Interfacial Reactions in Al-Mg (5083)/SiCp Composites during Fabrication and Remelting

The interfaces of aluminum alloy composites (5083) reinforced by SiC particles (as-received, oxidized 3.04 wt pct and 14.06 wt pct) were studied. The composites were fabricated by compocasting and certain samples were also remelted at 800 °C for 30 minutes. The reaction mechanisms between SiC _p and liquid Al and between the SiO₂ layer and Al(Mg) are discussed. The crystal boundaries of the MgO (or MgAl₂O₄) reaction products are believed to be the diffusion paths (or channels) during the interfacial reactions. A SiO₂ layer, formed by oxidation of the SiC particles prior to their incorporation into the melt, plays an important role in preventing the SiC _p from being attacked by the matrix. The interfacial reaction products are affected by both the alloy composition and the thickness of the initial SiO₂ layer.     

The equilibrium partitioning of titanium between Ti3+ and Ti4+ valency states in CaO-SiO2-TiO x slags

The redox behavior of titanium in CaO-SiO₂-TiO _x melts was investigated using a slag-gas equilibrium technique. Titanium partitioning between Ti³⁺ and Ti⁴⁺ valency states and the ratio of activity coefficients of TiO_1.5 and TiO₂ were determined as functions of oxygen partial pressure, temperature, and slag composition. The equilibrium experiments were carried out at temperatures between 1783 and 1903 K under CO-CO₂-Ar gas atmosphere with oxygen partial pressure ranging from 10⁻¹² to 10⁻⁷ atm (1.01×10⁻¹⁰ kPa to 1.01×10⁻⁵ kPa). The slags had CaO/SiO₂ ratios between 0.55 and 1.35 and total titanium oxide concentrations from 7 to 50 mass pct. Experimental results showed that the Ti³⁺/Ti⁴⁺ ratio in CaO-SiO₂-TiO _x slags, containing up to 50 mass pct TiO _x , increased with decreasing oxygen partial pressure and decreased with increasing CaO/SiO₂ ratio and decreasing temperature. Measured variation of the redox ratio Ti³⁺/Ti⁴⁺ with oxygen partial pressure closely followed the ideal behavior. Increasing the CaO/SiO₂ ratio increased the ratio of activity coefficients of TiO_1.5 and TiO₂. The effect of total titania content on this ratio was more complex and in accord with Raman spectroscopy data.     

Fabrication of Ni-Ti Alloy by Self-Propagating High-Temperature Synthesis and Spark Plasma Sintering Technique

This work is focused on the possibilities of preparing Ni-Ti46 wt pct alloy by powder metallurgy methods. The self-propagating high-temperature synthesis (SHS) and combination of SHS reaction, milling, and spark plasma sintering consolidation (SPS) are explored. The aim of this work is the development of preparation method with the lowest amount of undesirable phases (mainly Ti₂Ni phase). The SHS with high heating rate (approx. 200 and 300 K min^?1) was applied. Because the SHS product is very porous, it was milled in vibratory disk milling and consolidated by SPS technique at temperatures of 1173 K, 1273 K, and 1373 K (900 °C, 1000 °C, and 1100 °C). The microstructures of samples prepared by SHS reaction and combination of SHS reaction, milling, and SPS consolidation are compared. The changes in microstructure with increasing temperature of SPS consolidation are observed. Mechanical properties are tested by hardness measurement. The way to reduce the amount of Ti₂Ni phase in structure is leaching of powder in 35 pct hydrochloric acid before SPS consolidation.     

