Chemical and thermodynamic properties of several Al–Ni–R systems

The standard enthalpies of formation at 300 K of the RNiAl phases (R=rare earth) have been obtained by using a high temperature direct reaction drop calorimeter and an aneroid isoperibol calorimeter. State and composition of the samples were checked by X-ray diffraction analysis. Metallographic examination was performed and the phases were further identified by electron microscopy and electron probe microanalysis. The results obtained are discussed and compared with those available for the binary RNi₂ and RAl₂ compounds.     

The effects of ceria on the mechanical properties and thermal shock resistance of thermal sprayed NiAl intermetallic coatings

The effects of ceria addition to thermal sprayed NiAl intermetallic coatings were investigated through micro-indentation, thermal shock testing and microstructural analysis techniques (scanning electron microscopy with energy-dispersive X-ray spectrometry and X-ray diffraction analysis). It has been found that the addition of CeO₂ to NiAl coatings reduces the tendency of brittle peeling during thermal spraying. This reduction in peeling is presumably due to the improved wetting of the substrate by the molten coating material, which leads to better coating adhesion. The addition of CeO₂ resulted in higher coating hardness and elastic modulus. The coatings containing CeO₂ also exhibited significant increases in thermal shock resistance compared with that of the pure NiAl coating. The NiAl coating containing 2 wt.%CeO₂ had the highest hardness, elastic modulus and thermal shock resistance of the four NiAl-based coatings tested. The possible mechanisms responsible for the improvement of the properties upon addition of CeO₂ are addressed.     

Formation of NiAl intermetallic by gradual and explosive exothermic reaction mechanism during ball milling

NiAl intermetallic has been produced by mechanical alloying in a high energy vibrator mill using elemental Ni and Al powder mixture. The NiAl powders were formed in two ways. One by a gradual exothermic reaction mechanism during a long time continuous milling and the other by explosive exothermic reaction mechanism that occurred when opening the milling vessel to the air atmosphere after a short time milling. Prolonged milling for both cases resulted in change of morphology and refinement of grain size down to nano scale.     

Influence of non-reactive particles on the microstructure of NiAl and NiAl–ZrO2 processed by thermal explosion

Nickel aluminide intermetallic alloy and NiAl–ZrO₂ composites were synthesized in a hot press by sintering reaction and thermal explosion (or Self-propagating High temperature Synthesis, SHS). The addition of a post-SHS heat treatment allows a control of the microstructure and an enhancement of the mechanical characteristics. Thus, NiAl properties processed by self-combustion are above those obtained by reactive sintering (RS). For all these syntheses, the role played by the non-reactive particles is determining. Indeed, the product granulometry is a function of the diluent size distribution since this latter acts as nucleation sites during the reactive processes. These particles can also enhance mechanical properties by specific reinforcement mechanisms and exercise an influence on SHS reaction parameters by controlling its reactivity and the thermal exchanges during self-combustion.     

Thermodynamic activity measurements in the B2 phases of the Fe–Al and Ni–Al systems

The vaporisation of Fe–Al and Ni–Al alloys has been investigated in the temperature range 1140–1600 K and 1178 to 1574 K, respectively, by Knudsen effusion mass spectrometry (KEMS). Eleven different Fe–Al and also eleven Ni–Al compositions have been investigated in the composition ranges 30–51 at.% Al and 38–53 at.% Al, respectively. The Fe–Al samples have been investigated mostly in the B2 region of the phase diagram. The partial pressures and thermodynamic activities were evaluated directly from the measured ion intensities formed from the equilibrium vapour over the alloy and the pure element. From the temperature dependence of the activities the partial and integral molar enthalpies and entropies of mixing have been obtained. These are the most accurate data obtained by mass spectrometry on Fe–Al and Ni–Al systems so far. Nearly temperature independent integral enthalpies and entropies of mixing over the wide temperature range investigated were found, with the mixing entropies being large and negative.     

