In situ XRD studies on Al–Ni and Al–Ni–Sr alloys prepared by rapid solidification

In this paper the structure and stability of Al–17 wt.%Ni(Al–17Ni) and Al–17 wt.%Ni–2 wt.%Sr alloys prepared by rapid solidification was investigated by means of XRD techniques. Our work demonstrates that both alloys are crystalline and composed of fcc (Al–Ni) solid solution and orthorhombic Al₃Ni phases. The ternary alloy shows in addition the presence of small amount of tetragonal Al₄Sr phase. In situ XRD experiment demonstrates the stability of the solute solution up to 650 °C, Al₃Ni above 750 °C while Al₄Sr overcomes melting of the major phases at 800 °C. High-temperature structure analysis proved strong bindings between Al and Ni atoms in Al₃Ni phase, corroborating its covalent nature, linear and faster increase of the fcc volume with annealing temperature. The linear correlation between constituting atoms decreases with increase of the temperature.The work also documents the applicability of pair distribution function (PDF) analysis to the study of multiphase crystalline systems.     

The Zn-rich corner of the 450 °C isothermal section of the Zn–Bi–Fe–Ni quaternary system

Following up on recent studies of the isothermal section of the Zn–Fe–Ni, Zn–Fe–Bi and Zn–Bi–Ni ternary systems at 450 °C, the Zn-rich corner of the 450 °C isothermal section of the Zn–Bi–Fe–Ni quaternary system with the Zn being fixed at 93 at.% was determined experimentally using the equilibrated alloys approach. The specimens were investigated by means of scanning electron microscopy (SEM) equipped with energy dispersive X-ray spectroscopy (EDS), and X-ray diffraction (XRD). It was found there exist 4 two-phase regions, 5 three-phase regions and 2 four-phase regions. Two liquid L (Zn) and L (Bi) can coexist with T, ζ and δ-Ni in this isothermal section, no new phase was found in this study.     

Experimental determination of phase equilibria in the Fe–Nb–V ternary system

The phase equilibria in the Fe–Nb–V ternary system were investigated by means of optical microscopy, electron probe microanalysis and X-ray diffraction. Four isothermal sections in the Fe–Nb–V ternary system at 1000 °C, 1100 °C, 1200 °C and 1300 °C were firstly experimentally established. Present experimental results indicate that: (1) there is a large (Nb, V) continuous bcc solid solution; (2) there are the larger solubilities of V in the FeNb and Fe₂Nb phases. The newly determined phase equilibria in this system will provide important support for the development of hydrogen storage materials and microalloyed steels.     

Synthesis of ultrafine (Ti, W, Mo, V)(C, N)–Ni composite powders by low-energy milling and subsequent carbothermal reduction–nitridation reaction

Ultrafine (Ti, W, Mo, V)(C, N)–Ni composite powders with globular-like particles of 50–300 nm were synthesized at static nitrogen pressure from oxides by a simple and cost-effective route which combines traditional low-energy milling plus carbothermal reduction–nitridation (CRN) techniques. Reaction path of the (Ti, W, Mo, V)(C, N)–Ni system was discussed by X-ray diffraction (XRD) and thermogravimetry–differential scanning calorimetry (TG–DSC), and microstructure of the milled powders and final products was studied by scanning electron microscopy (SEM) and transmission electron microscope (TEM), respectively. The results show that CRN reaction has been enhanced by nano-TiO₂ and nano-carbon powders. Thus, the preparation of (Ti, 15W, 5Mo, 0.2V)(C, N)–20Ni is at only 1300 °C for 1 h. During synthesizing reaction, Ni solid solution phase forms at about 700 °C and reduction–carbonization of WO₂ and MoO₂ occurs below 900 °C. The reactions of TiO₂ → Ti₃O₅, Ti₃O₅ → Ti(C, O) and Ti(C, O) → Ti(C, N) take place at about 930 °C, 1203 °C and 1244 °C, respectively.     

