Corrosion behavior of Mg,AZ31, and AZ91 alloys in dilute NaCl solutions

Corrosion behavior of extruded Mg, extruded AZ31 alloy, and cast AZ91 alloy was investigated by electrochemical measurements in dilute NaCl solutions. Corrosion products and passivation films were analyzed by X-ray diffraction and X-ray photoelectron spectroscopy. All specimens exhibit the corrosion and passivation zones in dilute NaCl solutions. The aluminum content and alloy microstructure influence the corrosion and passivation processes. AZ91 alloy shows the broadest passivation zone followed by AZ31 alloy and Mg. AZ91 alloy reveals a highest corrosion resistance, and preferential attack is located at the primary Mg phase. Its relatively fine β-phase (Mg₁₇Al₁₂) network and Al₂O₃/Al(OH)₃ compounds produced on the passivation film are the main factors which limit the corrosion progress as compared with AZ31 alloy and Mg. The thick passivation product on AZ31 alloy is the key factor which restricts the corrosion attack in dilute solutions.     

Crystallographic, electronic and magnetic studies of Ce4Ni6Al23: a new ternary intermetallic compound in the cerium-nickel-aluminum phase diagram

The Al-rich portion of the ternary Ce-Ni-Al has been investigated and a new ternary phase of composition Ce₄Ni₆Al₂₃ has been found. This compound crystallizes in the monoclinic space group C2/m with the cell parameters a=16.042(8), b=4.140(4), c=18.380(8) Å and β=113.24(5)°. The structure has been determined by single crystal X-ray diffraction. The local environment of Ni and Ce is close to what is observed in the CeNi₂Al₅ and CeNiAl₄ structures. Band structure calculations, using the tight-binding-linear muffin-tin orbital-atomic-spheres approximation (TB-LMTO-ASA) method, have been performed to understand the electronic structure of Ce₄Ni₆Al₂₃ and the results are discussed in connection with those two other Ce-Ni-Al intermetallic compounds, which possess heavy-fermion behavior. Magnetic and heat capacity measurements have also been measured to analyze the low-temperature magnetic behavior of this new compound.     

Influence of Ag substitution on the local structure and glass-forming ability of Al86Ni(8-x)Y6Agx (X = 0,1,2) liquids

The local structure of Al₈₆Ni_(8-x)Y₆Ag_x (X = 0,1,2) molten and glassy alloy was investigated by ab initio molecular dynamics simulation. It transpired that the Al₈₆Ni_(8-x)Y₆Ag_x alloy can be considered as a combination of Ni- and Y-centred Al clusters with Ag as ‘glue atoms’. First and second Ag–Ag coordination was scarcely found in Al₈₆Ni₇Y₆Ag₁, but a medium-range order between 7.5 and 9 Å was observed. The enhanced glass-forming ability and thermal stability of the alloy compared with Al₈₆Ni₈Y₆ can be attributed to the medium-range order of the Ag–Ag correlation. A second Ag–Ag coordination occurs in Al₈₆Ni₆Y₆Ag₂ and results in a decrease in glass-forming ability. The inter-atomic distances between all constituting elements increase during cooling. This increase is ascribed to a change in distribution of clusters around Al atoms towards clusters with higher coordination number around Al.     

