Fabrication and new electrochemical properties of nanoporous Cu by dealloying amorphous Cu–Hf–Al alloys

To produce monolithic nanoporous Cu (NPC) ribbons with good mechanical integrity, we investigate chemical dealloying behavior of an amorphous Cu_52.5Hf₄₀Al_7.5 alloy with good mechanical properties by immersion in 0.5 M HF solution for different times. With the design concept of adding ductile amorphous supporter to NPC ribbons, an amorphous alloy-containing interlayer with a certain thickness is successfully fabricated in the NPC ribbon by controlling dealloying time to ensure the good bendability of the dealloyed product. New electrochemical properties of the obtained NPC ribbon are further developed. The current signal and the specific capacitance of the NPC-supported MnO₂ composite electrode are remarkably enhanced as compared to those of pure MnO₂ powders. NPC substrate with large specific surface areas and excellent electrical conductivity can effectively promote the morphological change of MnO₂ from globular particles to nanoflakes for larger specific surface area and improve the utilization of MnO₂ surface active sites, which reveal new electrochemical properties of NPC in a potential application for supercapacitor composite electrodes.     

Zr65Al7.5Ni10Cu17.5块状非晶晶化过程的电镜研究

用透射电镜对Zr65Al7.5Ni10 Cu17.5块状非晶合金的晶化过程进行了研究。发现晶化过程的不同阶段相的组成是不同的。710K时 ,主要是tI CuZr2 相和tP Al2 Zr3 相 ,两者有固定的取向关系 :[0 10 ]tI∥ [0 10 ]tP,(10- 3) tI∥(2 0 2 ) tP。在 76 0K时 ,除了前面的两个相外 ,又出现了hP2 Al2 NiZr6相和hP3 α Zr相 ,两者也有固定取向关系 :[113]hP2 ∥ [0 0 1]hP3 ,(14- 1) hP2 ∥ (2 1- 0 ) hP3 。根据它们的晶格常数的相似性可以把晶化相归纳为两类 :tI ,oC ,hP3 和tP ,hP1,hP2 。这些相都是Zr基的 ,但前者富Cu和Ni,后者富Al。用电镜得到的结果来标定X射线衍射谱 ,结果吻合很好。     

Zr65Al7.5Ni10Cu17.5和Zr65Al10Ni10Cu15合金的非晶和晶态薄带吸氢行为研究

研究两种不同成分具有较大过冷液相区的四元合金Zr65Al7.5Ni10Cu17.5和Zr65Al10Ni10Cu15，非晶和晶态薄带吸氢行为，结果表qt两种薄带的吸氢量均随着温度的升高而增大，非晶薄带的吸氢量要小于同等条件下的晶态薄带的吸氢量且只有在673K吸氢后形成了氢化物，Zr65Al7.5Ni10Cu17.5非晶和晶态薄带吸氢后分别生成了Zr2NiH4.7和ZrH2；而Zr65Al10Ni10Cu15非晶和晶态两种薄带最后生成的氢化物同为ZrH2。     

Phases in the crystallization process of Zr_(65)Al_(7.5)Ni_(10)Cu_(17.5)metallic glass

The crystallization process of metallic glass Zr65Al7.5Ni10Cu17.5, (atom fraction in %) were studied by transmission electron microscopy and X-ray diffraction. Two stages of crystallization process, which are indicated by the two exothermic peaks in the differential scanning calorimetry diagram, were studied separately. It is found that the phases in the various stage of the crystallization are different, In the first stage, it consists mainly of tI-CuZr2 and tP-Al2Zr3 phases, between which a definite orientation relationship is found. While in the second stage, in addition to the above phases, phase hP2-Al2NiZr6 and phase hP3-α-Zr appear, between which another orientation relationship is also found. At the same time, a comparison is made based on the study of the phases exist in the arc-melted master ingot. The lattice parameters of the identified phases were determined and some interesting similarities were found. According to these similarities, all the phases were classified into two groups. The fi     

