Evaluation of Ni–Ni3Al(5 wt.%)–Al(3 wt.%) as an anode electrode for molten carbonate fuel cell. Part II: wetting ability and performance in unit cell operation

In part I of this paper, the sintering and creep resistances of the five kinds of anode electrodes were compared and those of Ni–Ni₃Al(5)–Al(3) were even better than any other electrodes. In part II of this paper, the wetting abilities of the same five kinds of anode electrodes to the electrolyte and their performance in unit cell operation were investigated. Their contact angles, which indicate the wetting ability, were within the range between 77 and 84°. The contact angles of Al- and/or Ni₃Al-added electrodes such as Ni–Al(5), Ni–Ni₃Al(7) and Ni–Ni₃Al(5)–Al(3) were relatively lower than those of Cr-added electrodes. Although there was no evidence that the effect of Al and/or Ni₃Al addition to pure Ni could enhance the number of pores or improve their structure for more wetting ability, it could be clearly known that the component of Al and/or Ni₃Al in anode electrode could make the electrode be wetted by the electrolyte very well.

In unit cell operation, the electric resistance of Ni–Al(5) and Ni–Ni₃Al(5)–Al(3) were relatively lower than those of any other electrodes. After 120 h operation of the unit cell, the cell performance and the endurance of Ni–Ni₃Al(5)–Al(3) were even better than those of any other electrodes. And also its thickness shrinkage and porosity changes after unit cell operation were the least in five kinds of electrodes. The performance of Ni–Ni₃Al(5)–Al(3) as anode seems to be caused by the synergy effect between the strengthening characteristics of Ni₃Al and electric conductivity of Al.     

Sigmoidal creep of Ni3(Al, Ta)

Incremental creep tests have been used to explore the time-dependent plastic behavior of single-slip oriented Ni₃(Al, Ta) at low temperatures in the anomalous flow regime. For selected incremental creep experiments at 20 and 100 °C, it was discovered that Ni₃Al exhibited sigmoidal creep, where there is a significant time delay before the plastic strain rate accelerates to a maximum value during a creep experiment. Several of the factors that affect the sigmoidal creep response have been identified. The origin of sigmoidal creep is accounted for using a simple model of work hardening in Ni₃Al, where the acceleration of the creep rate is a direct result of the annihilation of the existing dislocation substructure.     

Morphology of M23C6 precipitation in L12-ordered Ni3(Al, Cr)

A transmission electron microscope investigation has been performed on the morphology of M₂₃C₆ precipitation in L1₂-ordered Ni₃(Al, Cr) containing 0.1–0.5 mol% of carbon. By aging at temperatures around 1073 K after solution annealing at 1423 K, fine octahedral-shaped precipitates of M₂₃C₆ bounded by {111} facets appear first on the dislocations and then in the matrix. The shapes of the precipitates are not always equilateral but tetragonal or elongated octahedral ones appear during aging. Planar growth faults were observed in some of the octahedral precipitates. After prolonged aging or by aging at higher temperatures, these shapes of precipitates become unstable. The M₂₃C₆ precipitates then adopt a rod-like morphology elongated parallel to the 100 directions and characterized by steps bounded by {111} facets.     

Two-phase intermetallic alloy Ni3(Al, Si):microstructure and mechanical properties

Yield stress in compression (0.2% flow stress) from ambient temperature up to 800 °C has been studied on Ni₃(Al, Si) alloy with the atomic composition Ni₇₈Al₁₁Si₁₁. When annealed at 1000 °C, the alloy has a pure L1₂ (γ′) ordered structure. After subsequent annealing at 750 °C, the disordered solid solution of Al and Si in Ni (face centred cubic, γ) precipitates in fine coherent particles. Calorimetry helps to describe the various phase transformations necessary to obtain the last microstucture. Solute addition of Si, which replaces Al atoms, increases the 0.2% flow stress of Ni₃Al in the fully γ′ microstructure. The γ precipitation shifts the peak stress towards higher temperatures and stresses.     

