Production of tungsten boride from CaWO4 by self-propagating high-temperature synthesis followed by HCl leaching

In this study, the conditions of producing tungsten boride powder from calcium tungstate (CaWO₄) by self-propagating high-temperature synthesis (SHS) followed by HCl leaching techniques were investigated. In the first stage of the experimental study, the SHS products consisting of borides and other compounds were obtained starting with different initial molar ratios of CaWO₄, Mg and B₂O₃. It was found that increasing B₂O₃ content in the initial mixture resulted in an increase of W₂B₅/WB ratio along with Mg₃B₂O₆ in the SHS product. In the second step, Mg and Ca containing byproducts (i.e. MgO, Mg₃B₂O₆ and Ca₃B₂O₆) found in the SHS product were leached out by using aqueous HCl solution to obtain a clean tungsten boride product. The effects of particle size, temperature, time, acid concentration and solid/liquid ratio were selected as leaching parameters. The acid leaching experiments of the SHS product synthesized at 1:8:2.5 initial molar ratio of CaWO₄:Mg:B₂O₃ showed that optimum leaching conditions could be achieved by using 2.85 M HCl at 1/10 S/L ratio and the temperature of 80 °C for 60 min.     

Preparation of single phase molybdenum boride

The formation of MoB through volume combustion synthesis (VCS), and through mechanochemical synthesis (MCS) followed by annealing has been investigated. MoO₃, B₂O₃ and Mg were used as reactants while MgO and NaCl were introduced as diluents. Products were leached in dilute HCl solution and were subjected to X-ray diffraction (XRD) analysis and scanning electron microscopy (SEM) examinations. Mo was the major phase component in the VCS products under all the experimental conditions. Mo₂B, MoB, MoB₂ and Mo₂B₅ were found as minor phases. Products of MCS contained a mixture of Mo₂B, MoB, MoB₂ and Mo. After annealing the MCS product at 1400 °C for 3 h, single phase α-MoB was obtained.     

Heat treatment induced phase separation and phase transformation of ZrNxOy thin films deposited by ion plating

Nanocrystalline ZrN_xO_y thin films were deposited on p-type Si (100) substrates using hollow cathode discharge ion-plating (HCD-IP) and the films were annealed at 700 and 900 °C in the controlled atmosphere. The purpose of this study was to investigate the phase separation, phase transformation and the accompanying change of properties of the heat-treated ZrN_xO_y films deposited by ion plating. With the increase of oxygen flow rate ranging from 0 to 10 sccm, the primary phase of the as-deposited films evolved from ZrN to nearly amorphous structure and further to monoclinic ZrO₂ (m-ZrO₂). After heat treatment at 700 and 900 °C, phase transformation occurred in the samples deposited at 8 and 10 sccm O₂, where a stoichiometric crystalline Zr₂ON₂ was found to derive from m-ZrO₂ with dissolving nitrogen (m-ZrO₂(N)). The hardness of the ZrN_xO_y thin films could be correlated to the fraction of Zr₂ON₂ + m-ZrO₂. The film hardness decreased significantly as the fraction of ZrO₂ + Zr₂ON₂ exceeded ~ 60%, which was due to phase transition by increasing oxygen flow rate or phase transformation induced by heat treatment. The phase separation of m-ZrO₂ from ZrN with dissolving oxygen (ZrN(O)) may relieve the residual stress of the ZrN_xO_y specimens deposited at 5 and 8 sccm O₂, while direct formation of m-ZrO₂ increased the stress of the film deposited at 10 sccm O₂. On the other hand, the phase transformation from m-ZrO₂(N) to Zr₂ON₂ by heat treatment at both 700 and 900 °C may effectively relieve the residual stress of the ZrN_xO_y films.     

Phase transition and mechanical properties of ZrNxOy thin films on AISI 304 stainless steel