Zr65Al7.5Cu17.5Ni10大块非晶态合金的制备及晶化过程

采用直接水淬法成功制备直径５ｍｍ球状Ｚｒ６５Ａｌ７．５Ｃｕ１７．５Ｎｉ１０大块非晶态合金。Ｘ射线衍射、透射电镜检验证明样品完全为非晶态。采用Ｘ射线衍射、差示扫描热分析仪（ＤＳＣ）分析了Ｚｒ６５Ａｌ７．５Ｃｕ１７．５Ｎｉ１０非晶态合金的晶化过程,利用Ｋｉｓｓｉｎｇｅｒ方程求得Ｚｒ６５Ａｌ７．５Ｃｕ１７．５Ｎｉ１０非晶合金的晶化表观激活能。Ｘ射线衍射实验结果表明,Ｚｒ６５Ａｌ７．５Ｃｕ１７．５Ｎｉ１０非晶态合金的晶化是按下面的次序进行的,非晶态合金→体心立方晶相Ｚｒ２（Ｎｉ,Ａｌ）＋非晶相→体心立方相Ｚｒ２（Ｎｉ,Ａｌ）＋体心立方相Ｚｒ２（Ｃｕ,Ａｌ）。     

非晶态Zr65Cu17.5Ni10Al7.5合金氧化和晶化过程研究

利用X射线衍射（XRD）和差示扫描量热法（DSC）研究了在连续加热条件下非晶态Zr65Cu17.5Ni10Al7.5合金在空气中的氧化和晶化过程。结果表明，在450℃以下，非晶态Zr65Cu17.5Ni10Al7.5合金表面的ZrO2晶粒长大过程服从抛物线规律；当温度超过450℃时，由于非晶基体内部发生晶化过程，阻碍了表面氧化过程的发展，此时ZrO2晶粒大小满足线性规律，并给出了ZrO2晶粒尺寸与温度的函数表达式。非晶态Zr65Cu17.5Ni10Al7.5合金的晶化过程是先形成二十面体相，然后转变为稳定的晶化相。     

Precipitation of the icosahedral phase in amorphous Zr65Cu17.5−xAl7.5Ni10Agx (x=0,2.5, 5, 7.5 and 10) alloys

An amorphous phase in Zr₆₅Al_7.5Cu_17.5Ni₁₀ crystallizes via co-precipitation of the I-phase and NiZr₂ phase in the first crystallization step, followed by decomposition of the I-phase into the CuZr₂ and NiZr₂ phases. The NiZr₂ phase transforms to a stable Zr₆NiAl₂ phase at a high temperature. The alloys containing Ag crystallize via a two-step process: firstly, the I-phase nucleates homogeneously and grows in an amorphous matrix; secondly, the quasicrystal and remaining amorphous phase transforms into the stable CuZr₂ and Zr₆NiAl₂ phases. With increasing Ag, the I-phase becomes more thermally stable and the grain size in the I-phase decreases due to increased frequency of homogeneous nucleation. The quasi-lattice constant of the I-phase decreases with increasing Ag content. This article is based on a presentation made in the “Symposium on Metastable Phases”, held at Korea Institute of Science and Technology, Seoul, Korea, November 10, 2000 sponsored by The Korean Institute of Metals and Materials.     

Microstructure studies of Zr65Cu17.5Al7.5Ni10 and Zr65Cu15Al10Ni10 glass forming alloys: Phase morphologies and undercooled melt solidification

Zr₆₅Cu_17.5Al_7.5Ni₁₀ (at.%) and Zr₆₅Cu₁₅Al₁₀Ni₁₀ (at.%) glass forming alloy microstructures have been investigated by means of optical and electron microscopies. They are composed of a fine eutectic matrix with eutectic dendrites (EDs) that have peculiar morphologies. Al and Cu concentrations, in these alloys, favour primary dendrites and determine the ED morphologies and compositions. Their locations within the microstructures suggest a two-step solidification process of the two undercooled melts. The identified crystalline phases indicate the occurrence of solid state phase transformations in agreement with the structural defects observed in the grains. The crystalline phases can be classified into Zr-rich, Cu-rich, Ni-rich and Al-rich compounds resulting from competing diffusion between Cu, Ni, and Al in the melts.     

Multicomponent nanoporous metals prepared by dealloying Pd80−xNixP20 metallic glasses

We report the formation of Pd-based multicomponent nanoporous metals by electrochemically dealloying the Pd_80−xNi_xP₂₀ metallic glasses. It was found that both the compositions and the pore sizes of the nanoporous metals can be tailored by the Ni content in the glassy Pd_80−xNi_xP₂₀ precursors. Moreover, the Pd-based nanoporous metal with the optimized composition and the pore size exhibits better electrocatalytic performance towards the oxidation of the formic acid when compared with the commercial Pd/C catalyst.     