Oxidation and Diffusion in Ti-Al-(Mo, Nb) Intermetallics

The oxidation resistance of Ti-Al intermetallics is superior to many of their counterparts at high temperatures. High-temperature stability of these intermetallics appears to improve with a ternary alloying addition such as Mo, Nb, etc. A detailed analysis of oxidation of the Ti₃Al intermetallics, Ti₃Al-2.9 at. pct Mo and Ti₃Al-1.1 at. pct Nb, in pure oxygen using crystallographic and microscopic techniques is presented here. The alloy containing 1.1 at. pct Nb did not show an improvement in oxidation resistance over the base alloy but that containing 2.9 at. pct Mo showed marked resistance to oxidation. Activation energies of oxidation for both the alloys were comparable with those reported in the literature for similar compositions. TiO₂ and Al₂O₃ were the major phases present in the oxide scales of the oxidized alloys. The crystal orientations from the X-ray diffraction (XRD) patterns and the morphologies from scanning electron microscopy (SEM) were in good agreement and were helpful in further analysis of the oxidation process. The effective diffusion of oxygen in the oxide layers was calculated using the mole fraction of individual oxide and the diffusivity of oxygen in pure oxide. The activation energy for the effective diffusion of oxygen through the oxide layers was determined to be ~24 kJ/mol. The activation energy for the oxidation process was higher than that of the diffusion of oxygen. Hence, it can be concluded that the oxidation process in both the alloys studied is not diffusion controlled.     

Interdiffusion in the TiO2 oxidation product of Ti3Al

Oxidation experiments have been conducted on Ti₃Al in the temperature range 1023 to 1273 K in a one-atmosphere pure oxygen environment. The oxidation products were analyzed using the scanning electron microscope (SEM), energy-dispersive spectrometer (EDS), and X-ray diffraction (XRD) techniques and found to be predominantly TiO₂ (rutile). The oxidation rate was observed to obey the parabolic rate law. Diffusivity data were obtained using the parabolic rate constant for interdiffusion of Ti and O in the oxide layer. Parabolic rate constants were calculated from oxidation rate data, and Valenci equations for flat sheets were used to calculate diffusion coefficients. The activation energy, Q, was found to be 295.43±5.90 kJ/mol, and the frequency factor, D ₀, was calculated to be 0.68±0.01 m²/s for oxygen in the TiO₂. The activation energy obtained in this study matches closely with that of oxygen diffusion in TiO₂ reported in the literature.     

Selective Oxidation of TWIP Steel During Continuous Annealing

The selective oxidation of Al‐free and Al‐added TWIP steel after full austenitic annealing at 800°C in a N₂ + 10%H₂ gas atmosphere with a dew point of ?17°C was investigated by means of transmission electron microscopy. A thick MnO layer was formed at the surface of Al‐free TWIP steel after the recrystallization annealing. Small crystalline c‐xMnO · SiO₂ (x > 2) particles and amorphous a‐xMnO · SiO₂ (x < 0.9) particles were found at the MnO/steel interface. In the subsurface, the Mn depletion resulted in the formation of a narrow ferrite layer. The annealing of the Al‐added TWIP steel also resulted in the formation of a thick MnO surface layer. At the MnO/steel interface, Kirkendall voids were formed between the amorphous a‐xMnO · SiO₂ (x < 0.9) oxide and crystalline c‐xMnO · Al₂O₃ oxide in the case of Al‐added TWIP steel. In the subsurface, a thin layer was depleted of Mn and the original austenite had transformed into ferrite. Internal oxidation of Al to Al₂O₃ and the formation of crystalline c‐xMnO · Al₂O₃ (x > 1) compound oxide particles were found to occur at the grain boundaries of the Mn‐depleted ferritic zone. The present contribution highlights the implications of the selective oxidation of TWIP steels for their processing in continuous annealing and continuous hot dip galvanizing lines.     

Rapid synthesis of ternary carbide Ti3SiC2 through pulse-discharge sintering technique from Ti/Si/TiC powders