Low-temperature brazing of titanium by the application of a Zr–Ti–Ni–Cu–Bebulk metallic glass (BMG) alloy as a filler

Titanium (Ti) was successfully brazed at low temperatures below 800 °C by employing a Zr_41.2Ti_13.8Ni_10.0Cu_12.5Be_22.5 (at.%) bulk metallic glass (BMG) alloy as a filler. Through the use of this alloy filler, the detrimental segregation of Zr–Cu–Ni filler elements was completely eliminated by heating to well below 800 °C, so the resultant joint was quite homogeneous with a coarse acicular structure. The disappearance of the Zr–Cu–Ni segregated region was rate-controlled by the diffusion of the filler elements in the Ti base metal. Remarkably, the mechanical property and corrosion resistance of the homogeneous joint brazed at 800 °C for 10 min were mostly comparable to those of bulk Ti.     

Electrochemical hydrogen storage of NdMg12–Ni composites modified with carbon nanotubes and BN particles

In this work, the electrochemical performance of NdMg₁₂–Ni composite electrode in alkaline solution and the effect of the surface modification with carbon nanotubes (CNTs) and boron nitride (BN) particles on the NdMg₁₂–Ni composite were investigated. The NdMg₁₂ alloy was synthesized by a salt-cover-melting and a subsequent quenching process. The NdMg₁₂–Ni–BN and NdMg₁₂–Ni–CNTs composites were prepared by ball-milling NdMg₁₂ alloy, Ni powders and CNTs or BN particles. It is found that CNTs or BN particles are mainly attached onto the surface of the NdMg₁₂–Ni composite after the ball-milling process. The electrochemical experiment results indicate that the NdMg₁₂–Ni composites modified with CNTs or BN particles have the improved electrochemical performance. In particular, the NdMg₁₂–Ni–5 wt.% CNTs and NdMg₁₂–Ni–3 wt.% BN composites have the higher initial discharge capacity of 416.6 mAh/g and 442.9 mAh/g, respectively, larger than the original NdMg₁₂–Ni composite. The large amount of grain boundaries and crystalline defects, induced during the ball-milling process, can accelerate the bulk hydrogen diffusion and provide more surface active sites for the electrochemical reaction of the composites. However, the cycle stability of the composites modified by CNTs or BN particles is still not satisfactory for the practical application.     

Analysis of hydrogen distribution on Mg–Ni alloy surface by scanning electron-stimulated desorption ion microscope (SESDIM)

Hydrogen distribution and behavior on a Mg–Ni alloy surface are studied by using a time-of-flight electron-stimulated desorption (TOF-ESD) microscopy and a scanning electron microscope with energy dispersive X-ray spectroscopy (SEM-EDX). The desorbed hydrogen ions are energy-discriminated and distinguished into two characters in the adsorbed states, which belong to Mg₂Ni grains and the other to oxygen-contaminated Mg phase at the grain boundaries. Adsorbed hydrogen is found to be stable up to 150 °C, but becomes thermally unstable around at 200 °C.     

Reinforcement of Al–Fe–Ni alloys with the in situ formation of composite materials

One of the most effective methods for the improvement of the mechanical properties of metals is their reinforcement with non-metallic materials. In the present work powder of K₂TiF₆ and KBF₄ was added in an Al–Fe–Ni alloy while the alloy was in liquid form at 1060 °C with a 5 wt.% mixture of powders and with simultaneous stirring for 30 min. The liquid was squeeze-casted at 150 bar. The as-cast specimens were examined with electron microscopy and X-ray diffraction. SEM analysis revealed that the as-formed material is composed by needle-like crystallites along with a dentritic form and an interdendritic phase. The composition of the needle-like crystallites may presumably be expressed by the formula (Fe-Ni)Al₃. The rest of the matrix consists of almost pure Al grown dentritically, while the interdendritic phase contains Fe and Ni dissolved in Al. EDS analysis also proved the existence of spots with high Ti concentration, which probably refer to the Ti–B compounds. Finally TEM verified the presence of nanocrystals in the matrix.     