Nano-porous surface states of Ti–Y–Al–Co phase separated metallic glass

A novel nano-porous state was fabricated at the surface of the Ti-based metallic glass by selective etching technique. By transforming the surface of the Ti₄₅Y₁₁Al₂₄Co₂₀ phase separated alloy from smooth towards rough with nano-pores in an oxidised state, the passivation behaviour of the glassy alloy in simulated body fluid condition was remarkably improved leading to corrosion resistance significantly higher than that of the Ti–6Al–4V alloy, one of the favourite candidate materials for implant applications.     

Hydrogen storage characteristics of Ti2Ni alloy synthesized by the electro-deoxidation technique

Ti₂Ni alloy was synthesized in the molten CaCl₂ electrolyte by the electro-deoxidation method at 900 °C and the electrochemical hydrogen storage characteristics of the synthesized alloy was observed. The X-ray diffraction peaks indicated that stoichiometric oxides in TiO₂–ZrO₂–NiO mixture reduced to Ti₃O₅, CaTiO₃, CaZrO₃, Ni and Ti₂O₃ within 5 h electro-deoxidation process. Extension of the electro-deoxidation time to 10 h caused formations of TiO and equilibrium Ti₂Ni phase. After 24 h electro-deoxidation the target alloy with the equilibrium Ti₂Ni phase structure and the maximum amount of the dissolved Zr in it was obtained. It was observed that the synthesized alloy had maximum discharge capacity of 200 mA h g⁻¹. Upon increase in the charge/discharge cycles, however, the discharge capacity decayed sharply. According to the gathered EIS data at various DODs, the rapid degradation in the electrode performance of Ti₂Ni alloy was attributed to the developed barrier oxide layer on the electrode surface.     

The effects of heat treatment and zirconium on the corrosion behaviour of Mg-3Nd-0.2Zn-0.4Zr (wt.%) alloy

The corrosion behaviours of Mg-3Nd-0.2Zn (wt.%) (NZ) and Mg-3Nd-0.2Zn-0.4Zr (wt.%) (NZK) alloys were investigated in as-cast (F), solution-treated (T4) and artificially-aged (T6) conditions in 5% NaCl solution using immersion test and electrochemical measurements. The immersion test indicates that both NZ and NZK alloys exhibit better corrosion resistances in T4 and T6 states than in the F condition due to the galvanic corrosion between the cathodic Mg₁₂Nd compound and the anodic α matrix in the F condition. The NZK alloy demonstrates lower corrosion rates than the NZ alloy in three conditions, which indicates that the addition of zirconium has a beneficial effect on the corrosion resistance. It was discovered by field emission scanning electron microscope (FE-SEM) that the corrosion products of NZK-T6 formed in salt solution are composed of sandwich shape compounds, while that of NZ-T6 is composed of fine needle-like compounds and small particles. The former are more uniform and compact than the latter and can play a more protective role for the alloy. Electrochemical measurements also confirmed that the more protective film formed on the NZK than on the NZ alloy.     

Mechanical properties and oxidation behaviour of two-phase iron aluminium alloys with Zr(Fe,Al)2 Laves phase or Zr(Fe,Al)12 τ1 phase

Two-phase Fe-rich Fe–Al–Zr alloys have been prepared consisting of binary Fe–Al with a very low solubility for Zr and the ternary Laves phase Zr(Fe,Al)₂ or τ₁ phase Zr(Fe,Al)₁₂. Yield stress, flexural fracture strain, and oxidation behaviour of these alloys have been studied in the temperature range between room temperature and 1200 °C. Both the Laves phase and the τ₁ phase act as strengthening phases increasing significantly the yield stress as well as the brittle-to-ductile transition temperature. Alloys containing disordered A2+ ordered D0₃ Fe–Al show strongly increased yield stresses compared to alloys with only A2 or D0₃ Fe–Al. The binary and ternary alloys with about 40at.% Al and 0 or 0.8at.% Zr show the effect of vacancy hardening at low temperatures which can be eliminated by heat treatments at 400 °C. At higher Zr contents this effect is lost and instead an increase of low-temperature strength is observed after the heat treatment. The increase of the high-temperature yield strength of Fe-40at.% Al by adding Zr is much stronger than by other ternary additions such as Ti, Nb, or Mo. Tests on the oxidation resistance at temperatures up to 1200 °C indicate a detrimental effect of Zr already for additions of 0.1at.%.     