ZrN_xO_y thin films were deposited on AISI 304 stainless steel (304SS) substrates by reactive magnetron sputtering. The specimens were produced by sputtering a Zr target at 500 °C and the reactive gasses were N₂ and O₂ at various flow rates (ranging from 0 to 2 sccm). The purpose of this study was to investigate the effect of oxygen flow rate on the phase transition and accompanying mechanical properties of the ZrN_xO_y thin films. The oxygen contents of the thin films increased significantly with increasing oxygen flow rate. X-ray diffraction (XRD) revealed that the characteristics of the films can be divided into three zones according to the major phase with increasing oxygen content: Zone I (ZrN), Zone II (Zr₂ON₂) and Zone III (m-ZrO₂). The hardness of the ZrN_xO_y films decreased with increasing oxygen content due to the formation of the soft oxide phase. Modified XRD sin²ψ method was used to respectively measure the residual stresses of ZrN, Zr₂ON₂ and m-ZrO₂ phases. The results showed that the residual stress in ZrN was relieved as the oxygen content increased, and Zr₂ON₂ and m-ZrO₂ were the phases with lower residual stress. Compositional depth profiles indicated that there was a ZrO₂ interlayer near the film/substrates interface for all samples except the mononitride ZrN specimen. Contact angle was used as an index to assess the wettability of the film on substrate. The contact angles of ZrN, Zr₂ON₂ and m-ZrO₂ on stainless steel were indirectly measured using Owens-Wendt method. The results showed that ZrO₂ possessed the lowest wettability on 304SS among the three ZrN_xO_y phases, indicating that the ZrO₂ interlayer may account for the spallation of the ZrN_xO_y films after salt spray tests.     

The repeated thermal shock behaviors of a ZrB2-SiC composite heated by electric resistance method

Repeated thermal shocks of ZrB₂-20 vol.% SiC (ZrB₂-SiC) composite was investigated by the electric resistance method with 330 A and 4 V. It was found that the maximum temperature of the specimen center was obtained in 20 s and the specimen was cooled down to room temperature in 10 s due to a coolant system, and then the specimen was heated again. The thermal shock treatment increased the flexural strength with a peak at 20 cycles. Even though 30 cycles showed the minimum strength, it was still higher than that of the unshocked specimen. The increase in the strength was attributed to the formation of the oxide layer and the compression stress that resulted from volume expansion upon conversion of ZrB₂ and SiC, to ZrO₂, B₂O₃ and SiO₂.     

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.     

Reaction mechanism of self-propagating magnesiothermic reduction of ZrB2 powders

Fine zirconium diboride （ZrB2） powders with high purity were successfully prepared by combustion synthesis through magnesiothermic reduction process in Mg-B2O3-ZrO2 system. The reaction mechanism was investigated by differential thermal analysis and quenching experiment. The results show that the whole magnesio-thermic reduction process includes three stages： first, molten B2O3 and Mg formed above the temperature of 650 ℃, and glassy B2O3 and solid ZrO2 particles were coated on the surface of the molten Mg; thus, the hollow balls can be formed when the molten Mg was exuded under capillary function. Second, ZrO2 particles reacted with molten Mg to form Zr and MgO with dissolution-precip-itation mechanism, which released a large amount of heat to induce the diffusion reaction between B203 and Mg to form B and MgO. Last, Zr reacted with B to form ZrB2 grains. The preparation of ZrB2 by self-propagating syn-thesis in Mg-B2O3-ZrO2 system is a solid-liquid-liquid reaction.     

Preparation, structure and electrical conductivity of the pyrochlore-type phase Sm2Zr2O7 codoped with bivalent magnesium and trivalent dysprosium cations

The pyrochlore-type phases with the compositions of SmDy_1−xMg_xZr₂O_7−x/2 (0 ≤ x ≤ 0.20) have been prepared by pressureless-sintering method for the first time as possible solid electrolytes. The structure and electrical conductivity of SmDy_1−xMg_xZr₂O_7−x/2 ceramics have been studied by the X-ray diffraction (XRD), scanning electron microscopy (SEM) and impedance spectroscopy measurements. SmDy_1−xMg_xZr₂O_7−x/2 (x = 0, 0.05, 0.10) ceramics exhibit a single phase of pyrochlore-type structure, and SmDy_1−xMg_xZr₂O_7−x/2 (x = 0.15, 0.20) ceramics consist of pyrochlore phase and a small amount of the second phase magnesia. The total conductivity of SmDy_1−xMg_xZr₂O_7−x/2 ceramics obeys the Arrhenius relation, and the total conductivity of each composition increases with increasing temperature from 673 to 1173 K. SmDy_1−xMg_xZr₂O_7−x/2 ceramics are oxide-ion conductors in the oxygen partial pressure range of 1.0 × 10⁻⁴ to 1.0 atm at all test temperature levels. The highest total conductivity value is about 8 × 10⁻³ S cm⁻¹ at 1173 K for SmDy_1−xMg_xZr₂O_7−x/2 ceramics.     

