Microstructure and creep properties of a cast intermetallic Ti–46Al–2W–0.5Si alloy for gas turbine applications

The microstructure and creep properties including minimum creep rate, time to 1% creep deformation and creep fracture time of a cast TiAl-based alloy with nominal chemical composition Ti–46Al–2W–0.5Si (at.%) were investigated. The creep specimens were prepared from investment-cast plate and two large turbine blades. Constant load creep tests were performed in air at applied stresses ranging from 150 to 400 MPa in the temperature range 973–1073 K. The microstructure of the specimens is characterised by optical, scanning and transmission electron microscopy before and after creep deformation. The minimum creep rate is found to depend strongly on the applied stress and temperature. The power law stress exponent of minimum creep rate is n = 7.3 and the apparent activation energy for creep is Q_a = 427 ± 14 kJ/mol. The initial microstructure of the creep specimen is unstable. The ₂(Ti₃Al)-phase transforms to γ(TiAl)-phase and needle-like B2-precipitates during long-term creep testing at all testing temperatures. At lower applied stresses, the creep specimens fail by the growth and coalescence of cavities and small cracks formed along the γ/₂ interfaces. At the highest applied stresses, the specimens fail by nucleation and propagation of cracks.     

Influence of Mn doping on microstructure and DC-accelerated aging behaviors of ZnO–V2O5-based varistors

The microstructure, electrical properties, dielectric characteristics, and DC-accelerated aging behavior of the ZnO–V₂O₅–MnO₂ system sintered were investigated for MnO₂ content of 0.0–2.0 mol% by sintering at 900 °C. For all samples, the microstructure of the ZnO–V₂O₅–MnO₂ system consisted of mainly ZnO grain and secondary phase Zn₃(VO₄)₂. The incorporation of MnO₂ to the ZnO–V₂O₅ system was found to restrict the abnormal grain growth of ZnO. The nonlinear properties and stability against DC-accelerated aging stress improved with the increase of MnO₂ content. The ZnO–V₂O₅–MnO₂ system added with MnO₂ content of 2.0 mol% exhibited not only a high nonlinearity, in which the nonlinear coefficient is 27.2 and the leakage current density is 0.17 mA/cm², but also a good stability, in which %ΔE_1 mA = −0.6%, %Δ = −26.1%, and %Δtan δ = +22% for DC-accelerated aging stress of 0.85E_1 mA/85 °C/24 h.     

Characterization of Cat-CVD grown Si–C and Si–C–O dielectric films for ULSI applications

Si–C films with the Si compositions ranging from 40 to 70% have been grown by Cat-CVD using dimethylsilane [DMSi, Si(CH₃)₂H₂] compounds. Tetraethoxysilane [TEOS, Si(OC₂H₅)₄] and dimethyldimethoxysilane [DMDMOS, Si(CH₃)₂(OCH₃)₂] gas source gave us Si–C–O (C-doped SiO_x) films with wide ternary alloy compositions. The dielectric constant of a Si–C film has been evaluated by C–V measurements (at 1 MHz) using Al/Si–C/n-Si(001)/Cu MIS structure. The relative dielectric constant value of a Si–C film was estimated to be 3.0. The resistivity of the Si–C layer with 1 mm diameter and 0.24 μm thickness was estimated to be more than 24.5 Gohm·cm. These results gave us promising characteristics of Si–C and Si–C–O films grown by alkylsilane- and alcoxysilane-based Cat-CVD.     

On orientation relationship of the Ti5Si3 precipitates in a TiAl alloy

The orientation relationship (OR) and interface structure between ζ-Ti₅Si₃ precipitates and γ-TiAl phase in a Ti–Al based alloy composed of γ-TiAl and ₂-Ti₃Al lamellae have been investigated using transmission electron microscopy. Various orientation relationships defined by a pair of parallel directions and planes are discussed with the method of basic vector transformation matrix in the reciprocal space from γ-TiAl to ζ-Ti₅Si₃ precipitate phase and two new kinds of orientation relationships between ζ-Ti₅Si₃ and γ-TiAl phases have been found. Periodical interface fringes at γ-TiAl/ζ-Ti₅Si₃ interface are analyzed according to the Moiré fringes and interface misfit dislocations.     

Thermo-mechanical stability of forged Ti-25Al-11Nb (at.%)

Dynamic material modeling (DMM) has been applied to the analysis of the mechanical behavior of a (Widmanstätten + primary ₂ + β) Ti-25Al-11Nb alloy to establish the flow stress-strain rate-temperature-strain criteria for stable flow.

