Reactive synthesis of <Emphasis Type="Italic">in-situ</Emphasis> ZrAl<Subscript>3</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-Al composites

In this work, a reactive synthesis process is proposed to obtain ZrAl₃-Al₂O₃ particulate-reinforced aluminum matrix composites. The process involves the in-situ formation of Al₂O₃ and ZrAl₃ from Al-ZrO₂ green compacts. Upon compact heating, it is found that reduction of ZrO₂ by molten aluminum occurs at temperatures above 750 °C, leading to the development of ZrAl₃ and Al₂O₃ phases. Thermodynamically, it is found that the reduction of zirconium oxide is driven mainly by the dissolution of Zr in molten aluminum. Because the solubility of Zr in liquid aluminum is extremely small, the formation of ZrAl₃ is favored after relatively small Zr dissolutions. The first Zr-Al intermetallics to form at the lowest temperatures seem to be metastable, as infered from the measured atom ratios for Al : Zr of 2.83 : 1. At increasing temperatures, the reaction comes into completion, resulting in the formation of equilibrium intermetallic ZrAl₃ phases. The results obtained from differential scanning calorimetry (DSC) indicate that by increasing the scanning rates, both the reaction temperature and the exothermic peak intensity also increase. Alternatively, it is found that by reducing the amount of ZrO₂ in the green compact, the in-situ reaction temperatures also shift toward higher values.     

A reinvestigation of phase equilibria in the system Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript>-ZnO

The phase equilibria and liquidus temperatures in the binary SiO₂-ZnO system and in the ternary Al₂O₃-SiO₂-ZnO system at low Al₂O₃ concentrations have been experimentally determined using the equilibration and quenching technique followed by electron probe X-ray microanalysis. In the SiO₂-ZnO system, two binary eutectics involving the congruently melting willemite (Zn₂SiO₄) were found at 1448±5 °C and 0.52±0.01 mole fraction ZnO and at 1502±5 °C and 0.71±0.01 mole fraction ZnO, respectively. The two ternary eutectics involving willemite previously reported in the Al₂O₃-SiO₂-ZnO system were found to be at 1315±5 °C and 1425±25 °C, respectively. The compositions of the eutectics are 0.07, 0.52, and 0.41 and 0.05, 0.28, and 0.67 mole fraction Al₂O₃, SiO₂, and ZnO, respectively. The results of the present investigation are significantly different from the results of previous studies.     

Effect of Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Concentration on Density and Structure of (CaO-SiO<Subscript>2</Subscript>)-xAl<Subscript>2</Subscript>O<Subscript>3</Subscript> Slag

The effect of Al₂O₃ concentration on the density and structure of CaO-SiO₂-Al₂O₃ slag was investigated at multiple Al₂O₃ mole percentages and at a fixed CaO/SiO₂ ratio of 1. The experiments were conducted in the temperature range of 2154 K to 2423 K (1881 °C to 2150 °C) using the aerodynamic levitation technique. In order to understand the relationship between density and structure, structural analysis of the silicate melts was carried out using Raman spectroscopy. The density of each slag sample investigated in this study decreased linearly with increasing temperature. When the Al₂O₃ content was less than 15 mole pct, density decreased with increasing Al₂O₃ content due to the coupling of Si (Al), whereas above 20 mole pct density of the slag increased due to the role of Al³⁺ ion as a network modifier.     

Solid-state reactions during heating mechanically milled Al/TiO<Subscript>2</Subscript> composite powders

Solid-state reactions between Al and TiO₂ during heating high-energy mechanically milled Al/TiO₂ composite powders have been investigated by using a combination of thermal analysis, X-ray diffraction (XRD), and various microstructural characterization techniques. When the TiO₂ particles and their interparticle spacing in the Al/TiO₂ composite powder particles are sufficiently large, the reaction between Al and TiO₂ proceeds by two steps. The low-temperature step is an interfacial reaction, which starts at a temperature close to 660 °C. The high-temperature step is a reaction facilitated by bulk diffusion and starts at a temperature above 820 °C. The first phase formed from the reaction is always Al₃Ti irrespective of the starting powder composition or milling time. Al₂O₃ is difficult to form at temperatures below 800 °C. The formation of the α-Ti(Al,O) phase proceeds slowly and requires either continuous heating to a temperature above 1000 °C or holding at a temperature close to 1000 °C for a period of time. Mechanical milling of the Al/TiO₂ powder enhances the interfacial reaction between Al and TiO₂. This enhancement is originated from the establishment and refinement of Al/TiO₂ composite microstructure.     