热处理温度对La-Y-Ni合金相结构和电化学性能的影响

采用磁悬浮感应熔炼法制备了组分为LaY_2Ni_(9.7)Mn_(0.5)Al_(0.3)的合金,在不同温度(1 073～1 373 K)下对合金进行热处理,利用X射线衍射法(XRD)、电子探针(EPMA)和电化学性能测试等方法,系统地研究了热处理温度对合金相结构和电化学性能的影响。结果表明,热处理可以显著提高合金的相均匀度,随着热处理温度的升高合金中的主相Ce_2Ni_7相先增加后减少。电化学研究表明,合金电极的最大放电容量、倍率性能和循环稳定性随着热处理温度的升高均呈现先升高后降低的趋势,与Ce_2Ni_7相含量的变化一致。电化学压力-组成-温度(P-C-T)测试表明,合金具有2个放氢平台,且随着热处理温度的升高合金的放氢坪台压增加。当热处理温度为1 273 K时,合金的Ce_2Ni_7相含量最高为86.53%(w/w),电化学性能最佳,最大放电容量为386.80 mAh·g~(-1)(60mA·g~(-1)),在电流密度为900 mA·g~(-1)时的高倍率性能HRD_(900)=89.45%,循环300周后的容量保持率S_(300)=72.18%(300 mA·g~(-1))。     

On the structural and magnetic properties of the ternary silicides Ce6M1.67Si3 (M=Co, Ni) and Ce5Ni1.85Si3

Contrary to that reported previously, the ternary silicide “Ce₆Ni₂Si₃” does not exist. The melting of this alloy, followed or not by annealing, leads to the existence of the two new ternary compounds, Ce₆Ni_1.67Si₃ and Ce₅Ni_1.85Si₃. The investigation of these ternary silicides based on nickel and Ce₆Co_1.67Si₃ by X-ray diffraction on single crystal reveals an ordered distribution between Ni (or Co) and Si atoms. The nickel or cobalt positions in the chains of face-shared octahedra of cerium are not fully occupied with a strong delocalisation of their electron density. The structural investigations of these compounds confirm that the “Ce₆Ni₂Si₃” and “Ce₅Ni₂Si₃” structural type have to be rewritten as Ce₆Ni_2−xSi₃ and Ce₅Ni_2−xSi₃. Magnetisation and specific heat measurements evidence a magnetic ordering at 3.8(2) K for Ce₆Ni_1.67Si₃ and a heavy fermion behaviour for Ce₆Co_1.67Si₃.     

Effect of Co substitution for Ni on the microstructure and electrochemical properties of La-R-Mg-Ni-based hydrogen storage alloys

Hydrogen storage alloys La_0.63Gd_0.2?Mg_0.17Ni_3.35?x Co _x Al_0.15 (x?=?0, 0.1, 0.3, 0.5, 1.0, 1.5, 2.0) were prepared by induction melting followed by annealing treatment in argon atmosphere. The electrochemical properties of La_0.63Gd_0.2?Mg_0.17Ni_3.35?x Co _x Al_0.15 (x?=?0, 0.1, 0.3, 0.5, 1.0, 1.5, 2.0) alloy electrodes depended on the alloy structure type. XRD patterns and EPMA showed that the alloys consisted of Ce₂Ni₇-type (Gd₂Co₇-type), CaCu₅-type, Pr₅Co₁₉-type, and PuNi₃-type phase structure. Pr₅Co₁₉-type and Ce₂Ni₇-type phase increased with the increase of Co content x. However, CaCu₅-type phase firstly decreased then increased as Co content increased. Rietveld analysis showed that the c-axis lattice parameters and cell volumes of the component phases increased with increasing Co content. The electrochemical measurements showed that as the Co content increased, the maximum discharge capacity and the cyclic stability of the annealed alloys both first increased and then decreased. The La_0.63Gd_0.2?Mg_0.17Ni_3.05Co_0.3Al_0.15 alloy electrode exhibited the maximum discharge capacity (392.92 mAh/g), and La_0.63Gd_0.2?Mg_0.17Ni_1.85Co_1.5Al_0.15 alloy electrode showed the best cyclic stability (S₁₀₀?=?96.1 %). The electrochemical kinetics studies indicate that La_0.63Gd_0.2?Mg_0.17Ni_1.85Co_1.5Al_0.15 exhibited a higher rate dischargeability (HRD₉₀₀?=?86.3 %). Electrochemical analyses showed that the control process of alloy electrode reaction is charge-transfer rate in surface film of alloy.     