Unstable and stable flow regimes predicted by DMM were correlated to microstructural observations. Unstable flow zones were related to transformation of orthorhombic O → ₂, kinking of the ₂ lamellae, shear band formation and coarsening of the dynamically recrystallized grain structure; stable flow regimes were shown to be associated with dissolution of the Widmanstätten ₂, coarsening of primary ₂ and dynamic spheroidization of the lamellar ₂ microconstituents.     

Synthesis and sintering of hydroxyapatite–zirconia composites

Hydroxyapatite (HA) has been synthesised in presence of 10–30 wt.% of m-ZrO₂ by solid state reaction between tricalcium phosphate (TCP) and Ca(OH)₂ at 1000 °C for 8 h. The m-ZrO₂ was partly converted into t-ZrO₂ by partial consumption of CaO which in turn resulted in a mixture of β-TCP and HA. On sintering these HA–β-TCP–ZrO₂ composite powders at 1100–1400 °C for 2 h, the HA is further decomposed into β-TCP and CaO. The CaO so produced reacts further with m-ZrO₂/t-ZrO₂ generating a mixture of t-ZrO₂ and CaZrO₃ in different proportions. These various phases formed interfere with the sinterability of the composites due to their differential shrinkages leading to a overall reduced density as compared to that of pure HA. The composites show a T-onset of decomposition at around 1150 °C and a 40% HA yield was obtained at the highest sintering temperature of 1400 °C. The products were subjected to XRD for phase analysis and the microstructural features were studied by SEM.     

Catalytic CVD growth of Si–C and Si–C–O alloy films by using alkylsilane and related compounds

Cat-CVD method has been applied to the growth of Si–C and Si–C–O alloy thin films. Growth mechanism has been studied with emphasis on the effects of filament materials. Growth rates and alloy compositions were measured for W, Ta, Mo and Pt filaments at the filament temperatures ranging from 1300 to 2000 °C. Si_1−xC_x films with x ranging from 0.38 to 0.7 could be grown by using single molecule source Si(CH₃)₂H₂ (dimethylsilane). Si–C–O ternary alloy films was successfully prepared by using Si(OC₂H₅)₄ (tetraethoxysilane) and Si(CH₃)₂(OCH₃)₂ (dimethyldimethoxysilane) molecules.     

Corrosion of magnesia–chrome brick in molten MgO–Al2O3–SiO2–CaO–FetO slag

The corrosion of magnesia–chrome (MgO–Cr₂O₃) brick in molten MgO–Al₂O₃–SiO₂–CaO–Fe_tO slag has been characterized using a dynamic rotary slag corrosion testing for various test cycles at 1650 °C. The open porosity decreases from 15.3 to 4.0% for three cycles, then it gradually increases from 4.0 to 4.8% when the test is extended to nine cycles, in which the permeating depth of the slag maintains at about 20 mm. The XRD pattern of the permeated layer shows the presence of the MgO, MgCr₂O₄ and CaMgSiO₄ phases. In the interior of the permeating layer cracks are formed and corrosion starts at the pores and cracks of MgO and decreases gradually. However, at 20–40 mm beneath the permeated layer edge, different shapes of MgO particles are found.     

Effect of Al2O3 particles on mechanical properties of directionally solidified intermetallic Ti–46Al–2W–0.5Si alloy

The effect of Al₂O₃ particles on microhardness and room-temperature compression properties of directionally solidified (DS) intermetallic Ti–46Al–2W–0.5Si (at.%) alloy was studied. The ingots with various volume fractions of Al₂O₃ particles and mean ₂–₂ interlamellar spacings were prepared by directional solidification at constant growth rates ranging from 2.78×10⁻⁶ to 1.18×10⁻⁴ ms⁻¹ in alumina moulds. The ingots with constant volume fraction of Al₂O₃ particles and various mean interlamellar spacings were prepared by directional solidification at a growth rate of 1.18×10⁻⁴ ms⁻¹ and subsequent solution annealing followed by cooling at constant rates varying between 0.078 and 1.889 K s⁻¹. The mean ₂–₂ interlamellar spacing λ for both DS and heat-treated (HT) ingots decreased with increasing cooling rate according to the relationship λ∝ ^−0.46. In DS ingots, microhardness, ultimate compression strength, yield strength and plastic deformation to fracture increased with increasing cooling rate. In HT ingots, microhardness and yield strength increased and ultimate compression strength and plastic deformation to fracture decreased with increasing cooling rate. The yield stress increased with decreasing interlamellar spacing and increasing volume fraction of Al₂O₃ particles. A linear relationship between the Vickers microhardness and yield stress was found for both DS and HT ingots. A simple model including the effect of interlamellar spacing and increasing volume fraction of Al₂O₃ particles was proposed for the prediction of the yield stress.     

