Fabrication and properties of Si3N4 based ceramics using combustion synthesized powders

Silicon nitride (Si₃N₄) based ceramics were fabricated with β-SiAlON and Si₃N₄ powders synthesized by combustion synthesis method via power injection molding (PIM). In the PIM process, the solids loading for each material was first determined from the results of the torque rheometer experiment. The mixing process was repeated to produce the homogeneous feedstock, and homogeneity of feedstocks was evaluated by observing the shear viscosity with time at a constant shear rate. The rheological behavior of feedstocks was investigated using capillary rheometer. It found that both feedstocks have no problem in injection molding. The binder decomposition behavior was also investigated, and a wax-polymer binder system was nearly removed by the optimized solvent and thermal debinding processes. Thereafter, the debound samples were sintered at 1750 and 1800 °C for 4 h in nitrogen atmosphere. Regardless of sintering temperature, the relative density of higher than about 96% was achieved. When comparing mechanical properties including bending strength, Vickers hardness and fracture toughness, Si₃N₄ with 2 wt% Y₂O₃ and 5 wt% Al₂O₃ (Si₃N₄+2Y5A) had higher values than β-SiAlON with 4 wt% Y₂O₃ (β-SiAlON+4Y) regardless of sintering temperature. It was supported by observing the microstructures of the plasma-etched samples.     

Preparation of a CeO2–ZrO2 based nano-composite with enhanced thermal stability by a novel chelating precipitation method

In this study, a chelating agent is introduced to prepare CeO₂–ZrO₂ nano-composite through a precipitation process. The physicochemical properties of the oxide precursors, nano composite materials are strongly dependent on the preparation method and whether a chelating agent is used. Adding an appropriate quantity of chelating agent SO₄²⁻ can facilitate thermal stability and phase structure uniformity of CeO₂–ZrO₂ mixed oxides. The calculation results showed that the Gibbs free energy of chelating complex of [ZrSO₄]²⁺ (ΔG = −127.2469 kJ/mol) is higher than the [Ce(III)SO₄]⁺ (ΔG = -29.8279 kJ/mol). The precipitation chemical potential of Zr⁴⁺ moves close to the precipitation chemical potential of Ce³⁺. The novel and low-cost chelating precipitation method can modify the homogeneity of the compounds at the atomic scale, which can offer a powerful opportunity for, and provide direction in, the design of materials with exceptional properties.     

A zirconium-free glaze system for sanitary ceramics with SiO2-CaCO3-TiO2 composite opacifier containing anatase: Effect of interface combination among SiO2, CaCO3 and TiO2

TiO₂ is an ideal substitute to ZrSiO₄ ceramic opacifier, yet it is limited to application because of the undesirable yellowing resulting from rutile formation. Herein, the SiO₂-CaCO₃-TiO₂ composite opacifier (Si-Ca-Ti) was constructed. The glaze used Si-Ca-Ti presents a superior opacification performance than ZrSiO₄ opacified glaze without causing yellowing, showing L*, a*, b* values of 94.81, -0.67 and 3.23. By comparison, the glaze using SiO₂, CaCO₃, and TiO₂ mixture shows lower opacification and yellowish surface with L* and b* values of 92.99 and 5.36. It is revealed that there is a close interface bonding among SiO₂, CaCO₃ and TiO₂ in Si-Ca-Ti, which promotes their combination reaction to generate opacification phase titanite and inhibit rutile formation when sintering, resulting in the white surface and opacification improvement of the glaze. This study proposes a green and efficient strategy to achieve white and highly opacified glaze for sanitary ceramics, exhibiting good application prospect.     

Probing the degenerate pattern growth of {100}<011> orientation in a directionally solidified Al-4.5 wt% Cu alloy

Degenerate pattern is a seemingly disordered morphology but it exhibits the inherently ordered crystal connected with tip-splitting and limited stability which makes it difficult to observe in the metallic system. Here we employ (100)[011] orientated planar-front seeds using directional solidification and reveal the fundamental origins of the degenerate pattern growth in an Al-4.5 wt% Cu alloy. We find that the spacing of the tip-splitting (λ) in the degenerate of the alloys followed a power law, λ∝V^−0.5, and the frequency (f) of the splitting was related to the growth velocity (V) by ƒ∝V^1.5. The dimensionless growth direction (θ/θ₀) increased monotonously and approached 0.6 with faster velocity, attributed to its anisotropy in the interface kinetics. Once growth velocity exceeded a threshold, two types of pattern transitions from degenerate to regular dendrites were proposed. One of them exhibited a random and chaotic mode and the other underwent a rotation in growth direction.     