INTERACTION OF H 2O AND O 2 WITH INTERMETALLIC ALLOYS

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Evaluation of Ni–Ni3Al(5 wt.%)–Al(3 wt.%) as an anode electrode for molten carbonate fuel cell: Part I: Creep and sintering resistance

To develop an anode electrode of molten carbonate fuel cell (MCFC) that has higher creep and sintering resistance and more stable reactivity than the traditional anode electrode, the five kinds of nickel anode electrodes such as Ni–Al(5), Ni–Cr(10), Ni–Ni₃Al(7), Ni–Ni₃Al(5)–Cr(5) and Ni–Ni₃Al(5)–Al(3) (number in parenthesis means the weight percent of its component) were prepared and their performance were investigated under the same conditions of MCFC operation. In part I of our study, their relative creep and sintering resistance were compared.

The Ni–Ni₃Al(5)–Al(3) anode electrode was the most resistant against the sintering and its porosity was kept over 60% even at 1000 °C. And its porosity decrease and thickness shrinkage by creep were the least among the five kinds of anode electrodes. Thus, the effects of the aluminum and nickel–aluminum intermetallic compound (Ni₃Al) addition to nickel as the dispersant strengthening and the solid solution strengthening agents were confirmed by comparative tests for sintering and creep resistance of five kinds of anode electrodes.

Besides these results, we could also know that the creep of anode electrode for MCFC mostly proceeded within 60 h from the start of operation irrespective of the kinds of anode electrodes. And in part II of paper, for more information about the wetting ability and cell performances of these five kinds of anode electrodes, the measurement of wetting ability and unit cell operations were carried out.     

金属间化合物Ni3Al薄膜制备工艺

采用直流磁控共溅射法,通过一步法、两步法工艺在衬底为SiO₂基体上制备了厚度为500 nm的Ni₃Al薄膜,X射线衍射(XRD)和透射电镜(TEM)等测试表明,一步法工艺制备的Ni₃Al薄膜为(111)取向的多晶型晶体结构金属间化合物优于两步法工艺。采用光学显微镜观察Ni-Al合金薄膜和金属间化合物Ni₃Al薄膜经高温氧化后的形貌,结果表明,Ni₃Al金属间化合物薄膜的高温抗氧化性能明显优于Ni-Al合金薄膜。     

Reaction synthesis of Ni/Ni3Al multilayer composites using Ni and Al foils: High-temperature tensile properties and deformation behaviour

The effects of temperature on the tensile properties and deformation behaviour of Ni/Ni₃Al multilayer composites have been systematically investigated. With increasing tensile test temperature from room temperature to 600 °C, the ultimate tensile strength decreased. The ‘abnormal’ strengthening of Ni₃Al gave rise to a reduction in the capability for cooperative deformation between the Ni and the Ni₃Al layers at elevated temperatures. As a result, the ultimate tensile strength of the multilayer composites decreased at elevated temperatures. A mixture of transgranular cleavage and intergranular failure at relatively low temperatures, and an intergranular failure at elevated temperatures were observed in the fracture surfaces of the Ni₃Al layers in the multilayer composites. The splitting of the coarse precipitates along the {0 0 1} planes at 800 °C resulted from the differences in solubility of Al in Ni between room temperature and 800 °C.     

Dislocation dissociations and fault energies in Ni3Al alloys doped with palladium

