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.     

Formation of interfacial voids in cast and micro-grained γ′-Ni3Al during high temperature oxidation

Specimens of cast and micro-grained γ′-Ni₃Al, which were produced with vacuum casting and unbalanced magnetron sputter deposition, respectively, were isothermally oxidised in air at 1473 K for different periods of time. The formation of interfacial voids at the alloy/oxide interface was observed with SEM, which indicated that there were more interfacial voids formed in the cast Ni₃Al than in the micro-grained alloy under the same oxidation conditions. A phenomenological equation describing the fraction of the void projected areas was established, in which the impingement and coalescence between voids during their growth was taken into consideration. It was elucidated that low vacancy density in the micro-grained Ni₃Al due to the high creep, re-crystallisation and the enhanced Al diffusion reduced the void percentage. Also, it was confirmed that aluminium evaporation, perhaps supplemented by surface diffusion, supplied most Al to the oxide scales formed above the interfacial voids.     

Deformation behavior of Ni3Al single crystals during nanoindentation

The deformation behavior of (1 1 1), (1 1 0) and (0 0 1) oriented Ni₃Al single crystals was investigated by means of nanoindentation. Upon loading with the blunt and sharp indenter tips, the crystal deforms elastically in the initial stage followed by plastic deformation of which the onset is characterized by an obvious displacement burst (or pop-in) in the loading curve. This pop-in corresponds to homogeneous nucleation of dislocation loops under the indenter. When a sharp indenter tip was used, a major pop-in can be identified at a large load (7 mN for (1 1 1) crystal) in the plastic regime on loading. The major pop-in may be correlated with the special dislocation structure of the K–W locks in the Ni₃Al crystals that are formed during loading. The pop-in behavior during plastic deformation of Ni₃Al crystals is found to be closely related to the crystal orientation, pre-existing dislocation density in the sample surface, loading rate, and holding (at a constant sub-critical load) time as well. Pop-ins were also observed at critical loads in unloading processes.     

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.     

Effect of directional solidification and heat treatments on the microstructure and mechanical properties of multiphase intermetallic Zr-doped Ni–Al–Cr–Ta–Mo alloy

The effect of directional solidification and heat treatments on the microstructure and mechanical properties of intermetallic Ni–21.29Al–7.04Cr–1.46Ta–0.64Mo–0.57Zr (at.%) alloy was studied. Increasing growth rate is found to decrease primary dendrite arm spacing and to increase volume fraction of β(NiAl)-based dendrites and low melting point γ′(Ni₃Al)/Ni₅Zr eutectic. Room-temperature tensile yield strength and ultimate tensile strength increase and plastic elongation to fracture decreases with the increasing growth rate. Two types of heat treatments of directionally solidified (DS) specimens including two-step ageing at temperatures of 1273 and 1123 K and two-step solution annealing at 1373 and 1493 K were performed. Ageing at 1273 and 1123 K decreases volume fractions of the dendrites and eutectic regions and leads to a coarsening of spherical -Cr and needle-like γ′ precipitates within the β-phase. Annealing at 1373 K for 100 h is shown to be sufficiently long to completely dissolve the eutectic regions. Compressive yield strength increases with increasing temperature reaching a peak value at about 1023 K and then decreases at higher temperatures. Minimum creep rate is found to depend strongly on the applied stress and temperature according to a power law. The power law stress exponent n is determined to be 5.1 and apparent activation for creep Q_a is measured to be 326 kJ/mol.     

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.     

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.     

