Abnormal growth of TiB<Subscript>2</Subscript> crystals during sintering of TiB<Subscript>2</Subscript>-Ni<Subscript>3</Subscript>(Al,Ti) cemented borides

TiB₂-Ni₃(Al,Ti) cermets present both normal and abnormal growth of faceted titanium diboride (TiB₂) grains during liquid-phase sintering. Abnormal grain growth (AGG) is preferentially found at high sintering temperatures in specimens processed from powder mixtures with a wide particle size distribution. The WC additions to the initial powder mixtures have proved efficient in reducing the number and size of these large TiB₂ grains. However, the sinterability of these materials is dramatically reduced, which suggests that TiB₂ AGG control is obtained by decreasing TiB₂ dissolution kinetics in the liquid phase. On the other hand, an alternative method based on intensive powder milling not only reduces TiB₂ AGG but also the porosity levels obtained by previous powder processing routes. TiB₂ cermets produced by aggressive milling present a higher amount of alumina particles in the matrix after sintering, which, in addition, appear more homogeneously dispersed in the microstructure. The distortion produced by these particles on the facets of TiB₂ growing grains suggests a possible dragging effect responsible for the AGG reduction found in these cermets. Moreover, aggressive milling removes large TiB₂ particles from the powder mixtures, which could act as seeds for TiB₂ uncontrolled growth. TiB₂-Ni₃(Al,Ti) cermets obtained by intensive milling combine hardness over 20 GPa with K _IC of about 10 MPa √m, data clearly out of the range covered so far by other TiB₂-based materials.     

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.     

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.     

Enhancing physical and mechanical properties of Mg using nanosized Al<Subscript>2</Subscript>O<Subscript>3</Subscript> particulates as reinforcement

A magnesium-based composite with 1.1 volume percentage of nanosized Al₂O₃ particulates reinforcement was fabricated using an innovative disintegrated melt deposition technique followed by hot extrusion. Al₂O₃ particulates with an equivalent size of 50 nm were used as reinforcement. Microstructural characterization of the materials revealed grain refinement of magnesium matrix due to incorporation, retention, and uniform distribution of reinforcement. Physical properties characterization revealed that the addition of nano-Al₂O₃ particulates as reinforcement improves the dimensional stability of pure magnesium. Mechanical properties characterization revealed that the presence of nano-Al₂O₃ particulates as reinforcement leads to a significant increase in microhardness, dynamic elastic modulus, 0.2 pct yield strength (YS), ultimate tensile strength (UTS), and ductility of pure magnesium. The results revealed that the combined tensile properties of these materials are superior when compared to Mg reinforced with much higher volume percentage of SiC. An attempt is made in the present study to correlate the effect of nano-Al₂O₃ particulates as reinforcement with the microstructural, physical, and mechanical properties of magnesium.     

Effect of heat treatments on <Emphasis Type="Italic">In-Situ</Emphasis> Al<Subscript>2</Subscript>O<Subscript>3</Subscript>/TiAl<Subscript>3</Subscript> composites produced from squeeze casting of TiO<Subscript>2</Subscript>/A356 composites

In-situ Al₂O₃/TiAl₃ intermetallic matrix composites were fabricated via squeeze casting of TiO₂/A356 composites heated in the temperature range from 700 °C to 780 °C for 2 hours. The phase transformation in TiO₂/A356 composites employing various heat-treatment temperatures (700 °C to 780 °C) was studied by means of differential thermal analysis (DTA), microhardness, scanning electron microscopy (SEM), electron probe microanalysis (EPMA), and X-ray diffraction (XRD). From DTA, two exothermic peaks from 600 °C to 750 °C were found in the TiO₂/A356 composites. The XRD showed that Al₂O₃ and TiAl₃ were the primary products after heat treatment of the TiO₂/A356 composite. The fabrication of in-situ Al₂O₃/TiAl₃ composites required 33 vol pct TiO₂ in Al and heat treatment in the range from 750 °C to 780 °C. The hardness (HV) of the in-situ Al₂O₃/TiAl₃ composites (1000 HV) was superior to that of nonreacted TiO₂/A356 composites (200 HV). However, the bending strength decreased from 685 MPa for TiO₂/A356 composites to 250 MPa for Al₂O₃/TiAl₃ composites. It decreased rapidly because pores occurred during the formation of Al₂O₃ and TiAl₃. The activation energy of the formation of Al₂O₃ and TiAl₃ from TiO₂ and A356 was determined to be about 286 kJ/mole.     