Enthalpies of formation of selected Pd2YZ Heusler compounds

Standard enthalpies of formation of selected ternary Pd-based Heusler type compositions Pd₂YZ (Y = Cu, Hf, Mn, Ti, Zr; Z = Al, Ga, In, Ge, Sn) were measured using high temperature direct synthesis calorimetry. The measured enthalpies of formation (in kJ/mole of atoms) of the Heusler compounds are, Pd₂HfAl (−81.6 ± 2.4); Pd₂HfGa (−79.9 ± 2.9); Pd₂HfIn (−76.4 ± 1.4); Pd₂HfSn (−77.6 ± 1.6); Pd₂MnSn (−54.6 ± 3.1); Pd₂TiGa (−65.6 ± 3.6); Pd₂TiIn (−69.9 ± 2.1); Pd₂TiSn (−78.6 ± 2.4); Pd₂ZrAl (−85.3 ± 3.0); Pd₂ZrGa (−76.2 ± 1.9); Pd₂ZrIn (−85.1 ± 3.9); Pd₂ZrSn (−92.2 ± 3.1); for the B2 compounds, Pd₂MnAl (−87.1 ± 3.0); Pd₂MnGa (−54.5 ± 1.7); Pd₂MnIn (−41.0 ± 2.5); Pd₂TiAl (−81.4 ± 1.9); for the tetragonal compound Pd₂CuAl (−55.2 ± 3.0) and for the orthorhombic compound Pd₂CuSn (−43.1 ± 2.3). Values were compared with those from published first principles calculation and the Open Quantum Materials Database (OQMD). Lattice parameters of these compounds were determined by X-ray diffraction analysis (XRD). Microstructures were identified using scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). Selected alloys were annealed at various temperatures to investigate phase transformations and phase relationships.     

FeAl and Mo–Si–B intermetallic coatings prepared by thermal spraying

FeAl and Mo–Si–B intermetallic coatings for elevated temperature environmental resistance were prepared using high-velocity oxy-fuel (HVOF) and air plasma spray (APS) techniques. For both coating types, the effect of coating parameters (spray particle velocity and temperature) on the microstructure and physical properties of the coatings was assessed. Fe–24Al (wt%) coatings were prepared using HVOF thermal spraying at spray particle velocities varying from 540 to 700 m/s. Mo–13.4Si–2.6B coatings were prepared using APS at particle velocities of 180 and 350 m/s. Residual stresses in the HVOF FeAl coatings were compressive, while stresses in the APS Mo–Si–B coatings were tensile. In both cases, residual stresses became more compressive with increasing spray particle velocity due to increased peening imparted by the spray particles. The hardness and elastic moduli of FeAl coatings also increased with increasing particle velocity. For Mo–Si–B coatings, plasma spraying at 180 m/s resulted in significant oxidation of the spray particles and conversion of the T1 phase into amorphous silica and -Mo. The T1 phase was retained after spraying at 350 m/s.     

Porous FeAl intermetallics fabricated by elemental powder reactive synthesis

Fabrication of porous FeAl intermetallics has been realized through the Fe and Al elemental powder reactive synthesis. The swelling behavior, synthesis process and microstructure of the porous FeAl intermetallics fabricated by reactive synthesis have been systematically studied. The pore structural parameters as a function of the sintering temperature have also been systematically investigated. It has been confirmed that the pore evolution in the porous FeAl intermetallics is attributed to the following four steps: the inter-particle pores formed during the pressing procedure, the Kirkendall pores formed during the solid-state sintering, pore formed through the liquid Al reaction, and the phase transformation during the high temperature sintering.     

Nanostructured intermetallics prepared by dealloying from single crystal nickel-based superalloys

Two-nanostructure intermetallics (nanoporous film and nanocube) on single crystal nickel-based superalloys were fabricated by electrochemical dealloying in an aqueous electrolyte containing 1 wt% (NH₄)₂SO₄ and 1 wt% citric acid solution respectively. Electrochemical properties of two phases in single crystal nickel-based superalloys are different, and it has been utilized to dissolve preferentially γ matrix phase and γ′ phase remains passive. The electrochemical corrosion behavior of a Ni-based superalloy after high temperature creep was investigated using an EG&G PAR M273 potentiostat. The results indicated that the microstructure after high temperature creep determined the morphology of the resultant γ′ phase intermetallics after dealloying. The morphologies and structure of nanoporous film and nanocube were characterized using a JSM-6700 (Japan) field emission scanning electron microscope (FE-SEM) and JEM-3010 high resolution transmission electron microscopy (HRTEM).     

