Influence of liquid nitrogen quenching on the evolution of metastable phases during plasma spraying of (ZrO2–5 wt.% Y2O3)–20 wt.% Al2O3 coatings

The preparation of nanostructured (ZrO₂–5 wt.% Y₂O₃)–20 wt.% Al₂O₃ coatings by atmospheric plasma spraying of commercially available micron-scale powders is reported. Materials were prepared by means of a standard spraying technique and by using an improved technique that allows for the quenching of the material using liquid nitrogen-cooled substrates. Quenching leads to the controlled formation of metastable phases. The influence of liquid nitrogen cooling on the formation of the metastable phases was studied by X-ray diffraction under a grazing incidence angle of 1°. A significant increase in the amount of the metastable zirconia phase and a more homogeneous composition along the thickness were found compared to the regularly sprayed coatings. All materials were subjected to a thermal treatment for 1 h at 1400 °C to study the evolution of stable phases.     

Crystal structure and microwave dielectric properties of ZnTi(Nb1−xTax)2O8 ceramics

The crystal structure and microwave dielectric properties of ZnTi(Nb_1−xTa_x)₂O₈ (0 ≤ x ≤ 1) ceramics sintered at 1200 °C for 2 h were investigated. For x < 0.5, solid solution phases with the α-PbO₂ structure, typical of ZnTiNb₂O₈, were obtained, whereas for 0.5 ≤ x < 1, mixtures of two solid solutions each respectively based on the α-PbO₂ structure and a trirutile structure, were obtained. The relative amount of the trirutile-structured phases increased as the Ta content increased in a given region, and the end member ZnTiTa₂O₈ formed a single phase with the trirutile structure. The microwave dielectric properties were closely related to the crystal structures. A material with a near zero temperature coefficient of resonant frequency could be obtained for x = 0.8, and its dielectric constant and quality factor (Q × f) were 40.5 and 41,000 GHz, respectively.     

The corrosion of two NiNb alloys under 1 atm O2 at 600–800 °C

The oxidation of two NiNb alloys containing 15 and 30 wt% Nb has been studied at 600–800 °C in pure oxygen under 1 atm O₂ at 600–800 °C. The scales formed on both alloys under all conditions show an external scale, generally duplex, containing an outermost layer of nearly pure NiO and an innermost region of NiO mixed with the double NiNb oxide NiNb₂O₆. Moreover, the samples corroded at all temperatures also show a region of internal oxidation composed of a mixture of alpha nickel and niobium oxides (Nb₂O₅ or/and NbO₂), which formed from both alloy phases Ni₈Nb and Ni₃Nb. No important depletion of niobium was observed in the alloy close to the interface with the zone of internal oxidation, while the depth of this region is generally much higher than measured for the corrosion of the same alloys under low oxygen pressures at the same temperatures. The corrosion mechanism of these alloys is examined with special reference to the effects of the low solubility of niobium in nickel.     

Phase formation in rapidly solidified R2T17 intermetallics

Rapid solidification was utilized to produce a series of light and heavy rare earth-transition metal intermetallics in the R_H–Co, R_L–Co/Fe, and Sm–Co(Fe) systems with R_H = Dy and Tb and R_L = Pr and Sm. The influence of Nb–C and Zr–C additions on phase formation in the binary and ternary alloys has also been investigated. The X-ray diffraction patterns obtained with synchrotron radiation were refined by the Rietveld method for structural phase determination and analysis. It was found that the ability to create disorder strongly depended on the rare earth element, with light rare earth systems possessing more disorder, and rapid solidification effectively suppressed the development of long-range order in these compounds. Cobalt in contrast to iron favored the formation of disordered structures. Replacement up to two out of the three of the cobalt atoms with iron in the Sm–Co–Fe system has retained the establishment of the disordered TbCu₇-variant and exhibited complete cobalt–iron solubility. Additions of Nb–C and Zr–C have also greatly influenced the order formation. The comparison of lattice parameters of the intermetallic compounds obtained by rapid solidification to the parameters of equilibrium 2–17 phases summarized in the literature revealed that formation of partially ordered and disordered structures was associated with expansion of the both a- and c-axes in Th₂Zn₁₇- and Th₂Ni₁₇-type phases for all binary compounds.     

