Synthesis and Non-isothermal Carbothermic Reduction of FeTiO<Subscript>3</Subscript>-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> Solid Solution Systems

To investigate the carbothermic reduction behaviors of xFeTiO₃·(1 ? x)Fe₂O₃ solid solutions, the solid solutions with different x values were synthesized and used in the corresponding reactions. With an increase in x, the temperature pertaining to the onset of carbothermic reduction increased, while the rate of reduction of the solid solutions, α, decreased. The lattice parameters calculated from XRD patterns indicated that the solid solution with a higher x led to a larger lattice distortion. The non-isothermal kinetics were calculated, and an average activation energy E value of 3.0 × 10² kJ/mol was obtained.     

Monte Carlo Simulation Study of Diffuse Scattering in PZT,Pb(Zr,Ti)O<Subscript>3</Subscript>

Transverse polarized diffuse streaks have been observed in diffraction patterns of Pb(Zr_1?x Ti _x )O₃ (PZT) ceramics for compositions ranging from x = 0.3 (rhombohedral phase) to x = 0.7 (tetragonal phase) including the important morphotropic phase boundary (MPB) region (x = 0.48). The streaks correspond to diffuse planes of scattering in three dimensions, and these are oriented normal to the (cubic) \( \langle 111\rangle_{c} \) directions. A Monte Carlo (MC) model has been developed that convincingly reproduces the observed diffraction patterns. In this model, the displacements of Pb ions running in chains along each of the \( \langle 111\rangle_{c} \) directions are directed along the chain and are strongly correlated from cell to cell. There is no evidence of lateral correlation. Neighboring chains are essentially independent. At this stage, it is not clear what role the local order revealed by the scattering might play in governing the exceptional piezo-electric properties of the material, but its presence requires the currently accepted models for the average structure to be reassessed.     

Kinetics study on non-isothermal crystallization of Cu<Subscript>50</Subscript>Zr<Subscript>50</Subscript> metallic glass

In this paper, the crystallization kinetics of melt-spun Cu₅₀Zr₅₀ amorphous alloy ribbons has been investigated using differential scanning calorimetry. Moreover, the Kissinger, Ozawa and isoconversional approaches have been used to obtain the crystallization kinetic parameters. As shown in the results, the onset crystallization activation energy E _x is less than crystallization peak activation energy E _p. The local activation energy E _α increases at the crystallized volume fraction α < 0.2 and decreases at the rest, which suggests that crystallization process is increasingly hard (α < 0.2) at first, after which it become increasingly easy (α > 0.2). The nucleation activation energy E _nucleation is greater than grain growth activation energy E _growth, indicating that the nucleation is harder than growth. In terms of the local Avrami exponent n(α), it lies between 1.27 and 8, which means that crystallization mechanism in the non-isothermal crystallization is interface-controlled one- two- or three-dimensional growth with different nucleation rates.     

Microstructure and Properties of Fe<Subscript>3</Subscript>Al-Fe<Subscript>3</Subscript>AlC<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> Composite Prepared by Reactive Liquid Processing

A Fe₃Al-Fe₃AlC _x composite was prepared using reactive liquid processing (RLP) through controlled mixture of carbon steel and aluminum in the liquid state. The microstructure and phases of the composite were assessed using X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy, optical microscopy, and differential scanning calorimetry. In addition, the density, hardness, microhardness, and elastic modulus were evaluated. The Fe₃Al-Fe₃AlC _x composite consisted of 65 vol pct Fe₃Al and 35 vol pct Fe₃AlC _x (κ). The κ phase contained 10.62 at. pct C, resulting in the stoichiometry Fe₃AlC_0.475. The elastic modulus of the Fe₃Al-Fe₃AlC_0.475 composite followed the rule of mixtures. The RLP technique was shown to be capable of producing Fe₃Al-Fe₃AlC_0.475 with a microstructure and properties similar to those achieved using other processing techniques reported in the literature.     

