产微波炉和全聚器氟乙烯密封溶器结合，系统地考查了微波炉溶解茶叶及茶树叶，利用ICP-AES测定的可行性，并与湿式消解法，加压密封法等进行了比较，获得满意结果。首先，我们选择了微波炉消化处理的最佳条件，确定了最佳溶解方案，已证明HNO_3-HF(5:1)混合酸溶解样品是令人满意的。又研究了微波炉加热对分析无素挥发性的影响。结果表明，微波炉加热与不经微波炉加热样品的浓度没有明显差异。按上述确定的工作条件，我们分析茶叶及茶树叶样品，并与不同的处理方法进行了比较。采用干灰化法处理茶叶（茶树叶）至少需8小时，而且还极易损失和沾污，但干灰化法用的酸量较少，空白较低，对Cr等的测定有利。湿法消解由于使用HClO_4-HF混酸，B大部分损失或完全挥发挥失。然而采用微波炉完全溶解样品只需19分钟即可，而且由于未使用HClO_4，样品溶液最后只需蒸至近干，有效地防止了易挥发元素的损失及某些不溶性高氯酸盐的生成。微波炉混合酸消酸系统是一种合适的溶解各种各样样品的技术，它为分解各种各样样品以进行多元素测定提供了一种快速、准确、经济的方法。该方法对于通常在敞口溶器中分解易于损失的挥发性元素特别有用，而且还特别适用于样品个数多，量少的生物样品等的微量元素的分析测定。

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

Ti-based icosahedral quasicrystalline phase (I-phase) exhibited excellent hydrogen storage property for special structure. Unfortunately, the application as the negative electrode material of the nickel-metal hydride batteries was limited due to the poor electrochemical kinetics. Meanwhile, rare-earth element was beneficial to the electrochemical properties of Ti, Zr-based alloy.

Structure and electrochemical characteristics of melted composite Ti0.10Zr0.15V0.35Cr0.10Ni0.30-LaNi5 hydrogen storage alloys

The structure and electrochemical characteristics of melted composite Ti0.10Zr0.15V0.35Cr0.10Ni0.30+x% LaNi5 (x=0, 1, 5 and 10) hydrogen storage alloys have been investigated systematically. XRD shows that the matrix phase structure of V-based solid solution phase with a BCC structure and C14 Laves phase with hexagonal structure is not changed after adding LaNi5 alloy. However, the amount of the secondary phase increases with increasing LaNi5 content. Field emission scanning electron microscopy-energy dispersive spectroscopy (FESEM-EDS) shows that the C14 Laves phase contains more Zr and the white lard phase has a composition close to (Zr, Ti)(V, Cr, Ni, La)(2).

Phase separation and crystallization in a melt-spun Ti45Zr35Ni17Cu3 alloy

Structure and crystallization behavior of amorphous and quasicrystalline Ti45Zr35Ni17Cu3 alloy have been studied. DSC trace of the amorphous alloy obtained during continuous heating to 1300 K shows distinctly an exothermic peak and two endothermic peaks.

Electrochemical hydrogen storage in (Ti1-xVx)(2)Ni (x=0.05-0.3) alloys comprising icosahedral quasicrystalline phase

For (Ti1-xVx)(2)Ni (x = 0.05,0.1,0.15,0.2 and 0.3) ribbons, synthesized by arc-melting and subsequent melt-spinning techniques, an icosahedral quasicrystalline phase was present, either in the amorphous matrix or together with the stable Ti2Ni-type phase. With increasing x values, the maximum discharge capacity of the alloy electrodes increased until reached 271.3 mAh/g when x = 0.3. The cycling capacity retention rates for these electrodes were approximately 80% after a preliminary test of 30 consecutive cycles of charging and discharging.

Crystallographic and electrochemical characteristics of Ti-Zr-Ni-Pd quasicrystalline alloys

Ti45Zr35Ni20-xPdx (x = 0, 1, 3, 5 and 7, at%) alloys were prepared by melt-spinning. The phase structure and electrochemical hydrogen storage performances of melt-spun alloys were investigated. The melt-spun alloys were icosahedral quasicrystalline phase, and the quasi-lattice constant increased with increasing x value. The maximum discharge capacity of alloy electrodes increased from 79 mAh/g (x = 0) to 148 mAh/g (x = 7). High-rate dis-chargeability and cycling stability were also enhanced with the increase of Pd content. The improvement in the electrochemical hydrogen storage characteristics may be ascribed to better electrochemical activity and oxidation resistance of Pd than that of Ni.