Obtaining ZrO<Subscript>2</Subscript> + CeO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> + TiO<Subscript>2</Subscript>/Ti compositions by plasma-electrolytic oxidation of titanium and investigating their properties

Regularities of the effect produced by Ce₂(SO₄)₃ salt introduced in an aqueous electrolyte containing Zr(SO₄)₂ on the plasma-electrolytic formation of oxide coatings on titanium, their composition, and structure are studied. ZrO₂ + CeO _x + TiO₂ three-phase oxide coatings with a thickness about 10 μm are obtained. The coatings involve ZrO₂ cubic phase. The ZrO₂-to-TiO₂ phase ratio in the coatings can be controlled. The zirconium content in the coatings reaches 20 at %, while that of cerium is 3–5 at %. The surface layer (∼3-nm thick) contains Ce³⁺ (∼30%) and Ce⁴⁺ (∼70%). Pores in the surface part of coatings have diameters around or smaller than 1 μm and are regularly arranged. The obtained systems have a certain catalytic activity with respect to the oxidation of CO to CO₂ at temperatures above 400–450°C. The coatings are corrosion-resistant in chloride-containing environments. The thickness h of coatings depending on the charge Q supplied to the cell is described by the equation h = h ₀(Q/Q ₀) ⁿ , where n = 0.35 and h ₀ is the thickness of the coating formed at Q ₀ = 1 C/cm².     

Orientation dependence of superelasticity in ferromagnetic single crystals Co<Subscript>49</Subscript>Ni<Subscript>21</Subscript>Ga<Subscript>30</Subscript>

Dependence of the amount of reversible deformation on the orientation of the crystal axis and testing temperature has been studied using [001] and [$ \bar 1 $ \bar 1 24] single crystals of the Co₄₉Ni₂₁Ga₃₀ (at %) alloy upon compression. It has been shown that in the [001] crystals with T ≤ M _s (M _s is the temperature of the onset of the forward martensitic transformation upon cooling) the reversible deformation is equal to 5.5–6.5% and consists of the deformation connected with the shape-memory effect (SME) equal to 4–4.2%, and of “ferroelastic” deformation equal to 1.5–2.2%, which is reversible upon unloading. The total reversible deformation exceeds the lattice deformation ɛ₀ observed upon the B2-L1₀ martensitic transformation, which is equal to 4.5%. At T > A _f (A _f is the finish temperature of the reverse martensitic transformation upon heating), the reversible deformation in [001] crystals is equal to 6.5%. It has been shown electron-microscopically that the reversible deformation equal to 1.5–2.2% in the temperatures range of T = 77−300 K is connected with the development of mechanical twinning in the L1₀ martensite on (110) _L10 planes, which proves to be reversible in the [001] crystals and can be partly irreversible in the [$ \bar 1 $ \bar 1 24] crystals. Upon heating, the (110) _L10 twins of the stabilized L1₀ martensite pass into the ($ \bar 1 $ \bar 1 12) _B2 twins of the B2 phase.     

HVOF thermal spray deposited Y<Subscript>2</Subscript>O<Subscript>3</Subscript>-stabilized ZrO<Subscript>2</Subscript> coatings for thermal barrier applications

High velocity oxy-fuel (HVOF) thermal spray has been successfully used to deposit yttria-stabilized zirconia (YSZ) for thermal barrier coating (TBC) applications. Adherent coatings were obtained within a limited range of spray conditions using hydrogen as fuel gas. Spray parameters such as hydrogen-to-oxygen ratio, spray distance, and substrate cooling were investigated. Spray distance was found to have a pronounced effect on coating quality; adherent coatings were obtained for spray distances between 75 and 125 mm from the gun exit for the hydrogen-to-oxygen ratios explored. Compared to air plasma spray (APS) deposited YSZ coatings, the HVOF deposited coatings were more fully stabilized in the tetragonal phase, and of similar density, surface roughness, and cross-sectional microhardness. Notably, fracture surfaces of the HVOF coatings revealed a more homogeneous structure. Many theoretical models predict that it should not be possible to melt YSZ in an HVOF flame, and therefore it should not be possible to deposit viable YSZ coatings by this process. The experimental results in the present work clearly contradict those expectations. The present results can be explained by taking into account the effect of partial melting and sintering on particle cohesion, as follows. Combustion chamber pressures (P _o) of ∼3.9 bar (58.8 psi) realized during HVOF gun operation allows adiabatic flame temperature values that are above the zirconia melting temperature. Under these conditions, the Ranz-Marshall heat transfer model predicts HVOF sprayed particle surface temperatures T _p that are high enough for partial melting of small (∼10 μm) zirconia particles, T _p=(1.10−0.95)T _m. Further analysis shows that for larger particles (38 μm), adherent coatings are produced when the particle temperature, T _p=0.59−0.60 T _m, suggesting that sintering may have a role in zirconia particle deposition during HVOF spray. These results suggest two different bonding mechanisms for powders having a broad particle size distribution.     