Formation and properties of BaxFe3−xO4 with spinel structure by mechanochemical reaction of α-Fe2O3 and BaCO3

Magnetic Ba_xFe_3−xO₄ (x  0.23) with spinel structure was fabricated by ball milling of mixture of BaCO₃ and nonmagnetic α-Fe₂O₃ powders, and the molar ratio of BaCO₃ and α-Fe₂O₃ is 1:6. In the milling process, a mechanochemical reaction took place between BaCO₃ and α-Fe₂O₃, and Ba cation incorporated into α-Fe₂O₃ with rhombohedral structure to form a α-(Fe,Ba)₂O₃ solid solution. The Ba content in the α-(Fe,Ba)₂O₃ increased with increasing milling time, when the Ba content exceeded a limited solubility, the α-(Fe,Ba)₂O₃ transformed into a phase of Ba_xFe_3−xO₄ with spinel structure, where the Ba cation occupied an octahedral site or tetrahedral site. The product obtained in the balling process was different from that prepared in the annealing process at atmospheric pressure, which was BaFe₂O₄ with orthorhombic structure. Accompanying the crystal structure transition from α-(Fe,Ba)₂O₃ to Ba_xFe_3−xO₄, the magnetic properties also changed from nonmagnetism into ferromagnetism. The saturation magnetization was 53.3 emu/g and coercivity was 113.7 Oe. The mechanism of transitions of the crystal structure was discussed in the present work.     

Electrochemical performances of Ag–(Bi2O3)0.75(Y2O3)0.25 composite cathodes

The electrochemical performances of Ag–Y_0.25Bi_0.75O_1.5 (YSB) composite cathodes on Ce_0.8Sm_0.2O_1.9 (SDC) electrolytes have been investigated at intermediate temperature using AC impedance spectroscopy. The results indicated that the electrochemical performances of these composites are quite sensitive to the compositions and the microstructures of the cathode. The optimum YSB addition to Ag resulted in 10 times lower area specific resistance. The ASR of Ag-50 vol.% YSB was about 0.12 Ωcm² at 700 °C as compared to 3.9 Ωcm² for Ag cathodes. The observed high performance of Ag–YSB composite cathodes might be due to the high oxygen-ion conductivity of YSB and its high catalytic activity for oxygen reduction.     

Critical evaluation and optimization of the thermodynamic properties and phase diagrams of the CrO-Cr2O3, CrO-Cr2O3-Al2O3, and CrO-Cr2O3-CaO systems

Available thermodynamic and phase diagram data have been critically assessed for all phases in the CrO-Cr₂O₃, CrO-Cr₂O₂-Al₂O₃, and CrO-Cr₂O₂-CaO systems from 298 K to above the liquidus temperatures and for oxygen partial pressures ranging from equilibrium with metallic Cr to equilibrium with air in the case of the first two systems and toP _{O 2} = 10⁻³ atm for the CrO-Cr₂O₃-CaO system. All reliable data have been simultaneously optimized to obtain one set of model equations for the Gibbs energy of the liquid slag and all solid phases as functions of composition and temperature. The modified quasichemical model was used for the slag. The models permit phase equilibria to be calculated for regions of composition, temperature, and oxygen potential where data are not available.     

Critical evaluation and optimization of the thermodynamic properties and phase diagrams of the CrO-Cr2O3-SiO2 and CrO-Cr2O3-SiO2-Al2O3 systems

Available thermodynamic and phase diagram data have been critically assessed for all phases in the CrO-Cr₂O₃-SiO₂ and CrO-Cr₂O₃-SiO₂-Al₂O₃ systems from 298 K to above the liquidus temperatures and for oxygen partial pressures ranging from equilibrium with metallic Cr to equilibrium with air. All reliable data have been simultaneously optimized to obtain one set of model equations for the Gibbs energy of the liquid slag and all solid phases as functions of composition and temperature. The modified quasi-chemical model was used for the slag. The models permit phase equilibria to be calculated for regions of composition, temperature, and oxygen potential where data are not available.     

Preparation of nanometric CeO2–ZrO2–Nd2O3 solid solution and its catalytic performances

A kind of nanometric CeO₂–ZrO₂–Nd₂O₃ (CZN) solid solution for a carrier in the automotive three-way catalysts was synthesized by a coprecipitation method and characterized by means of X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), nitrogen adsorption–desorption (BET), scanning electron microscopy (SEM) and oxygen storage capacity (OSC). For the purpose of comparison, an unincorporated CeO₂–ZrO₂ (CZ) was also synthesized. The XRD measurements disclose the prepared CeO₂–ZrO₂–Nd₂O₃ have a face-centered cubic fluorite structure and nanoparticle sizes. According to the results of XPS, Nd³⁺ ions can enter the CZ lattice and form a homogenous solid solution. Oxygen storage capacity measurements reveal that CeO₂–ZrO₂–Nd₂O₃ display high oxygen mobility at a low temperature. The results of the activity tests show that the catalyst exhibits good three-way catalytic activity and fairly wide range of air-to-fuel ratios.     

