Microstructure analysis and mechanical properties of a new class of Al2O3–WC nanocomposites fabricated by spark plasma sintering

We report the synthesis of a new class of Al₂O₃–WC nanocomposites for the first time by using metal–organic chemical vapor deposition process in a spouted bed followed by spark plasma sintering technique. The microstructure and mechanical properties of these prepared nanocomposites have been analyzed for various sintering parameters. From microstructure observation, it is found that the nanosized WC particles are dispersed within alumina matrix grains and intergrains. The microstructure of transgranular and step-wise fracture surface are found in these nanocomposites. The basic mechanical properties like density, hardness, and toughness also have been analyzed and the results are interpreted by correlating with that of corresponding microstructures.     

Thermal-assisted cold sintering study of Al2O3 ceramics: Enabled with a soluble γ-Al2O3 intermediate phase

Thermal-assisted cold sintering process (TA-CSP) has been applied to fabricate high dense α-Al₂O₃ ceramics with submicron grain sizes. The α-Al₂O₃ (80 wt%) and γ-Al₂O₃ (20 wt%) powders are firstly mixed and then cold sintered at 300 °C to produce a green bulk with a relatively high density of ～ 86.9 %, and then later a second heat treatment (800–1350 °C) is applied to finally fabricate (～ 98 % dense) α-Al₂O₃ ceramics with grain sizes of 720 nm. A microstructural analysis with XRD and TEM suggests that the TA-CSP samples not only complete the final densification but also drive a phase transition of γ-Al₂O₃ to α-Al₂O₃. To put into perspective the Hardness and Young's modulus of TA-CSP samples reach ～ 14 GPa and ～ 335 GPa, respectively, which is comparable to conventional sintered samples processed at higher temperatures of 1500–1700 °C. Therefore, it is feasible to utilize TA-CSP to prepare α-Al₂O₃ ceramics with small grain sizes at low sintering temperatures.     

氢氧化钡[Ba(OH)_2·8H_2O]

正1)性质。氢氧化钡易形成结晶水合物,其中Ba(OH)2·8H2O最常见。Ba(OH)2·8H2O是白色粉末或单斜晶系晶体,加热至77.9℃溶于自身结晶水。溶于水,水溶液呈碱性。还溶于稀酸和甲醇。难溶于乙醇、丙酮。在空气中吸收二氧化碳变成碳酸钡。加热到约800℃失去结晶水而生成氧化钡。有毒。2)用途。用于制造钡盐、有机钡化合物、钡基润滑脂。用于精制动植物油类、蔗糖、甜菜。用作塑料稳定剂、造纸添加剂、密     

High dielectric Al2O3-(20–30 wt%) HDPE composites processed via cold sintering

In the present work, the dielectric properties of cold sintered alumina (Al₂O₃) reinforced with 20–30 wt% HDPE composite was investigated. The Al₂O₃-HDPE composites were successfully processed via cold sintering at extremely low temperature in the range of 80–120 °C for 120 min with the application of uniaxial pressure of 500 MPa under vacuum. In fact, cold sintering is a promising method to consolidate ceramic-polymer composites with very large difference in melting points and other thermo-physical/chemical properties. In the present work, high dielectric constant (ε’) of 11.73 and low dielectric loss (tanδ) of 0.0076 measured for Cold Sintering Processed (CSPed) Al₂O₃-20HDPE and a little low ε’ of 9.13 and low tanδ of 0.0066 was evident for CSPed-Al₂O₃-30HDPE at 1 MHz. Such differences in the dielectric properties of the Al₂O₃-20,30 HDPE composites depend on the crystallite size, dangling bond density and microstrain of the materials. Increase in ε’ with temperature is noticed for CSPed-A20H. Moreover, for CSPed-A20H at 1 MHz the temperature variation of dielectric constant (TCC) of 186.94 ppm/°C (or 0.018694 %/°C) was estimated and it reflects a marginal variation of ε’ with temperature. The coefficient of thermal expansion (CTE) of 87.25 × 10⁻⁶ °C⁻¹ and 109.3 × 10⁻⁶ °C⁻¹ was estimated for CSPed-A20H and CSPed-A30H, respectively. Overall, the cold sintered Al₂O₃-20HDPE composites exhibited comparable or better dielectric properties than Al₂O₃ based materials (as reported in the literature) processed by conventional sintering or cold sintering processes.     