Fabrication and Properties of Plasma-Sprayed Al<Subscript>2</Subscript>O<Subscript>3</Subscript>/ZrO<Subscript>2</Subscript> Composite Coatings

Al₂O₃ /xZrO₂ (where x = 0, 3, 13, and 20 wt.%) composite coatings were deposited onto mild steel substrates by atmospheric plasma spraying of mixed α-Al₂O₃ and nano-sized monoclinic-ZrO₂ powders. Microstructural investigation showed that the coatings comprised well-separated Al₂O₃ and ZrO₂ lamellae, pores, and partially molten particles. The coating comprised mainly of metastable γ-Al₂O₃ and tetragonal-ZrO₂ with trace of original α-Al₂O₃ and monoclinic-ZrO₂ phases. The effect of ZrO₂ addition on the properties of coatings were investigated in terms of microhardness, fracture toughness, and wear behavior. It was found that ZrO₂ improved the fracture toughness, reduced friction coefficient, and wear rate of the coatings.     

Preparation and characterization of nanostructured Bi<Subscript>2</Subscript>Se<Subscript>3</Subscript> and Sn<Subscript>0.5</Subscript>-Bi<Subscript>2</Subscript>Se<Subscript>3</Subscript>

Nanostructured Bi₂Se₃ and Sn_0.5-Bi₂Se₃ were successfully synthesized by hydrothermal coreduction from SnCl₂·H₂O and the oxides of Bi and Se. The products were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and field emission scanning electron microscope (FESEM). Bi₂Se₃ powders obtained at 180°C and 150°C consist of hexagonal flakes of 50–150 nm in side length and nanorods of 30–100 nm in diameter and more than 1 μm in length. The product obtained at 120°C is composed of thin irregular nanosheets with a size of 100–200 nm and several nanometers in thickness. The major phase of Sn_0.5-Bi₂Se₃ synthesized at 180°C is similar to that of Bi₂Se₃. Sn_0.5-Bi₂Se₃ powders are primarily nanorod structures, but small amount of powders demonstrate irregular morphologies.     

RETRACTED ARTICLE: Dislocation-particle interaction in precipitation strengthened Ll<Subscript>2</Subscript>-ordered Ni<Subscript>3</Subscript>Al

Transmission electron microscope investigation has been performed on the particle-dislocation interactions in Ni₃Al-based intermetallics containing various types of fine precipitates. In an Ll₂-ordered Ni₃Al alloy with 4 mol.% of chromium and 0.2–0.5 mol.% of carbon, fine octahedral precipitates of M₂₃C₆ type carbide, which has a cube-cube orientation relationship with the matrix, appear during aging. Typical Orowan loops are formed in Ni₃Al containing fine dispersions of M₂₃C₆ particles. In the alloys with appropriate titanium content, fine precipitates of coherent disordered γ are formed during aging. The γ precipitates are initially spherical or rounded cubic in shape and grow into platelets as aging proceeds. Loss of coherency is initiated by the introduction of dislocations at the γ/γ′ interface and results in step formation at the dislocations. The γ precipitates become globular after the loss of coherency. In the γ′ phase hardened by the precipitation of the disordered γ phase, dislocations are attracted into the disordered γ phase and cut through the particles during deformation at any stage of aging. In Ni₃Al containing a fine dispersion of disordered γ, superdislocations are strongly attracted to the disordered particles and dissociate on the (111) plane in the γ particles, while they dissociate on the (010) plane in the matrix. It is shown by comparison that the strengthening due to attractive interaction is more effective than that due to repulsive interaction. The roles of the variation of the interaction modes and of the dissociation of superdislocations in the matrix and particles are discussed in connection with the optimum microstructures of Ll₂-ordered intermetallics as high temperature structural materials.     

MO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>–ZrO<Subscript>2</Subscript> coatings with M=Al,Mg, Zr,Ti, and Nb on valve metals

Coatings formed on aluminum, titanium, magnesium, zirconium, and niobium by means of plasma-electrolytic oxidation in an aqueous electrolyte containing MgZrF are studied. All elements involved in the composition of the complex compound are present in the coatings. Contents of the elements involved in the inner sphere are the largest. Phase and elementary compositions of the coatings depend on the nature of the valve metal. All coatings contain ZrO₂ in either cubic or monoclinic modifications. The main phase of the coatings formed on magnesium is MgF₂. According to the surface structure, the coatings can be divided into three groups: large-pore (on Mg, Al, and Ti), small-pore (on Nb), and compact with a wavy surface (on Zr).     