Ti/Si/TiC powders with molar ratios of 1:1:2 (M1) and 2:2:3 (M2) were prepared for the synthesis of a ternary carbide Ti₃SiC₂ by using the mixture method for 24 hours in an Ar atmosphere. The synthesis process was conducted at 1200 °C to 1400 °C under a pressure of 50 MPa, using the pulse-discharge sintering (PDS) technique. After sintering, the phase constituents and microstructures of the samples were analyzed by X-ray diffraction (XRD) technique and observed by optical microscopy and scanning electron microscopy. The results showed that the phases in all the samples consisted of Ti₃SiC₂ and small amounts of TiC, and the optimum sintering temperature was found to be in the relatively low range of 1250 °C to 1300 °C. By the standard additive method, the relative content of Ti₃SiC₂ was calculated. For the M1 samples, the lowest TiC content can be only decreased to about 3 to 4 wt pct, whereas the content of Ti₃SiC₂ in the M2 samples is always lower than that in the M1 samples. When the M2 powder was sintered at 1300 °C for 8 to 240 minutes, the TiC peaks were found to show a very low intensity, and the corresponding content of Ti₃SiC₂ was calculated to be higher than 99 wt pct. The grain size of Ti₃SiC₂ increased from 5 to 10 μm to 80 to 100 μm in the entire applied sintering temperature range. The relative density of the M2 samples was measured to be higher than 99 pct at sintering temperatures above 1275 °C. It indicates that the PDS technique can rapidly synthesize high-content Ti₃SiC₂ from the Ti/Si/TiC powders in a relatively low temperature range.     

Investigation of the Effect of Magnesium on the Microstructure and Mechanical Properties of NiTi Shape Memory Alloy Prepared by Self-Propagating High-Temperature Synthesis

This work aims to describe the effect of magnesium on the microstructure, phase composition, amount of undesirable Ti₂Ni phase, martensitic transformation, mechanical properties, and corrosion resistance of NiTi alloy. To minimize the quantity of Ti₂Ni phase, we use the magnesium as an element with high affinity to oxygen, because this phase is stabilized by oxygen. Various quantities of magnesium (1, 3, and 5 wt pct) were tested. Self-propagating high-temperature synthesis (SHS) was used as a production method of the alloys. The samples prepared by SHS were pulverized by a vibrating mill, and the obtained powders were used for consolidation by means of spark plasma sintering. Results showed a significant reduction of the content of undesirable Ti₂Ni phase by the addition of magnesium. Further, magnesium increased corrosion resistance and yield strength.

     

Processing copper and silver matrix composites by electroless plating and hot pressing

A simple process was developed to fabricate ceramic-reinforced copper and silver matrix composites by electroless plating and hot pressing at 873 K and 300 MPa, in air. Composites were produced containing 10 to 40 vol pct ceramic reinforcements of different sizes and shapes including silicon carbide whiskers (SiC _w ), alumina particles (Al₂O_3p ), carbon short fibers (Carbon _sf ), and Saffil short fibers (Saffil _sf ) (3.8 pct SiO₂-96.2 pct Al₂O₃) uniformly distributed within the matrix. The hardness and bending strength of the composites were much higher than those of the pure matrices. The electrical conductivity, measured by a four-point probe method, was similar to that of traditional CdO/Ag electrical contact materials. The surface morphologies and cross-sectional microstructures of the arc-eroded Al₂O_3p /Ag composites were similar to those of conventional CdO/Ag and SnO₂/Ag and exhibited a good arc-erosion resistance. These composites combine the high strength and elevated-temperature stability of the ceramic reinforcements with the good electrical and thermal conductivity of the two metallic matrices.     

Kinetics studies on the dissolution of nitrogen in the CaO-Al2O3-SiO2 and CaO-Al2O3-TiO x melts

The rate of nitrogen dissolution in CaO-Al₂O₃-SiO₂ and CaO-Al₂O₃-TiO _x melts was measured by ¹⁴N–¹⁵N isotope exchange reaction. The rate constant for the CaO-Al₂O₃-SiO₂ melts at the ratio of mass pct CaO/mass pct Al₂O₃ = 1 increases as SiO₂ content increases, whereas the rate constant for the same melts at the ratio of mass pct CaO/mass pct SiO₂ = 1 increases as Al₂O₃ content increases. The rate constant for the CaO-Al₂O₃-TiO _x melts at the ratio of mass pct CaO/mass pct Al₂O₃ = 1 decreases as the TiO _x content increases. The activation energies of nitrogen dissolution in CaO-Al₂O₃-SiO₂ melts are about 1.5 to 3 times larger than that of molten pure iron. Moreover, the rate constant of nitrogen dissolution is independent of the ratio of Ti³⁺/Ti⁴⁺.     

