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.     

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.     

Crystal and Electronic Study of Neodymium-Substituted CuFeO<Subscript>2</Subscript> Oxide

Neodymium-substituted CuFeO₂ samples were investigated according to their crystal and electronic properties via the general formula Nd _x Cu_1?x FeO₂. The crystal structure analysis results revealed polycrystalline formations in the sample and a change in crystalline sizes with the substituted heavy fermion “Nd.” Increasing the Nd amount in the sample was determined to cause a disturbance on the Cu-Fe planes that supports the formation of crystal structures with low crystal symmetries such as monoclinic or triclinic geometries. To obtain the background mechanisms of the crystal properties, the X-ray absorption fine structure spectroscopy technique was used to study the electronic properties of the samples. Prominent changes in the crystal structures due to 4f electrons’ contributions from the substituted Nd atoms as the main “role player” in the phase transitions were determined. The Nd atoms were observed as the key element guiding the entire phenomenon as a result of their large size and narrow 4f levels. Also, magnetic properties of the samples were tested at room temperature and without an applied magnetic field by X-ray magnetic circular dichroism study due to previous studies that reported the parent oxide CuFeO₂ to have magnetic ordering at T _N = 11 K (?262 °C). Except the sample for x = 1.0 (NdFeO₃), no magnetic ordering was observed at room temperature; i.e., all of the samples showed paramagnetic behaviors.     

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.     

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.     

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.     

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.     

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.     

<Emphasis Type="Italic">In Situ</Emphasis> Investigation of the Evolution of Lattice Strain and Stresses in Austenite and Martensite During Quenching and Tempering of Steel

Energy dispersive synchrotron X-ray diffraction was applied to investigate in situ the evolution of lattice strains and stresses in austenite and martensite during quenching and tempering of a soft martensitic stainless steel. In one experiment, lattice strains in austenite and martensite were measured in situ in the direction perpendicular to the sample surface during an austenitization, quenching, and tempering cycle. In a second experiment, the sin² ψ method was applied in situ during the austenite-to-martensite transformation to distinguish between macro- and phase-specific micro-stresses and to follow the evolution of these stresses during transformation. Martensite formation evokes compressive stress in austenite that is balanced by tensile stress in martensite. Tempering to 748 K (475 °C) leads to partial relaxation of these stresses. Additionally, data reveal that (elastic) lattice strain in austenite is not hydrostatic but hkl dependent, which is ascribed to plastic deformation of this phase during martensite formation and is considered responsible for anomalous behavior of the 200 _γ reflection.     

Effect of Slag Composition on the Crystallization Kinetics of Synthetic CaO-SiO<Subscript>2</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-MgO Slags

The crystallization kinetics of CaO-SiO₂-Al₂O₃-MgO (CSAM) slags was studied with the aid of single hot thermocouple technique (SHTT). Kinetic parameters such as the Avrami exponent (n), rate coefficient (K), and effective activation energy of crystallization (E _A ) were obtained by kinetic analysis of data obtained from in situ observation of glassy to crystalline transformation and image analysis. Also, the dependence of nucleation and growth rates of crystalline phases were quantified as a function of time, temperature, and slag basicity. Together with the observations of crystallization front, they facilitated establishing the dominant mechanisms of crystallization. In an attempt to predict crystallization rate under non-isothermal conditions, a mathematical model was developed that employs the rate data of isothermal transformation. The model was validated by reproducing an experimental continuous cooling transformation diagram purely from isothermal data.     

Peculiarities of the technology and physicomechanical properties of a laminated Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-Al cermet

A technological approach permitting one to obtain laminated Al₂O₃-Al cermet is considered. The industrial PAP-2 powder with laminated particles served as the starting crude. The powder billets were obtained by compaction under pressure (P) from 100 to 1000 MPa and thermally treated in air by heating in the furnace to 600°C. It is established that either the solid-phase sintering or reaction sintering of the billets in the mode of filtration combustion can be achieved depending on the value of P. In the produced composite, the content of the oxide phase varies from 5 to 40%, while the density and strength upon bending vary in the limits 2.53–2.00 g/cm³ and 330-98 MPa, respectively. The laminated structure of the material is retained after thermal aging in air at t= 600°C for no less than 1000 h.     

Kinetics of Reduction of CaO-FeO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>-MgO-PbO-SiO<Subscript>2</Subscript> Slags by CO-CO<Subscript>2</Subscript> Gas Mixtures

Kinetics of the reaction of lead slags (PbO-CaO-SiO₂-FeO _x -MgO) with CO-CO₂ gas mixtures was studied by monitoring the changes in the slag composition when a stream of CO-CO₂ gas mixture was blown on the surface of thin layers of slags (3 to 10 mm) at temperatures in the range of 1453 K to 1593 K (1180 °C to 1320 °C). These measurements were carried out under conditions where mass transfer in the gas phase was not the rate-limiting step and the reduction rates were insensitive to factors affecting mass transfer in the slag phase. The results show simultaneous reduction of PbO and Fe₂O₃ in the slag. The measured specific rate of oxygen removal from the melts varied from about 1 × 10^?6 to 4 × 10^?5 mol O cm^?2 s^?1 and was strongly dependent on the slag chemistry and its oxidation state, partial pressure of CO in the reaction gas mixture, and temperature. The deduced apparent first-order rate constant increased with increasing iron oxide content, oxidation state of the slag, and temperature. The results indicate that under the employed experimental conditions, the rate of formation of CO₂ at the gas-slag interface is likely to be the rate-limiting step.     