Grain boundary self-diffusion of Ni in pure and boron-doped Ni3Al

Grain boundary (gb) self-diffusion in pure Ni-rich Ni₃Al was measured between 882 and 1374 K using the radiotracer ⁶³Ni, a serial sectioning technique and sensitive liquid scintillation counting. The results of the gb diffusivity P = δD_gb (δ : gb width, D_gb : gb diffusion coefficient) can be represented by the Arrhenius parameters P₀ = 3.27 · 10¹³and Q_gb = 168 kJ/mol. Additionally gb diffusion was investigated in boron-doped (0.24 at%) Ni-rich Ni₃Al in the range from 882 to 1352 K yielding P₀ = 1.24 · 10⁻¹² m³/s and Q_gb = 187 kJ/mol. The increase in the activation enthalpy Q_gb and the decrease of P upon boron-doping is explained by the segregation of B in Ni₃Al gbs, which may lead to an increase in the vacancy formation enthalpy and to a blocking of energetically favourable diffusion paths in the gbs. For comparison gb self-diffusion in pure Ni was remeasured yielding Q_gb = 112 kJ/mol. Ordering of the lattice and the preservation of ordering up to the gb planes, as predicted in Ni₃Al, therefore has a pronounced decelerating influence on gb diffusion, stronger than on bulk diffusion. Applying the semi-empirical relation of Borisov et al. (Phys. Met. Metallogr., 17 (1964) 80) gb energies γ_gb were determined for arbitrary high angle gbs in pure and B-doped Ni₃Al, resulting in 915 and 870 mJ/m², respectively, at 1100 K.     

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.     

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.     

Hot deformation behaviour and grain refinement of intermetallic compound Ni3Al

The paper describes the preparation of Ni₃Al-based intermetallic compounds and investigations of their structures in the ascast, worked, and annealed states. The performed experimental works approved a possibility of hot working of the highly brittle polycrystalline intermetallic compound Ni₃Al with large grain cast structure. The facility of originating the recrystallization seems to be surprising in such a material. On the other hand, the growth of recrystallization nuclei is strongly retarded. The case is further complicated by the fact of heterogeneous deformation in the microvolume. Microalloying with boron or zirconium influenced the original structure parameters as well as the optimum deformation temperature. Simultaneously the probability of a transgranular cleavage fracture increased. For the stoichiometric Ni₃Al intermetallic compound the optimum deformation temperature 1150 °C has been assessed. At temperature 1250 °C, the alloy Ni₃Al + 0,1 at. % B manifested the best plasticity. The special type of rotary working combined with friction heating gave the best results from point of view of obtaining a fully recrystallized region.     

Shear-induced chemical disordering in Ni3Al at different temperatures

Molecular dynamics simulations have been used to study shear-induced chemical disordering in Ni₃Al lattices at different temperatures and strain rates. Shearing determines the formation of an amorphous layer, the thickness of which increases linearly with the square root of time. The rate at which the amorphous layer grows is both shearing rate- and temperature-dependent. A linear correlation between the amorphous layer growth rate and the shear modulus is found. This suggests that mechanical properties could play a central role in shear-induced disordering processes.     

On the peritectoid formation of Ni5Al3

The peritectoid formation of Ni₅Al₃ from the two phases NiAl and Ni₃Al was studied in a Ni---Al alloy containing 66 at% Ni by means of transmission electron microscopy. The product phase does not form as a uniform layer between the two initial phases as expected and already observed in a few systems. In the system studied here there are only very few nucleation sites located at the NiAl/Ni₃Al interface. The further growth of Ni₅Al₃ takes place only into one of the initial phases which is NiAl. A strict orientation relationship between NiAl and Ni₅Al₃ was observed; the growth direction was [221]. The transformation is presumably diffusion controlled; it is very sluggish and it can be described by a nucleation and growth process. From the study presented here we conclude that the formation of Ni₅Al₃ proceeds by a micromechanism which differs from that normally assumed for peritectoid reactions.     

The strengthening effect of (Ni,Fe)Al precipitates on the mechanical properties at high temperatures of ferritic Fe–Al–Ni–Cr alloys

Strengthening through a homogeneous distribution of a second phase is a concept that is widely employed in high-temperature materials. The most prominent among this group are nickel-based superalloys which owe their high-temperature strength to finely dispersed Ni₃Al particles. Similar microstructures can be obtained in the Fe–Al–Ni–Cr system with B2-ordered (Ni,Fe)Al precipitates in a ferritic matrix. These precipitates lead to an increase of high-temperature strength compared to conventional iron-base high-temperature alloys. However, secondary precipitates form during air cooling from high temperatures and affect the ductility. The results show that the ductility can be improved by a two-step aging treatment. Within the stress and temperature range investigated, the dependence of the secondary creep rate on the applied stress of aged alloys can be described by a power law if a threshold stress is introduced.     