Synthesis and characterization of Al2O3-Ce0.5Zr0.5O2 powders prepared by chemical coprecipitation method

Al₂O₃-Ce_0.5Zr_0.5O₂ catalytic powders were synthesized by the coprecipitation (ACZ-C) and mechanical mixing (ACZ-M) methods, respectively. As-synthesized powders were characterized by XRD, Raman spectroscopy, surface area and thermogravimetric analyses. It was found that the mixing extent of Al³⁺ ions affected the phase development, texture and oxygen storage capacity (OSC) of the Ce_0.5Zr_0.5O₂ powder. Single phase of ACZ-C could be maintained without phase separation and inhibit α-Al₂O₃ formation up to 1200 °C. The specific surface area value of ACZ-C (81.5 m²/g) was larger than that of ACZ-M (62.1 m²/g) and Ce_0.5Zr_0.5O₂ (17.1 m²/g) powders, which were calcined at 1000 °C. In comparison with ACZ-C and Al₂O₃, which were calcined at high temperature (900–1200 °C), it was found that the degradation rate of specific surface area of ACZ-C was lower than that of Al₂O₃. ACZ-C sample showed a higher thermal stability to resist phase separation and crystallite growth, which enhanced the oxygen storage capacity property for Ce_0.5Zr_0.5O₂ powders.     

Preparation and thermal conductivities of Gd2Ce2O7 and (Gd0.9Ca0.1)2Ce2O6.9 ceramics for thermal barrier coatings

Two kinds of rare earth cerium oxides Gd₂Ce₂O₇ and (Gd_0.9Ca_0.1)₂Ce₂O_6.9 were prepared by solid state reaction method at 1600 °C for 10 h. The phase compositions, microstructures, and their thermal conductivities of these materials were investigated. XRD results revealed that single phase Gd₂Ce₂O₇ and (Gd_0.9Ca_0.1)₂Ce₂O_6.9 with fluorite structure were synthesized. Results of SEM and EDS showed that the microstructures of these materials were dense and no other phases existed among grains. Because of phonon scattering resulted by the oxygen vacancies and difference in atomic mass between substitutional atoms and host atoms, thermal conductivities of Gd₂Ce₂O₇ and (Gd_0.9Ca_0.1)₂Ce₂O_6.9 are lower than that of 8YSZ at 800 °C, and thermal conductivity of (Gd_0.9Ca_0.1)₂Ce₂O_6.9 is lower than that of Gd₂Ce₂O₇. These results imply the Gd₂Ce₂O₇ and (Gd_0.9Ca_0.1)₂Ce₂O_6.9 can be used as novel candidate materials for thermal barrier coatings in the future.     

In situ formation of La containing dispersed phase on the sinter skin of La2O3 and Cr3C2 unitedly doped WC–Co cemented carbide

The as-sintered sinter skin of WC–11 wt% Co–0.71 wt% Cr₃C₂–0.06 wt% La₂O₃ cemented carbide was observed and analyzed by scanning electron microscopy, energy dispersive X-ray spectroscopy and X-ray diffraction. It was unexpectedly discovered that lanthanum which was added in the form of oxide could migrate directionally from the alloy to the sinter skin during the sintering process. As a result, La₂O₂S and LaCoO₃ phases were formed in situ on the sinter skin. It is significant that both phases are characterized with layered-structure related self-lubricating function and high melting point. Noteworthily, La₂O₂S grains preferentially grew up along a group of parallel faces with orientation index [0 0 1] in the WC + β matrix. It was revealed that the alloy had a diffusion-resulted dual structure (i.e., core and skin structure), i.e., WC + β + η three-phase structure in the inner part and WC + β + La₂O₂S + LaCoO₃ four-phase structure on the sinter skin. Cr₃C₂ with carbon-donation ability and the impurity elements from the sintering atmosphere with much bigger electronegative parameters than lanthanum are thought to be the driving force behind the directional migration.     