Structure of Al–Ni intermetallic composite layers produced on the Inconel 600 by the glow discharge enhanced-PACVD method

The Plasma Assisted Chemical Vapor Deposition (PACVD) treatment conducted under glow discharge conditions in an atmosphere of trimethylaluminum vapors applied to an Inconel 600 substrate yielded composite surface layers built of intermetallic phases of the Al–Ni system with the outer zone composed of aluminum oxides. Such layers have very advantageous performance properties, such as high hardness, good corrosion and frictional wear resistance and, good adherence to the substrate.The present study is dedicated to microstructure characterization of the layers. The layers were examined using a variety of methods. Based on the results of these examinations, the microstructure of the composite layers was described as a multizone one with an outer Al₂O₃ zone, an intermediate AlNi₃ + Al₂O₃ zone and a diffusion zone of type Ni(Al,Cr,Fe) + AlNi₃ + Cr₇C₃. The mechanism of layer formation as well as the correlation between the microstructure and the observed improvement of the surface properties of the Inconel 600 alloy are discussed.     

Effects of Ni vacancy,Ni antisite,Cr and Pt on the third-order elastic constants and mechanical properties of NiAl

Effects of Ni vacancy, Ni antisite in Al sublattice, Cr in Al sublattice, Pt in Ni sublattice on the second-order elastic constants (SOECs) and third-order elastic constants (TOECs) of the B2 NiAl have been investigated using the first-principles methods. Lattice constant and the SOECs of NiAl are in good agreement with the previous results. The brittle/ductile transition map based on Pugh ratio G/B and Cauchy pressure P_c shows that Ni antisite, Cr, Pt and pressure can improve the ductility of NiAl, respectively. Ni vacancy and lower pressure can enhance the Vickers hardness H_v of NiAl. The density of states (DOS) and the charge density difference are also used to analysis the effects of vacancy, Ni antisite, Cr and Pt on the mechanical properties of NiAl, and the results are in consistent with the transition map.     

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.     

Martensitic transformation of Ni64Al34Re2 shape memory alloy

As-rolled and annealed Ni₆₄Al₃₄Re₂ shape memory alloy (SMA) exhibits B2 → L1₀ (3R) martensitic transformation with M_s temperature up to about 210 °C. Experimental results indicate that the annealing temperature is the major factor that affects the M_s temperature. It is found that adding 2 at.% Re to replace Al in Ni₆₄Al₃₆ binary SMA can significantly refine the alloy's grain size and enhance the softening behavior during transformation. Meanwhile, Re has the same trend as Ni to affect the M_s temperature, but it has a less effect than Ni. The lattice constants and microstructures of NiAl-B2 phase, NiAl-L1₀ (3R) martensite and Ni₃Al-L1₂ phase are almost similar to those of Ni–Al binary SMAs.     

Effect of Dy on the microstructures of directionally solidified NiAl–Cr(Mo) hypereutectic alloy at different withdrawal rates

The effect of various Dy content on the microstructure of Ni–31Al–32Cr–6Mo hypereutectic alloy was studied at the withdrawal rates of 6, 30 and 90 μm/s. The results show that the solid–liquid interface morphology has an evolutionary process of planar → cellular → dendritic interface with the increasing withdrawal rate. The primary Cr(Mo) dendrites are gradually weeded out through competitive growth between the primary phase and the eutectic phase. The volume fraction of primary Cr(Mo) dendrites decreases with the modest addition of Dy (0.05 wt.%) at 6 μm/s. When the withdrawal rate increases to 30 μm/s, the appropriate addition of Dy (0.1 wt.%) refines the microstructure, such as the width of intercellular zone and the lamellar thickness in the intercellular zone. With the increase of withdrawal rate to 90 μm/s, the addition of Dy has no significant effect on the microstructure. In addition, the white Dy-containing phase can occur in the boundary of eutectic cells when the Dy content is no less than 0.1 wt.%.     

Oxidation protection of γ-TiAl-based alloys – A review

Alloys based on γ-TiAl are lightweight materials with attractive mechanical properties at high temperatures. Although these alloys reveal a superior resistance against environmental attack compared to titanium and 2-based alloys, efficient protection is required for industrial applications at temperatures between 800 and 1050 °C. Extensive research in order to solve this problem started more than 30 years ago. This review provides a summary of the different concepts based on surface modification techniques developed for the environmental protection of γ-TiAl alloys at high temperatures, including overlay and diffusion coatings, as well as the halogen effect. The discussion includes a comparison between the most promising coating types under long-term high temperature exposure and an assessment of their processing routes from a technological point of view. Therefore, a mass gain of 1 mg/cm² after at least 1000 h of exposure was set as a benchmark to evaluate these protection systems.