Thermodynamic optimization of the Na<Subscript>2</Subscript>O-B<Subscript>2</Subscript>O<Subscript>3</Subscript> pseudo-binary system

The Na₂O-B₂O₃ system is thermodynamically optimized by means of the CALPHAD method. A two-sublattice ionic solution model, (Na⁺¹)_P(O⁻²,BO₃ ⁻³,B₄O₇ ⁻²,B₃O_4.5)_Q, has been used to describe the liquid phase. All the solid phases were treated as stoichiometric compounds. A set of thermodynamic parameters, which can reproduce most experimental data of both phase diagram and thermodynamic properties, was obtained. Comparisons between the calculated results and experimental data are presented.     

Magnetoresistance of the La<Subscript>0.7</Subscript>Ca<Subscript>0.3</Subscript>MnO<Subscript>3</Subscript> single crystal

The dependence of the resistance ρ of the La_0.7Ca_0.3MnO₃ single crystal on the temperature (in a range of 77 < T < 410 K) and magnetic field H is studied. The dependence of the magnetoresistance Δρ/ρ of the ferromagnetic phase on the field is shown to be determined by the competition of two mechanisms. In low magnetic fields, the magnetoresistance is positive Δρ/ρ > 0 and is determined by changes in the resistance with changing magnetization orientation with respect to the crystallographic axes; in high magnetic fields, the magnetoresistance is negative Δρ/ρ < 0, since it is the suppression of spin fluctuations in the magnetic field that plays the principal role. The phase transition from the ferromagnetic to paramagnetic state is a first-order transition close to the second-order one. In the transition range, the magnetoresistance is determined by the resistivity in the zero field ρ(T) and by the shift of the transition temperature T _C(H) in the magnetic field. In the paramagnetic state, the resistivity ρ(T) has an activation character; similarly to the magnetoresistance of other lanthanum manganites, the magnetoresistance of this single crystal is controlled by a change in the activation energy in the magnetic field.     

Cr doping effect in B-site of La<Subscript>0.75</Subscript>Sr<Subscript>0.25</Subscript>MnO<Subscript>3</Subscript> on its phase stability and performance as an SOFC anode

La_0.75Sr_0.25Cr _y Mn_1−y O₃ (LSCM) (y = 0.0–0.6) composite oxides were synthesized by a complexing process of combining ethylene diamine tetraacetic acid (EDTA) and citrate. X-ray diffraction (XRD), temperature-programmed reduction, electrical conductivity, I–V polarization, and impedance spectroscopy were conducted to investigate the Cr doping effect of La_0.75Sr_0.25MnO₃ on its phase stability and electrochemical performance as a solid-oxide fuel cell (SOFC) anode. The chemical and structural stabilities of the oxides increased steadily with increasing Cr doping concentration, while the electrical conductivity decreased on the contrary. At y ≥ 0.4, the basic perovskite structure under the anode operating condition was sustained. a cell with 0.5-mm-thick scandia-stabilized zirconia electrolyte and La_0.75Sr_0.25Cr _y Mn_1−y O₃ anode delivered a power density of ∼15 mW·cm⁻² at 850°C.     

Microstructures of Ti<Subscript>50</Subscript>Al<Subscript>45</Subscript>Mo<Subscript>5</Subscript> alloy powders produced by plasma rotating electrode process

Microstructures of Ti₅₀Al₄₅Mo₅ (at.%) alloy powders produced by the plasma rotating electrode process (PREP) were investigated. The powders have inhomogeneous structures, which consist of dendrites and rounded grains. The dendrites, which show a “rosettelike” morphology, are formed on the powder surface and around the rounded grains. The rosettelike dendrites are of hexagonal α ₂ (D0₁₉) phase even though the dendrites have an equiaxial morphology, and a small amount of β ₂ (B2) phase is also contained inside. It is suggested that the solidification to α (hcp-A3) phase occurred by the peritectic reaction between the primary β (bcc-A2) dendrites and the liquid: L+β→L+β+α. The rounded grains, on the other hand, are of β ₂ phase in which acicular α or α ₂ laths are precipitated with the Burgers orientation relationship. Antiphase domain boundaries in the β ₂ matrix are intersected by α(α ₂) laths. It is interpreted that the α(α ₂) laths were formed by the solid-state transformations: β ₂→β ₂+α→β ₂+α ₂. The formation of the two different microstructures in the powder particles is rationalized in terms of the changes in local composition of the liquid phase during the rapid solidification process.     