Formation of nanocrystalline structure of Ti–6Al–4V alloy by cyclic hydrogenation–dehydrogenation treatment

Ti–6Al–4V (Ti64) sheet specimens were cathodically hydrogenated in sulfuric acid solution at ambient conditions. The hydrogenated specimens were then sent to go through the designed thermohydrogen processing (THP) twice to obtain a nano-sized grain structure. The average grain size of resulted microstructure was found to be 10–20 nm obtained by TEM. Qualitative and quantitative analyses performed by employing X-ray diffractometry (XRD) and elemental analysis (EA) showed that the addition of As₂O₃ as hydrogenation promoter in electrolyte significantly increased the hydrogen uptake. The high concentration of hydrogen arising from promoter action is the key factor in grain refinement. The optimal processing parameter found for grain-refining Ti64 was: (1) electrolytic hydrogenation at 100 mA cm⁻² for 3 h in 1 N H₂SO_4(aq) by adding 0.1 g L⁻¹ As₂O₃; (2) β transformation carried out at 850 °C for 1 h in air furnace, followed by a furnace cooling to 590 °C and held for 6 h; (3) oxide film removed and then dehydrogenated at 650 °C and 1.0 × 10⁻⁶ Torr for 10 h; (4) repeated the same processes once more.     

Thaumasite––direct, woodfordite and other possible formation routes

Two main formation routes for thaumasite exist below 15 °C. One is the direct route from C–S–H reacting with appropriate carbonate, sulfate, Ca²⁺ ions and excess water. The other route is the woodfordite route from ettringite reacting with C–S–H, carbonate, Ca²⁺ ions and excess water, in which thaumasite arises through the intermediate formation of the solid solution woodfordite. The woodfordite route for thaumasite formation appears to be relatively quicker (although still slow) than the direct route, presumably because with the former the ettringite already has the octahedral [M(OH)₆] units that can facilitate the critical change from [Al(OH)₆]³⁻ to [Si(OH)₆]²⁻ groupings. Both routes are mutually dependent on each other. The presence of magnesium salts can modify the path to thaumasite formation. High pressure might be able to stabilise [Si(OH)₆]²⁻ groupings and allow thaumasite to become formed above 15 °C. This possibility is discussed.     

Effect of prior cold work on age hardening of Cu–3Ti–1Cr alloy

The influence of 50%, 75% and 90% cold work on the age hardening behavior of Cu–3Ti–1Cr alloy has been investigated by hardness and tensile tests, and light optical and transmission electron microscopy. Hardness increased from 118 Hv in the solution-treated condition to 373 Hv after 90% cold work and peak aging. Cold deformation reduced the peak aging time and temperature of the alloy. The yield strength and ultimate tensile strength reached a maximum of 1090 and 1110 MPa, respectively, following 90% deformation and peak aging. The microstructure of the deformed alloy exhibited elongated grains and deformation twins. The maximum strength on peak aging was obtained due to precipitation of the ordered, metastable and coherent β′-Cu₄Ti phase, in addition to high dislocation density and deformation twins. Over-aging resulted in decreases in hardness and strength due to the formation of incoherent and equilibrium β-Cu₃Ti phase in the form of a cellular structure. However, the morphology of the discontinuous precipitation changed to a globular form on high deformation. The mechanical properties of Cu–3Ti–1Cr alloy are superior to those of Cu–2.7Ti, Cu–3Ti–1Cd and the commercial Cu–0.5Be–2.5Co alloys in the cold-worked and peak-aged condition.     