Microstructural analysis of Zr55Cu30Al10Ni5 bulk metallic glasses by laser surface remelting and laser solid forming

The crystallization behavior of Zr₅₅Cu₃₀Al₁₀Ni₅ bulk amorphous alloy during laser solid forming (LSF) was analyzed. Since laser surface remelting (LSM) is a key process for the LSF, the crystallization behavior of as-cast Zr₅₅Cu₃₀Al₁₀Ni₅ bulk metallic glasses (BMGs) during LSM was also investigated. It was found that the amorphous state of the as-cast BMGs was maintained when they were repeatedly remelted four times in a single-trace LSM, and as for the LSF of Zr₅₅Cu₃₀Al₁₀Ni₅ bulk amorphous alloy, the crystallization primarily occurred in the HAZ between the adjacent traces and layers after the two layers were deposited. The as-deposited microstructure exhibited a series of phase evolutions from the molten pool to the HAZ as follows: the amorphous → NiZr₂–type nanocrystal + amorphous → NiZr₂–type equiaxed dendrite + amorphous → Cu₁₀Zr₇–type dendrite + NiZr₂–type nanocrystal. Among these microstructural patterns, the NiZr₂–type nanocrystals and equiaxed dendrites primarily formed from the rapid solidification of the remelted liquid in the laser processing process, and the Cu₁₀Zr₇–type dendrites in the HAZ primarily formed by the crystallization of pre-existed nuclei in the already-deposited amorphous substrate.     

Energy of formation, lattice parameter and bulk modulus of (Ni,X)Ti alloys with X = Fe, Pd, Pt, Au, Al, Cu, Zr, Hf

An analysis of the ternary ‘bridge’ Ni_50−yX_yTi₅₀ alloys with X = Fe, Pd, Pt, Au, Al, Cu, Zr, and Hf was performed using the BFS method for alloys. The lattice parameter, bulk modulus and energy of formation were determined for all the intermediate states in the (B2) transition NiTi to XTi.     

Microstructure and electrochemical behavior of Ti-coatedZr55Al10Ni5Cu30 bulk metallic glass

In this study, pure Ti was coated on Zr₅₅Al₁₀Ni₅Cu₃₀ bulk metallic glass (BMG) using a physical vapour deposition (PVD) technique with magnetron sputtering. Microstructures of Ti coating, BMG substrate and interface were investigated by conventional and high-resolution transmission electron microscopy (TEM and HREM). The electrochemical behavior of Ti-coated Zr₅₅Al₁₀Ni₅Cu₃₀ BMG was studied by potentiodynamic polarization curves and electrochemical impedance spectroscopy (EIS) in Hanks' solution. Scanning electron microscopy (SEM) was used to characterize the surface morphology of the coating after electrochemical testing. HRTEM observation reveals that the sputtering Ti coating consists of α-Ti nano-scale particles with the size about 10 nm. The polarization curves revealed that the open-circuit potential shifted to a more positive potential and the passive current density was lower after Ti coating was applied in comparison with that of the monolithic Zr₅₅Al₁₀Ni₅Cu₃₀ BMG. Electrochemical impedance spectroscopy (EIS) measurements showed that the Bode plots of Ti-coated Zr₅₅Al₁₀Ni₅Cu₃₀ BMG presented one time constant for 1 h and 12 h immersion and two time constants after 24 h immersion. The good bonding condition between Ti coating and Zr₅₅Al₁₀Ni₅Cu₃₀ BMG substrate may be responsible for the high corrosion resistance of Ti-coated Zr₅₅Al₁₀Ni₅Cu₃₀ BMG.     

Electrochemical noise analysis on the pit corrosion susceptibility of Mg–10Gd–2Y–0.5Zr, AZ91D alloy and pure magnesium using stochastic model

Pit corrosion susceptibilities of Mg–10Gd–2Y–0.5Zr alloy, AZ91D alloy and pure magnesium were investigated by means of electrochemical noise (EN). The EN data have been analyzed based upon the combined stochastic theory and shot-noise theory. Pit initiation process has been modeled as a nonhomogeneous Poisson process and analyzed using a Weibull distribution function. Pit growth process has been simulated by a nonhomogeneous Markov process and analyzed using Gumbel distribution function. The EN results implied that Mg–10Gd–2Y–0.5Zr alloy had the highest pit initiation rate and pit growth probability, which revealed that Mg–10Gd–2Y–0.5Zr alloy had the highest pit susceptibility.