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     

A Developed Method for Fabricating <Emphasis Type="Italic">In-Situ</Emphasis> TiC<Subscript><Emphasis Type="Italic">p</Emphasis></Subscript>/Mg Composites by Using Quick Preheating Treatment and Ultrasonic Vibration

Quick preheating treatment of the Al-Ti-C pellets and high-intensity ultrasonic vibration are introduced in the fabrication of in-situ TiC _p /Mg composites. Al-Ti-C pellets are preheated for about 130 seconds in the furnace at 1023 K (750 °C), in which magnesium is melted as well. In this process, plenty of heat can be accumulated due to the reactive diffusion between liquid aluminum and solid titanium in Al-Ti-C, and a small amount of Al₃Ti phase is formed as well. After adding the preheated Al-Ti-C into the molten magnesium, thermal explosion takes place in a few seconds. In the meantime, high-intensity ultrasonic vibration is applied into the melt to disperse in-situ formed TiC particles into the matrix and degas the melt as well. Microstructural characterization indicates that in-situ formed TiC particles are spherical in morphology and smaller than 2 μm in size. Furthermore, a homogeneous microstructure with low porosity of the magnesium composite is obtained due to the effect of ultrasonic vibration. A novel approach using the quick preheating treatment technique and high-intensity ultrasonic vibration to synthesize in-situ TiC _p /Mg composites is proposed in our research.     

Effect of LiF as Sintering Agent on the Densification and Phase Formation in Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-4 Wt Pct Nb<Subscript>2</Subscript>O<Subscript>5</Subscript> Ceramic Compound

Different amounts of LiF were added to an Al₂O₃-4 pct Nb₂O₅ basic ceramic, as sintering agent. Improved new ceramics were obtained with LiF concentrations varying from 0.25 to 1.50 wt pct and three sintering temperatures of 1573 K, 1623 K, and 1673 K (1300 °C, 1350 °C, and 1400 °C). The addition of 0.5 wt pct LiF yielded the highest densification, 94 pct of the theoretical density, in association with a sintering temperature of 1673 K (1400 °C). Based on X-ray diffraction (XRD), this improvement was due not only to the presence of transformed phases, more precisely Nb₃O₇F, but also to the absence of LiAl₅O₈. The preferential interaction of LiF with Nb₂O₅, instead of Al₂O₃, contributed to increase the alumina sintering ability by liquid phase formation. Scanning electron microscopy (SEM) results revealed well-connected grains and isolated pores, whereas the chemical composition analysis by energy dispersive energy (EDX) indicated a preferential interaction of fluorine with niobium, in agreement with the results of XRD. It was also observed from thermal analysis that the polyethylene glycol binder burnout temperature increased for all LiF concentrations. This may be related to the formation of hydrogen bridge bonds.     

Effect of CaO-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-MgO slags on the formation of MgO-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> inclusions in ferritic stainless steel

A thermodynamic equilibrium between the Fe-16Cr melts and the CaO-Al₂O₃-MgO slags at 1823 K as well as the morphology of inclusions was investigated to understand the formation behavior of the MgO-Al₂O₃ spinel-type inclusions in ferritic stainless steel. The calculated and observed activities of magnesium in Fe-16Cr melts are qualitatively in good agreement with each other, while those of aluminum in steel melts exhibit some discrepancies with scatters. In the composition of molten steel investigated in this study, the log (X _MgO/X _{Al 2}O₃) of the inclusions linearly increases by increasing the log [a _Mg/a _Al ² ·a _O ² ] with the slope close to unity. In addition, the relationship between the log (X _MgO/X _{Al 2}O₃) of the inclusions and the log (a _MgO/a _{Al 2}O₃) of the slags exhibits the linear correlation with the slope close to unity. The compositions of the inclusions are relatively close to those of the slags, viz. the MgO-rich magnesia-spinel solid solutions were formed in the steel melts equilibrated with the highly basic slags saturated by CaO or MgO. The spinel inclusions nearly saturated by MgO were observed in the steel melts equilibrated with the slags doubly saturated by MgO and MgAl₂O₄. The spinel and the Al₂O₃-rich alumina-spinel solid solutions were formed in the steel melts equilibrated with the slags saturated by MgAl₂O₄ and MgAl₂O₄-CaAl₂O₄ phases, respectively. The apparent modification reaction of MgO to the magnesium aluminate inclusions in steel melts equilibrated with the highly basic slags would be constituted by the following reaction steps: (1) diffusion of aluminum from bulk to the metal/MgO interface, (2) oxidation of the aluminum to the Al³⁺ ions at the metal/intermediate layer interface, (3) diffusion of Al³⁺ ions and electrons through the intermediate layer, and (4) magnesium aluminate (MgAl₂O₄ spinel, for example) formation by the ionic reaction.     

