Correlation between oxidation resistance and crystallinity of Ti–Al as a barrier layer for high-density memories

The Ti–Al intermetallic material system has been investigated for application as a conducting diffusion barrier in a three-dimensional stacked capacitor–transistor geometry. La–Sr–Co–O (LSCO)/Pb–Zr–Ti–Nb–O/La–Sr–Co–O ferroelectric capacitors were fabricated on Ti–Al/polycrystalline-Si/Si substrates. The electrical and ferroelectric properties are found to correlate strongly with the crystallinity of the Ti–Al layer. The crystalline Ti–Al layer shows a distinct chemical reaction with the bottom LSCO electrode thus preventing ohmic electrical contact between the ferroelectric capacitor and transistor. In contrast, the amorphous Ti–Al layer does not react and forms an ohmic contact to LSCO. For crystalline Ti–Al, X-ray photoelectron spectroscopy (XPS) shows the formation of Al₂O₃ induced by the segregation of Al to the LSCO/Ti–Al interface. For amorphous Ti–Al, XPS reveals that no Al₂O₃ layer is formed. In addition, Rutherford backscattering analysis shows almost no difference in the Ti-peak spectrum before and after deposition of LSCO.     

Investigation of the strength of steel–titanium diffusion welded joints

The results of investigation of the structure and mechanical properties in tensile loading and structural strength at 20°C of diffusion welded joints between 08Cr18Ni10Ti steel and PT-3V and PT-5V are presented.     

Microstructure,residual stresses and mechanical properties of diffusion bonded tungsten–steel joint using a V/Cu composite barrier interlayer

Diffusion bonding is a preferred method to join W and steel for divertor applications. To minimize the residual stress induced by the large mismatch of thermal expansion coefficients and to inhibit the formation of brittle intermetallic phases, a V/Cu composite barrier interlayer was designed and examined to produce a joint between W and steel. The diffusion bonding was carried out at 1050 °C for 1 h under a 10 MPa pressure in vacuum. Metallographic analysis revealed excellent bonding at all of the joining interfaces. Neither intermetallic compounds nor other brittle phases were found in the bonded region. Nano-indentation test across the joint interfaces demonstrated the effect of solid solution strengthening in the diffusion zone. The strength of the joint was as high as 402 MPa and the failure occurred predominantly at the W substrate near the W/V interface due to the residual stress concentration.     

Ta–Rh binary alloys as a potential diffusion barrier between Cu and Si: Stability and failure mechanism of the Ta–Rh amorphous structures

Thermodynamic calculations were carried out to derive the Gibbs free energy diagram for the amorphous and crystalline phases in the Ta–Rh system. These calculations predicted that the compositional range for the amorphous Ta–Rh phase was within 37–66 at.% Ta, which was validated by X-ray diffraction (XRD) analysis, high-resolution transmission electron microscopy (HRTEM) observations and resistivity measurements of as-deposited films. The thermodynamic modeling provided a valuable guide for selecting an amorphous composition suitable for diffusion barrier applications. The stability and metallurgical failure mechanism for TaRh_x diffusion barriers in contact with Cu and/or Si were investigated by resistivity measurements, XRD analysis and detailed electron microscopy on samples annealed in 5% H₂/95% N₂ gas for 30 min at various temperatures. Amorphous TaRh_x in contact with the Si substrate was stable up to 700 °C, whereupon TaRh_x decomposed and reacted to form TaSi₂ and RhSi. Si/amorphousTaRh_x (13 nm)/Cu stacks, on the other hand, were stable only up to 550 °C. Failure occurred by reaction of Rh with the Si substrate to form RhSi at the interface. The large density of defects formed in the barrier layer as a result of outward diffusion of Rh facilitated diffusion of Cu to the Si/TaRh_x interface to form Cu₃Si particles. The formation of Cu₃Si was observed to trigger further silicidation of the barrier to form a discontinuous TaSi₂ layer.     

Fe–W–C thermodynamics and in situ preparation of tungsten carbide-reinforced iron-based surface composites by solid-phase diffusion

Tungsten carbide (WC)-reinforced Fe-based surface composites were prepared by in situ solid-phase diffusion at 1423 K for 4, 6, and 8 h. The thermodynamics, phase composition, microstructure, microhardness, and wear-resistance of the Fe–W–C ternary system of the samples were examined by X-ray diffraction, scanning electron microscopy, Vickers hardness test, and wear test, respectively. Thermodynamic calculations showed that the thermodynamically favored products of the Fe–W–C system were W₂C, WC, and Fe₃C. W also exhibited a stronger carbide-forming tendency than Fe. The Gibbs free-energies of W₂C and WC, which were stable carbides, significantly decreased with increased temperature. The main phases of the composite were WC, γ-Fe, Fe₃C, graphite, and η-carbide (M₆C) with fishbone-like morphology. The longitudinal section of the composite could be easily divided into three reaction zones, namely, WC layer, “no graphite area,” and M₆C-reinforced area. WC particles in the WC layer were irregularly shaped with 0.3–12 μm particle size, with volume fraction of up to > 80%. The average microhardness value of the dense ceramic layer was 2152 HV_0.1. The maximum relative wear-resistance, which was 230.4 times higher than that of gray cast iron, was obtained at 20 N. The high wear-resistance of the composite was due to the in situ formation of dense and hard WC particulates that acted as a reinforcement phase.     

