Structural Transitions and Magnetic Properties of Ni<Subscript>50</Subscript>Mn<Subscript>36.7</Subscript>In<Subscript>13.3</Subscript> Particles with Amorphous-Like Phase

The high-energy ball-milling method was used for fabricating Ni₅₀Mn_36.7In_13.3 fine-sized particles. The as-melt polycrystalline Ni₅₀Mn_36.7In_13.3 alloy exhibits a 14 M modulated martensite structure at room temperature (RT). The atomic pair distribution function analysis together with the differential scanning calorimetry technique proved that the 14 M modulated martensite transformed to a metastable amorphous-like structure after ball milling for 8 hours. Annealing of the ball-milled particles with the amorphous-like phase first led to the crystallization to form a B2 structure at 523 K (250 °C), and then an ordered Heusler L2₁ structure (with a small tetragonal distortion) at 684 K (411 °C). The annealed particles undergo different structural transitions during cooling, tailored by the atomic arrangements of the high-temperature phase. Low-field thermomagnetization measurements show that the ball-milled particles with the amorphous-like structure or the atomically disordered crystalline structure exhibit a magnetic transition from the paramagnetic-like to the spin-glass state with decreasing temperature, whereas the crystalline particles with the ordered Heusler L2₁ structure present a ferromagnetic behavior with the Curie temperature T _c ≈ 310 K (37 °C).     

The Thermal Stability of R<Subscript>3</Subscript>Pt<Subscript>4</Subscript> Compounds

Alloys of the rare earths R (including La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Y, Ho, Er) with platinum, having the composition R₃Pt₄, have been synthesized and investigated by X-ray diffraction (XRD) and differential thermal analysis (DTA). At temperatures above about 900 °C and below 250 °C, all the single phases R₃Pt₄ are formed, which crystallize with the same structure of the rhombohedral Pu₃Pd₄ type. Over the temperature range of about 250 °C to 900 °C, they occur at an eutectoid decomposition into RPt and RPt₂ compounds neighboring in the corresponding phase diagram, R₃Pt₄ → RPt + RPt₂. The stability of these phases R₃Pt₄ may be restricted to a radius ratio r _R/r _Pt range of 1.27 to 1.35.     

Phase transitions in the magnetic superconductor (Dy<Subscript>0.8</Subscript>Y<Subscript>0.2</Subscript>)Rh<Subscript>4</Subscript>B<Subscript>4</Subscript>

A new (Dy_0.8Y_0.2)Rh₄B₄ superconductor (the superconducting transition temperature is T _c ≈ 5.5 K), which has an inherent magnetic subsystem whose properties are determined by the crystal structure of the superconductor, is synthesized at a high pressure (∼8 GPa) and t ≈ 1800°. The magnetic sublattice of the (Dy_0.8Y_0.2)Rh₄B₄ compound is found to substantially affect its superconducting properties and, in a number of cases, to lead to their anomalous variations, namely, to the absence of the traditional Meissner effect and an anomalously abrupt increase in magnetic induction B _k2 (upper critical field) upon a transition of the magnetic subsystem into the antiferromagnetic state. Upon cooling from 250 to 1.6 K, the (Dy_0.8Y_0.2)Rh₄B₄ compound undergoes a number of phase transformations, namely, a paramagnet-ferrimagnet transition at a Curie temperature T _C ≈ 30 K, a superconducting transition at T _c ≈ 5.5 K against the background of a ferrimagnetic order, and a ferrimagnet-antiferromagnet transition (the Neel temperature is T _N ≈ 2.8 K) in the retained superconducting state.     

A Eutectoid Reaction for the Decomposition of Austenite into Pearlitic Lamellae of Ferrite and M<Subscript>23</Subscript>C<Subscript>6</Subscript> Carbide in a Mn-Al Steel