CVD deposition and characterization of coloured Al2O3/ZrO2 multilayers

Coloured Al₂O₃/ZrO₂ multilayers have been deposited onto WC-Co based inserts by a CVD process. Through physical as well as optical analysis of such multilayers, colour is believed to originate from interference. The coatings are obtained with good process reproducibility. It was found that the ZrO₂ process used in the multilayer, with ZrCl₄ as the only metal chloride precursor, results in a mixture of tetragonal and monoclinic ZrO₂ phases. However by adding a relatively small amount of AlCl₃ during such a process results in ZrO₂ layers being composed of predominantly tetragonal ZrO₂ phase. Corresponding multilayers seem to have a more fine grained and smoother morphology whereas multilayers containing monoclinic ZrO₂ phase seem to be less perfect with existence of larger grains of ZrO₂ which are believed to scatter light and alter the reflectance of such a multilayer. In addition to this, such multilayers were found to be free of or with greatly reduced amount of thermal cracks, normally present in pure CVD grown Al₂O₃ layers.It is believed that, in the studied Al₂O₃/ZrO₂ multilayers, the observed tetragonal ZrO₂ phase is the result of a size effect, where small enough ZrO₂ crystallites energetically favor the tetragonal phase. However as the ZrO₂ crystallite size distribution is shifted to larger sizes it is believed that a mixture of crystallites with both stable and metastable tetragonal phases as well as a stable monoclinic phase is obtained. The proposed metastable tetragonal ZrO₂ phase may in fact explain the absence of thermal cracks in such multilayers through a transformation toughening mechanism, well known in ZrO₂ based ceramics.     

Nanocarbon-dependent synthesis of ZrB2 in a binary ZrO2 and boron system

Thermodynamically, ZrO₂ may react with boron to form B₂O₃/B₂O₂ and ZrB₂ at room temperature. However, this reaction is incomplete at temperatures lower than 1550 °C, even with the use of metastable reactants, i.e., as-synthesized amorphous hydrous nano-ZrO₂ and amorphous boron powders. In this study, a complete disintegration of ZrO₂ was achieved by introducing nanocarbon to the binary system of ZrO₂ and boron at 1550 °C. The metastable reactants affected the temperature required for the solid-state reactions and also strongly affected the kinetics of the transformation. Single crystal and plate-like ZrB₂ particles with a uniform distribution and a size of ca. 1.0 μm in two-dimensions were obtained using 5 wt.% nanocarbon and a B/Zr molar ratio of 4.     

On the properties of the eutectic alloy Al3(Nb,Cr) + Cr(Al,Nb)

The eutectic alloy Al₃(Nb,Cr) + Cr(Al,Nb) forms an in situ composite and the Al₃Nb presents high specific strength and low oxidation rate that may be improved by the combination with other phases. The purpose of this work is to investigate physical, mechanical and oxidation properties of the eutectic alloy. Therefore, Rietveld analysis was carried out for furnace cooled and water quenched samples and oxidation tests were performed on directional solidified samples. Compressive tests were performed for the eutectic alloy and also for the Nb–74.8% Cr–24.6% Al alloy in the as-cast condition. The alloy presents 12.9% Cr(Al,Nb) at room temperature, retained from the transformation Cr(Al,Nb) to Al(Nb)Cr₂. The combination of Al₃Nb with Cr(Al,Nb) and Al(Nb)Cr₂ considerably improves mechanical behaviour, leading the yield strength to 1525 MPa at 800 °C and 925 MPa at 900 °C. The oxidation tests showed the formation of several oxides at all temperatures studied and that from 900 °C on alfa Al₂O₃ is formed both in air and O₂ except under O₂ at 1000 °C. It is believed that the Cr(Al,Nb) phase acts as an Al reservoir for the formation of the various Al₂O₃ scales.     

Crystallization kinetics of new compound of V2O5–PbO–Li2O–Fe2O3 glass using differential thermal analysis

Different glasses with nominal compositions of (70 − x)V₂O₅–xPbO–20Li₂O–10Fe₂O₃ (0 ≤ x ≤ 12.5 mol.%) were successfully obtained by the melt quenching technique. Crystallization kinetics of these glasses was studied under non-isothermal conditions using the formal theory of transformations for heterogeneous nucleation. The procedure was applied to the experimental data obtained by differential thermal analysis, using several measurements at different heating rates. In addition, from the heating rate dependence of the glass transition temperature, the glass transition activation energy was derived. The crystallization results are analyzed and both the activation energy of crystallization process and the crystallization mechanism are characterized in terms of Gao–Wang method. The phases at which the glass crystallizes after the thermal process have been identified by X-ray diffraction. The diffractogram of the transformed material indicates the presence of microcrystallites of LiV₁₅O_35.5, Pb₃(VO₄)₂ and PbO₂ beside the remaining an additional amorphous matrix.     