Tribological Behavior of A356/Al2O3 Surface Nanocomposite Prepared by Friction Stir Processing

Surface A356 aluminum alloy matrix composites containing micro and nanosized Al₂O₃ are prepared by a new approach utilizing high-velocity oxy-fuel spraying and friction stir processing (FSP). Optical and scanning electron microscopy, microhardness, and wear tests were used to characterize the surface composites. Results indicated that, the presence of Al₂O₃ in matrix can improve the mechanical properties of specimens. The microhardness of surface composites containing micro and nanosized Al₂O₃ were 89.8 ± 2.6 HV and 109.7 ± 2.5 HV, respectively, which were higher than those for the as-received (79.6 ± 1.1 HV) and the FSPed A356-T6 with no alumina powder (66.8 ± 0.9 HV). Surface composites revealed low friction coefficients and wear rates, which were significantly lower than those obtained for substrate. The wear mass losses of the as-received, the FSPed, and surface micro and nanocomposite specimens after 500-m sliding distance were 50.5, 55.6, 31, and 17.2 mg, respectively. Scanning electron microscopy tests revealed different wear mechanisms on the surface of the wear test specimens.     

Synthesis of Al-Zr Alloys <Emphasis Type="Italic">Via</Emphasis> ZrO<Subscript>2</Subscript> Aluminum-Thermal Reduction in KF-AlF<Subscript>3</Subscript>-Based Melts

Physical–chemical investigations of KF-AlF₃ melts were carried out in order to develop the scientific basis of the technology for Al-Zr alloy synthesis. The possibility of Al-Zr alloy synthesis via the aluminum-thermal method was shown. The liquidus temperatures of KF-AlF₃ and KF-NaF-AlF₃ melts with additions of Al₂O₃ and ZrO₂ were determined using the thermal analysis method in the temperature range from 873 K to 1173 K (600 °C to 900 °C). The dependency of the solubility of ZrO₂ in KF-AlF₃ and KF-NaF-AlF₃ melts on Al₂O₃ concentration was measured.     

Diffusional reactions during processing of TIMETAL 21S/Al2O3 composites

The stability of an Al₂O₃ reinforcement in TIMETAL 21S has been investigated by annealing diffusion couples and consolidated fiber composites at 1100 °C, 900 °C, and 750 °C. Diffusion couple studies indicate that γ-TiAl, α ₂-Ti₃Al, and α-Ti(Al,O) phases can form upon annealing above the β transus of TIMETAL 21S, but γ-TiAl, α ₂-Ti₃Al, and a ternary T phase form during annealing below the β transus. The phases developed during diffusional interaction define a diffusion path between TIMETAL 21S and Al₂O₃. A coating of Nb, Mo, or Ta between TIMETAL 21S and Al₂O₃ acts as a diffusion barrier, but the coatings can diffuse into TIMETAL 21S at high temperature. In agreement with a kinetics analysis, a 2-μm-thick interface coating of Nb, Mo, or Ta in the TIMETAL 21S/Al₂O₃ composite can prevent the reaction during processing (2 hours at 850 °C or 900 °C) with no detectable diffusion into the matrix. If there are imperfections such as pinholes or cracks present in the diffusion barrier, the reaction quickly starts at the interface and does not remain confined at the imperfection; rather, it progresses along the interface. The mechanism for progressive development of interface reaction at a discontinuity in the diffusion barrier has been proposed. The analysis of the diffusional interface reactions in this work has identified some of the governing design concepts for development of robust high-temperature titanium-based composites.     

Effect of ball milling on reaction between TiO<Subscript>2</Subscript> and Al

Titanium Aluminide based composites with Al₂O₃ reinforcement can be produced via reaction of Al with TiO₂. These composites are considered as low price materials for high temperature applications. In this research, the effect of ball milling on 3TiO₂/7Al system was investigated. On the basis of obtained results, ball milling for 0 to 60 h does not lead to reduction of TiO₂ by Al. but reduces the temperature of exothermic reaction. The article is published in the original.     

Study of 6061-Al2O3p composites produced by reciprocating extrusion

A reciprocating extrusion process was developed to consolidate 6061-Al₂O_3p composites from mixed powders. The 6061 alloy powder was first dehydrated in a vacuum chamber at 450 °C and then mixed with 12.5 μm Al₂O₃ powder in various volume fractions: 0, 5, 10, 20, and 30 pct. The mixed powders were hot pressed at 300 °C under a pressure of 300 MPa and finally extruded reciprocatingly 14 times at 460 °C. The results show that the composites were fully densified, with no sign of pores or oxide layers observable in the optical microscope. The Al₂O₃ particles were distributed uniformly in the matrix. As compared with 6061 alloys, the composites demonstrated a smaller precipitation hardening and elongation, but exhibited a higher Young’s modulus and a larger work hardening capacity. The degradation of precipitation hardening was due to the loss of Mg, which reacts with Al₂O₃ to form MgAl₂O₄. The large work-hardening capacity is attributable to the incompatibility between Al₂O₃ and the matrix, which possibly generates more dislocations to harden the matrix. The composites had much higher friction coefficients and greater wear resistances than the 6061 alloy against steel disc surface. The friction coefficient of the 6061-30 vol pct Al₂O_3p composite was double that of the 6061 alloy and the wear resistance was 100-fold. As compared with similar composites reported previously, these composites possessed much higher elongation at the same strength level. A 30 vol pct Al₂O_3p still displayed an elongation of 9.8 pct in the T6 condition. All of these improvements are attributed to the merits, including full densification of the bulk, uniform dispersion of the Al₂O₃ particles in the matrix, and strong binding between the Al₂O₃ particles and the matrix resulting from reciprocating extrusion.     