Effect of boron doping on the mechanical properties of ordered Ni–Mo alloys

HASTELLOY B-2 alloy was found to exhibit environmental embrittlement when tested in air and hydrogen at ambient temperature after atomic ordering introduced by a heat treatment at 700 °C for 24 h. Molybdenum in the HASTELLOY B-2 alloy was probably reactive enough to dissociate water vapor in air to generate atomic hydrogen, resulting in hydrogen embrittlement. The percentage of transgranular fracture increased as the test environment changed from hydrogen gas to moist air or water vapor, and vacuum or oxygen. With the addition of 100 wt ppm B, the environmental embrittlement was completely eliminated, with the tensile properties independent of both test environment and strain rate. The fracture mode remained the same, i.e. ductile dimpling, after B-doping when tested in different environments. The immunity of the B-doped B2 alloy to environmental sensitivity remained even after long-term heat treatment. Auger analysis does not detect any boron segregation at the grain boundaries. The mechanism of boron doping in eliminating the environmental embrittlement in the Ni–Mo alloy is apparently different from that in many L1₂-type alloys such as Ni₃Al and Ni₃Si.     

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.     

Effect of Trace O Element on High-temperature Wettability Between Ni_3Al Melt and Y_2O_3 Ceramic

Effect of trace O element on the high-temperature wettability between Ni_3Al scrap melt and Y_2O_3 ceramic at 1873 K is investigated. With the increase in O content in Ni_3Al scrap melt from 6 to 21 ppm, the equilibrium contact angle decreases from 93.3° to 88.9°. The initial surface tension and adhesive work of molten Ni_3Al scrap drop from 3153.5 to 807.4 mN m~(-1) and from 2974.6 to 882.2 mN m~(-1), respectively. The average spreading rate increases from 0.03° s~(-1) to 0.17° s~(-1). The whole wetting processes are divided into four periods. The main driving force for spreading in period(1) is the adsorption and diffusion of active atoms around the interface. Trace O content in Ni_3Al scrap has a significant impact on interfacial reactions which mostly take place in the second stage, and can accelerate the spreading process on Y_2O_3 substrate. The reaction products during wetting process are Y_3Al_5O_(12), YAlO_3 and Al_2O_3.     

等离子喷涂氮化硼纳米片增强Ni3Al复合涂层的摩擦学性能

采用等离子喷涂技术在钛合金表面制备出六方氮化硼纳米片(BNNP)增强Ni₃Al复合涂层。结果表明,涂层物相主要为原位生成的Ni₃Al和少量Al₂O₃。相比于Ni₃Al涂层,BNNP优异的力学性能和自润滑性能赋予复合涂层良好的减摩耐磨性能,其耐磨性能提高了约1.5倍。Ni₃Al涂层的主要磨损机制是脆性断裂和三体磨粒磨损,BNNP/Ni₃Al复合涂层的主要磨损机制则转变为轻微的磨粒磨损,且磨损表面BNNP润滑转移膜的形成有益于抑制对磨偶件的接触损伤。     

Recrystallization and grain growth in Ni3Al with and without boron

The recrystallization and grain growth of boron-free and boron-doped (500 ppm by weight) Ni₃Al polycrystals were investigated in the temperature range 700–1000°C. The levels of deformation were 17% reduction in length in compression for both alloys and 40% rolling reduction applied only to the boron-doped alloy. For alloys with or without boron, the Kolmogorov-Johnson-Mehl-Avrami relationship holds, with the Avrami exponent near unity, and the recrystallization rate is very slow. The activation energies for recrystallization are respectively 480 and 492 kJ/mol for boron-free and boron-doped to 40%. The grain growth kinetics obey a power law with the time exponent ranging from 0·2 to 0·4. The boron effect at 500 ppm was found to be small on both recrystallization and grain growth in Ni₃Al.     

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。