Differential thermal analysis (DTA) on the reaction mechanism in Fe–Ti–B4C system

Differential thermal analysis (DTA) was undertaken to determine the reaction mechanism in the Fe–Ti–B₄C system under argon. When the mixtures were heated to about 786 °C, Fe₂B and C appeared as a result of Fe reacting with B₄C. As the temperature continued to increase, FeTi formed by an interdiffusion between Fe and Ti. When the mixtures were heated to 1089 °C, FeTi reacted with Ti, leading to the formation of a Fe–Ti melt, into which the displaced C and B from B₄C dissolve, forming a Fe–Ti–C–B melt. Finally, when the concentration of C and B attained a certain value, Ti reacted with C and B, yielding TiC and TiB₂ in the melt, and simultaneously considerable heat released.     

Nanocrystalline Al–Fe intermetallics – light weight alloys with high hardness

Nanocrystalline Al–Fe alloys containing 60–85 at.% Al were produced by consolidation of mechanically alloyed nanocrystalline or amorphous (Al85Fe15 composition) powders at 1000 °C under a pressure of 7.7 GPa. The hardness of the alloys varied between 5.8 and 9.5 GPa, depending on the Al content. The specific strength, calculated using an approximation of the yield strength according to the Tabor relation, was between 544 and 714 kNm/kg. Based on the results obtained, we infer that application of high pressure affected crystallisation of amorphous Al₈₅Fe₁₅ alloy, influencing the phase composition of the crystallisation product, and phase changes in nanocrystalline Al₈₀Fe₂₀ alloy, inhibiting them.     

The phase equilibria of the Al–Ce–Ni system at 500 °C

The phase equilibria at 500 °C in the Al–Ce–Ni system in the composition region of 0–33.3 at.% Ce are investigated using XRD and SEM/EDX techniques applied to equilibrated alloys. The previously reported ternary phases and the variation of the lattice parameters versus the composition for different solid solution phases are investigated. It is confirmed that τ₂(Al₂CeNi) exists at 500 °C, while τ₃(Al₅Ce₂Ni₅) does not exist at 500 °C. A new compound τ₉ with composition of about Al₃₅Ce_16.5Ni_48.5 is found. The solubility of Ni in Al₁₁Ce₃ and αAl₃Ce is generally about 1 at.%, while the solubility of Ni in Al₂Ce is measured to be 2.7 at.%. The solubility of Ce in Al₃Ni, Al₃Ni₂, AlNi and AlNi₃ is all less than 1 at.%. The solubility of Al in CeNi₅, Ce₂Ni₇ and CeNi₃ is measured to be 30.4, 4.8 and 9.2 at.%, respectively, while there is no detectable solubility for Al in CeNi₂. A revised isothermal section at 500 °C in the Al–Ce–Ni system has been presented.     

Influence factors and microstructure evolution during preparation of nanocrystalline (Ti, W, Mo, V)(C, N)–Ni composite powders

Nanocrystalline (Ti, W, Mo, V)(C, N)–Ni composite powders with crystalline size of about 35 nm were synthesized at 1300 °C from oxides by a simple and cost-effective route which combines traditional low-energy milling plus carbothermal reduction–nitridation techniques. Influence of main technological parameters was investigated by X-ray diffraction, and microstructure of the milled powders and reaction products was studied by scanning electron microscopy. The results show that the phase evolution of TiO₂ follows TiO₂ → Ti₃O₅ → Ti(C, N), and (Ti, W, Mo, V)(C, N)–Ni composite powders with higher nitrogen content and smaller crystalline size can be produced by introducing high nitrogen pressure. By contrast with high nitrogen pressure, high synthesizing temperature and long isothermal time can contribute to dissolution of W, Mo and V atoms into Ti(C, N). In addition, synthesizing temperature has a significant effect on the microstructure evolution of (Ti, W, Mo, V)(C, N)–Ni composite powders.     