We discovered a eutectoid reaction in an Fe-13.4Mn-3.0Al-0.63C (wt pct) steel after solution heat treatment at 1373 K (1100 °C) and holding at temperatures below 923 K (650 °C). The steel is single austenite at temperatures from 1373 K to 923 K (1100 °C to 650 °C). A eutectoid reaction involves the replacement of the metastable austenite by a more stable mixture of ferrite and M₂₃C₆ phases at temperatures below 923 K (650 °C). The mixture of ferrite and M₂₃C₆ is in the form of pearlitic lamellae. The morphology of the lamellae of the product phases is similar to that of pearlite in steels. Thus, we found a new pearlite from the eutectoid reaction of the Mn-Al steel featuring γ  → α + M₂₃C₆. A Kurdjumov–Sachs (K-S) orientation relationship exists between the pearlitic ferrite (α) and M₂₃C₆ (C6) grains, i.e., (110)_α // (111)_C6 and [[`1] \overline{1} 11]<sub>α</sub> // [0[`1] \overline{1} 1]_C6. The upper temperature limit for the eutectoid reaction is between 923 K and 898 K (650 °C and 625 °C).     

Evaluating the Diffusion Coefficient of Sulfur in Low-Silica CaO-SiO<Subscript>2</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Slag

The chemical diffusion coefficient of sulfur in the ternary slag of composition 51.5 pct CaO-9.6 pct SiO₂-38.9 pct Al₂O₃ slag was measured at 1680 K, 1700 K, and 1723 K (1403 °C, 1427 °C, and 1450 °C) using the experimental method proposed earlier by the authors. The P_\textS2 P_{{{\text{S}}_{2} }} and P_\textO2 P_{{{\text{O}}_{2} }} pressures were calculated from the Gibbs energy of the equilibrium reaction between CaO in the slag and solid CaS. The density of the slag was obtained from earlier experiments. Initially, the order of magnitude for the diffusion coefficient was taken from the works of Saito and Kawai but later was modified so that the concentration curve for sulfur obtained from the program was in good fit with the experimental results. The diffusion coefficient of sulfur in 51.5 pct CaO-9.6 pct SiO₂-38.9 pct Al₂O₃ slag was estimated to be in the range 3.98 to 4.14 × 10⁻⁶ cm²/s for the temperature range 1680 K to 1723 K (1403 °C to 1450 °C), which is in good agreement with the results available in literature     

High-Temperature Oxidation of Alloy 617 in Helium Containing Part-Per-Million Levels of CO and CO<Subscript>2</Subscript> as Impurities

The objective of this study was to determine the mechanisms of carburization and decarburization of alloy 617 in impure helium. To avoid the coupling of multiple gas/metal reactions that occurs in impure helium, oxidation studies were conducted in binary He + CO + CO₂ gas mixtures with CO/CO₂ ratios of 9 and 1272 in the temperature range 1123 K to 1273 K (850 °C to 1000 °C). The mechanisms were corroborated through measurements of oxidation kinetics, gas-phase analysis, and surface/bulk microstructure examination. A critical temperature corresponding to the equilibrium of the reaction 27Cr + 6CO ↔ 2Cr₂O₃ + Cr₂₃C₆ was identified to lie between 1173 K and 1223 K (900 °C and 950 °C) at CO/CO₂ ratio 9, above which decarburization of the alloy occurred via a kinetic competition between two simultaneous surface reactions: chromia formation and chromia reduction. The reduction rate exceeded the formation rate, preventing the growth of a stable chromia film until carbon in the sample was depleted. Surface and bulk carburization of the samples occurred for a CO/CO₂ ratio of 1272 at all temperatures. The surface carbide, Cr₇C₃, was metastable and nucleated due to preferential adsorption of carbon on the chromia surface. The Cr₇C₃ precipitates grew at the gas/scale interface via outward diffusion of Cr cations through the chromia scale until the activity of Cr at the reaction site fell below a critical value. The decrease in activity of chromium triggered a reaction between chromia and carbide: Cr₂O₃ + Cr₇C₃ → 9Cr+3CO, which resulted in a porous surface scale. The results show that the industrial application of the alloy 617 at T > 1173 K (900 °C) in impure helium will be limited by oxidation.     