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.     

Investigation into the solubility of nanopowders of the ZrO<Subscript>2</Subscript>–Y<Subscript>2</Subscript>O<Subscript>3</Subscript>–CeO<Subscript>2</Subscript>–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> system in the aqueous medium at various pH

Nanopowders of ZrO₂–Y₂O₃–CeO₂ and ZrO₂–Y₂O₃–CeO₂–Al₂O₃ systems are investigated with the purpose of studying the influence of pH of the dispersed medium on the solubility of nanopowder particles of a complex composition in an aqueous medium after membrane filtration and centrifugation to further prepare the stable dispersions necessary for toxicological investigations of nanoparticles. Concentrations of elements remaining in a supernatant after the sample preparation, which includes membrane filtration and centrifugation, are measured by inductively coupled plasma optical emission spectroscopy. It is established that that the largest aggregative stability of the nanopowder dispersion without the Al₂O₃ additive corresponds to the optimal range of pH 5.5–9.5, while with the Al₂O₃ additive, it is region pH 7.0. The results evidence that, when dispersing these powders, the hydrosol of yttrium oxyhydroxide, which is dissolved at pH < 6.0, is formed. When dissolving in water of the powder with the Al₂O₃ additive in the neutral medium, aluminum hydroxide is formed; in the acidic medium (pH < 6), it is replaced by main soluble aluminum salts; and in the alkali medium (pH > 7), amphoteric aluminum hydroxide is dissolved because of the formation of aluminates.     

The Viscous Behavior of FeO<Subscript>t</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript> Copper Smelting Slags

Understanding the viscous behavior of copper smelting slags is essential in increasing the process efficiency and obtaining the discrete separation between the matte and the slag. The viscosity of the FeO_t-SiO₂-Al₂O₃ copper smelting slags was measured in the current study using the rotating spindle method. The viscosity at a fixed Al₂O₃ concentration decreased with increasing Fe/SiO₂ ratio because of the depolymerization of the molten slag by the network-modifying free oxygen ions (O²⁻) supplied by FeO. The Fourier transform infrared (FTIR) analyses of the slag samples with increasing Fe/SiO₂ ratio revealed that the amount of large silicate sheets decreased, whereas the amount of simpler silicate structures increased. Al₂O₃ additions to the ternary FeO_t-SiO₂-Al₂O₃ slag system at a fixed Fe/SiO₂ ratio showed a characteristic V-shaped pattern, where initial additions decreased the viscosity, reached a minimum, and increased subsequently with higher Al₂O₃ content. The effect of Al₂O₃ was considered to be related to the amphoteric behavior of Al₂O₃, where Al₂O₃ initially behaves as a basic oxide and changes to an acidic oxide with variation in slag composition. Furthermore, Al₂O₃ additions also resulted in the high temperature phase change between fayalite/hercynite and the modification of the liquidus temperature with Al₂O₃ additions affecting the viscosity of the copper smelting slag.     

Development of TiB<Subscript>2</Subscript> reinforced in-situ Ti aluminide matrix composite through reaction synthesis

TiB₂ reinforced in-situ titanium aluminide matrix composite was made through reaction synthesis process using high purity elemental powders of Ti, Al, Cr, Nb and B. XRD of the synthesized block showed presence of mainly Al₃Ti and TiB₂ phases. To obtain γ Ti aluminide based matrix, the material was homogenized in two phase region (α₂+γ). Presence of γ phase matrix alongwith α₂ was confirmed through XRD, SEM and TEM. Uniform distribution of TiB₂ phase was confirmed through elemental mapping and by analyzing specimens of different locations. Differential scanning calorimetry of powder mixture showed presence of endothermic peak for Al melting and exothermic peak of Ti aluminide and TiB₂ formation.     