Isothermal oxidation of TiAl alloy

Isothermal oxidation behavior of Ti-48.6 at. pct Al alloy was studied in pure dry oxygen over the temperature range 850 °C to 1000 °C. The oxidation was essentially parabolic at all temperatures with significant increase in the rate at 1000 °C. Effective activation energy of 404 kJ/mol was deduced. The oxidation products were a mixture of TiO₂ (rutile) and α-Al₂O₃ at all temperatures. An external protective layer of alumina was not observed on this alloy at any of the temperatures studied. A layered structure of oxides was formed on the alloy at 1000 °C.     

Reduction of titanium dioxide in a nonequilibrium hydrogen plasma

Plasma processing offers improved thermodynamics and kinetics over conventional, thermal processing. In the current work, the reduction of TiO₂ was investigated in a moderate-pressure (p<46 torr) nonequilibrium hydrogen plasma at temperatures below 1273 K; the effect of plasma power, plasma pressure, time, and applied voltage on the extent of the reduction was examined. Reduction of powdered TiO₂ at the surface of a packed bed has produced up to 60 pct conversion of TiO₂ to Ti₂O₃ in only 5 minutes of plasma-specimen contact. While the plasma-assisted reduction occurs at the surface, the reduction of TiO₂ to Ti₅₀O₉₉ within the interior of the bed by diatomic hydrogen establishes a value of that leads to the reoxidation of the Ti₂O₃. The continued reduction of the surface material by monatomic hydrogen from the plasma balances this oxidation process, and a steady-state condition is established. When the interior of the bed is completely reduced to Ti₅₀O₉₉, the partial pressure of water vapor declines, and further reduction of Ti₂O₃ at the surface can proceed. It is hypothesized that the reduction process involves the formation of a Magneli-like oxide between Ti₂O₃ and TiO.     

Thermodynamics of TiO x in blast furnace-type slags

Equilibrium studies between CaO-SiO₂-10 pct MgO-Al₂O₃-TiO_1.5-TiO₂ slags, carbon-saturated iron, and a carbon monoxide atmosphere were performed at 1773 K to determine the activities of TiO_1.5 and TiO₂ in the slag. These thermodynamic parameters are required to predict the formation of titanium carbonitride in the blast furnace. In order to calculate the activity of titanium oxide, the activity coefficient of titanium in carbon-saturated iron-carbon-titanium alloys was determined by measuring the solubility of titanium in carbon-saturated iron in equilibrium with titanium carbide. The solubility and the activity coefficient of titanium obtained were 1.3 pct and 0.023 relative to 1 wt pct titanium in liquid iron or 0.0013 relative to pure solid titanium at 1773 K, respectively. Over the concentration range studied, the effect of the TiO _x content on its activity coefficient is small. In the slag system studied containing 35 to 50 pct CaO, 25 to 45 pct SiO₂, 7 to 22 pct Al₂O₃, and 10 pct MgO, the activity coefficients of TiO_1.5 and TiO₂ relative to pure solid standard states range from 2.3 to 8.8 and from 0.1 to 0.3, respectively. Using thermodynamic data obtained, the prediction of the formation of titanium carbonitride was made. Assuming hypothetical ‘TiO₂,’ i.e., total titanium in the slag expressed as TiO₂, and using the values of the activity coefficients of TiO_1.5 and TiO₂ determined, the equilibrium distribution of titanium between blast furnace-type slags and carbon-saturated iron was computed. The value of [pct Ti]/(pct ‘TiO₂’) ranges from 0.1 to 0.2.     

The high temperature oxidation of Al-4.2 Wt Pct Mg alloy

The high temperature oxidation of Al-Mg alloys is characterized by the rapid formation of thick, micro-crystalline oxide films. The oxidation kinetics of an Al-4.2 wt pct Mg alloy under dry and moist 20 pct O₂/Ar have been measured, and oxide films grown on bulk specimens complementary to the weight gain curves have been characterized using electron optical techniques (TEM, SEM). Initial oxidation takes place by the nucleation and growth of primary crystalline oxides at the oxide/metal interface and by the formation of secondary oxides of MgO by the reduction of the original amorphous over-layer of γ-Al₂O₃ by Mg. Subsequent oxidation is dominated by the further nucleation and growth of primary oxides. The presence of water vapor in the oxidizing environment initially reduces oxidation rates through a modification of the mechanical properties of the amorphous overlayer but does not affect the overall oxidation mechanism. A microstructural model has been developed which describes oxidation of Al-Mg alloys in terms of fracture of the original air-formed film by primary MgO nucleation and growth and modification to this film by the presence of water vapor in the oxidizing environment.     