Solubilities of Chlorine in CaO-SiO<Subscript>2</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-MgO Slags: Correlation Between Sulfide and Chloride Capacities

To derive a correlation between sulfide and chloride capacities through our own systematic experimental studies by using a gas equilibrium technique involving Ar-H₂-H₂O-HCl gas mixtures, the solubilities of chlorine were determined for CaO-SiO₂-MgO-Al₂O₃ slags at temperatures between 1673 K and 1823 K (1400 °C and 1550 °C). As a formula to correlate sulfide and chloride capacities, the following equation that is the function of temperature only was obtainable;

On the fracture and fatigue properties of Mo-Mo<Subscript>3</Subscript>Si-Mo<Subscript>5</Subscript>SiB<Subscript>2</Subscript> refractory intermetallic alloys at ambient to elevated temperatures (25 °C to 1300 °C)

The need for structural materials with high-temperature strength and oxidation resistance coupled with adequate lower-temperature toughness for potential use at temperatures above ∼1000 °C has remained a persistent challenge in materials science. In this work, one promising class of intermetallic alloys is examined, namely, boron-containing molybdenum silicides, with compositions in the range Mo (bal), 12 to 17 at. pct Si, 8.5 at. pct B, processed using both ingot (I/M) and powder (P/M) metallurgy methods. Specifically, the oxidation (“pesting”), fracture toughness, and fatigue-crack propagation resistance of four such alloys, which consisted of ∼21 to 38 vol. pct α-Mo phase in an intermetallic matrix of Mo₃Si and Mo₅SiB₂ (T₂), were characterized at temperatures between 25 °C and 1300 °C. The boron additions were found to confer improved “pest” resistance (at 400 °C to 900 °C) as compared to unmodified molybdenum silicides, such as Mo₅Si₃. Moreover, although the fracture and fatigue properties of the finer-scale P/M alloys were only marginally better than those of MoSi₂, for the I/M processed microstructures with coarse distributions of the α-Mo phase, fracture toughness properties were far superior, rising from values above 7 MPa √m at ambient temperatures to almost 12 MPa √m at 1300 °C. Similarly, the fatigue-crack propagation resistance was significantly better than that of MoSi₂, with fatigue threshold values roughly 70 pct of the toughness, i.e., rising from over 5 MPa √m at 25 °C to ∼8 MPa √m at 1300 °C. These results, in particular, that the toughness and cyclic crack-growth resistance actually increased with increasing temperature, are discussed in terms of the salient mechanisms of toughening in Mo-Si-B alloys and the specific role of microstructure.     

Microstructural Evolution and Mechanical Properties of Nanointermetallic Phase Dispersed Al<Subscript>65</Subscript>Cu<Subscript>20</Subscript>Ti<Subscript>15</Subscript> Amorphous Matrix Composite Synthesized by Mechanical Alloying and Hot Isostatic Pressing

The structure and mechanical properties of nanocrystalline intermetallic phase dispersed amorphous matrix composite prepared by hot isostatic pressing (HIP) of mechanically alloyed Al₆₅Cu₂₀Ti₁₅ amorphous powder in the temperature range 573 K to 873 K (300 °C to 600 °C) with 1.2 GPa pressure were studied. Phase identification by X-ray diffraction (XRD) and microstructural investigation by transmission electron microscopy confirmed that sintering in this temperature range led to partial crystallization of the amorphous powder. The microstructures of the consolidated composites were found to have nanocrystalline intermetallic precipitates of Al₅CuTi₂, Al₃Ti, AlCu, Al₂Cu, and Al₄Cu₉ dispersed in amorphous matrix. An optimum combination of density (3.73 Mg/m³), hardness (8.96 GPa), compressive strength (1650 MPa), shear strength (850 MPa), and Young’s modulus (182 GPa) were obtained in the composite hot isostatically pressed (“hipped”) at 773 K (500 °C). Furthermore, these results were compared with those from earlier studies based on conventional sintering (CCS), high pressure sintering (HPS), and pulse plasma sintering (PPS). HIP appears to be the most preferred process for achieving an optimum combination of density and mechanical properties in amorphous-nanocrystalline intermetallic composites at temperatures ≤773 K (500 °C), while HPS is most suited for bulk amorphous alloys. Both density and volume fraction of intermetallic dispersoids were found to influence the mechanical properties of the composites.     