Low temperature sintering and microwave dielectric properties of (Mg0.7Zn0.3)0.95Co0.05TiO3 ceramics with BaCu(B2O5) additions

The effects of BaCu(B₂O₅) additives on the sintering temperature and microwave dielectric properties of (Mg_0.7Zn_0.3)_0.95Co_0.05TiO₃ ceramics were investigated. The (Mg_0.7Zn_0.3)_0.95Co_0.05TiO₃ ceramics were not able to be sintered below 1000 °C. However, when BaCu(B₂O₅) were added, they were sintered below 1000 °C and had the good microwave dielectric properties. It was suggested that a liquid phase with the composition of BaCu(B₂O₅) was formed during the sintering and assisted the densification of the (Mg_0.7Zn_0.3)_0.95Co_0.05TiO₃ ceramics at low temperature. BaCu(B₂O₅) powders were produced and used to reduce the sintering temperature of the (Mg_0.7Zn_0.3)_0.95Co_0.05TiO₃ ceramics. Good microwave dielectric properties of Q × f = 35,000 GHz, ?_r = 18.5.0 and τ_f = −51 ppm/°C were obtained for the (Mg_0.7Zn_0.3)_0.95Co_0.05TiO₃ ceramics containing 7 wt.% mol% BaCu(B₂O₅) sintered at 950 °C for 4 h.     

ZrB2-玻璃陶瓷复合材料氧化分析

对ZrB₂-玻璃陶瓷复合材料氧化行为进行热力学分析,对氧化形成的氧化层进行物相分析和显微结构分析。结果表明：在1000°C-1400°C的反应温度范围内,ZrB₂氧化生成ZrO₂,B₂O₃玻璃相,氧化产物ZrO₂与SiO₂反应生成ZrSiO₄,当温度低于1177°C(1450K)时,氧化层主要包括ZrO₂,B₂O₃玻璃相,ZrSiO₄。当氧化温度超过1177°C(1450K)时,B₂O₃玻璃相蒸发,此时SiO₂玻璃相具有良好的流动性,氧化层主要包括ZrO₂,SiO₂玻璃相,ZrSiO₄。氧化过程中的反应产物B₂O₃玻璃相,ZrSiO₄和流动性良好的SiO₂玻璃相,均对氧气向基体的扩散均起到了良好的阻碍作用。     

Thixoforming of AA 2017 aluminum alloy composites

A comparative evaluation has been carried out on the microstructure of aluminum based SiC and Al₂O₃ particle reinforced composites produced by semi-solid direct squeeze forming of composite powder at temperatures of 635-645 °C. The study is focused on the distribution of the reinforcement and the intermetallic phases, the porosity content, the microstructure of the matrix phase, the interfacial state and mechanical properties. The particle size of the reinforcements, the time of the high-energy ball milling procedure for the fabrication of composite powder and the semi-solid forming temperature had a strong influence on the quality of sample in terms of distribution of reinforcement and interfacial interaction. Ball milling improves the interface formation between reinforcement and matrix and influences the remelting behaviour. Increasing ball milling time and decreasing semi-solid forming temperature with isothermal holding time resulted in relatively homogenous microstructures and in a reduced amount of interaction between SiC and metal matrix. Best results were obtained for 5 vol.% SiC_p composites after 3 h ball milling, semi-solid formed at 635 °C and held for 10 min.     

Spark plasma sintering of B4C ceramics: The effects of milling medium and TiB2 addition

Boron carbide (B₄C) ceramics, with a relative density up to 98.4% and limited grain growth, were prepared at 1600-1800 °C by spark plasma sintering (SPS) technique. The effects of powder milling medium (water and 2-propanol) on the powders' surface characteristics and TiB₂ addition on the sintering densification were investigated. The ball milling processing of B₄C powders in water can promote the sintering of B₄C ceramics. A B₂O₃ layer on B₄C particle surface is concluded to promote the densification of the B₄C ceramics at an early sintering stage. This B₂O₃ layer, which normally inhibits the densification process at the final stage of the sintering, can be reduced through reaction with TiB₂ particles, resulting in further densification of the B₄C ceramics.     

Combustion synthesis of CaB6 powder from calcium hexaborate and Mg

As one of the important metal-borides, calcium hexaboride (CaB₆) is applied in refractory materials, metal deoxidant, neutron absorbent, wear-resisting agent and functional ceramic materials. Generally, CaB₆ is produced from B₄C or B₂O₃ which is obtained at high temperature and high cost. In this study, the CaB₆ powder was prepared through combustion synthesis by using calcium hexaborate and magnesium as starting materials. The calculated adiabatic temperature of CaB₆O₁₀–Mg system reached 2406.69 K. The XRD analyses of combustion products showed that there existed a small amount of Mg₃B₂O₆ and Ca₃(BO₃)₂ besides CaB₆ and MgO. The XRD patterns of products leached by HCl indicated the major part of the leached sample is comprised by CaB₆, showing that MgO and by-products were efficiently leached out. In addition, the technological conditions for combustion synthesis were investigated. It is resulted that larger particle size of CaB₆O₁₀ and higher compacting pressure is beneficial to the production of CaB₆.     