Thermo-mechanical Response and Damping Behavior of Shape Memory Alloy–MAX Phase Composites

NiTi/Ti₃SiC₂ interpenetrating composites that combine two unique material systems—a shape memory alloy (SMA) and a MAX phase—demonstrating two different pseudoelastic mechanisms, were processed using spark plasma sintering. The goal of mixing these two material systems was to enhance the damping behavior and thermo-mechanical response of the composite by combining two pseudoelastic mechanisms, i.e., reversible stress-induced martensitic transformation in SMA and reversible incipient kink band formation in MAX phase. Equal volume fractions of equiatomic NiTi and Ti₃SiC₂ were used. Microstructural characterization was conducted using scanning electron microscopy to study the distribution of NiTi, Ti₃SiC₂, and remnant porosity in the composite. Thermo-mechanical testing in the form of thermal cycles under constant stress levels was performed in order to characterize shape memory behavior and thereby introducing residual stresses in the composites. Evolution of two-way shape memory effect was studied and related to the presence of residual stresses in the composites. Damping behavior, implying the energy dissipation per loading–unloading cycle under increasing compressive stresses, of pure NiTi, pure Ti₃SiC₂, as-sintered, and thermo-mechanically cycled (TC) NiTi/Ti₃SiC₂ composites, was investigated and compared to the literature data. In this study, the highest energy dissipation was observed for the TC composite followed by the as-sintered (AS) composite, pure NiTi, and pure Ti₃SiC₂ when compared at the same applied stress levels. Both the AS and TC composites showed higher damping up to 200 MPa stress than any of the metal—MAX phase composites reported in the literature to date. The ability to enhance the performance of the composite by controlling the thermo-mechanical loading paths was further discussed.     

MAX phases in titanium and aluminum alloys

The crystalline structures in the Ti-Al-C and Ti-Si-C systems are analyzed, and experiments are conducted with VT6 titanium alloy and eutectoidal Silumin (Al-12% Si) subjected to electroexplosive alloying and electron-beam treatment. Diffraction analysis reveals the formation of MAX phases (Ti₃SiC₂ and Ti₃AlC) in the modified layer of these alloys.     

In situ observations of crystalline oxide formation during aluminum and aluminum alloy oxidation

Anin situ morphological study of the oxidation of electron transparent specimens of aluminum and aluminum alloys containing zinc and magnesium has been carried out in the temperature range 400 to 520°C using the hot stage of a 1 MeV transmission electron microscope. The structure and morphology of the crystalline oxide produced in each alloy has been carefully examined by selected area electron diffraction and stereomicroscopy. In pure aluminum, oxidation takes place after a temperature dependent induction period, by the nucleation of crystalline γ-Al₂O₃ at the amorphous oxide/metal interface. This process is delayed by additions of zinc which modify the structure of the oxide. In alloys containing magnesium, oxidation takes place by the rapid nucleation and growth of MgAl₂O₄ or MgO, with a secondary form of magnesia developing from the reduction of the amorphous γ-Al₂O₃ surface layer.

     

Development and elemental powder metallurgy of a Y-containing two-phase TiAl alloy