Carbo-oxidising of titanium by diffusion treatment in carbon–oxygen containing media

Abstract

The surface engineering of titanium with TiC_xO_1?x coatings through diffusion carbo-oxidising from graphite in oxygen containing media is investigated. The effect of oxygen partial pressure on phase composition of coatings during carbo-oxidising is evaluated. The interval of oxygen partial pressure allowing the carbo-oxide TiC_xO_1?x to form is defined as 10^?2–10³ Pa. The effects of process temperature and time on evolution of TiC_xO_1?x composition and morphology of surface layer have been investigated. It is determined that increases in temperature and process time favour an increase in carbon content in TiC_xO_1?x. It is revealed that at temperatures above the transformation temperature T_α?β, TiC_xO_1?x is formed not only in coating but also throughout grain boundaries of diffusion layer. The stages of carbo-oxide formation during diffusion carbo-oxidising of commercially pure titanium are explained as follows: surface saturation with oxygen; formation of TiO₂ film; oxide dissolution and formation of diffusion layer; formation of non-stoichiometric TiC_x and TiO_x and their interaction resulting in TiC_xO_1?x formation. Corrosion properties of carbo-oxide coatings tested in 80%H₂SO₄ are compared with nitride and oxide coatings. It is revealed that carbo-oxide coating demonstrates better corrosion resistance. The tribological properties of carbo-oxide, nitride and oxide coatings tested with bronze counterbody are compared, and carbo-oxide coating demonstrates better wear resistance.     

Oxidation of orthorhombic titanium aluminide Tl-22AL-25NB in air between 650 and 1000 °C

The oxidation behavior of orthorhombic titanium aluminide alloy Ti-22Al-25Nb was studied in air between 650 and 1000 °C by isothermal thermogravimetry and postoxidation scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and x-ray diffraction. Microhardness measurements were performed after exposure to gage hardening due to nitrogen and oxygen ingress. The parabolic rate constant of Ti-22Al-25Nb was of the same order as conventional titanium alloys and Ti₃Al-based titanium aluminides at and below 750 °C. Between 800 and 1000 °C, the oxidation resistance of Ti-22Al-25Nb was as good as that of γ-TiAl based aluminides; however, the growth rate changed from parabolic to linear after several tens of hours at 900 and 1000 °C. The mixed oxide scale consisted of TiO₂, AlNbO₄, and Al₂O₃, with TiO₂ being the dominant oxide phase. Underneath the oxide scale, a nitride-containing layer formed in the temperature range investigated, and at 1000 °C, internal oxidation was observed below this layer. In all cases, oxygen diffused deeply into the subsurface zone and caused severe embrittlement. Microhardness measurements revealed that Ti-22Al-25Nb was hardened in a zone as far as 300 μm below the oxide scale when exposed to air at 900 °C for 500 h. The peak hardness depended on exposure time and reached five times the average hardness of the bulk material under the above conditions.     

Grinding–hardening using dry air and liquid nitrogen: Prediction and verification of temperature fields and hardened layer thickness

This paper investigates the grinding–hardening both theoretically and experimentally with a plunge surface-grinding process. Theoretically, the paper presents a temperature-dependent finite element heat transfer model, incorporating a triangular moving heat source and various cooling conditions, to investigate the phase transformation kinetics, thus to predict the thickness of a layer hardened. The temperature variation and thickness of the hardened layer were also investigated experimentally on quenchable steel 1045 using dry air and liquid nitrogen as the cooling media. The predictions were in good agreement with the experimental results. It was found that the phase transformation follows the martensitic kinetics. The application of liquid nitrogen enhances the transformation of retained austenite to martensite and results in a refinement of the martensitic structure.     

Phase stability and structural distortion of NiO under high pressure

The phase stability and structural distortion of NiO under high pressure were investigated using first-principles calculations based on density-functional theory. Different forms of exchange-correlation functional including LDA, GGA and GGA＋U were used in the present calculations. All of the three methods predict NiO to be AFM II ordering with the cell slightly compressed along [111] direction and also indicate that there is no structural phase transition of NiO under pressure up to 140 GPa, which are in agreement with the experiment. However, both LDA and GGA incorrectly predict the structural distortion under pressure especially above 60 GPa. Only when strong correlations are included in form of GGA＋U, structural distortion under high pressure can qualitatively agree with the experiment. The related mechanism was also analyzed and discussed. These results suggest that the strong electronic correlations still play a very important role in the properties of NiO under high pressure.     