Self-propagating high-temperature synthesis of ceramic materials based on the M<Subscript><Emphasis Type="Italic">n</Emphasis> + 1</Subscript>AX<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript> phases in the Ti-Cr-Al-C system

Compact ceramic materials based on the M_{n + 1}AX _n phases in the Ti-Cr-Al-C system are produced by forced self-propagating high-temperature synthesis (SHS) compaction. The mechanisms of the structure and phase formation in synthetic products, as well as the combustion macrokinetics of the SHS mixture, are studied. Complex investigations of the structure, phase composition, and physical and mechanical properties of new Ti_{2 ? x} Cr _x AlC ceramic materials synthesized at different charging parameters (x = 0, 0.5, 1, 1.5, and 2) are performed. The highest content (96–98%) of the M_{n + 1}AX _n phase in the composition of synthetic products is found to be in samples where just one of the host elements (titanium (x = 0) or chromium (x = 2)) is present. The produced materials have a high heat resistance, and the increase in the chromium concentration is favorable to an appreciable growth in resistance to high-temperature oxidation.     

Infrared Brazing of Ti<Subscript>50</Subscript>Ni<Subscript>50</Subscript> Shape Memory Alloy and Inconel 600 Alloy with Two Ag-Cu-Ti Active Braze Alloys

Infrared brazing of Ti₅₀Ni₅₀ SMA and Inconel 600 alloy using Cusil-ABA and Ticusil filler metals has been investigated. The joints were dominated by Ag-Cu eutectic with proeutectic Cu in the Cusil-ABA brazed joint and with proeutectic Ag in the Ticusil one. A continuous curved belt composed of a Ni₃Ti layer and a (Cu _x Ni_1?x )₂Ti layer formed in the brazed Ti₅₀Ni₅₀/Ticusil/Inconel 600 joint. On the Ti₅₀Ni₅₀ SMA side, an intermetallic layer of (Cu _x Ni_1?x )₂Ti formed in all joints, with x values around 0.81 and 0.47. Layers of (Cu _x Ni_1?x )₂Ti, Ni₃Ti, and mixed Ni₃Ti and Ni₂Cr intermetallics were observed next to the Inconel 600 substrate in the brazed Ti₅₀Ni₅₀/Cusil-ABA/Inconel 600 joint. The maximum shear strengths of the joints using the Cusil-ABA filler metal and the Ticusil filler metal were 324 and 300 MPa, respectively. In the Cusil-ABA brazed joint, cracks with cleavage-dominated fracture propagated along the (Cu _x Ni_1?x )₂Ti interfacial layer next to the Ti₅₀Ni₅₀ SMA substrate. In the Ticusil brazed joint, ductile dimple fracture occurred in the Ag-rich matrix near the Inconel 600 alloy substrate. The absence of a detrimental Ti-Fe-(Cu) layer on the Inconel 600 substrate side can effectively improve the shear strength of the joint.     

Separation of Fine Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Inclusion from Liquid Steel with Super Gravity

An innovative approach of super gravity was proposed to separate fine Al₂O₃ inclusions from liquid steel in this study. To investigate the removal behaviors of inclusions, the effects of different gravity coefficients and time on separating the inclusions were studied. The results show that a large amount of Al₂O₃ inclusions gathered at the top of the sample obtained by super gravity, whereas there were almost no inclusions appearing at the bottom. The volume fraction and number density of inclusions presented a gradient distribution along the direction of the super gravity, which became steeper with increasing gravity coefficient and separating time. As a result of the collision between inclusions, a large amount of inclusions aggregated and grew during the moving process, which further decreased the removal time. The experimental required removal time of inclusions is close to the theoretical values calculated by Stokes law under gravity coefficient G ≤ 80, t ≤ 15 minutes, and the small deviation may be because the inclusion particles are not truly spherical. Under the condition of gravity coefficient G = 80, t = 15 minutes, the total oxygen content at the bottom of the sample (position of 5 cm) is only 8.4 ppm, and the removal rate is up to 95.6 pct compared with that under normal gravity.     

Phase Stability and Transformations in the Zr<Subscript>2</Subscript>Ni<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Cu<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript> Amorphous System

Since Ni and Cu differ by only one valence electron, yet have nearly identical atomic sizes (1.27 vs 1.28 Å for Cu and Ni, respectively), the amorphous Zr₂Ni _x Cu_1?x system is ideal for isolating the effects of electronic structure on short- and medium-range order and the concomitant influence of both the structure and order on devitrification pathways. Thermal analysis, time-resolved high-energy X-ray diffraction (HEXRD), and transmission electron microscopy (TEM) were used to follow metastable and stable crystalline phase formation during devitrification. Using HEXRD, we observed that the first devitrification product in the Zr₂Ni system is the C16 structure, if oxygen is kept sufficiently low, while the Zr₂Cu system forms the C11b structure. For x = 0.25, the initial devitrification involves forming coexisting C11b and C16 phases. When Ni is increased to x ≥ 0.50, the initial devitrification only involves the C16 structure. These results are in complete accord with electronic structure calculations showing that the enthalpy of formation for the C11b phase is favored for x = 0, while enthalpies for C11b and C16 are nearly identical for x = 0.25; the C16 phase has the most negative enthalpy for all compositions in which x > 0.25.     