The Y modification of a two-phase (γ+α ₂) TiAl-(Mn,Mo,C) alloy was studied with an aim to improve, mainly, the oxidation resistance and the mechanical properties in a high-temperature air environment. The experimental alloy was prepared by the elemental powder metallurgy (EPM) method. The addition of up to 0.6 at. pct Y resulted in a significant improvement in tensile properties and compressive yield strength and an anomalous yielding phenomenon withal. Two structural characteristics were identified: first, microstructural refinement in terms of the grain size as well as the interlamellar spacing, and second, precipitation of fine oxides that might scavenge harmful oxygen. Deformation was found to be mainly provided by 1/2<110] ordinary dislocations and a much lesser amount of <011] superdislocations as compared to what has been reported in other (γ+α ₂) TiAl alloys. The oxidation resistance of the experimental alloy was evaluated by air-exposure tests at 800 °C, from which the oxidation kinetics and the morphological and phase characteristics of the oxide scales were analyzed. With a Y addition, the constituents of the oxide scale changed from those of the Y-free alloy. In the case of the Y-free alloy, the oxide scale which formed upon extended air exposure (350 hours) at 800 °C consisted of a mixture of TiO₂ and α-Al₂O₃. In the case of the alloy modified with Y (0.6 at. pct), however, the oxide scale formed in an identical environment was considerably different: it consisted of a complex mixture of TiO₂, α-Al₂O₃, Y₂O₃, and Al₅Y₃O₁₂. The formation of the multiphase (Y,Al)O-rich oxide scale impedes the oxygen transport and the thermal-expansion stress in the Al₂O₃ layer. It is also suggested that a Y addition reduces the oxygen solubility and concentration of oxygen vacancices in the TiO₂ layer. This article is based on a presentation made in the symposium entitled “Fundamentals of Structural Intermetallics,” presented at the 2002 TMS Annual Meeting, February 21–27, 2002, in Seattle, Washington, under the auspices of the ASM and TMS Joint Committee on Mechanical Behavior of Materials.     

The high temperature oxidation of Al-4.2 wt pct Mg alloy

The high temperature oxidation of Al-Mg alloys is characterized by the rapid formation of thick, micro-crystalline oxide films. The oxidation kinetics of an Al-4.2 wt pct Mg alloy under dry and moist 20 pct O₂/Ar have been measured, and oxide films grown on bulk specimens complementary to the weight gain curves have been characterized using electron optical techniques (TEM, SEM). Initial oxidation takes place by the nucleation and growth of primary crystalline oxides at the oxide/metal interface and by the formation of secondary oxides of MgO by the reduction of the original amorphous over-layer of γ-Al₂O₃ by Mg. Subsequent oxidation is dominated by the further nucleation and growth of primary oxides. The presence of water vapor in the oxidizing environment initially reduces oxidation rates through a modification of the mechanical properties of the amorphous overlayer but does not affect the overall oxidation mechanism. A microstructural model has been developed which describes oxidation of Al-Mg alloys in terms of fracture of the original air-formed film by primary MgO nucleation and growth and modification to this film by the presence of water vapor in the oxidizing environment. Formerly at Imperial College, London.     

Microstructure, mechanical properties, and fracture mechanism of As-cast (Ti0.5Cu0.25Ni0.15Sn0.05Zr0.05)100−x Mo x composites

Copper mold cast cylinders of (Ti_0.5Cu_0.25Ni_0.15Sn_0.05Zr_0.05)_100−x Mo _x composites are prepared. Addition of Mo in the bulk glass-forming alloy induces the formation of a dendrite/matrix composite. For 3-mm-diameter cylinders, the matrix exhibits a homogenous ultrafine microstructure for Mo content of 2.5 at. pct, and a fine eutectic microstructure for 5 at. pct Mo. For 5-mm-diameter cylinders, the matrix exhibits a dendritic microstructure for 2.5 at. pct Mo, and exhibits a coarser eutectic microstructure for 5 at. pct Mo. Despite the formation of a dendrite/nanostructured matrix composite in the cylinders, the quenched surface layer with a nanoscale grain size dominates the deformation and fracture of the 3-mm-diameter cylinders. More than 56 vol pct quenched layer leads to a distensile fracture mode and the samples exhibit high fracture strength and high Young’s modulus but low ductility. For 5-mm-diameter cylinders, the composite microstructure becomes dominant due to its more than 64 vol pct volume fraction leading to a cone-shaped fracture surface. The samples exhibit lower yield strength and lower Young’s modulus but better ductility compared to the 3-mm-diameter cylinders. The mechanical behavior of the Mo-bearing composites strongly depends on the microstructural homogeneity and casting defects formed upon solidification.