Synthesis and structure of K2[HMo6VIVVO22(NH3CH2COO)3]·8H2O: a new example of a polyoxomolybdovanadate coordinated by a glycinato ligand

A new complex of formula K₂[HMo₆^VIV^VO₂₂(NH₃CH₂COO)₃]·8H₂O has been prepared from molybdenum(VI) oxide and vanadium(V) oxide in aqueous solution by adding glycine and potassium chloride, and its structure determined by X-ray structure analysis. The molybdovanadate anion is built up of six MoO₆ edge-sharing octahedra connected into a ring centered by a VO₄ tetrahedron. The MoO₆ octahedra are in pairs linked by the bridging glycine-carboxylato ligands.     

Processing of Al2O3/SiC nanocomposites—part 2: green body formation and sintering

Pressure filtration was used to form green compacts from aqueous slurries of alumina with 5 vol.% silicon carbide. Green densities of 64%TD were achieved for slurries containing a 50 vol.% solids loading. Lower green densities were obtained for a very fine alumina due to the practical limits on maximum slurry solids loading when using finer powders. The samples were dried in a purposely built humidity cabinet to limit sample cracking. It was found that a higher consolidated layer permeability gave a higher initial drying rate. Near fully dense (99% TD) nanocomposites were produced, via pressureless sintering at 1900 °C. Poor sintered densities were obtained in the case of the fine alumina because of localised sintering of these low green density compacts. The required intra/inter-granular nanocomposite microstructures have been obtained for several different systems, with an average grain size of approximately 5 μm. Abnormal grain growth was noted for samples containing the larger particle size silicon carbide. This shows that a maximum particle size limit exists when selecting the powders for a 5 vol.% nanocomposite.     

Crystal structure and dielectric properties of germanate melilites Ba2MGe2O7 (M = Mg and Zn) with low permittivity

Two melilite-structured ceramics, Ba₂MgGe₂O₇ and Ba₂ZnGe₂O₇, were fabricated using the simple solid-state sintering route and their microwave dielectric properties were reported for the first time. Rietveld refinements revealed that both ceramics crystallized in a tetragonal system with a space group P-42₁m. In contrast to Ba₂MgGe₂O₇ that was single phase in the whole sintering range, Ba₂ZnGe₂O₇ exhibited a second phase BaZnGeO₄ which was confirmed by SEM and Raman analysis. The sintering temperature could optimize the relative density and dielectric properties. Dense Ba₂MgGe₂O₇ and Ba₂ZnGe₂O₇ ceramics could be obtained at 1280?°C and 1180?°C with low relative permittivity(ε_r) of 7.76 and 9.0, high quality factor (Q?×?f) of 20,700 and 13,950?GHz, and negative temperature coe?cient of resonant frequency (τ_f) of ?55 and ?75?ppm/°C, respectively. Their differences in microwave dielectric properties were analyzed based on ionic polarizability and packing fraction. The thermal stability of Ba₂MgGe₂O₇ was tuned through the solid solution formation with TiO₂ and the τ_f value was adjusted successfully.     

Electrical properties and microstructural evolution of ZrO2–Al2O3–TiN nanocomposites prepared by spark plasma sintering

Electroconductive ZrO₂–Al₂O₃–25 vol% TiN ceramic nanocomposites were prepared by spark plasma sintering at 1200 °C for 3 min. The electrical resistivity of the composites decreased from 4.5 × 10^?4 Ω m to 3 × 10^?5 Ω m as the Al₂O₃ content in the ZrO₂–Al₂O₃ matrix increased from 0 to 100 vol%. SEM images graphically presented the microstructural evolution of the composites and a geometrical percolation model was applied to investigate the relationship between the electrical property and the microstructure. The results indicated that the addition of Al₂O₃ to ZrO₂–TiN improved the electrical conductivity of the material by tailoring the structure from “nano–nano” type for ZrO₂–TiN to “micro–nano” type for ZrO₂–Al₂O₃–TiN.     