Dependence of lattice distortion of monoclinic phase on film thickness in Pb(Zr0.58Ti0.42)O3 thin films

In this paper, the chosen composition of PZT film falls in rhombohedral phase region and the dependence of lattice distortion on film thickness in sol-gel derived Pb(Zr_0.58Ti_0.42)O₃ thin films was systematically investigated. The results confirm that the Pb(Zr_0.58Ti_0.42)O₃ films have monoclinic phase even though the composition falls in the rhombohedral phase region. The mixed textures of (1 0 0) and (1 1 1) occur in the PZT films. In the case of mixed textures, a method using ψ-scan XRD to characterize the phase type of Pb(Zr_0.58Ti_0.42)O₃ film is presented. It is found that the phase type of (1 0 0)-oriented grains is M_A phase, and that of (1 1 1)-oriented grains is M_B phase. Moreover, the lattice constants of both M_A and M_B phases are sensitive to the film thickness. The lattice distortion of monoclinic phase becomes smaller as film thickness increases.     

The effects of temperature and composition on the thermal conductivities of [(ZrO2)1−x(CeO2)x]0.92(Y2O3)0.08 (0 ? x ? 1) solid solutions

The thermal conductivities of [(ZrO₂)_1−x(CeO₂)_x]_0.92(Y₂O₃)_0.08 (0 ? x ? 1) solid solutions are studied in this paper. The incorporation of ZrO₂ and CeO₂ in the solid solution decreases the thermal conductivity compared with their end members (YSZ and YDC). The thermal conductivities of the solid solutions show clearly different temperature dependences in the ZrO₂-rich (0 ? x ? 0.5) region and in the CeO₂-rich region (0.5 ? x ? 1). The composition and the temperature dependence of the thermal conductivities are discussed based on established phonon scattering theories. We have concluded that the composition dependence of the thermal conductivity of this system is mainly controlled by the mass difference between Zr⁴⁺ and Ce⁴⁺, while the thermal conductivity-temperature relationship is dominated by the randomness of the defect distribution.     

Investigations on synthesis of ZrB2 and development of new composites with HfB2 and TiSi2

This paper presents the results of experimental investigations carried out on the synthesis of pure ZrB₂ by boron carbide reduction of ZrO₂ and densification with the addition of HfB₂ and TiSi₂. Process parameters and charge composition were optimized to obtain pure ZrB₂ powder. Monolithic ZrB₂ was hot pressed to full density and characterized. Effects of HfB₂ and TiSi₂ addition on densification and properties of ZrB₂ composites were studied. Four compositions namely monolithic ZrB₂, ZrB₂ + 10% TiSi₂, ZrB₂ + 10% TiSi₂ + 10% HfB₂ and ZrB₂ + 10% TiSi₂ + 20% HfB₂ were prepared by hot pressing. Near theoretical density (99.8%) was obtained in the case of monolithic ZrB₂ by hot pressing at 1850 °C and 35 MPa. Addition of 10 wt.% TiSi₂ resulted in an equally high density of 98.9% at a lower temperature (1650 °C) and pressure (20 MPa). Similar densities were obtained for ZrB₂ + HfB₂ mixtures also with TiSi₂ under similar conditions. The hardness of monolithic ZrB₂ was measured as 23.95 GPa which decreased to 19.45 GPa on addition of 10% TiSi₂. With the addition of 10% HfB₂ to this composition, the hardness increased to 23.08 GPa, close to that of monolithic ZrB₂. Increase of HfB₂ content to 20% did not change the hardness value. Fracture toughness of monolithic sample was measured as 3.31 MPa m^1/2, which increased to 6.36 MPa m^1/2 on addition of 10% TiSi₂. With 10% HfB₂ addition the value of K_IC was measured as 6.44 MPa m^1/2, which further improved to 6.59 MPa m^1/2 with higher addition of HfB₂ (20%). Fracture surface of the dense bodies was examined by scanning electron microscope. Intergranular fracture was found to be a predominant mode in all the samples. Crack propagation in composites has shown considerable deflection indicating high fracture toughness. An oxidation study of ZrB₂ composites was carried out at 900 °C in air for 64 h. Specific weight gain vs time plot was obtained and the oxidized surface was examined by XRD and SEM. ZrB₂ composites have shown a much better resistance to oxidation as compared to monolithic ZrB₂. A protective glassy layer was seen on the oxidized surfaces of the composites.     