The third-element effect in the oxidation of Ni–xCr–7Al (x = 0, 5, 10, 15 at.%) alloys in 1 atm O2 at 900–1000 °C

The oxidation in 1 atm of pure oxygen of Ni–Cr–Al alloys with a constant aluminum content of 7 at.% and containing 5, 10 and 15 at.% Cr was studied at 900 and 1000 °C and compared to the behavior of the corresponding binary Ni–Al alloy (Ni–7Al). A dense external scale of NiO overlying a zone of internal oxide precipitates formed on Ni–7Al and Ni–5Cr–7Al at both temperatures. Conversely, an external Al₂O₃ layer formed on Ni–10Cr–7Al at both temperatures and on Ni–15Cr–7Al at 900 °C, while the scales grown initially on Ni–15Cr–7Al at 1000 °C were more complex, but eventually developed an innermost protective alumina layer. Thus, the addition of sufficient chromium levels to Ni–7Al produced a classical third-element effect, inducing the transition between internal and external oxidation of aluminum. This effect is interpreted on the basis of an extension to ternary alloys of a criterion first proposed by Wagner for the transition between internal and external oxidation of the most reactive component in binary alloys.     

Martensitic transformation and anomalies in resistivity of (Ti–50Ni)1−xCx (x = 0.1, 0.5 at.%) shape memory alloys

Phase transformation of solid solution (Ti–50Ni)_1−xC_x (x = 0.1, 0.5 at.%) alloys have been studied by using differential scanning calorimetry, physical property measurement system and optical microscope. The transformation temperature decreases due to the existence of titanium carbide (TiC) particles compared with that of near-equiatomic Ti–Ni shape memory alloy. The resistivity vs. temperature curves show hysteresis. Thermoelastic martensitic transformation occurred in two alloys despite the difference in TiC content. Nevertheless, the resistivity results show different martensitic transformation routes. A one-step B2 → B19′ transformation occurred in the low TiC content alloy and an R transformation appeared in another alloy, suggesting that the martensitic transformation routes depended on the TiC content. The cumulative effect of the TiC particles causes the local stress field and lattice distortion to restrain the transformation of the B19′. On the other hand, the TiC content has an effect on the temperature coefficient of electrical resistivity (TCR) of alloys. The Ti–Ni–0.5C alloy shows a negative TCR in the range 100–300 K during which transformation occurs. Another alloy shows the opposite result. The cause of the negative TCR is briefly discussed.     

Growth of single-crystal W whiskers during humid H2/N2 reduction of Ni, Fe–Ni, and Co–Ni doped tungsten oxide

Numbers of W whiskers were obtained by reducing Ni, Ni–Fe, and Ni–Co doped tungsten oxide in a mixed atmosphere of humid H₂ and N₂. The phases and morphologies of the reduction products were characterized by XRD and SEM. Intensive TEM and EDS analyses showed that the obtained whiskers were W single crystals which typical have alloyed particles (Ni–W, Fe–Ni, or Co–Ni–W) at the growth tips. The formed W whiskers were presumed to be induced by the alloyed particles. Our experimental results revealed that, during the reduction process of tungsten oxide, the pre-reduced Ni, Fe–Ni, or Co–Ni particles not only served as nucleation aids for the initial growth of W phase from W oxide but also played the roles of catalysts during the reductive decomposition of gaseous WO₂(OH)₂.     

Effect of Zr, Mn and Sc additions on the grain size of Mg–Gd alloy

The effect of Zr, Mn and Mn + Sc additions on the grain size of Mg–10Gd alloy has been investigated and the grain refinement mechanisms are also suggested. The results reveal that the addition of Zr results in a significant grain refinement of as-cast Mg–10Gd alloy by generating nucleants. However, it cannot restrict grain growth during homogenization treatment at 520 °C, and completely loss the grain refining effect for extruded alloy sample. Mn has a negligible effect on grain size of as-cast Mg–10Gd alloy, but α-Mn particles precipitate during homogenization treatment, which helps to refine the grains of extruded alloy sample due to α-Mn particles restricting recrystallization grain growth during extrusion. Successful grain refinement can be obtained by the addition of Mn + Sc. It is effective to refine microstructure of as-cast Mg–10Gd alloy, inhibit grain growth during homogenization treatment and also have a significant grain refining effect on extruded Mg–10Gd alloy sample, which are ascribed to the precipitation of a large number of Mn₂Sc particles.     