Mechanical characterisation and hydrothermal degradation of Al2O3-15 vol% ZrO2 nanocomposites consolidated by two-step sintering

The objective of this work was to study two-step sintering as a means of controlling the microstructure of Al₂O₃ matrix nanocomposites containing nanometric inclusions of ZrO₂ 15% by volume and evaluate its hydrothermal degradation as function of time and its mechanical properties. Powders of Al₂O₃ and ZrO₂ were prepared and compacted by means of isostatic pressing and sintering in different heating cycles. The results showed that two-step sintering allowed a more efficient microstructural control than single-step sintering, resulting in good mechanical properties. The studied nanocomposites showed excellent resistance to hydrothermal degradation compared to commercial ZrO₂ and ZrO₂ TZ-3Y-E.     

High-pressure behavior and phase stability of Na2B4O6(OH)2·3H2O (kernite)

The high-pressure behavior of kernite [ideally Na₂B₄O₆(OH)₂·3H₂O, a ~ 7.02 Å, b ~ 9.16 Å, c ~ 15.68 Å, β = 108.9°, Sp Gr P2₁/c, at ambient conditions], an important B-bearing raw material (with B₂O₃ ≈ 51 wt%) and a potential B-rich aggregate in radiation shielding materials, has been studied by single-crystal synchrotron X-ray diffraction up to 14.6 GPa. Kernite undergoes an iso-symmetric phase transition at 1.6-2.0 GPa (to kernite-II). Between 6.6-7.5 GPa, kernite undergoes a second phase transition, possibly iso-symmetric in character (to kernite-III). The crystal structure of kernite-II was solved and refined. The isothermal bulk modulus (K_V0 = β^-1_P0,T0, where β_P0,T0 is the volume compressibility coefficient) of the ambient-pressure polymorph of kernite was found to be K_V0 = 29(1) GPa and a marked anisotropic compressional pattern, with K(a)₀: K(b)₀: K(c)₀~1:3:1.5., was observed. In kernite-II, the K_V0 increases to 43.3(9) GPa and the anisotropic compressional pattern increases pronouncedly. The mechanisms, at the atomic scale, which govern the structure deformation, have been described.     

High dielectric permittivity and dielectric relaxation behavior in a Y2/3Cu3Ti4O12 ceramic prepared by a modified Sol−Gel route

In this work, Y_2/3Cu₃Ti₄O₁₂ ceramics were fabricated via a modified sol?gel route. Structural, dielectric, and electrical parameters were systematically investigated. The XRD results indicate that a CaCu₃Ti₄O₁₂ phase (JCPDS No. 75–2188) is present in every sintered sample. SEM images of Y_2/3Cu₃Ti₄O₁₂ ceramics disclose a fine-grained ceramic microstructure. Interestingly, high dielectric permittivity, ～6600–7600, with loss tangents of ～0.918–1.086 were achieved in the sintered Y_2/3Cu₃Ti₄O₁₂ samples. Density functional theory (DFT) calculations were used to investigate the most stable structure of the Y_2/3Cu₃Ti₄O₁₂ ceramics. Our DFT results reveal that two calcium vacancies (V_Ca) are isolated from each other. We also determined the lowest energy configuration of an oxygen vacancy (V_O) in the Y_2/3Cu₃Ti₄O₁₂ ceramics occurred during the sintering process. We found that the V_O is trapped close to the Y atom in this structure. Both computational and experimental studies specify that the oxygen vacancy is located close to the Y atom in the Y_2/3Cu₃Ti₄O₁₂ lattice and it might be a bivalent oxygen vacancy. As a result, due to charge balance, charge compensation of the transition ions, i.e., Cu and Ti ions, might take place. The charge compensation mechanisms in the Y_2/3Cu₃Ti₄O₁₂ lattice were verified using an XPS technique. Impedance spectroscopy confirms the presence of an inhomogeneous microstructure consisting of semiconducting grains and insulating grain boundaries in the sintered Y_2/3Cu₃Ti₄O₁₂ ceramics. This electrical result is consistent with the computational analysis, showing that a charge compensation mechanism might be involved in generation of the grains' semiconductive region due to the presence of a V_O. Consequently, high dielectric permittivity in Y_2/3Cu₃Ti₄O₁₂ may have originated from an internal barrier layer capacitor (IBLC) effect.     