Mechanochemical synthesis of nanocrystalline ZnWO4 at room temperature

Single nanocrystalline ZnWO₄ powders were successfully synthesized by ball milling at room temperature. A stoichiometric mixture of ZnO and WO₃ in a 1:1 molar ratio was subjected to intense mechanical treatment in air using a planetary ball mill (Fritsch - Premium line - Pulversette No. 7) for a period varying from 5 to 300 min. The influence of the four different milling conditions was investigated on the formation of ZnWO₄. The products obtained were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), Brunauer-Emmer-Teller (BET) surface area, infrared (IR) spectroscopy and X-ray photoelectron spectroscopy (XPS). The synthesis of ZnWO₄ powder started after 5 min milling time and finished after 30 min milling time at a higher speed (1000 rpm). The mechanical treatment up to 300 min did not lead to phase and structure change of ZnWO₄. The product obtained contained nanoparticles with a size of about 50 nm. The photocatalytic activity of the ZnWO₄ powders obtained was investigated by degradation of a model aqueous solution of Malachite Green (MG) upon UV-light irradiation.     

Microstructure and mechanical properties of laminated ZrB2-SiC ceramics with ZrO2 interface layers

Laminated ZrB₂-SiC ceramics with ZrO₂ interface layers were successfully prepared by tape casting, laminating and hot pressing. The flexural strength and fracture toughness are 561 ± 20 MPa and 14.4 ± 0.3 MPa m^1/2 for parallel direction, and 432 ± 18 MPa and 5.8 ± 0.3 MPa m^1/2 for perpendicular direction. The fracture toughness for parallel direction is improved significantly compared to monolithic ZrB₂-SiC ceramics. The toughening mechanism was attributed to the deflection and branch of the crack and the new microcracks, which would increase the propagation path and fracture work.     

Photocatalytic performance of nano-photocatalyst from TiO2 and Fe2O3 by mechanochemical synthesis

Nano-particles of homogeneous solid solution between TiO₂ and Fe₂O₃ (up to 10 mol%) have been prepared by mechanochemical milling of TiO₂ and yellow Fe₂O₃/red Fe₂O₃/precipitated Fe (OH)₃ using a planetary ball mill. Such novel solid solution cannot be prepared by conventional co-precipitation technique. A preliminary investigation of photocatalytic activity of mixed oxide (TiO₂/Fe₂O₃) on photo-oxidation of different organic dyes like Rhodamine B (RB), Methyl orange (MO), Thymol blue (TB) and Bromocresol green (BG) under visible light (300-W Xe lamp; λ > 420 nm) showed that TiO₂ having 5 mol% of Fe₂O₃ (YFT1) is 3-5 times higher photoactive than that of P25 TiO₂. The XRD result did not show the peaks assigned to the Fe components (for example Fe₂O₃, Fe₃O₄, FeO₃, and Fe metal) on the external surface of the anatase structure in the Fe₂O₃/TiO₂ attained through mechanochemical treatment. This meant that Fe components were well incorporated into the TiO₂ anatase structure. The average crystallite size and particle size of YFT1 were found to be 12 nm and 30 ± 5 nm respectively measured from XRD and TEM conforming to nanodimensions. Together with the Fe component, they absorbed wavelength of above 387 nm. The band slightly shifted to the right without tail broadness, which was the UV absorption of Fe oxide in the Fe₂O₃/TiO₂ particle attained through mechanochemical method. This meant that Fe components were well inserted into the framework of the TiO₂ anatase structure. EPR and magnetic susceptibility show that Fe³⁺ is in low spin state corresponding to μ_B = 1.8 BM. The temperature variation of μ_B shows that Fe³⁺ is well separated from each other and does not have any antiferromagnetic or ferromagnetic interaction. The evidence of Fe³⁺ in TiO₂/Fe₂O₃ alloy is also proved by a new method that is redox titration which is again support by the XPS spectrum.     

Mechanochemical synthesis of Al2O3-TiB2 nanocomposite powder from Al-TiO2-H3BO3 mixture

Alumina-titanium diboride nanocomposite (Al₂O₃-TiB₂) was produced using mixtures of titanium dioxide, acid boric and pure aluminum as raw materials via mechanochemical process. The phase transformation and structural characterization during mechanochemical process were utilized by X-ray diffractometry (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and thermogravimetric analyses (TG-DTA) techniques. A thermodynamic appraisal showed that the reaction between TiO₂, B₂O₃ and Al is highly exothermic and should be self-sustaining. XRD analyses exhibited that the Al₂O₃-TiB₂ nanocomposite was formed after 1.5 h milling time. The results indicate that increasing milling time up to 40 h had no significant effect other than refining the crystallite size.