基于电化学噪声研究缓蚀剂对AA6063铝合金点蚀的影响

采用电化学噪声(ECN)、电化学阻抗谱(EIS)和极化曲线研究了AA6063 铝合金在3% (w) NaCl 溶液中的亚稳态点蚀萌发和稳态点蚀生长特征, 着重探讨了CeCl₃、Na₂CrO₄、8-羟基喹啉(8-HQ)等三种不同类型缓蚀剂对亚稳态和稳态点蚀的抑制机理. 结果表明: 当铝合金表面阴极相(Al-Si-Fe)周边的Al 基体发生局部溶解后,会导致邻近区域pH值升高(>8.4), 引起Ce(OH)₃在蚀点中心区的阴极相表面优先沉积, 从而抑制局部腐蚀的阴极去极化过程. 随着缓蚀剂浓度的提高, 亚稳态噪声峰的平均积分电量(q)随之递减, 但噪声峰的平均寿命几乎没有变化, 表明Ce³⁺并不能直接加速亚稳态蚀点的修复, 但可降低蚀点内金属Al 的溶解速率. CrO₄^2-不但可加速蚀点修复, 还可降低亚稳态蚀点的形核速率. 8-HQ主要与Al³⁺、Mg²⁺等形成不溶性螯合物并沉积在铝合金表面,提高了铝基体的全面抗腐蚀能力, 但并不能显著提高其耐点蚀能力.     

The electrochemical properties of Al–Si–Ni alloys composed of nanocrystal and metallic glass for lithium-ion battery anodes

Melt-spun Al_75?X Si₂₅Ni _X (X?=?2, 4, 7, and 10?mol%) alloys were investigated as anode materials for lithium-ion batteries. The Al₆₈Si₂₅Ni₇ anode showed a maximum capacity of 840?mA?h?g^?1 at the fifth cycle and maintained 661?mA?h?g^?1 after 40 cycles with a high coulumbic efficiency of 93%. The specific capacity increased as the decrease in the Ni content during the first 20 cycles, but the cycle performance became poorer. For the Al₆₅Si₂₅Ni₁₀ anode, the specific capacity increased slowly as the cycles increased and reached 370?mA?h?g^?1 after 40 cycles. When the Al₆₈Si₂₅Ni₇ ribbons were annealed, their initial capacity became higher, but much poorer cycle performance and low coulumbic efficiency occurred. Except Al₆₅Si₂₅Ni_10, the AlLi compound could be detected in the anodes after lithiation. However, the capacity faded rapidly due to the formation of excessive AlLi in the Al₇₃Si₂₅Ni₂ and annealed Al₆₈Si₂₅Ni₇ anodes. The experiments revealed that the as-quenched ribbons consisted of the nanoscaled α-Al, metallic glass and α-Si, and their fractions were dependent on the Ni content. The α-Al was a supersaturated solid solution of Si and Ni in fcc-Al. For the as-quenched Al₆₈Si₂₅Ni₇ ribbons, the α-Al grains were embedded in the amorphous matrix. It can be understood that metallic glass can store Li, and the supersaturated solid solution can store Li even more easily compared with other known Al–Si-based alloys. A conclusion can be drawn that the microstructure that the nanoscaled α-Al embedded in the metallic glass matrix is beneficial to improve the structure stability, restrain serious structural evolution, and limit the volume variation and pulverization during electrochemical cycles.     

Crystallographic and hydriding properties of the system La1−xCexY2Ni9 (xCe=0, 0.5 and 1)