DO22–(Cu,Ni)3Sn intermetallic compound nanolayer formed in Cu/Sn-nanolayer/Ni structures

The present work conducts crystal characterization by High Resolution Transmission Electron Microscopy (HRTEM) on Cu/Sn-nanolayer/Ni sandwich structures associated with the use of Energy Dispersive X-ray (EDX) analysis. The results show that DO₂₂–(Cu,Ni)₃Sn intermetallic compound (IMC) ordered structure is formed in the sandwich structures at the as-electrodeposited state. The formed DO₂₂-(Cu,Ni)₃Sn IMC is a homogeneous layer with a thickness about 10 nm. The DO₂₂–(Cu,Ni)₃Sn IMC nanolayer is stable during annealing at 250 °C for 810 min. The formation and stabilization of the metastable DO₂₂–(Cu,Ni)₃Sn IMC nanolayer are attributed to the less strain energy induced by lattice mismatch between the DO₂₂ IMC and fcc Cu crystals in comparison with that between the equilibrium DO₃ IMC and fcc Cu crystals.     

Complex impedance analysis of (Y2O3 + CeO2)-YCr0.5Mn0.5O3 composite NTC ceramics

Ceramic compositions based on (aY₂O₃ + bCeO₂)-0.4YCr_0.5Mn_0.5O₃ (a + b = 0.6) were prepared by conventional solid state reaction at 1200 °C, and sintered under air atmosphere at 1600 °C. For 0 ≤ a < 0.6, XRD patterns have shown that the major phases presented in the calcined powders are Y₂O₃, CeO₂ and orthorhombic perovskite YCr_0.5Mn_0.5O₃ phase, respectively. SEM and EDAX observations confirm the YCr_0.5Mn_0.5O₃ phases mostly exist at the grain, whereas the Y₂O₃ and CeO₂ phases mainly exist at the grain boundaries. Complex impedance analysis shows that, for 0 < a ≤ 0.6, single semicircular arc whose shape does not show any change with temperature. Nevertheless, for a = 0, two overlapping semicircular arcs are observed at and above 300 °C. The grain boundary properties exhibit thermistor parameters with a negative temperature coefficient characteristic. The relaxation behavior and conduction for the grain boundary could be due to a space-charge relaxation mechanism and oxygen vacancies, respectively.     

Enhancement of the low temperature chlorination of ilmenite with CCl4 by adding Cl2

This work reports a simple and effective way to enhance the chlorination of natural ilmenite with carbon tetrachloride (CCl₄) at low temperature by using chlorine gas (Cl₂). The phase transition of ilmenite during chlorination was characterized by X-ray diffraction (XRD) method and transmission electron microscopy (TEM). It is found that CCl₄ and Cl₂ can act as the oxidant to convert ilmenite to M₅O₉ and M₁₃O₂₃ intermediate compounds which are members of a M₃O₅–M₂O₄ intergrowth structure series, and then further chlorinate it to produce titanium tetrachloride (TiCl₄). The solid phase transition from ilmenite to the intermediate phases was the rate controlling step. Cl₂ can significantly enhance this process by promoting the formation of the intermediate phases. The enhanced process can be commercially exploited as an environmental protection technology to produce TiCl₄ at low temperature.     

Preparation and characterization of nano TiO2/micron Cr2O3 composite particles

Nano-TiO₂/micro-size Cr₂O₃ composite particles were first prepared by hydrolysis of Ti(OBu)₄ in an abundant acidic aqueous solution without calcinations at room temperature. XPS analysis shows that the element C, O, Ti and Sn existed on the surfaces of the composite particles. Observation by field emission scanning electronic microscope shows TiO₂ particles of 10-15 nm covers on Cr₂O₃ powder surfaces to form nanometer/micron composite particles. UV-vis spectra show a red shift of the absorption edge and a significant increase of absorption intensity in the visible region. These results confirm that TiO₂ of anatase type can be synthesized on the surface of Cr₂O₃.