Toward Oxidation-Resistant ZrB<Subscript>2</Subscript>-SiC Ultra High Temperature Ceramics

Ultra high temperature ceramics (UHTCs), including ZrB₂-SiC, are designed for extreme environment applications in which temperatures exceed 2273 K (2000 °C). A key material property of UHTCs in many applications is their resistance to oxidation. Recent research into UHTCs is described, revealing a variety of different methods for improving the oxidation performance, which include control of starting powders, composition and size distribution, mixing, and densification techniques. The use of additives has also been researched widely, for example, to increase the viscosity of any liquid phase formed or provide protective refractory phases at high temperatures. SiC additions are effective in forming protective silica but only in static environments and to ~1873 K (1600 °C). For higher temperature applications, additions of La lead to the formation of a dense ZrO₂ scale probably via liquid phase sintering. Such ceramic systems, which produce self-generating refractory oxidation barriers or dense ZrO₂ scales, show the greatest promise in providing oxidation-resistant UHTCs.     

Dissolution and Interface Reactions between Palladium and Tin(Sn)-Based Solders: Part II. 63Sn-37Pb Alloy

The interface microstructures and dissolution behavior were studied, which occur between 99.9 pct Pd substrates and molten 95.5Sn-3.9Ag-0.6Cu (wt pct, Sn-Ag-Cu) solder. The solder bath temperatures were 513 K to 623 K (240 °C to 350 °C). The immersion times were 5 to 240 seconds. The IMC layer composition exhibited the (Pd, Cu)Sn₄ (Cu, 0 to 2 at. pct) and (Pd, Sn) solid-solution phases for all test conditions. The phases PdSn and PdSn₂ were observed only for the 623 K (350 °C), 60 seconds test conditions. The metastable phase, Pd₁₁Sn₉, occurred consistently for the 623 K (350 °C), 240 seconds conditions. Palladium-tin needles appeared in the Sn-Ag-Cu solder, but only at temperatures of 563 K (290 °C ) or higher, and had a (Pd, Cu)Sn₄ stoichiometry. Palladium dissolution increased monotonically with both solder bath temperature and exposure time. The rate kinetics of dissolution were represented by the expression At ⁿ exp(∆H/RT), where the time exponent (n) was 0.52 ± 0.10 and the apparent activation energy (∆H) was 44 ± 9 kJ/mol. The IMC layer thickness increased between 513 K and 563 K (240 °C and 290 °C) to approximately 3 to 5 μm, but then was less than 3 μm at 593 K and 623 K (320 °C and 350 °C). The thickness values exhibited no significant time dependence. As a protective finish in electronics assembly applications, Pd would be relatively slow to dissolve into molten Sn-Ag-Cu solder. The Pd-Sn IMC layer would remain sufficiently thin and adherent to a residual Pd layer so as to pose a minimal reliability concern for Sn-Ag-Cu solder interconnections.     

Air-Oxidation Behavior of a [(Co50Cr15Mo14C15B6)97.5Er2.5]93Fe7 Bulk-Metallic Glass at 873?K to 973?K (600?°C to 700?°C)

The oxidation behavior of a [(Co₅₀Cr₁₅Mo₁₄C₁₅B₆)_97.5Er_2.5]₉₃Fe₇ bulk-metallic glass (Co7-BMG) was studied over the temperature range of 873?K to 973?K (600?°C to 700?°C) in dry air. The oxidation kinetics of the Co7-BMG generally followed the parabolic-rate law, as its oxidation rates increased with temperature. The scaling rate of the Co7-BMG was significantly lower than that of pure Co, which indicates a better oxidation resistance for the amorphous alloy. The scales formed on the Co7-BMG consisted mostly of CoMoO₄ and Co₃O₄, as well as minor amounts of CoO, Cr₂O₃, and uncorroded Co₃B. The formation of CoMoO₄ and Cr₂O₃ is responsible for the lower oxidation rates of the glassy alloy with respect to those of pure Co. In addition, the presence of Co₃B further indicated that the crystallization of the amorphous substrate during the oxidation was taken place.     

Confocal Microscopic Studies on Evolution of Crystals During Oxidation of the FeO-CaO-SiO<Subscript>2</Subscript>-MnO Slags

The current work investigates dynamic phenomena at the microstructural level during iron and manganese recovery from the liquid FeO-CaO-SiO₂-MnO slags using an oxidation method. A hot-stage-equipped confocal scanning laser microscope (CSLM) was used to analyze the kinetic behavior of crystallization in synthetic slags. Based on observed precipitations on cooling in the 1273 K (1000 °C) to 1873 K (1600 °C) temperature range, a time–temperature–transformation (TTT) diagram has been created. The crystallization studies were conducted in air.     