Dislocation structures in polycrystalline Ni₃A1 alloy doped with palladium deformed at room temperature have been investigated by transmission electron microscopy. The structure consists mainly of dislocations dissociated into a/2<0 1 1> super partials bounding an anti-phase boundary (APB). Dislocations dissociated into a/3<112> super Shockley partials bounding a superlattice intrinsic stacking fault (SISF) were often observed. The majority of the SISFs are truncated loops, i.e. the partials bounding the SISF are of similar Burgers vector. These faulted loops are generated from APB-coupled dislocations, according to a mechanism for formation of SISFs proposed by Suzuki et al. (Suzuki K, Ichihara M, Takeuchi S. Acta Metall 1978;26:183) and recently modified by Chiba et al. (Chiba A, Hanada S. Philos Mag 1994;69:751). The APB energies for {111} and {100} slip planes are measured to be 144±20 and 102±11 mJ/m², respectively, and the SISF energy has been estimated to be 12 mJ/m² in this alloy. It is concluded that the dislocation structure in Ni_74.5Pd₂Al_23.5 alloy deformed at room temperature is similar to that in binary Ni₃Al and the difference in fault energies between these two alloys is small. Thus, it seems unlikely that the enhancement of ductility of Ni_74.5Pd₂Al_23.5 results from only such a small decrease of the ordering energy of the alloy. SISF bounding dislocations also have no apparent influence on the ductilization of Ni_74.5Pd₂Al_23.5 alloy.     

Microscopic Phase-Field Simulation for the Influence of Interatomic Potential on the Precipitation Process of Ni_(75)Al_(14)Mo_(11) Alloy

The process of γ' phase precipitating from Ni_(75)Al_(14)Mo_(11) is studied by a computational simulation technique based on microscopic phase-field kinetics model. We studied the phase transformation with the purpose of clarifying the influence of the nearest interatomic potential V_(Ni–Al)(the nearest interatomic potential) on the precipitation process of γ' phase. The result demonstrates that there are two kinds of ordered phases, respective L1_0 and L1_2 in the early stage, and L1_0 phase transforms into L1_2 phase subsequently. For L1_2 phase, Ni atoms mainly occupy α site(face center positions),while Al and Mo atoms occupy β sites(the vertex positions). When V_(Ni–Al) is increased by 10 MeV, the occupation probability of Ni atoms on α sites and Al atoms on β sites are enhanced. Enhanced V_(Ni–Al) facilitates clustering and ordering of Al atom, which promotes the formation of the γ' phase. At last, the simulation result was discussed by employing the thermodynamic stability.     

Effects of H2O2 pretreatment on surface characteristics and bioactivity of NaOH-treated NiTi shape memory alloy

The effects of H₂O₂ pretreatment on the surface characteristics and bioactivity of NaOH-treated NiTi shape memory alloy(SMA) were investigated by scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, Raman spectra, Fourier transform infrared spectroscopy as well as a simulated body fluid(SBF) soaking test. It is found that the H₂O₂ pretreatment can lead to the direct creation of more Ti—OH groups and the decrease in the amount of Ni₂O₃, Na₂TiO₃ and remnant NiTi phases on the surfaces of bioactive NiTi SMA prepared by NaOH treatment. As a result, the induction period of apatite formation is shortened by dispensing with the slow kinetic formation process of Ti—OH groups via an exchange of Na⁺ ions from Na₂TiO₃ phase with H₃O⁺ ions in SBF, which indicates that the bioactivity of NaOH-treated NiTi SMA can be further improved by the H₂O₂ pretreatment.     

High temperature thermal expansion characteristics of Ni3Al alloys

The thermal expansion of Ni₃Al alloys with and without ternary additions have been investigated with the aid of a dilatometer. The Ni₃Al alloys were studied over the temperature range 25–1000 °C. The coefficient of thermal expansion of all the aluminides studied in this investigation varies linearly with the temperature. The coefficient of thermal expansion of Ni₃Al is found to show an increase with the decrease in Al content from stoichiometric composition. B and Zr additions decrease the value of Ni₃Al alloys at room temperature while Hf and Ti additions do not alter it significantly.     