Liquid Inclusions in Heat-Resistant Steel Containing Rare Earth Elements

Abundant thermodynamic data of pure substances were incorporated in the coupled thermodynamic model of inclusion precipitation and solute micro-segregation during the solidification of heat-resistant steel containing rare earth elements. The liquid inclusions Ce_2x Al_2y Si_1?x?y O _z (0 < x < 1, 0 < y < x and z = 1 ? x ? y) were first introduced to ensure the model more accurately. And the computational method for generation Gibbs free energy of liquid inclusions in molten steel was given. The accuracy of accomplished model was validated through plant trials, lab-scale experiments, and the data published in the literature. The comparisons of results calculated by FactSage with the model were also discussed. Finally, the stable area of liquid inclusions was predicted and the liquid inclusions with larger size were found in the preliminary experiments.     

Magnetostriction Increase of Polycrystalline Fe-Al-B Thin Sheets after Thermomechanical Process

Magnetostrictive materials are applied in several types of sensors, actuators, and energy harvesting. In particular, for AC devices, thin materials are desired to reduce eddy current losses. It is well known that the magnetostriction of single crystals and textured materials is higher than in polycrystalline ones, however, the cost and manufacture speed are crucial to be used as parts of commercial devices. Therefore, polycrystalline samples are strong candidates for common applications. In this work, (Fe _x Al_100?x )_98.4B_1.6 (x = 86.6, 82 and 79.4) alloys were rolled down to 0.7 mm of thickness and annealed at 1473 K (1200 °C) for 2 hours aiming to reduce the thickness of the samples without deteriorating the magnetic properties. The alloys, even with higher contents of Al, were easily deformed to the thickness of 0.7 mm and this ability is attributed to the presence of the Fe₂B phase. After the thermomechanical process, new isotropic recrystallized grains emerged and the longitudinal magnetostriction increased to 75.8, 16.9, and 3.2 pct, achieving 28.3, 28.4, and 28.8 ppm, respectively, for x = 86.6, 82, and 79.4. The piezomagnetic coefficient obtained of 4 nm/A is a suitable actuating sensitivity.     

Suppression of Martensitic Transformation in Co<Subscript>2</Subscript>Cr(Ga,Si) Heusler Alloys by Thermal Cycling

We have investigated the influence of thermal cycles on martensitic transformation of a Co₂Cr(Ga,Si) ferromagnetic Heusler alloy. The as-quenched specimen exhibits successive L2₁(L)–D0₂₂–L2₁(H) martensitic transformation in the cooling process, which is known as reentrant martensitic transformation. However, heating to 800 K (527 °C) for reverse D0₂₂–L2₁ transformation with a rate of 10 K/min (10 °C/min) stabilizes the parent phase, meaning that the martensitic transformation is suppressed by the thermal cycles. We found precipitate after thermal cycles, and it will be the reason for the stabilization of parent phase.     

Elasticity of Ni<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>W<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript> (<Emphasis Type="Italic">x</Emphasis> ≤ 0.1875) Alloys from First Principles Calculations

The elastic properties of Ni _x W_1?x alloys up to x = 0.1875 have been determined from first principles calculations. We have used stress–strain relationships to calculate the C _ij elastic coefficients and the Voigt–Reuss–Hill approximations to determine the bulk and shear moduli of polycrystals. The W alloying increases the compression modulus while the shear modulus remains almost constant. Furthermore, the W alloying has a minor effect on the elastic anisotropy and, therefore, on its contribution to the indentation modulus.     