Effect of ferroic domain pattern changes on the Raman spectra of some ferroic crystals

The influence of changes in the pattern of ferroic domain structure on the Raman spectra of β-LiNH₄SO₄ and (NH₄)₃H(SO₄)₂ single crystals were studied. It was shown that the Raman spectra of β-LiNH₄SO₄ passed from the ferroelastic phase differ from those of “as-grown” crystal and those of the crystal, which was in the paraelectric phase. Significant changes could be observed in the Raman bands related to triply degenerated ν₃ and ν₄ vibrations of the SO₄ tetrahedron. Detailed temperature studies of the Raman spectra of β-LiNH₄SO₄ close to the paraelectric–ferroelectric phase transition, exhibit anomaly of some internal vibrations of SO₄ in the temperature range where a regular large-scale structure is observed. Different types of evolution of the ferroelastic domain structure and temperature behaviour of the donor and acceptor vibrations were shown while heating and cooling the (NH₄)₃H(SO₄)₂ crystal. Different values of temperature hysteresis were found in temperature studies of the ferroelastic domain structure (ΔT_S  3–5 K) and in Raman spectra studies (ΔT_S  12 K). No changes were observed in the pattern of ferroelastic domain structure at the temperature T_II–III  265 K, at which C2/c → P2/n structural phase transition takes place. On the other hand, at T_III–IV  135 K additional domains with W′-type of domain wall orientation were found.     

Solid-Phase Syntheses of Two Deacetyl-Thymosin β4 Analogues with Substitution at Position 12 and Their Effects on Impaired Blastogenic Response of T Lymphocytes of Uremic Patients

Two deacetyl-thymosin β₄ analogues containing Phe(4Br) or D-Phe(4Br) as position 12 were synthesized by the manual solid-phase method, and their immunological effects on the impaired blastogenic response of phytohemagglutinin-stimulated T lymphocytes of uremic patients with infectious diseases were studied. Bromination of the p-position of Phe¹² resulted in a marked restorative effect on the impaired blastogenic response of T lympocytes compared with that of our synthetic deacetyl-thymosin β₄ The synthetic [Phe(4Br)¹²]deacetyl-thymsin β₄ was approximately equal in potency to our synthetic [Phe(4F)¹²]deacetyl-thymosin β₄ in uremic patients, but the other analogue, [D-Phe(4Br)¹²]deacetyl-thymosin β₄, had no effect.     

Controllable formation of Er–Yb codoped Al2O3 films by the non-aqueous sol–gel method

1 mol%Er³⁺–10 mol%Yb³⁺ codoped Al₂O₃ thin films have been prepared on thermally oxidized SiO₂/Si(110) substrates by a dip-coating process in the non-aqueous sol–gel method from the hydrolysis of aluminum isopropoxide [Al(OC₃H₇)₃] under isopropanol environment. Addition of N,N-dimethylformamide (DMF) as a drying control chemical additive (DCCA) into the sol suppresses formation of the cracks in the Er³⁺–Yb³⁺ codoped Al₂O₃ thin films when the rare-earth ion is doped with a high doping concentration. Homogeneous, smooth and crack-free Er³⁺–Yb³⁺ codoped Al₂O₃ thin films form at the conditions by a molar ratio of 1:1 for DMF:Al(OC₃H₇)₃. A strong photoluminescence spectrum with a broadband extending from 1.400 to 1.700 µm centered at 1.533 µm is obtained for the Er³⁺–Yb³⁺ codoped Al₂O₃ thin films, which is unrelated to the addition of DMF. Controllable formation of the Er³⁺–Yb³⁺ codoped Al₂O₃ thin films may be explained by the fact that the DMF assisted the deprotonation process of Al–OH at the surfaces of gel particles, resulting in enhancement of the degree of polymerization of sols and improvement of the mechanical properties of gel thin films.     

Influence of Si content on microstructure of TiAl alloys

A systematic study of four ternary TiAl-based alloys with constant Ti content of 52.2at.% and variable Si content ranging from 0.3 to 2.7at.% (Al in balance) was conducted. The alloys were prepared from elemental powders via a route including powder mixing, precompaction, cold extrusion, and reactive hot-isostatic pressing. All investigated alloys contain the intermetallic compounds γ-TiAl, ₂-Ti₃Al, and ζ-Ti₅(Si,Al)₃. The microstructure can be described as a duplex structure (i.e., lamella γ/₂ regions distributed in a γ matrix) containing ζ precipitates. With increasing Si content, the number of primary ζ precipitates increased and the γ grain size became finer while the lamellar volume fraction decreased slightly.     

