Development of Mo(Si,Al)<Subscript>2</Subscript>-base oxidation-resistant coating on Nb-base structural materials

Mo(Si,Al)₂-base oxidation-resistant coatings for Nb-base structural materials have been studied. The coating is composed of a Mo(Si,Al)₂-base Al reservoir and Al₂O₃ interlayer to suppress interface reactions between the Al reservoir and the substrate. To develop a suitable Al-reservoir material, some Mo(Si_0.6,Al_0.4)₂-HfB₂ composites were prepared. Their oxidation resistance and coefficients of thermal expansion were investigated, in addition to their chemical reactivity with the Nb substrate at high temperatures. As a result, Mo(Si_0.6,Al_0.4)₂-20 vol pct HfB₂ was selected as one of the satisfactory Al reservoirs. The introduction of a stable Al₂O₃ interlayer was attempted using a novel powder metallurgical process to overlay the Nb substrates with the Al reservoir, where the Nb substrates were subjected to a slight surface oxidation prior to the coating process. The Nb specimens, which are thoroughly coated with the Al reservoir and Al₂O₃ interlayer, can be successfully fabricated by this method. The coated Nb specimens are not damaged at all after prolonged exposure in flowing Ar-20 pct O₂ at 1673 K for 120 hours. Furthermore, the Al₂O₃ interlayer is very effective and no reactions occur at the interface. Thus, this Mo(Si,Al)₂-base oxidation-resistant coating is applicable to Nb. The utility of the coating system is also confirmed for a Nb_SS/Nb₅Si₃ composite. This article is based on a presentation made in the symposium entitled “Beyond Nickel-Base Superalloys,” which took place March 14–18, 2004, at the TMS Spring meeting in Charlotte, NC, under the auspices of the SMD-Corrosion and Environmental Effects Committee, the SMD-High Temperature Alloys Committee, the SMD-Mechanical Behavior of Materials Committee, and the SMD-Refractory Metals Committee.     

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.     

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.     

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.     

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.     

<Emphasis Type="Italic">In-Situ</Emphasis> Synthesis of Cu/Cr-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Nanocomposite by Mechanical Alloying and Heat Treatment

In this article, a novel method has been used to prepare a copper matrix nanocomposite containing Cu-10 wt pct Cr-10 wt pct Al₂O₃ by heat treatment of the mechanically activated Cu, Al, and Cr₂O₃ powder mixture. Structural evolutions were investigated using the X-ray diffraction (XRD) technique. The microstructure of samples was examined using scanning electron microscopy (SEM). It was found that during the milling process, Cu(Al) solid solution and Cu₉Al₄ phase were formed as the intermediate products, and therefore, Al activity was decreased. Hence, the reduction of Cr₂O₃ with Al was prevented during the ball milling stage. Further heat treatment carried out under argon atmosphere at 900 °C for 8 hours resulted in completion of Cr₂O₃ reduction by Al.     

Thermal diffusivity measurements of some synthetic CaO-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript> slags

In an attempt to systematize the knowledge of the heat conduction of liquid silicates, the effective thermal diffusivities of some synthetic slags containing CaO, Al₂O₃, and SiO₂ have been measured, using the three-layer laser-flash method on a differential scheme in the temperature range of 1625 to 1825 K. The effective thermal diffusivities measured, which are a combination of the phononic and photonic heat-transfer mechanisms, were found to increase with increasing temperature for all the presently investigated slags. The slag compositions were chosen in such a way that the changes in the effective thermal diffusivities would reflect the changes in the structure of the slags. It was observed that, at a CaO/Al₂O₃ molar ratio of 4.42, an increase of the SiO₂ content had very little effect on the effective thermal diffusivity values. On the other hand, addition of SiO₂ to a slag with the CaO/Al₂O₃ molar ratio of 2.59 resulted in a significant increase in the effective thermal diffusivity. The addition of Al₂O₃ to slags with a constant CaO/SiO₂ molar ratio resulted in a marked increase in the effective thermal diffusivity. Both these trends indicate that there might be an influence of the network formation in silicate melts on the effective thermal diffusivity.     