The structural properties of the system La_1−xCe_xY₂Ni₉ with x_Ce=0, 0.5 and 1 have been investigated by electron probe microanalysis, powder X-ray diffraction and absorption spectroscopy. The compound LaY₂Ni₉ adopts a rhombohedral structure of PuNi₃-type (R-3m space group, Z=3). It can be described as an intergrowth between RM₅ (Haücke phase) and RM₂ (Laves phase) type structures. Among the two available crystallographic sites for R atoms, lanthanum occupies preferentially the site 3a leading to a partially ordered ternary compound. Substitution by cerium involves anisotropic variations of the cell parameter with a decrease of a and an increase of c leading to an overall cell volume reduction. Increasing cerium content does not induce any symmetry change but leads to a statistical distribution of the rare earths over the two sites 3a and 6c involving an evolution toward a pseudo-binary compound. This behavior is related to the intermediate valence state of cerium observed by X-ray absorption spectroscopy. The hydriding properties of the two compounds LaY₂Ni₉ and CeY₂Ni₉ are described in relation with their crystallographic structure.     

Structural and electrochemical properties of high-capacity Ml-Mg-Ni-based hydrogen storage alloys

The Ml-Mg-Ni-based (Ml = La-rich mixed lanthanide) hydrogen storage alloy Ml_0.88Mg_0.12Ni_3.0-Mn_0.10Co_0.55Al_0.10 was prepared by inductive melting. The micro-structure was analyzed by XRD and SEM. The alloy consists mainly of CaCu₅-type phase, Ce₂Ni₇-type phase and Pr₅Co₁₉-type phase. The electrochemical measurements show that the maximum discharge capacity is 386 mAh/g, 16.3% higher than that of the commercial AB₅-type alloy (332 mAh/g). At discharge current density of 1 100 mA/g, high rate dischargeability is 62%, while that of the AB5-type alloy is only 45%. The discharge capacity decreases to 315 mAh/g after 300 charge/ discharge cycles, 81.5% of the maximum discharge capacity. __________ Translated from Journal of Xi’an Jiao Tong University, 2008, 42(3) (in Chinese)     

Electrochemical behaviour of Ni-Co amorphous alloys in alkaline solutions

The dissolution processes of amorphous G15 (Ni₅₈Co₂₀B₁₂Si₁₀) and G16 (Ni₂₅Co₅₀B₁₀Si₁₅) alloys in carbonate-bicarbonate buffers (8.9≤pH≤10.5) have been studied using voltammetry and stationary polarization techniques combined with electrochemical impedance spectroscopy and X-ray photoelectron spectroscopy (XPS) measurements. Results indicate that the electrochemical processes are dependent on the applied potential, the alloy composition, and the pH and ionic strength of the electrolyte. An enhancement of the corrosion processes is observed when the pH and the ionic strength are increased and when the Co content of the alloy diminishes. Furthermore, XPS provided information about the composition of the surface layer. Electronic Publication     

Effect of Thermal Treatment of the Melt on Crystallization Kinetics of Al91La5Ni4 Amorphous Ribbons Prepared by Rapid Quenching

Differential scanning calorimetry (DSC) and X-ray diffraction techniques were used to study the crystallization kinetics of Al₉₁La₅Ni₄ amorphous alloys prepared by a rapid quenching method. The experimental results showed that the thermal treatment of the melt — temperature regime and exposure time — had a significant effect on the crystallinity of the ribbons prepared by rapid quenching, and hence on the crystallization kinetics of the ribbon alloys in the annealing process.     

稀土元素对R-Y-Ni系A2B7型无镁储氢合金微观结构和电化学性能的影响

采用真空电弧熔炼及退火处理制备R-Y-Ni系A_2B_7型R0.3Y0.7Ni3.25Mn0.15Al0.1(R=Y,La,Pr,Ce,Nd,Gd,Sm)储氢合金,系统研究稀土元素R对合金微观组织与结构、储氢和电化学性能的影响。XRD和SEM-EDS分析表明,合金退火组织由Ce2Ni7型主相、PuNi3型及少量Ca Cu5型相组成,Ce2Ni7型主相的晶格常数a、c及晶胞体积V均随稀土R原子半径的减小而依次降低。该合金均具有明显的吸放氢平台,常温下最大吸氢容量为1.17%~1.48%(w/w),吸氢平台压Peq为0.037~0.194 MPa。电化学分析表明,退火合金电极的电化学活化性能优良,R=La合金具有最高的放电容量(389.2 mAh·g-1)和较佳的容量保持率(充放电循环100次后的S100=85.7%),其中合金微观组织的不均匀性及稀土元素的电化学腐蚀是影响电极循环稳定性的主要原因。合金电极的高倍率放电性能(电流密度为900 m A·g-1)HRD900=71.05%~86.94%,其电极反应动力学控制步骤主要由氢原子在合金体相中的扩散速率所控制。     