High-Accuracy X-Ray Diffraction Analysis of Phase Evolution Sequence During Devitrification of Cu<Subscript>50</Subscript>Zr<Subscript>50</Subscript> Metallic Glass

Real-time high-energy X-ray diffraction (HEXRD) was used to investigate the crystallization kinetics and phase selection sequence for constant-heating-rate devitrification of fully amorphous Cu₅₀Zr₅₀, using heating rates from 10 K/min to 60 K/min (10 °C/min to 60 °C/min). In situ HEXRD patterns were obtained by the constant-rate heating of melt-spun ribbons under synchrotron radiation. High-accuracy phase identification and quantitative assessment of phase fraction evolution though the duration of the observed transformations were performed using a Rietveld refinement method. Results for 10 K/min (10 °C/min) heating show the apparent simultaneous formation of three phases, orthorhombic Cu₁₀Zr₇, tetragonal CuZr₂ (C11_b), and cubic CuZr (B2), at 706 K (433 °C), followed immediately by the dissolution of the CuZr (B2) phase upon continued heating to 789 K (516 °C). Continued heating results in reprecipitation of the CuZr (B2) phase at 1002 K (729 °C), with the material transforming completely to CuZr (B2) by 1045 K (772 °C). The Cu₅Zr₈ phase, previously reported to be a devitrification product in C₅₀Zr₅₀, was not observed in the present study.     

Oxidation Behavior of CuZr-Based Glassy Alloys at 400 °C to 500 °C in Dry Air

The oxidation behavior of the Cu_47.5Zr_47.5Al₅ (Cu3) and Cu₄₇Ti₃₄Zr₁₁Ni₈ (Cu4) bulk metallic glasses (BMGs) was studied over the temperature range of 400 °C to 500 °C in dry air. The oxidation kinetics of both alloys generally followed a multistage parabolic-rate law, and the steady-state parabolic-rate constants (k _p values) fluctuated with temperature for the Cu3 BMG, but increased with increasing temperature for the Cu4 BMG. The scales formed on the BMGs were strongly dependent on the temperature and alloy composition, and were composed primarily of tetragonal-ZrO₂ (t-ZrO₂) and minor amounts of Al₂O₃, Cu₂O, and CuO at 400 °C for the Cu3 BMG, while the monoclinic-ZrO₂ (m-ZrO₂) phase is present at T ≥ 425 °C, and the Cu₂O phase is absent at 500 °C. Conversely, the scales formed on the Cu4 BMG consisted exclusively of CuO at 400 °C, while minor amounts of t-ZrO₂, TiO₂, and ZrTiO₄ formed at 425 °C to 450 °C, and TiO was also detected at higher temperatures. It was found that both amorphous Cu3 and Cu4 substrates transformed into different crystalline phases, and were strongly dependent on temperature and duration of time. This article is based on a presentation given in the symposium entitled “Bulk Metallic Glasses IV,” which occurred during the TMS Annual Meeting February 25–March 1, 2007, in Orlando, Florida under the auspices of the TMS/ASM Mechanical Behavior of Materials Committee.     

Kinetics of the Reaction of CO<Subscript>2</Subscript>/CO Gas Mixtures with Iron Oxide

The kinetics of the oxygen exchange reaction between carbon dioxide and carbon monoxide were measured on iron, wüstite, and magnetite surfaces. This was done through the use of an isotope exchange technique. The measured rate constants are dependent on the oxygen activity. This dependence is expressed by k_a = k_oa_O^−m. The parameter m was found to have values between 0 and 1. It was found that, in the iron region, the apparent rate constant was independent of the oxygen partial pressure (i.e., m = 0) at 1123 K (850 °C) and that it was inversely dependent on the oxygen partial pressure (i.e., m = 1) for the magnetite region at 1123 K (850 °C) and 1268 K (995 °C). In the wüstite region, m was found to be equal to 0.51, 0.66, and 1.0 for the w₁, w₂, and w₃ pseudo phases, respectively, at 1268 K (995 °C). At 1123 K (850 °C), in wüstite, m was found to be equal to 0.59 and to 1.0 for the w₁′ and w₃′ pseudo phases, respectively.     