The oxidation of nanocrystalline Ni3Al fabricated by mechanical alloying and spark plasma sintering

Nanocrystalline Ni₃Al was fabricated through mechanical alloying of elemental powders and spark plasma sintering. The nanocrystalline Ni₃Al has a nearly full density after being sintered at 1223 K for 10 min under a pressure of 65 MPa. Isothermal and cyclic oxidations of nanocrystalline Ni₃Al were tested at 1173–1373 K with intervals of 100 K. The results indicate that nanocrystalline Ni₃Al exhibits excellent isothermal and cyclical oxidation resistance. The oxide scales consist primarily of dense and continuous -Al₂O₃. The grain refinement is beneficial for improving the oxidation resistance of Ni₃Al by providing more nucleation centers for the Al₂O₃ formation, promoting the selective formation of Al₂O₃ and improving the adhesion of oxide scales to the matrix.     

Cr12MoV钢激光熔覆Ni-Al复合涂层的组织及性能

利用激光熔覆技术在Cr12MoV钢上熔覆了Ni-Al复合涂层,研究了Al含量对熔覆层组织形貌及力学性能的影响。结果表明:当熔覆层Al含量大于14%时,开始有裂纹出现;熔覆层的显微组织中无明显夹杂物,存在硬质相Al₂O₃及金属间化合物Ni₃Fe、AlNi₃;随着Al含量的增加,熔池边界逐渐消失,硬度、耐磨性呈先减小后增加的趋势。综合来看,Al含量为14%的熔覆层性能最佳。     

连接温度对TiAl/Ti3AlC2扩散焊接头界面结构及性能的影响

采用Ti/Ni复合中间层实现了TiAl合金和Ti₃AlC₂陶瓷的扩散连接,利用SEM,XRD等分析方法对接头界面结构进行了分析.结果表明,TiAl/Ti₃AlC₂接头典型界面结构为TiAl/Ti₃Al+Al₃NiTi₂/Ti₃Al/α-Ti+Ti₂Ni/Ti₂Ni/TiNi/Ni₃Ti/Ni/Ni₃(Ti,Al)/Ni₃Al+TiC_x+Ti₃AlC₂/Ti₃AlC₂.随着连接温度的升高,TiAl/Ti界面处的Ti_ss层逐渐减小,Ti₃Al化合物层逐渐变厚;TiNi化合物层厚度显著增加,Ti₂Ni和Ni₃Ti层厚度基本保持不变.接头抗剪强度随连接温度升高先增加后减小,当连接温度为850℃时,接头的抗剪强度最高可达到85.3 MPa.接头主要在Ni/Ti₃AlC₂界面及Ti₃AlC₂基体处发生断裂.     

Solid-State Diffusion Bonding of Nb_(SS)/Nb_5Si_3 Composite Using Ni/Al and Ti/Al Nanolayers

Diffusion bonding of refractory Nb–Si-based alloy was performed with Ni/Al and Ti/Al nanolayers under the condition of 1473 K/30 MPa/60 min. The Nb_(SS)/Nb_5Si_3 in situ composite with the nominal composition of Nb–22 Ti–16 Si–3 Cr–3 Al–2 Hf was used as the parent material. The joint microstructures were examined by using a scanning electron microscope equipped with an X-ray energy dispersive spectrometer. Shear test was conducted for the bonded joints at room temperature.Within the joint bonded with Ni/Al multilayer, element diffusion occurred between the base metal and the nanolayer, with the reaction products of AlNb_2 + Ni_3 Al, NiAl and AlNi_2 Ti phases. The average shear strength was 182 MPa. While using Ti/Al multilayer, the interface mainly consisted of TiAl,(Ti,Nb)Al and(Ti,Nb)_2 Al phases, and the corresponding joints exhibited an increased strength of 228 MPa. In this case, the fracture mainly took place in the TiAl phase and presented a typical brittle characteristic.     