Thermal stability and mechanical properties of Gd-Co-A1 bulk glass alloys

The glass forming ability of Gd-Co-A1 ternary alloy systems with a composition ranging from 50% to 70% （molar fraction） for Gd and from 5% to 40% （molar fraction） for AI were investigated by copper mold casting and Gd60Co25Al15 bulk glass alloy cylinders with the maximum diameter of 5 mm were obtained. The reduced glass transformation temperature （TG/Tm） and the distance of supercooling region ATx are 0.616 and 45 K, respectively for this Gd-Co-A1 alloy. The compressive fracture strength （σf） and elastic modulus （E） of Gd-Co-A1 glassy alloys are 1 170-1 380 MPa and 59-70 GPa, respectively. The Gd-AI-Co bulk glassy alloys with high glass forming ability and good mechanical properties are promising for the future development as a new type function materials.     

The effect of platinum on Al diffusion kinetics in β-NiAl: Implications for thermal barrier coating lifetime

First-principles density functional theory calculations are used to study Al diffusion in β-NiAl. The activation energy and diffusion constant pre-exponential factors are calculated for five previously postulated Al diffusion mechanisms: next-nearest-neighbor Al jumps, the triple defect mechanism and three variants of the six-jump cycle mechanism beginning with an Al vacancy. We predict that the triple defect mechanism has the lowest activation energy and is the mechanism by which Al diffusion occurs in NiAl. In order to elucidate why Pt has a beneficial effect on thermal barrier coating lifetime, the effect of Pt on each of these mechanisms is also examined. In all cases, Pt decreases the diffusion activation energy, which should enhance Al diffusion in the coatings.     

Mechanical alloying and magnetic saturation of tungsten–nickel powders

Alloying mechanism and magnetic saturation of tungsten and W-40 wt.% Ni milled powders were investigated using XRD, SEM and saturation magnetisation techniques. Mechanical alloying was proceeded by deformation of FCC Ni toward FCT phase and BCC to BCT in W, hence formation of supersaturated tetragonal Ni(W) solid solution. Milling of pure W yielded a product comprised of magnetic BCT and non-magnetic nanocrystalline BCC W powders. The magnetic saturation of W increased at the early milling stage and decreased later due to the transition of the BCC W structure toward anisotropic close packed crystal structure and formation of nanograins with high specific surface. Magnetic saturation of W–Ni powders decreased with milling time but increased after forming a metastable tetragonal solid solution.     

Thermochemical compatibility of ytterbia–(hafnia/silica) multilayers for environmental barrier coatings

Environmental barrier coating (EBC) systems consisting of multiple layers tailored to address individual protection needs may offer improved performance relative to conventional architectures. If the requirements of thermochemical and thermomechanical compatibility are met, the deposition of a segmented thermal barrier coating on a dense rare earth silicate EBC could provide additional thermal protection and resistance to attack by molten deposits. The thermochemical compatibility between silicates in the YbO_1.5–SiO₂ system and phases in the YbO_1.5–HfO₂ system was investigated by equilibrating powder compacts of selected ternary compositions; diffusion couples were used to simulate interactions at the layer interfaces in the proposed architectures. The deduced 1500 °C ternary isothermal section reveals that the ordered δ-Yb₄Hf₃O₁₂ and H₃–Yb₆HfO₁₁ phases are only compatible with ytterbium monosilicate (Yb₂SiO₅) EBC. Implementation of these hafnates in contact with ytterbium disilicate (Yb₂Si₂O₇) leads to interfacial reactions that facilitate layer debonding. The results provide criteria to guide the design of future thermal/environmental barrier coating architectures.     

Thermal properties of W–Cu composites manufactured by copper infiltration into tungsten fiber matrix

W–Cu composites were produced by the technique of copper infiltration into tungsten fiber preforms (CITFP) under vacuum circumstance. Fibrous structure preforms with various volume fraction of tungsten fiber were fabricated by the process of mold pressing and sintering. The molten copper was infiltrated into the open pores of the preforms under vacuum at 1473 K to 1573 K for 1 h to produce W–Cu composites with compositions of 10–30 wt.% copper balanced with tungsten. The microstructure, relative densities, and thermal properties of the composites were investigated and measured. The relative as-sintered density was enhanced with the increase of the sintering temperature. The thermal conductivity of the W–Cu30 composite with 28.2 wt.% Cu was 241 W/(m · K) at 298 K, 10% higher than that of the W–Cu alloy with similar copper content produced by conventional powder metallurgy process. The thermal expansion of the composites was decreased with the increase of tungsten content, keeping the same tendency as the prediction by the rule of weighted average of volume ratio of compositions.     