Electrochemical behavior of Ni-Al-Fe alloys in simulated human body solution

An investigation about the corrosion resistance of Ni-Al-Fe intermetallic alloys in simulated human body fluid environments has been carried out using electrochemical techniques. Tested alloys included 57 (wt%) Ni-(20 to 30) Al-(12 to 23) Fe using the Hank's solution because the high corrosion resistance provided by protective Al₂O₃ external layer. For comparison, AISI 316L type stainless steel has also been used. Electrochemical techniques included potentiodynamic polarization curves, electrochemical impedance spectroscopy, and electrochemical noise measurements. The different techniques have shown that these alloys showed a similar or higher corrosion resistance than conventional AISI 316L type stainless steel, and this corrosion resistance decreased as the Al content in the alloy increased. The alloys were susceptible to pitting type of corrosion on the interdendritic Ni-rich phases.     

Study on corrosion resistance of electroplating zinc–nickel alloy coatings

Electrodeposited zinc–nickel alloy coatings have been widely adopted for surface treatment of automobile body steel sheet for high corrosion resistance. The corrosion behavior of the coatings has been related with the components of nickel, and the zinc–nickel alloy passive coatings have much higher corrosion resistance than that of zinc–nickel alloy coatings. In the present paper, the corrosion resistance behavior of the zinc–nickel alloy coatings obtained by new process and formulation has been studied by means of the electrochemistry test and neutral salt spray test. And it is discovered that the properties of corrosion resistance of zinc–nickel alloy passive coatings were better than that of zinc passive coatings, Cadmium passive coatings and alloys of electrodeposited cadmium–titanium. The components of corrosion productions, in terms of X‐ray diffraction (XRD), are mainly ZnO, ZnCl₂ · 4Zn(OH)₂ and small quantity of 2ZnCO₃· 3Zn(OH)₂. The component of zinc–nickel alloy coatings has been investigated with Glow Discharge Optical Emission Spectrometry (GDA‐750). And it is found that as the thickness of zinc–nickel alloy coatings increases, the component of zinc increases from beginning to end, but the peak value of nickel appears and an enrichment of nickel in the coatings comes into being. Because the electrodeposited zinc–nickel alloy coatings exhibit different alloy phases as a function of their alloy composition, in this paper, the crystal structure changing with the different component of nickel has been studied in terms of XRD. The result shows that electrodeposited zinc–nickel alloy has different phases: α‐phase, a solid solution of zinc in nickel with an equilibrium solubility of about more than 79% nickel; γ‐phase, an intermediate phase with a composition Ni₅Zn₂₁; η‐phase, a solid solution of nickel in zinc with less than 5% nickel; and δ‐phase (Ni₃Zn₂₂) appeared from η‐phase to α‐phase with increasing content of nickel. Copyright © 2009 John Wiley & Sons, Ltd.     

Growth behaviour of cerium-based conversion coating on Zn-5%Al alloy

Cerium-based conversion coatings were deposited on a Zn-5%Al alloy by immersing the alloy in cerium nitrate aqueous solutions with various immersion times. The growth behaviour of the cerium-based conversion coating on the Zn-5%Al alloy was investigated by the electrochemical impedance spectroscopy (EIS), SEM, energy dispersive spectroscopy (EDS), and XPS techniques. The results reveal that the coating mainly consists of ZnO, Zn(OH)₂, Ce(OH)₄, Ce(OH)₃, CeO₂, and Ce₂O₃. The growth of the cerium-based conversion coating is accompanied by metal dissolution. The dissolution mainly occurs on the η-Zn surface of the phase boundary and continues to extend to the Zn-rich phase as the coating grows. EIS results show that with increasing immersion time, the corrosion resistance of the Ce conversion coating gradually increases in the early growth stage and then decreases when the cracks appear.     