Phase and structural transformations in the Ti<Subscript>49.5</Subscript>Ni<Subscript>50.5</Subscript> alloy with a shape-memory effect during torsion under high pressure

Results of investigations of structural and phase transformations that occur in the titanium-nickelide-based alloy Ti_49.5Ni_50.5 with a shape memory effect during severe plastic deformation by torsion under high pressure (HPT) are reported. The studies were performed using transmission and scanning electron microscopy, neutron and X-ray diffraction, and measurements of temperature dependences of electrical resistivity. The martensitic B2 → B19′ transformation was found to be induced in the alloy when applying a high pressure. After unloading, the martensitic B19′ phase is retained in the alloy. The fine structure of the B19′ martensite and its evolution into nanocrystalline and, subsequently, amorphous state during HPT with 1/4, 1/2, 1, 5, and 10 rev have been studied. It was shown that, after HPT, all nanosized crystallites whose sizes are less than 30–50 nm have a B2-type structure and, therefore, the reverse martensitic B19′ → B2 transformation is realized in the alloy at room temperature after unloading.     

Crystallization behaviour and high coercivity of （Nd,Pr）（13）Fe（80）Nb1B6 melt-spun ribbons

Amorphous (Nd,Pr)₁₃Fe₈₀Nb₁B₆ ribbons were crystallized at 670–730°C for 5–25 min to study the effects of isothermal crystallization on their behavior and magnetic properties. XRD results indicate that the isothermal incubation time is 12, 5, and less than 5 min at 670, 700, and 730°C, respectively. High coercivities, with the maximum value of _i H _c = 1616 kA/m at 700°C for 19 min, measured by a physical property measurement system, are obtained in the crystallized ribbons. This is mainly attributed to the addition of Pr and Nb, because Pr₂Fe₁₄B has a higher anisotropic field than Nd₂Fe₁₄B, and Nb enriched in the grain boundary regions can not only reduce the exchange-coupling effects among hard grains, but also impede grain growth during the crystallization process. In addition, it should also be related to the characteristics of the furnace that the authors designed.     

<Superscript>63</Superscript>Cu NMR spectra,magnetic susceptibility,and transmission electron microscopy of the rapidly quenched alloy Ti<Subscript>50</Subscript>Ni<Subscript>25</Subscript>Cu<Subscript>25</Subscript>

Methods of transmission and scanning electron microscopy and nuclear magnetic resonance (NMR) at ⁶³Cu nuclei, as well as measurements of the static magnetic susceptibility χ(T) have been used to study a shape-memory alloy (SMA) Ti₅₀Ni₂₅Cu₂₅, which experiences a thermoelastic martensite transformation. The alloy was obtained from an amorphous ribbon in a bimodal nano- and submicrocrystalline state via a crystallization annealing for 1 h at 770 K with a subsequent quenching to room-temperature water. The resultant B2 austenite is characterized by a fine structure of the ⁶³Cu NMR spectra, which is connected with the different distribution of ⁶³Cu atoms on the second coordination shell. The evolution of the shape of the spectra with decreasing temperature reveals a structural transition B2 → B19. In addition, the ⁶³Cu NMR spectra, just as the transmission electron microscopy, indicate the presence of phase separation in the alloy, with the precipitation of a TiCu (B11) phase. The temperature dependence of the static magnetic susceptibility χ(T) also indicates the occurrence of a structural transition and has a hysteretic nature of “stepped” type. The discovered stepped nature of the χ(T) dependence is explained by the bimodal size distribution of grains of the B2 phase due to the size effect of the martensitic transformation.     

Synthesis and Characterization of New Bismuth Lead Vanadate Pb<Subscript>2</Subscript>BiV<Subscript>3</Subscript>O<Subscript>11</Subscript>

It has been shown that BiVO₄ and Pb₂V₂O₇ react with each other, forming a new compound of the formula Pb₂BiV₃O₁₁ at molar ratio equal to 1:1. This compound has also been obtained from PbO, Bi₂O₃, and V₂O₅, mixed at a molar ratio of 4:1:3. It melts congruently at a temperature of 725 ± 5 °C and crystallizes in the triclinic system with unit-cell parameters: a = 0.710076 nm, b = 1.41975 nm, c = 1.42972 nm, α = 134.552°, β = 97.2875°, γ = 89.6083°, and Z = 4.     