In situ nanocrystalline Fe–Si coating by mechanical alloying

A new approach for deposition of in situ nanocrystalline Fe–Si alloy coating on mild steel substrate by mechanical milling has been proposed. The thickness of nanocrystalline coating was a function of milling time and speed. Milling speed of 200 rpm was the optimum condition for development of uniform, hard, adherent and dense 200–300 μm thick nanocrystalline coating. A possible mechanism, consisting of three steps like repeated impact, cold welding and delamination, has been proposed for the formation of coating. These coatings have resulted in the increase of the hardness to almost double the value before coating.     

Preparation of W–15 wt%Ti prealloyed powders

W–15 wt%Ti prealloyed powders were prepared by high-energy milling W and TiH₂ powders, and the prealloyed powders were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), transmission electron microscopy (TEM) and differential scanning calorimetry (DSC). The size of W and TiH₂ grains was estimated by Williamson–Hall formula from width of XRD peaks. The results show that the grain size decreases with increasing milling time, while the lattice parameter increases. After milling for 40 h, nanocrystalline β-W_xTi_1−x solid solution with the form of thin laminar exists in the W–TiH₂ prealloyed powders.     

Microstructure identification of devitrified Cu–Ti–Zr–Ni bulk amorphous alloy

The microstructures of devitrified Cu–Ti–Zr–Ni bulk amorphous alloy were identified by X-ray diffractometry (XRD) and transmission electron microscope (TEM). XRD and TEM examinations show that the deep eutectic structures of the tested alloy consist of CuTi₂–Cu₁₀Zr₇, Cu₃Ti–CuZr, Cu₃Ti–Cu₁₀Zr₇–CuZr low-order eutectics. Moreover, short-range ordering clusters in the melt with configuration similar to that of Cu₁₀Zr₇ compound may contribute to the glass forming ability of bulk amorphous Cu–Ti–Zr–Ni alloy.     

Microstructure evolution and thermal stability of an Fe-based amorphous alloy powder and thermally sprayed coatings

High velocity oxy-fuel (HVOF) thermal spraying has been used to produce coatings of an Fe–18.9%Cr–16.1%B–4.0%C–2.8%Si–2.4%Mo–1.9%Mn–1.7%W (in at.%) alloy from a commercially available powder (Nanosteel SHS7170). X-ray diffraction (XRD), differential scanning calorimetry (DSC) and scanning electron microscopy (SEM) were employed to investigate the powder, as-sprayed coatings and annealed coatings which had been heated to temperatures in the range of 550–925 °C for times ranging from 60 to 3900 min. Microhardness changes of the coatings were also measured as a function of annealing time and temperature. The powder was found to comprise amorphous and crystalline particles; the former had a maximum diameter of around 22 μm. The coating was composed of splat like regions, arising from rapid solidification of fully molten powder, and near-spherical regions from partially melted powder which had a largely retained its microstructure. The amorphous fraction of the coating was around 50% compared with 18% for the powder. The enthalpies and activation energies for crystallization of the amorphous phase were determined. Crystallization occurred in a two stage process leading to the formation of α-Fe (bcc), Fe_1.1Cr_0.9B_0.9 and M₂₃C₆ phases. DSC measurements showed that the first stage occurred at 650 °C. Annealing the coating gave a hardening response which depended on temperature and time. The as-sprayed coating had a hardness of 9.2 GPa and peak hardnesses of 12.5 and 11.8 GPa were obtained at 650 and 750 °C, respectively. With longer annealing times hardness decreased rapidly from the peak.