Understanding the Relationship Between Structure and Thermophysical Properties of CaO-SiO<Subscript>2</Subscript>-MgO-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Molten Slags

In the present work, the relationship between the microscopic structure and macroscopic thermophysical properties in a basic CaO-SiO₂-MgO-Al₂O₃ quaternary system was identified using Fourier transformation infrared, Raman and ²⁷Al magic angular spinning nuclear magnetic resonance (MAS-NMR) techniques. The Raman spectra quantitatively proved that with increasing Al₂O₃ content, the concentrations of the symmetric units of Q⁰(Si) and Q²(Si) decreased, while those of the asymmetric units of Q¹(Si) and Q³(Si) increased; consequently, the degree of polymerization of the networks increased, which resulted in an increase in slag viscosity. The ²⁷Al MAS-NMR spectra demonstrated that three structural units of Al atoms, namely, AlO₄, AlO₅, and AlO₆, mainly existed in the networks. With increasing Al₂O₃ content, the concentration of AlO₄ slightly decreased, while those of AlO₅ and AlO₆ increased; overall, Al₂O₃ acted as a network former in the present system. The increasing Al₂O₃ content led to additional AlO₆ and Si-NBO-Ca-NBO-Al frameworks, which replaced Si-NBO-Ca-NBO-Si in the networks (NBO: non-bridging oxygen) and induced a change in the primarily precipitated crystalline phase from Ca₂MgSi₂O₇ and Ca₂Al₂SiO₇ to MgAlO₄.     

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.     

Electrical conductivity of NaF-AlF<Subscript>3</Subscript>-CaF<Subscript>2</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> melts

The electrical conductivity of NaF-AlF₃-Al₂O₃ melts with a CaF₂ concentration of 5 wt % is measured at a continuously varying cell constant when the molar cryolitic ratio CR = [NaF]/[AlF₃] changes from 1.2 to 2.0 [1, 2]. The experimental data are used to obtain a regression equation to describe the dependence of the electrical conductivity of the melts under study on CR, the alumina content, and temperature {χ] = f(CR, [Al₂O₃], T)}.     

Temperature dependence of the refractive index of Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-Na<Subscript>2</Subscript>O-SiO<Subscript>2</Subscript> melts: Role of electronic polarizability of oxygon controlled by network structure

Refractive indexes for the Al₂O₃-Na₂O-SiO₂ system have been measured using an ellipsometer for a wavelength of 632.8 nm over a wide temperature range (1100 to 1800 K). Two kinds of sample were used: xAl₂O₃-(40-x)Na₂O-60SiO₂ and yAl₂O₃-yNa₂O-(100-2y)SiO₂, where x ranged between 6 and 20 mol pct and y between 12.5 and 25 mol pct. In the former samples, the temperature coefficient of refractive indexes changed from negative to positive on increasing the concentration of Al₂O₃. In the latter samples, the refractive indexes increased monotonically with decreasing concentration of SiO₂, and the temperature coefficient was always positive. It has been found that the temperature dependence of refractive indexes in these melts is determined by the coefficient of thermal expansion, which would be relevant to the degree of polymerization of the melts. In addition, the electronic polarizability of oxygen derived from the refractive indexes increased with increasing temperature in each melt. This suggests that the basicity of the alumino-silicate melts increases as temperature increases. The positive temperature coefficient of the electronic polarizability of oxygen can be attributed to an increase in the distance between cation and oxygen ion due to thermal expansion. The dependence of the electronic polarizability of oxygen on the concentration of Al₂O₃ has also been discussed in terms of the electronic polarizabilities of three types of oxygen contained in the melts. This article is based on a presentation given in the Mills Symposium entitled “Metals, Slags, Glasses: High Temperature Properties & Phenomena,” which took place at The Institute of Materials in London, England, on August 22–23, 2002.     