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).     

Carbothermic Reduction Kinetics of Phosphorous Vaporization from Tri-calcium Phosphate (TCP) Under Microwave Rapid Heating With/Without the Presence of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>

The kinetics of vapor phase dephosphorization from tri-calcium phosphate (TCP) by carbothermic reduction was studied with and without the presence of Fe₃O₄. Microwave heating was utilized to obtain large variations in the heating rate (HR). In the reduction of TCP alone, the phosphorous removal fraction (RF; equal to ?P₂O₅/P₂O ₅ ⁰ , where ?P₂O₅ is the weight change and P₂O ₅ ⁰ is the P₂O₅ weight before heating) decreased as the HR increased. In other words, a shorter residence time at a high temperature resulted in a smaller reduction fraction of TCP. An apparently third-order reaction was postulated to account for the kinetics using a fitting simulation based on the additive law of the reaction progress. On the other hand, the phosphorous removal (dephosphorization) rate (RR; equal to ?P₂O₃/t_MW, where t_MW is the microwave heating time period) increased as the HR increased above 1200 °C. The reduction ratio of Fe₃O₄ above 1100 °C is higher than 97 pct regardless of the heating rate. The reduction of TCP in the presence of Fe₃O₄ showed that RF increased slightly with increasing HR despite a shorter residence time at a high temperature. The RR also increased with the HR even though RF decreased to half of the values observed in the cases without Fe₃O₄ for temperatures above 1200 °C. The practicality and optimal operation conditions of phosphorus vapor removal were discussed.     

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.     

The Effect of Low Concentrations Nb and C on the Structure and High-Temperature Strength of Fe<Subscript>3</Subscript>Al Aluminide

The Fe₃Al iron aluminide alloyed by low concentrations of Nb and C (c _Nb, c _C) is studied. The influence of the c _Nb/c _C ratio on the structure and high-temperature yield strength of iron aluminide was investigated. The structure and phase composition were studied by scanning electron microscope equipped with EDS and EBSD. The strengthening mechanisms are detected as strengthening by incoherent precipitates of NbC and as a solid solution hardening by Nb atoms.     

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.     

Kinetics of Ni<Subscript>3</Subscript>S<Subscript>2</Subscript> sulfide dissolution in solutions of sulfuric and hydrochloric acids

The kinetics of Ni₃S₂ sulfide (heazlewoodite) dissolution in solutions of hydrochloric and sulfuric acids is studied. The process under study in the temperature range of 30–90°C is found to occur in a kinetic regime and is controlled by the corresponding chemical reactions of the Ni₃S₂ decomposition by solutions of inorganic acids (E _a = 67–92 kJ/mol, or 16–22 kcal/mol). The only exception is the Ni₃S₂-HCl system at elevated temperatures (60–90°C). In this case, the apparent activation energy decreases sharply to 8.8 kJ/mol (2.1 kcal/mol), which is explained by the catalytic effect of gaseous chlorine formed under these conditions. The studies performed are related to the physicochemical substantiation of the hydrometallurgical processing of the copper-nickel converter mattes produced in the industrial cycle of the Norilsk Mining Company.     

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.     

The Interface of TiB<Subscript>2</Subscript> and Al<Subscript>3</Subscript>Ti in Molten Aluminum

In the grain refinement of aluminum, Al₃Ti and TiB₂ particles are introduced to reduce the casting grain size down to 200 micrometer level, which makes cold working possible. The particles are brought in by the addition of Al-Ti-B-type master alloys. It is generally believed that TiB₂ particles are stable and nucleate α-Al grains in solidification in the presence of titanium in solution from the dissolution of Al₃Ti particles in the master alloys. The titanium in solution either forms Al₃Ti layers on the surface of TiB₂ particles to promote the nucleation of α-Al grains or remains as solute to restrict the growth of α-Al grains in solidification. However, a consensus on a grain refinement mechanism is still to be reached due to the lack of direct observation of the three phases in castings. This paper presents finding of the TiB₂/Al₃Ti interfaces in an Al-Ti-B master alloy. It demonstrates a strong epitaxial growth of Al₃Ti on the surface of TiB₂ particles, a sign of the formation of an Al₃Ti layer on the surface of TiB₂ particles in grain refinement practice. The Al₃Ti layer has a crystal coherency with α-Al and hence offers a substrate for heterogeneous nucleation of α-Al grains. However, the layer must be dynamic to avoid the formation of compounded Al₃Ti and TiB₂ particles leading to the loss of efficiency in grain refinement.