Processing, microstructure and properties of C40 Mo(Si,Al)2/Al2O3 composites

The C40 Mo(Si_0.75Al_0.25)₂/Al₂O₃ composites were prepared by spark plasma sintering (SPS) of mechanically alloyed (MA) powders. The Mo(Si_0.75Al_0.25)₂/0–20 vol.% Al₂O₃ materials, showing micron and submicron composite structure, possess a hardness of 13.9–14.6 GPa but a poor toughness of 1.78–1.80 MPa m^1/2. The addition of 30 vol.% Al₂O₃ leads to the formation of the micron C40 Mo(Si_0.75Al_0.25)₂/Al₂O₃ composite with an intergranular distribution of Al₂O₃, that results in a drop of the hardness to 10.2 GPa and an improvement of the toughness to 3.67 MPa m^1/2. The transition of the cleavage facets to the intergranular fracture with the addition of Al₂O₃ is assumed as the main toughening mechanism.     

Structural and optical properties of (100 − x)(Li2B4O7) − x(SrO–Bi2O3–0.7Nb2O5–0.3V2O5) glasses and glass nanocrystal composites

Glasses of various compositions in the system (100 − x)(Li₂B₄O₇) − x(SrO–Bi₂O₃–0.7Nb₂O₅–0.3V₂O₅) (10  x  60, in molar ratio) were prepared by splat quenching technique. The glassy nature of the as-quenched samples was established by differential thermal analyses (DTA). The amorphous nature of the as-quenched glasses and crystallinity of glass nanocrystal composites were confirmed by X-ray powder diffraction studies. Glass composites comprising strontium bismuth niobate doped with vanadium (SrBi₂(Nb_0.7V_0.3)₂O_9−δ (SBVN)) nanocrystallites were obtained by controlled heat-treatment of the as-quenched glasses at 783 K for 6 h. High resolution transmission electron microscopy (HRTEM) of the glass nanocrystal composites (heat-treated at 783 K/6 h) confirm the presence of rod shaped crystallites of SBVN embedded in Li₂B₄O₇ glass matrix. The optical transmission spectra of these glasses and glass nanocrystal composites of various compositions were recorded in the wavelength range 190–900 nm. Various optical parameters such as optical band gap (E_opt), Urbach energy (ΔE), refractive index (n), optical dielectric constant and ratio of carrier concentration to the effective mass (N/m^*) were determined. The effects of composition of the glasses and glass nanocrystal composites on these parameters were studied.     

Fracture-resistant ultralloys for space-power applications: Normal-spectral-emissivity and electron-emission studies of tungsten, rhenium, hafnium-carbide alloys at elevated temperatures

A series in this journal on high-temperature properties of “fracture-resistant ultralloys for space-power systems” preceded the present paper: the antecedent publications covered tungsten(W), rhenium(Re) alloys with and without thoria(ThO₂) (W, 23Re; W, 27Re; W, 30Re and W, 30Re, 1ThO₂). This paper reports radiative and thermionic effects of hafnium carbide(HfC) and Re variation in W alloys: normal spectral emissivity(ε_λ) is used in pyrometry to determine the true temperature of a surface. Effective work function (φ_e) is an important consideration in the selection of the electrode materials for high-temperature thermionic energy converters in space-power applications. The _0.535μ, ε_0.65μ and φ_e trends of W, Re, 0.35HfC with 5–20% Re were measured in the range of 1700–2500K. The results indicate that ε_λ decreases with increasing temperatures and Re contents. The presence of HfC produced higher ε_λ values than those of sintered materials with comparable W,Re alloy contents. The results also indicate that φ_e increases with rhenium contents. This can be explained as growth of the potential barrier at the metal, vacuum boundary associated with a volume effect—the decrease in the lattice constant of W.     

Characterization of fluorine-doped silicon dioxide film by Raman spectroscopy

We have measured Raman spectra of fluorine-doped SiO₂ (SiOF) films and quartz glass. From a comparison between Raman spectra of the SiO₂ film and quartz glass, it has been found that the SiO₂ film is under compressive stress and that it has more threefold ring defects than quartz glass. Raman bands from threefold and fourfold ring defects in SiOF films become week as the fluorine/oxygen (F/O) ratio increases and as the stress decreases. The decrease of intensities of these Raman bands shows that ring defects in SiOF films decrease as the F/O ratio increases and as the stress decreases. The triply degenerated ω₄ mode at 460 cm⁻¹ becomes sharp as the F/O ratio increases and as the stress decreases. Furthermore, the peak-frequency of ω₁ mode around 820 cm⁻¹ decreases with a decrease of stresses whereas that of ω₃ mode around 1065 cm⁻¹ increases. These results can be well understood in terms of a decrease of O-Si-O bonding angle caused by relaxation of stresses.