Trying out spraying modes and properties of wear-resistant flame Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–TiO<Subscript>2</Subscript> coatings fabricated using a flexible cord material

Samples of Al₂O₃–TiO₂ coatings are fabricated by the flame spraying of a flexible cord. The influence of process parameters and composition of the sprayed material on the structure, composition, and mechanical properties of coatings is investigated. It is shown that an increase in the spraying distance and feed rate of the sprayed material leads to a decrease in their density. An increase in the concentration of the low-melting TiO₂ component predetermines a decrease in the coating porosity and has no significant effect on the coating hardness. Being subjected to measuring scratching, Al₂O₃–TiO₂ flame coatings formed with minimal porosity (Π = 3.2%) are characterized by cohesion fracture behavior and no substrate opening under an indenter load of up to 90 N. The friction factor of coatings under study varies from 0.2 to 0.78 after 2800 counterbody revolutions (44 m of the friction path). This is associated with the accumulation of fatigue cracks in the coating material and its subsequent cohesive fracture by the formation of large fragments serving as an abrasive.     

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.     

Wear of Plasma Sprayed Conventional and Nanostructured Al<Subscript>2</Subscript>O<Subscript>3</Subscript> and Cr<Subscript>2</Subscript>O<Subscript>3</Subscript>, Based Coatings

An ever increasing demand for high-performance ceramic coatings has made it inevitable for developing techniques with precise control over the process parameters to enable the fabrication of coatings with the desired microstructure and improved structural properties. The literature on plasma sprayed nanostructured ceramic coatings such as of Al₂O₃, Cr₂O₃, and their composites obtained using reconstituted nano sized ceramic powders has been reviewed in this study. Ceramic coatings due to their enhanced properties are on the verge of replacing conventional ceramic coatings used for various applications like automotive systems, boiler components, power generation equipment, chemical process equipment, aircraft engines, pulp and paper processing equipment, land-based and marine engine components, turbine blades etc. In such cases, the advantage is greater longevity and reliability for realizing the improved performance of ceramic coatings. It has been observed that the plasma sprayed nanostructured ceramic coatings show improvement in resistance to wear, erosion, corrosion, and mechanical properties as compared to their conventional counterparts. This article reviews various aspects concerning the plasma sprayed ceramic coatings such as (i) the present understanding of formation of plasma-spray coatings and factors affecting them, (ii) wear performance of nanostructured Al₂O₃, Cr₂O₃ and their composite ceramic coatings in comparison to their conventional counterparts, and (iii) mechanisms of wear observed for these coatings under various conditions of testing.     

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.     

Fracture toughness of Ti–Al<Subscript>3</Subscript>Ti–Al–Al<Subscript>3</Subscript>Ti laminate composites under static and cyclic loading conditions

The static and cyclic fracture toughnesses of a Ti–Al₃Ti–Al–Al₃Ti laminate composite material containing at most 15 vol % intermetallic compound are studied. Composite specimens are prepared by terminating reaction sintering of titanium and aluminum foils under pressure. The fracture of the titanium layers is quasi-cleavage during cyclic crack growth and is ductile during subsequent static loading.     

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.     

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.     

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.     

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.     

Formation of CaS on Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-CaO inclusions during solidification of steels

In this article, the effect of CaS formation on the evolution of Al₂O₃-CaO inclusions in low-carbon Al-killed and Ca-treated steel during the solidification process is investigated through high-temperature confocal scanning laser microscopy (CSLM). The inclusions started as mostly liquid-globular inclusions that did not agglomerate with each other on the melt surface but during solidification were seen to change shape into an irregular morphology. The shape change was found to be due to the reaction between the Al₂O₃-CaO inclusions with the dissolved S and Al in the melt, resulting in the formation of dense CaS shells around the inclusions. The melt composition during solidification, estimated from the observed solid δ-front advance rate, was compared to the thermodynamic limit for CaS precipitation. The observed growth rate of the CaS shell was found to initially increase with decreasing temperature because of the higher, solid δ-front advance rates at lower temperatures, which results in higher rates of S and Al partitioning. Once CaS had precipitated, the inclusions were found to form agglomerates on the melt surface because of fluid flow, initially, and later, the capillary depression.     

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.