Microstructure and High Temperature Impression Creep Properties of Mg–3Ca–xZr (x = 0.3, 0.6, 0.9 wt%) Alloys

The current study has investigated the influence of zirconium (Zr) addition to Mg–3Ca–xZr (x = 0.3, 0.6, 0.9 wt%) alloys prepared using argon arc melting on the microstructure and impression properties at 448–498 K under constant stress of 380 MPa. Microstructural analysis of as-cast Mg–3Ca–xZr alloys showed grain refinement with Zr addition. The observed grain refinement was attributed to the growth restriction effect of Zr in hypoperitectic Mg–3Ca–0.3 wt% Zr alloys. Heterogeneous nucleation of α-Mg in properitectic Zr during solidification resulted in grain refinement of hyperperitectic Mg–3Ca–0.6 wt% Zr and Mg–3Ca–0.9 wt% Zr alloys. The hardness of Mg–3Ca–xZr alloys increased as the amount of Zr increased due to grain refinement and solid solution strengthening of α-Mg by Zr. Creep resistance of Mg–3Ca–xZr alloys increased with the addition of Zr due to solid solution strengthening of α-Mg by Zr. The calculated activation energy (Q_a) for Mg–3Ca samples (131.49 kJ/mol) was the highest among all alloy compositions. The Q_a values for 0.3, 0.6 and 0.9 wt% Zr containing Mg–3Ca alloys were 107.22, 118.18 and 115.24 kJ/mol, respectively.     

Heterogeneous Creep Deformations and Correlation to Microstructures in Fe-30Cr-3Al Alloys Strengthened by an Fe<Subscript>2</Subscript>Nb Laves Phase

A new Fe-Cr-Al (FCA) alloy system has been developed with good oxidation resistance and creep strength at high temperature. The alloy system is a candidate for use in future fossil-fueled power plants. The creep strength of these alloys at 973 K (700 °C) was found to be comparable with traditional 9 pct Cr ferritic–martensitic steels. A few FCA alloys with general composition of Fe-30Cr-3Al-.2Si-xNb (x = 0, 1, or 2) with a ferrite matrix and Fe₂Nb-type Laves precipitates were prepared. The detailed microstructural characterization of samples, before and after creep rupture testing, indicated precipitation of the Laves phase within the matrix, Laves phase at the grain boundaries, and a 0.5 to 1.5 μm wide precipitate-free zone (PFZ) parallel to all the grain boundaries. In these alloys, the areal fraction of grain boundary Laves phase and the width of the PFZ controlled the cavitation nucleation and eventual grain boundary ductile failure. A phenomenological model was used to compare the creep strain rates controlled by the effects of the particles on the dislocations within the grain and at grain boundaries. (The research sponsored by US-DOE, Office of Fossil Energy, the Crosscutting Research Program).     

LaCoO<Subscript>3 – δ</Subscript> as the Material of an Oxygen Electrode for a Molten Carbonate Fuel Cell: I. Electrophysical Properties of Lithiated LaCoO<Subscript>3 – δ</Subscript>

Oxides LaCoO_{3 – δ} + (z/2) Li₂O (0 ≤ z ≤ 0.15) are synthesized to determine the boundaries of changing the electrophysical properties of LaCoO_{3 – δ} due to its in situ lithiation in the (Li_0.62K_0.38)₂CO₃ eutectic melt. A perovskite-like solid solution (La_{1 – x}Li _x )(Li _x Co_{1 – x})O_{3 – δ}, where x = z/(z + 2), is found to form as a result of Li doping. The region of existence of the solution does not exceed 2x = 0.072. At a higher concentration of Li, LiCoO₂ forms along with the perovskite-like phase. At the operating temperature of the carbonate fuel cell (T = 920 K), the single-phase samples have metallic conduction and positive thermopower. The electrical conductivity of the Li-doped samples decreases as compared to that of LaCoO_{3 – δ} by no more than 1.5 times and varies from 3.2 × 10⁴ to 3.8 × 10⁴ S/m.     

High Entropy Alloys: Criteria for Stable Structure

An effort has been made to reassess the phase predicting capability of various thermodynamic and topological parameters across a wide range of HEA systems. These parameters are valence electron concentration, atomic mismatch (δ), electronegativity difference (Δχ), mixing entropy (ΔS _mix), entropy of fusion (ΔS _f), and mismatch entropy (S _σ ). In continuation of that, two new parameters (a) Modified Darken–Gurry parameter (A = Sσ * χ) and (b) Modified Mismatch Entropy parameter (B = δ* Sσ) have been designed to predict the stable crystal structure that would form in the HEA systems considered for assessment.     