Synthesis of Nanostructured and Nanoporous TiO<Subscript>2</Subscript>-AgO Mixed Oxide Derived from a Particulate Sol-Gel Route: Physical and Sensing Characteristics

Nanocrystalline TiO₂-AgO thin films and powders were prepared by an aqueous particulate sol-gel route at the low temperature of 573 K (300 °C). Titanium tetraisopropoxide and silver nitrate were used as precursors, and hydroxypropyl cellulose was used as a polymeric fugitive agent in order to increase the specific surface area. X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) revealed that the phase composition of the mixed oxide depends upon the annealing temperature, being a mixture of TiO₂ and AgO in the range 573 K to 773 K (300 °C to 500 °C) and a mixture of TiO₂, AgO, and Ag₂O at 973 K (700 °C). Furthermore, one of the smallest crystallite sizes was obtained for TiO₂-AgO mixed oxide, being 4 nm at 773 K (500 °C). Field emission–scanning electron microscopic (FE-SEM) and atomic force microscopic (AFM) images revealed that the deposited thin films had nanostructured and nanoporous morphology with columnar topography. Thin films produced under optimized conditions showed excellent microstructural properties for gas sensing applications. They exhibited a remarkable response toward low concentrations of CO gas (i.e., 25 ppm) at low operating temperature of 473 K (200 °C), resulting in an increase of the thermal stability of sensing films as well as a decrease in their power consumption. Furthermore, TiO₂-AgO sensors follow the power law for the detection of CO gas.     

Oxidation of Fe-V Melts Under CO<Subscript>2</Subscript>-O<Subscript>2</Subscript> Gas Mixtures

The oxidation mechanism of liquid Fe-V alloys with V content from 5 to 20 mass pct under different oxygen partial pressures using CO₂-O₂ mixtures with CO₂ varying from 80 pct to 100 pct was investigated by thermogravimetric analysis between 1823 K and 1923 K (1550 °C and 1650 °C). The products after oxidation were identified by scanning electron microscopy energy-dispersive spectrograph and X-ray diffraction. The results indicate that the oxidation process can be divided into the following steps: an apparent incubation period, followed by a chemical reaction step with a transition step before the reaction, and diffusion as the last stage. At the initial stage, a period of slow mass increase was observed that could be attributed to possible oxygen dissolution in the liquid iron-vanadium coupled with the vaporization of V₂O. The length of this period increased with increasing temperature as well as vanadium content in the melt and decreased with increasing oxygen partial pressure of the oxidant gas. This analysis was followed by a region of chemical oxidation. The oxidation rate increased with the increase of the O₂ ratio in the CO₂-O₂ gas mixtures. During the final stage, the oxidation seemed to proceed with the diffusion of oxygen through the product layer to the reaction front. The Arrhenius activation energies for chemical reaction and diffusion were calculated, and kinetic equations for various steps were setup to describe the experimental results. The transition from one reaction mechanism to the next was described mathematically as mixed-control equations. Thus, uniform kinetic equations have been setup that could simulate the experimental results with good precision.     

Intrinsic Kinetics of Chlorination of WO<Subscript>3</Subscript> Particles With Cl<Subscript>2</Subscript> Gas Between 973 K and 1223 K (700 °C and 950 °C)

Chlorination is one of the methods applied in extractive metallurgy for the treatment of minerals to obtain valuable metals, such as titanium and zirconium. The possibility of applying chlorination metallurgy to other metals such as tungsten was the major aim of this study. The kinetics of the chlorination of tungsten oxide (WO₃) particles has been investigated by thermogravimetry between 973 K and 1223 K (700 °C and 950 °C) and for partial pressures of chlorine ranging from 15 to 70 kPa. The starting temperature for the reaction of WO₃ with chlorine is determined to be about 920 K (647 °C). The influence of chlorine diffusion through the bulk gas phase and through the particle interstices in the overall rate was analyzed. In the absence of these two mass-transfer steps, a reaction order of 0.5 with respect to chlorine partial pressure, and an activation energy of 183 kJ/mol were determined. For tungsten oxide particles of less than 50-μm size, a complete rate expression has been obtained.