Effect of Heating Rate on Crystallization Kinetics of Amorphous Al91La5Ni4 Alloys by DSC

Crystallization kinetics of Al₉₁La₅Ni₄ amorphous ribbons produced by a melt-spinning method were studied by DSC analysis and X-ray diffraction. The effect of heating rate (from 4 to 200°C min^-1) was investigated in the temperature range from 298 to 700 K. Increases the heating rate from 4 to 200°C min^-1 resulted in increases of the temperature difference between the two stages of the transformation process: crystallization of Al and crystallization of the Al compounds from 148.9 to 167.4 K. The apparent activation energies for the first step, related to Al crystallization, and to the second step related to crystallization of Al₄La and Al₃Ni, were found to be 161±9 and 199±10 kJ mol^-1, respectively. The results indicate the possibility of tailoring the heating treatment to produce the required fraction of the amorphous phase. This revised version was published online in July 2006 with corrections to the Cover Date.     

镍锡析氢活性阴极的电化学制备及其在碱性溶液中的电催化机理

采用恒电流电沉积法在铜箔基底上获得镍锡合金镀层电极. 电子能谱(EDS)、X射线衍射(XRD)以及高分辨透射电镜(HRTEM)分析表明, 随着锡含量的增加, 镀层由镍晶胚与非晶镍锡构成的非晶态结构转变为Ni₃Sn₄与Ni₃Sn₂的混晶结构. 扫描电镜(SEM)分析发现, 非晶结构镍锡合金电极表面粒子分布均匀且粒径细小, Ni₃Sn₄与Ni₃Sn₂混晶结构的镍锡合金电极表面粗糙且断面呈分层自组装结构. 在25℃, 1 mol·L^-1 NaOH溶液中的稳态极化曲线表明非晶结构的镍锡合金电极具有良好的催化活性, 其析氢过电位仅为85 mV. 交流阻抗测试表明, 非晶以及混晶结构的镍锡合金在析氢电催化反应过程中由电化学吸附(Volmer)以及电化学脱附(Heyrovsky) 两个电荷转移过程控制, 且非晶结构电极相比于Ni₃Sn₄与Ni₃Sn₂混晶结构电极的高活性源于其活性氢具有更快的电化学吸附以及脱附速度.     

Interface analysis in metal matrix composites

Summary Using surface and microanalytical methods (Auger electron spectroscopy, X-ray photoelectron spectroscopy and analytical electron microscopy) the interface in the SiC fiber reinforced Ti6A14V alloy and in the Al₂O₃ fiber reinforced Al12SiCuMgNi alloy was investigated. The analytical methods can be used for an understanding of the interface reaction process taking place during composite processing and allow a judgment on the effectiveness of fiber coating in composites.

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Grenzflächenanalyse an Faserverbundwerkstoffen mit metallischer Matrix

     

Effect of sodium vanadate on corrosion of AD31 aluminum alloy in acid media

Scanning electron microscopy, potentiodynamic polarization method, and electrochemical impedance spectroscopy were used to study the corrosion behavior of AD31 (AA6063) aluminum alloy in acid (pH 3) 0.05 M NaCl solutions containing 3 mmol dm^–3 of NaVO₃ inhibitor. It was found that the corrosion of AD31 alloy in acid sodium chloride solutions predominantly occurs locally at aluminum/intermetallic particle phase boundaries and is limited by the electrochemical stage of charge transfer. It was shown that introduction of sodium vanadate can reduce the rate of selective dissolution of magnesium from the alloy and provides a protective effect on the level of 7–10%.