Development of Wear-Resistant Cu-10Cr-3Ag Electrical Contacts with Nano-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Dispersion by Mechanical Alloying and High Pressure Sintering

Cu-10Cr-3Ag (wt pct) alloy with nanocrystalline Al₂O₃ dispersion was prepared by mechanical alloying and consolidated by high pressure sintering at different temperatures. Characterization by X-ray diffraction and scanning electron microscopy or transmission electron microscopy shows the formation of nanocrystalline matrix grains of about 40 nm after 25 hours of milling with nanometric (<20 nm) Al₂O₃ particles dispersed in it. After consolidation by high pressure sintering (8 GPa at 400 °C to 800 °C), the dispersoids retain their ultrafine size and uniform distribution, while the alloyed matrix undergoes significant grain growth. The hardness and wear resistance of the pellets increase significantly with the addition of nano-Al₂O₃ particles. The electrical conductivity of the pellets without and with nano-Al₂O₃ dispersion is about 30 pct IACS (international annealing copper standard) and 25 pct IACS, respectively. Thus, mechanical alloying followed by high pressure sintering seems a potential route for developing nano-Al₂O₃ dispersed Cu-Cr-Ag alloy for heavy duty electrical contact.     

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.     

Thermodynamics of MnO-SiO<Subscript>2</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-MnS Liquid Oxysulfide: Experimental and Thermodynamic Modeling

The activities of MnO and MnS in a MnO-SiO₂-Al₂O₃(or AlO_1.5)-MnS liquid oxysulfide solution were investigated by employing the gas/liquid/Pt-Mn alloy chemical equilibration technique under a controlled atmosphere at 1773 K (1500 °C). Also, the sulfide capacity, defined as C _S = (wt pct S)(pO₂/pS₂)^1/2, in MnO-SiO₂-Al₂O₃ slag with a dilute MnS concentration was obtained from the measured experimental data. As X _SiO2/(X _MnO + X _SiO2) in liquid oxysulfide increases, the activity coefficient of MnO decreases, while that of MnS first increases and then decreases. As X(AlO_1.5) in liquid oxysulfide increases, the activity coefficient of MnS increases, while no remarkable change is observed for the activity coefficient of MnO. The behavior of the activity coefficient of MnS was qualitatively analyzed by considering MnO + A _x S _y (SiS₂ or Al₂S₃) = MnS + A _x O _y (SiO₂ or Al₂O₃) reciprocal exchange reactions in the oxysulfide solution. The behavior was shown to be consistent with phase diagram data, namely, the MnS saturation boundary. Quantitative analysis of the activity coefficient of the oxysulfide solution was also carried out by employing the modified quasichemical model in the quadruplet approximation.     

Effects of FeO and CaO/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Ratio in Slag on the Cleanliness of Al-Killed Steel

The slag composition plays a critical role in the formation of inclusions and the cleanliness of steel. In this study, the effects of FeO content and the C/A (CaO/Al₂O₃) ratio in the slag on the formation of inclusions were investigated based on a 10-minute slag–steel reaction in a MgO crucible. The FeO content in the top slag was shown to have a significant effect on the formation of MgO·Al₂O₃ spinel inclusions, and critical content exists; when the initial FeO content in the slag was less than 2 pct, MgO·Al₂O₃ spinel inclusions formed, and the T.O (total oxygen) was 20 ppm; when the initial FeO content in the slag was more than 4 pct, only Al₂O₃ inclusions were observed and the T.O was 50 ppm. It was clarified that the main source of Mg for the MgO·Al₂O₃ spinel inclusion formation was the top slag rather than the MgO crucible. In addition, the cleanliness of the steel increased as the initial FeO content in the top slag decreased. As regards the effects of the C/A ratio, the MgO amount in the observed inclusions gradually increased, whereas the T.O content decreased gradually with the increasing C/A ratio. Slag with a composition close to the CaO-saturated region had the best effect on the inclusion absorption.