Decavanadate with a novel coordination complex: Synthesis and characterization of (NH4)2[Ni(H2O)5(NH3)]2(V10O28)·4H2O

A new compound (NH₄)₂[Ni(H₂O)₅(NH₃)]₂[V₁₀O₂₈]·4H₂O (1) containing a {V₁₀O₂₈} ⁶⁻ anionic cluster and a novel complex cation, [Ni(H₂O)₅(NH₃)]^2 +, has been synthesized and fully characterized by single crystal X-ray crystallography, spectroscopy and thermogravimetric analysis. The presence of the ammonia ligand in the complex cation in 1 was established unambiguously by X-ray crystallography and variable temperature (200–400 °C) thermogravimetric analyses in combination with FTIR spectroscopic studies. The formation of the novel complex species {Ni(H₂O)₅(NH₃)}^2 + during the synthesis of 1 can be rationalized in terms of ligand substitution involving {Ni(H₂O)₆}^2 +.     

Nd(OH)3-Co3O4-Nb2O5纳米复合掺杂BaTiO3基陶瓷研究

钛酸钡(BaTiO3)材料具有铁电、压电、热电、介电等特性,广泛用于制造高介电容器、热敏电阻和换能器等,特别是用作多层陶瓷电容器(MLCC)的基质材料.目前,MLCC向高可靠性、高比容(小尺寸大容量)、低成本的趋势发展.因此,制备高纯超细的BaTiO3粉体以及掺杂改性的研究,是该领域研究的热点.本文制备了Nd(OH)3...     

Polydimethylsiloxane–PbZr0.52Ti0.48O3 nanocomposites with high permittivity: Effect of poling and temperature on dielectric properties

Polydimethylsiloxane (PDMS)/lead zirconate titanate (PbZr_0.52Ti_0.48O₃, PZT)-based nanocomposites with high dielectric constant (permittivity, k) are prepared through room temperature mixing. The effect of PZT loading on electrical and mechanical properties of the PDMS–PZT composites is extensively studied. It is found that there is significant increase in permittivity with PZT loading and decrease in volume resistivity. All the composites have low dielectric loss compared to permittivity value. It is observed that there is increase in permittivity and decrease in volume resistivity of composites after poling, which is due to the dipolar polarization. It is found that both permittivity (ε′) and alternating current conductivity (σ_ac) are increased with temperature at low frequency (1 Hz) and decreased with temperature at high frequency (1 MHz). The above composites are sensitive to external pressure and can be used as pressure/force sensor. The tensile strength and % elongation at break decreases with PZT loading, which is due to the nonreinforcing behavior of PZT ceramic. PZT particles distribution and dispersion in PDMS matrix are observed through field emission scanning electron microscopy, high resolution transmission electron microscopy, and atomic force microscopy/scanning probe microscopy. Thermal stability of composites increased with the PZT loading which is due to higher thermal stability of PZT particles compared to PDMS matrix. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47307.     

A highly nuclear vanadium-containing tungstobismutate: synthesis and crystal structure of K11H[(BiW9O33)3Bi6(OH)3(H2O)3V4O10]·25 H2O

A novel and large heteropolyanion [(BiW₉O₃₃)₃Bi₆(OH)₃(H₂O)₃V₄O₁₀]¹²⁻ has been synthesized by reaction of sodium metavanadate with Na₉[BiW₉O₃₃]·16H₂O in acetate buffer solutions (at pH 4.8). The present anion has a trilobal structure in which three α-B {BiW₉O₃₃} units are connected to each other by an unique core [Bi₆(OH)₃(H₂O)₃V₄O₁₀]¹⁵⁺. A central bismutate/vanadate-mixed core comprises three sets of two types of the BiO₆ pentagonal pyramid, the edge-sharing VO₅ square-pyramidal triad, and a VO₄ tetrahedron.     