Effect of magnetron sputtering conditions on the structure and magnetic properties of FeZrN films

Nanocrystalline Fe_{97 ? x} Zr₃N _x films produced by rf reactive magnetron sputtering onto rotating and stationary substrates are studied. X-ray diffraction analysis is used to study the structure of the as-sputtered and annealed (at 300–600°C) films. The maximum saturation induction B _s reached for the films under study is 1.8–1.9 T; the minimum coercive force H _c is 1.5–1.8 Oe. These magnetic properties are explained using the structural state of the films.     

Structure and magnetic properties of the Nd<Subscript>9.5</Subscript>Fe<Subscript>84.5</Subscript>B<Subscript>6</Subscript> alloy subjected to severe plastic deformation and annealing

The effect of severe plastic deformation (SPD) by torsion and subsequent annealing on the structure and magnetic properties of the cast Nd_9.5Fe_84.5B₆ alloy is studied. SPD by torsion is shown to lead to partial amorphization of the Nd₂Fe¹⁴B phase and the precipitation of α-Fe; subsequent annealing results in the crystallization of the amorphous phase and the formation of a nanocomposite Nd₂Fe₁₄B/α-Fe structure. After SPD by torsion at 20 revolutions and annealing at 873 K, the (101) texture is formed; in this case, the coercive force is H _c = 360 kA/m and the maximum energy product is (BH) _max = 166 kJ/m3. The residual magnetization and the squareness ratio of the hysteretic loop of the textured alloy decrease as the ambient temperature decreases.     

Bulk Nanolaminated Nickel: Preparation,Microstructure, Mechanical Property,and Thermal Stability

A bulk nanolaminated (NL) structure with distinctive fractions of low- and high-angle grain boundaries (f _LAGBs and f _HAGBs) is produced in pure nickel, through a two-step process of primary grain refinement by equal-channel angular pressing (ECAP), followed by a secondary geometrical refinement via liquid nitrogen rolling (LNR). The lamellar boundary spacings of 2N and 4N nickel are refined to ~ 40 and ~ 70 nm, respectively, and the yield strength of the NL structure in 2N nickel reaches ~ 1.5 GPa. The impacts of the deformation path, material purity, grain boundary (GB) misorientation, and energy on the microstructure, refinement ability, mechanical strength, and thermal stability are investigated to understand the inherent governing mechanisms. GB migration is the main restoration mechanism limiting the refinement of an NL structure in 4N nickel, while in 2N nickel, shear banding occurs and mediates one-fifth of the total true normal rolling strain at the mesoscale, restricting further refinement. Three typical structures [ultrafine grained (UFG), NL with low f _LAGBs, and NL with high f _LAGBs] obtained through three different combinations of ECAP and LNR were studied by isochronal annealing for 1 hour at temperatures ranging from 433 K to 973 K (160 °C to 700 °C). Higher thermal stability in the NL structure with high f _LAGBs is shown by a 50 K (50 °C) delay in the initiation temperature of recrystallization. Based on calculations and analyses of the stored energies of deformed structures from strain distribution, as characterized by kernel average misorientation (KAM), and from GB misorientations, higher thermal stability is attributed to high f _LAGBs in this type of NL structure. This is confirmed by a slower change in the microstructure, as revealed by characterizing its annealing kinetics using KAM maps.     

Fabrication of Porous Ti-rich Ti<Subscript>51</Subscript>Ni<Subscript>49</Subscript> by Evaporating NaCl Space Holder

Net-shaped porous Ti-rich Ti₅₁Ni₄₉ alloy with well-controlled porosity, pore size, and pore shape are fabricated by pressing-and-sintering compacts containing fine Ti and Ni powders and coarse NaCl powders. After sintering at 1323 K (1050 °C) for 30 minutes in a high vacuum, the NaCl space holder is removed by evaporation, and the remaining Ti and Ni powders are sintered with about 2.3 vol pct liquid phase. The sintered Ti₅₁Ni₄₉ compacts have porosities of 26, 64, 70, 78, and 85 pct, and no distortion is observed. DSC tests show that the M _S temperature and ΔH are about 347 K (74 °C) and 28 J/g, respectively, and that they are almost independent of the porosity and close to those of wrought Ti-rich TiNi alloys. These porous Ti₅₁Ni₄₉ compacts exhibit a homogeneous microstructure, and the compressive properties and porosity are close to those of human bones.