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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

Oxidation of Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Scale-Forming MAX Phases in Turbine Environments

High temperature oxidation of alumina-forming MAX phases, Ti₂AlC and Cr₂AlC, were examined under turbine engine environments and coating configurations. Thermogravimetric furnace tests of Ti₂AlC showed a rapid initial transient due to non-protective TiO₂ growth. Subsequent well-behaved cubic kinetics for alumina scale growth were shown from 1273 K to 1673 K (1000 °C to 1400 °C). These possessed an activation energy of 335 kJ/mol, consistent with estimates of grain boundary diffusivity of oxygen (~375 kJ/mol). The durability of Ti₂AlC under combustion conditions was demonstrated by high pressure burner rig testing at 1373 K to 1573 K (1100 °C to 1300 °C). Here good stability and cubic kinetics also applied, but produced lower weight gains due to volatile TiO(OH)₂ formation in water vapor combustion gas. Excellent thermal stability was also shown for yttria-stabilized zirconia thermal barrier coatings deposited on Ti₂AlC substrates in 2500-hour furnace tests at 1373 K to 1573 K (1100 °C to 1300 °C). These sustained a record 35 µm of scale as compared to 7 μm observed at failure for typical superalloy systems. In contrast, scale and TBC spallation became prevalent on Cr₂AlC substrates above 1423 K (1150 °C). Cr₂AlC diffusion couples with superalloys exhibited good long-term mechanical/oxidative stability at 1073 K (800 °C), as would be needed for corrosion-resistant coatings. However, diffusion zones containing a NiAl-Cr₇C₃ matrix with MC and M₃B₂ particulates were commonly formed and became extensive at 1423 K (1150 °C).     

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.     

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.     

Aging Temperature Dependence of <Emphasis Type="Italic">α</Emphasis>″-Martensite Decomposition Mechanism in Ti-Al-Fe-Si Alloy

The mechanism by which α″-martensite decomposes in Ti-4Al-4Fe-0.25Si-0.1O alloy is found to change depending on the aging temperature, with Fe-rich α first transforming in twins of α″-martensite. As the aging temperature increases, Fe is segregated at the boundaries between α″ and α. At temperatures >?773 K, the Fe-segregated boundaries provide a nucleation site for B2-structured TiFe intermetallic compounds. This process of α″-martensite decomposition is described as follows: α″?+?α″_Twin?→?α″_Fe-rich?+?α_Fe-rich,V1?→?α_Fe-lean,V2?+?α_Fe-lean,V1?+?TiFe.     

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.     

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).     

Morphology-Dependent Hardness of Cr<Subscript>7</Subscript>C<Subscript>3</Subscript>-Ni-Rich Alloy Composite <Emphasis Type="Italic">vs</Emphasis> Orientation Independent Hardness of Cr<Subscript>7</Subscript>C<Subscript>3</Subscript> Primary Phase in a Laser Clad Microstructure

Microstructural evolution with superheating was studied in chromium carbide-nickel coatings deposited by laser cladding. At lower superheating, selective growth of 〈0001〉 direction from the high density of Cr₇C₃ grains nucleated resulted in a columnar structure with (0001) texture. Increased superheating lead to the loss of columnar structure as well as the (0001) texture. The hexagonal Cr₇C₃ showed an unusual isotropic nanoindentation hardness evidently correlated with its low c/a ratio. However, the rod-like morphology of the carbide dendrites resulted in significant anisotropy in the hardness of the composite.     

Ferrite Formation Dynamics and Microstructure Due to Inclusion Engineering in Low-Alloy Steels by Ti<Subscript>2</Subscript>O<Subscript>3</Subscript> and TiN Addition

The dynamics of intragranular ferrite (IGF) formation in inclusion engineered steels with either Ti₂O₃ or TiN addition were investigated using in situ high temperature confocal laser scanning microscopy. Furthermore, the chemical composition of the inclusions and the final microstructure after continuous cooling transformation was investigated using electron probe microanalysis and electron backscatter diffraction, respectively. It was found that there is a significant effect of the chemical composition of the inclusions, the cooling rate, and the prior austenite grain size on the phase fractions and the starting temperatures of IGF and grain boundary ferrite (GBF). The fraction of IGF is larger in the steel with Ti₂O₃ addition compared to the steel with TiN addition after the same thermal cycle has been imposed. The reason for this difference is the higher potency of the TiO _x phase as nucleation sites for IGF formation compared to the TiN phase, which was supported by calculations using classical nucleation theory. The IGF fraction increases with increasing prior austenite grain size, while the fraction of IGF in both steels was the highest for the intermediate cooling rate of 70 °C/min, since competing phase transformations were avoided, the structure of the IGF was though refined with increasing cooling rate. Finally, regarding the starting temperatures of IGF and GBF, they decrease with increasing cooling rate and the starting temperature of GBF decreases with increasing grain size, while the starting temperature of IGF remains constant irrespective of grain size.     

Structure and phase composition of alloys of the Al-Ce-Cu system in the region of the Al-Al<Subscript>8</Subscript>CeCu<Subscript>4</Subscript> quasi-binary join

Phase diagram of the Al-Cu-Ce system is investigated in the region of the quasi-binary join Al-Al₈CeCu₄. The parameter of the eutectic reaction L → (Al) + CeCu₄Al₈ are found: T = 610°C; composition 14% Cu and 7% Ce. This eutectic has a dispersed structure, and the ternary compounds, which is involved in the eutectic, is capable to fragmentation and spheroidism in the course of heating starting from 540°C. It is shown that the region of optimal compositions of alloys based on the eutectic (Al) + CeCu₄Al₈ lies in narrow limits. This is caused by the fact that an abrupt decrease of the solidus and, as a consequence, significant broadening of the crystallization range occurs at a relatively small deviation from the ratio Cu: Ce = 2.