Amphoteric behavior of alumina in viscous flow and structure of CaO-SiO<Subscript>2</Subscript> (-MgO)-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> slags

The viscosity of CaO-SiO₂ (-MgO)-Al₂O₃ slags was measured to clarify the effects of Al₂O₃ and MgO on the structure and viscous flow of molten slags at high temperatures. Furthermore, the infrared spectra of the quenched slags were analyzed to understand the structural role of Al₂O₃ in the polymerization or depolymerization of silicate network. The Al₂O₃ behaves as an amphoteric oxide with the composition of slags; that is, the alumina behaves as a network former up to about 10 mass pct Al₂O₃, while it acts as a network modifier, in parts, in the composition greater than 10 mass pct Al₂O₃. This amphoteric role of Al₂O₃ in the viscous flow of molten slags at the Newtonian flow region was diminished by the coexistence of MgO. The effect of Al₂O₃ on the viscosity increase can be understood based on an increase in the degree of polymerization (DOP) by the incorporation of the [AlO₄]-tetrahedra into the [SiO₄]-tetrahedral units, and this was confirmed by the infrared (IR) spectra of the quenched slags. The influence of alumina on the viscosity decrease can be explained on the basis of a decrease in the DOP by the increase in the relative fraction of the [AlO₆]-octahedral units. The relative intensity of the IR bands for the [SiO₄]-tetrahedra with low NBO/Si decreased, while that of the IR bands for [SiO₄]-tetrahedra with high NBO/Si increased with increasing Al₂O₃ content greater than the critical point, i.e., about 10 mass pct in the present systems. The variations of the activity coefficient of slag components with composition indirectly supported those of viscosity and structure of the aluminosilicate melts.     

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.     

Phase-equilibrium data and liquidus for the system “MnO”-CaO-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript> at Al<Subscript>2</Subscript>O<Subscript>3</Subscript>/SiO<Subscript>2</Subscript> of 0.55 and 0.65

Phase-equilibrium data and liquidus isotherms for the system “MnO”-CaO-(Al₂O₃+SiO₂) at silicomanganese alloy saturation have been determined in the temperature range of 1373 to 1723 K. The results are presented in the form of the pseudoternary sections “MnO”-CaO-(Al₂O₃+SiO₂) with Al₂O₃/SiO₂ weight ratios of 0.55 and 0.65. The primary-phase fields have been identified in this range of conditions.     

Mechanochemical preparation of Ni<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Al<Subscript><Emphasis Type="Italic">y</Emphasis></Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> nanocomposites

The mechanochemical preparation of nickel aluminide/corundum (Ni _x Al _y /Al₂O₃) powder nanocomposites is shown to be possible during the mechanochemical aluminum reduction of nickel oxide at various weight proportions of the components.     

Thermodynamic effect of alloying addition on <Emphasis Type="Italic">in-situ</Emphasis> reinforced TiB<Subscript>2</Subscript>/Al composites

From the viewpoint of thermodynamics, using the Wilson equation and an extended Miedema model, the effect of the alloying element on the stability of the precipitated phases during the fabrication of in-situ reinforced TiB₂/Al composites was evaluated. The result shows that additions of alloying elements, such as Mg, Cu, Zr, Ni, Fe, V, and La, can promote the formation of Al₃Ti and TiB₂ phases. Particularly, Zr has the most pronounced effect among these alloying elements. In addition, alloying elements can hinder the formation of AlB₂ to a small extent. The calculation results also show that it is easier for magnesium to react with the salts to form TiB₂ than aluminum during the fabrication of in-situ reinforced TiB₂/Al using the flux-assisted synthesis (FAS) technology.     

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.