High temperature sintering of SiC with oxide additives: I. Analysis in the SiC–Al2O3 and SiC–Al2O3–Y2O3 systems

The vaporization behaviour of pure Al₂O₃, Y₂O₃ and SiC as well as SiC–Al₂O₃ and SiC–Al₂O₃/Y₂O₃ mixtures has been analysed by thermodynamic calculations in an open system. Pure Al₂O₃ and Y₂O₃ evaporate congruently in the 1200–2300 K temperature range. Pure SiC vaporizes in a non-congruent manner leading to graphite formation as by-product. A SiC–Al₂O₃ mixture evaporates congruently according to the main vaporization reaction, 2 SiC(s) + Al₂O₃(s) +Al₂O(g) ⇆ 2 SiO(g) + 2 CO(g) +4 Al(g), but the overall composition changes: for SiC rich samples, the mixture tends towards pure SiC in time, and for Al₂O₃ rich samples towards pure Al₂O₃. A SiC–Al₂O₃/Y₂O₃ mixture shows similar behaviour.     

A tetranuclear oxomolybdenum(V) complex with bridging squarate ligands, [MoV4O8(OH)2(H2O)2(C4O4)2]2−

The new tetranuclear polyoxomolybdate(V) ion [Mo^V₄O₈(OH)₂(H₂O)₂(C₄O₄)₂]²⁻ has been obtained in one step by the reaction of sodium molybdate, hydrazine and squaric acid in water and crystallized as a potassium salt. The structure has been solved by single-crystal X-ray diffraction showing the location of the hydroxo and water molecule ligands.     

Lead-free (Ba0.85Ca0.15)(Ti0.9Zr0.1)O3–CeO2 ceramics with high piezoelectric coefficient obtained by low-temperature sintering

Lead-free (Ba_0.85Ca_0.15)(Ti_0.9Zr_0.1)O₃–x%CeO₂(BCZT–xCe) piezoelectric ceramics have been prepared by the traditional ceramic process and the effects of CeO₂ addition on their phase structure and piezoelectric properties have been studied. The addition of CeO₂ significantly improves the sinterability of BCZT ceramics which results in a reduction of sintering temperature from 1540 °C to 1350 °C without sacrificing the high piezoelectric properties. X-ray diffraction data show that CeO₂ diffuses into the lattice of BCZT and a pure perovskite phase is formed. SEM images indicate that a small addition of CeO₂ greatly affects the microstructure. Main piezoelectric parameters are optimized at around x = 0.04 wt% with a high piezoelectric coefficient (d₃₃ = 600 pC/N), a planar electromechanical coefficient (k_p = 51%), a high dielectric constant (?_r = 4843) and a low dissipation factor (tan δ = 0.012) at 1 kHz, which indicates that the BCZT–xCe ceramics are promising for lead-free practical applications.     

Synthesis and nanostructure of [Mo(C6H4O2)3]·2(C4H8N2O) and the synthesis from 1,2-PDA to (C4H8N2O)

Continuing our work on the synthesis of MoO₂L₂ and MoO₃L_AL_B that show excellent anti-cancer activities in vitro, the MoL₃ have been synthesized by the solvothermal reaction of Na₂MoO₄ with catechols and 1,2-DPA in the mixed solvent of MeCN/MeOH. X-ray diffraction revealed that Mo in chiral octahedral geometry coordinate with three catechol ligands formed three five-membered rings, and the [Mo(C₆H₄O₂)₃] are linked by hydrogen bonds Mo(OC₆H₄)O…H–N(C₄H₈O)N–H…O(C₆H₄O)Mo through the by-product (C₄H₈N₂O) that are formed by one 1,2-DPA with one CO₂ on the catalysis of Mo-complex. Also, we have disassembled bulk crystal into nano-aggregates, and under TEM mono-lamella morphology of nanostructures was observed, which agrees well with the previous conclusion that the morphologies of the nano-aggregates are associated with the quantum motifs in their crystal lattices. [Mo(C₆H₄O₂)₃] have also been characterized by UV–vis spectra, cyclic voltammogram and thermogravimetric analysis.