Evaluation of in vitro and in vivo tests for surface-modified titanium by H<Subscript>2</Subscript>SO<Subscript>4</Subscript> and H<Subscript>2</Subscript>O<Subscript>2</Subscript> treatment

Titanium is widely used as an implant material for artificial teeth. Furthermore, various studies have examined surface treatment with respect to the formation of a fine passive film on the surface of commercial titanium and its alloys and to improve the bioactivity with bone. However, there is insufficient data about the biocompatibility of implant materials in the body. The purpose of this study was to examine whether surface modification affects the precipitation of apatite on titanium metal. Specimens were chemically washed for 2 min in a 1∶1∶1.5 (vol.%) mixture of 48 %HF, 60%HNO₃ and distilled water. The specimens were then chemically treated with a solution containing 97%H₂SO₄ and 30%H₂O₂ at the ratio of 1∶1 (vol.%) at 40°C for 1h, and subsequently heat-treated at 400°C for 1h. All the specimens were immersed in HBSS with pH 7.4 at 36.5°C for 15d, and the surface was examined with TF-XRD, SEM, EDX and XPS. In addition, specimens of commercial pure Ti, with and without surface treatment, were implanted in the abdominal connective tissue of mice for 28 d. Conventional aluminum and stainless steel 316L were also implanted for comparison. An amorphous titania gel layer was formed on the titanium surface after the titanium specimen was treated with a solution of H₂SO₄ and H₂O₂. The average roughness was 2.175 μm after chemical surface treatment. The amorphous titania was subsequently transformed into anatase by heat treatment at 400°C for 1h. The average thickness of the fibrous capsule surrounding the specimens implanted in the connective tissue was 47.1μm in the chemically treated Ti, and 52.2, 168.7 and 101.9μm, respectively, in the untreated commercial pure Ti, aluminum and stainless steel 316L.     

Effect of Ga addition on the magnetic properties and microstructure of nanocrystalline Nd_（12.3）Fe_（81.7）B_（6.0） ribbons

Nd 12.3 Fe 81.7 x Ga x B 6.0 (x = 0-1.8) ribbons were prepared by melt spinning at 22 m/s and subsequent annealing treatment. The influences of Ga addition and annealing conditions on the magnetic properties and microstructure of the nanocrystalline alloys were systematically investigated. After being annealed at 620℃ for 20 min, the J r and H ci increased from 0.85 T and 582.6 kA/m for Ga-free sample to 0.97 T and 734.6 kA/m for the x = 0.9 sample, respectively. The (BH) max for the x = 0.9 sample increased by about 40% from 96.3 to 135.5 kJ/m 3 compared with that of the Ga-free one. The significant improvement of magnetic properties originated from the refinement of grains in the samples by introducing Ga, which led to a stronger exchange coupling between the neighboring grains in comparison with that in Ga-free samples. The microstructure and magnetic properties of the samples depended strongly on annealing parameters, while the sensitivity of micro-structure to annealing conditions could be significantly suppressed by the addition of Ga element.     

Optical properties of Fe<Subscript>2</Subscript>NiAl and Fe<Subscript>2</Subscript>MnAl Heusler alloys

Results of the investigation of the optical properties and of the calculations of the electronic structure of Fe₂NiAl and Fe₂MnAl alloys are presented. The main attention is paid to the ellipsometric study of the spectral dependence of the real (ɛ₁) and imaginary (ɛ₂) parts of the dielectric constant in the range of wavelengths λ = 0.3–13 μm. An anomalous behavior of the optical conductivity σ(ω) at IR frequencies has been revealed in Fe₂MnAl, which differs substantially from that in Fe₂NiAl. The results obtained are discussed based on the calculations of the electronic structure of the alloys.     

Control of microwave dielectric properties in 0.42ZnNb<Subscript>2</Subscript>O<Subscript>6</Subscript>−0.58TiO<Subscript>2</Subscript> ceramics by the quantitative analysis of phase transition

Phase constitutions of ZnNb₂O₆−TiO₂ mixture ceramics were significantly changed according to the sintering temperature. Phase transition procedures and their effect on the microwave dielectric properties of 0.42ZnNb₂O₆−0.58TiO₂ were investigated using X-ray powder diffraction and a network analyzer. The fractions of the phases composing the mixture were calculated by measuring integral intensities of each reflection. The structural transitions in 0.42ZnNb₂O₆−0.58TiO₂ were interpreted as the association of two distinct steps: the columbite and rutile to ixiolite transition present at lower temperatures (900–950°C) and the ixiolite to rutile transition at higher temperatures (1150–1300°C). These transitions caused considerable variation of microwave dielectric properties. Importantly, τ_f was modified to around 0 ppm/°C in two sintering conditions (at 925°C for 2 hr and at 1300°C for 2 hr), by the control of phase constitution.