Thermal stability of B2 CuZr phase,microstructural evolution and martensitic transformation in Cu–Zr–Ti alloys

The effects of minor Ti addition on the thermal stability of B2 CuZr phase, the microstructure and the martensitic transformation (MT) in Cu₅₀Zr_50−xTi_x (x = 0, 2.5, 7.5 and 10 at%) alloys were investigated. It was found that the crystallization products, i.e. Cu₁₀Zr₇ and Cu(Ti, Zr)₂, of Cu–Zr–Ti amorphous alloys transform to B2 CuZr phase at high temperatures. The corresponding eutectoid transformation temperature gradually increases with increasing Ti content, implying the decrease of the thermodynamic stability of the B2 CuZr phase. The microstructures of Cu–Zr–Ti martensitic alloys were proven to contain B2 CuZr, CuZr martensite, Cu₁₀Zr₇, Cu(Ti, Zr)₂, and ZrTiCu₂ crystals. Dilatometric measurements reveal that the MT temperature reduces with increasing Ti content, which would be of electronic nature. With increasing thermal cycles, the MT temperature gradually decreases while the reverse MT temperature increases, which results from the enhancement of the dislocation density, the partial decomposition of the equiatomic CuZr crystals and the partially reversible MT.     

Thermal stability,mechanical properties and corrosion behavior of a Mg–Cu–Ag–Gd metallic glass with Nd addition

By the minor addition of Nb to a Mg-Cu-AgGd alloy,a Mg-Cu-Ag-Gd-Nb bulk metallic glass(BMG)with improved thermal stability and corrosion resistance as well as good mechanical properties was developed.Mg_(54)Cu_(26.5)Ag_(8.5)Gd_(11_x)Nb_x(x = 0,1) BMGs with a diameter of 2 mm were fabricated by copper-mold casting.The Mg_(54)Cu_(26.5)Ag_(8.5)Gd_(10)Nb_1 BMG exhibits enlarged supercooled liquid region of 58 K.Electrochemical measurements indicate that the addition of Nb improves the corrosion resistance of the Mg-based BMG in NaCl solution evidenced by the increased corrosion potential,though no significant effect of Nb on the corrosion behavior of the BMG in NaOH solution is observed.The Mg-Cu-Ag-GdNb BMG also shows high compressive strength up to890 MPa and elastic strain of about 1.9%.     

Formation and stability of tungsten boride nanocomposites in WO3–B2O3–Mg ternary system: Mechanochemical effects

Mechanochemical behavior of WO₃–B₂O₃–Mg ternary system to produce tungsten boride-based nanocomposites was investigated in terms of milling duration. To provide essential conditions for the occurrence of a mechanically induced self-sustaining reaction (MSR), a mixture of tungsten trioxide, boron oxide and elemental magnesium with the stoichiometric composition was activated using a high-energy planetary ball mill. Based on the obtained data, the adiabatic temperature was around 3659 K which confirmed that the reaction mode was MSR. Due to the occurrence of a combustion reaction at the beginning of milling, the phase compositions were W, WB, W₂B, and MgO. After 60 min of milling, WB disappeared completely and a ternary nanocomposite with the phase constituents of W₂B, W and MgO was obtained. With increasing the milling time to 1800 min, no phase transformation was observed and thus a nanocomposite powder with similar phase compositions was produced. However, the percentage of the detected phases fluctuated in terms of milling time. During the leaching process, MgO (unwanted phase) was completely removed and consequently a nanocomposite powder with the phase compositions of W₂B and W was formed. From the microscopic observations, the size of the composite particles was varied from 38 to 500 nm.     

Thermal stability,magnetic and mechanical properties of Fe–Dy–B–Nb bulk metallic glasses with high glass-forming ability

The effects of Dy addition on the thermal stability, glass-forming ability (GFA), magnetic and mechanical properties of quaternary (Fe_0.76−xDy_xB_0.24)₉₆Nb₄ (x = 0–0.07) bulk metallic glasses (BMGs) were investigated. Increasing Dy content from x = 0 to 0.05 extended the supercooled liquid region up to 112 K, allowing the fabrication by copper mold casting of BMGs rods with 5.5 mm in diameter. The high GFA was found to be related to the structure of primary crystalline phase. For the x = 0.05 alloy, the competitive formation process of the complex Fe₂₃B₆ and Dy₂Fe₁₄B phases enabled to obtain the largest GFA value. Moreover, the Fe–Dy–B–Nb BMGs exhibited good soft-magnetic properties, i.e., high saturation magnetization of 1.18–0.56 T and low coercive force of 1.9–21.6 A/m. In addition, the glassy alloy rods also showed high compressive fracture strengths of 4400–4150 MPa and high Vickers hardness of 1110–1090 kg/mm².