Effect of Magnesium on Microstructure Refinements and Properties Enhancements in High-Strength CuNiSi Alloys

Microalloying is an effective method to improve the comprehensive properties of copper alloys.The effects of magnesium on the microstructure,mechanical properties and anti-stress relaxation properties of CuNiSi alloys have been investigated.Results demonstrated that magnesium plays significant roles in refining the dendritic microstructure of the as-cast ingot,accelerating the precipitation decomposition,improving the mechanical properties and increasing the anti-stress relaxation properties.The incremental strength increase is due to the Orowan strengthening from the nanoscale Ni_2 Si and Ni_3 Al precipitates.As compared with the Cu-6.0 Ni-1.0 Si-0.5 Al(wt%) alloy,the ultimate tensile strength of the designed Cu-6.0 Ni-1.0 Si-0.5 Al-0.15 Mg(wt%) alloy increases from 983.9 to 1095.7 MPa,and the electrical conductivity decreases from 27.1 to 26.6% IACS,respectively.The stress relaxation rates of the designed Cu-6.0 Ni-1.0 Si-0.5 Al-0.15 Mg alloy are 4.05%at 25℃,6.62% at 100℃and 9.74% at 200℃after having been loaded for 100 h,respectively.Magnesium significantly promotes nucleation during precipitation and maintains small precipitate size.     

Evaluation of high temperature corrosion resistance of a Ni3Al (Mo) alloy

The sulfidation/oxidation and carburization resistances of a Ni₃Al(Mo) (IC-6) alloy at high temperatures were investigated in this work. The corrosion kinetics of the IC-6 alloy was found to follow parabolic rate law in an environment of high partial pressures of sulfur (10⁻⁵ atm) and low partial pressures of oxygen (<10⁻²⁰ atm) at 700 °C. Because the Ni sulfides are readily formed at the testing temperature, the sulfidation/oxidation resistance of the IC-6 alloy is similar to that of commercial Ni–Cr alloys in the current environments, although IC-6 is alloyed with Al. Compared with the HP heat resistant steel which is commonly used in the petrochemical industry, the IC-6 alloy possesses significantly improved resistance to carburization at 1100 °C. The mechanisms governing the corrosion attack in the environments used in this investigation were also discussed.     

中间层对可伐合金4J29/钼组玻璃DM308激光焊接接头结合性能的影响

采用YLS-6000型光纤激光器对可伐合金4J29与钼组玻璃DM308进行激光焊接,研究了中间层对接头强度、界面结构和界面结合机理的影响,分析了界面元素的扩散行为. 结果表明,Mo-Mn-Ni中间层可以减少接头边缘较大的裂纹,Ni₂O₃-MnO₂-B₂O₃中间层可以减少玻璃侧的微裂纹和气泡数目;4J29/DM308激光焊接头承载能力最弱的部位为靠近玻璃侧,穿过气泡发生断裂,Mo-Mn-Ni中间层接头的抗剪切强度最大为10.96 MPa,Ni₂O₃-MnO₂-B₂O₃中间层接头抗剪切强度最大值为13.46 MPa;Ni₂O₃-MnO₂-B₂O₃中间层接头界面过渡层的厚度大约为30 ~ 40 μm,过渡层存在明显的枝晶生长,接头界面XRD相分析结果表明,界面过渡层为Fe和Si立方晶系的复合氧化物FeSiO₃和Fe₇SiO₁₀,接头界面EDS分析结果表明,Fe,Co,Ni等元素在整个界面区域内发生了扩散融合,界面结合主要靠化学反应和元素扩散连接.     

The structure and bonding of Ni3Sn

The electronic structure of Ni₃Sn was calculated at ab initio levels for the crystal structure of the low-temperature modification of Ni₃Sn refined upon data of single-crystal X-ray diffractometry (P6₃/mmc, a=5.2950(7), c=4.247(1) Å, R=0.0288). The calculations were made with the use of fixed Gaussian (CRYSTAL98 software) and energy-dependent (Stuttgart TB-LMTO-ASA software) basis sets. Difference electron charge density maps were analysed and compared with that of a hypothetical hcp Ni in order to understand bonding in Ni₃Sn. It was found that bonding in Ni₃Sn has multicentre character with Ni–Sn interaction stronger than Ni–Ni one.