Closure of Internal Porosity in Continuous Casting Bloom During Heavy Reduction Process

Metallurgical and Materials Transactions B - To investigate the closure behavior of internal porosity (also referred to as internal void) in continuous casting bloom during heavy reduction (HR) and...     

Fabrication and performances of high lithium-ion conducting solid electrolytes based on NASICON Li1.3Al0.3Ti1.7-xZrx(PO4)3 (0≤ x≤ 0.2)

Solid electrolytes are the key component in designing all-solid-state batteries. The Li_1.3Al_0.3Ti_1.7(PO₄)₃ (LATP) structure and its derivatives obtained by doping various elements at Ti and Al site acts as good solid electrolytes. However, there is still scope for enhancing the ionic conductivity using simple precursors and preparation methods. In this study, the Li superionic conductors Li_1.3Al_0.3Ti_1.7-xZr_x(PO₄)₃ (LATZP) with 0 ≤ x ≤ 0.2 have been successfully prepared by the solid-state reaction route. The structural, morphological, and ionic transport properties were analyzed using several experimental techniques including powder X-ray diffraction (XRD), scanning electron microscopy (SEM), and impedance spectroscopy (IS). The presence of two relaxation processes corresponding to grain and grain boundary was studied using various formalisms. We have observed that grain effects dominate at lower temperatures (<100 °C) while the grain boundary at higher temperatures (> 200 °C) on ionic conductivity. The relaxation mechanisms of grain and grain boundaries were investigated by the Summerfield scaling of AC conductivity. The highest total ionic conductivity of 2.48 × 10^-4 S/cm at 150 °C and 5.50 × 10^-3 S/cm at 250 °C was obtained for x = 0.1 in Li_1.3Al_0.3Ti_1.6Zr_0.1(PO₄)₃ sintered at 950 °C/6 h in the air. The ionic conductivity value was found to be higher than the ionic conductivity reported for LATP prepared via solid-state reaction mechanism using the same precursors and conditions.     

Construction of BiVO4 microspheres sensitized TiO2 NTAs for the enhanced photocatalytic mineralization of organic dyes

In the present work, BiVO₄ microspheres were deposited on TiO₂ NTAs via the solvothermal method using urea as the mineralizer. The binary heterojunction formation significantly enhanced the solar response region and intensity, and the electron transfer path was built at the interface of two semiconductors, which was the main reason for the enhanced photoelectrochemical and photocatalytic performances. The S-2 electrode prepared with urea concentration of 2 mol/L displayed the high visible light photocurrent of 73.76 μA/cm² and photovoltage of −0.30 V. Furthermore, the S-2 photocatalyst also showed excellent photocatalytic decoloration ability of MO, RhB and MB dyes, and the corresponding decomposition efficiencies were 55.82%, 41.62% and 89.90% under solar irradiation. Except for the organic dyes, Cr(VI) ions also could be reduced into Cr(III), and the photocatalytic efficiency achieved 74.05% after 3 h solar irradiation. The active group and photocatalytic mechanism were proposed to illuminate the essential reason. The experimental results indicated that the novel BiVO₄/TiO₂ NTAs with binary heterojunction are attractive photocatalysts for the dyeing and printing water treatment.     

超低碳钢精炼过程中Fe-Al-Ti-O类复合氧化物夹杂的演变与控制

超低碳钢是一种重要的汽车用钢材料, 钢中通常添加钛元素, 使其形成析出物, 提高钢材的深冲性.然而钛元素作为一种脱氧能力较强的元素, 进入钢液中通常首先形成氧化物.为了减少含钛氧化物夹杂的生成, 基于"转炉-RH-连铸"的超低碳钢生产流程, 对RH精炼过程进行系统取样, 分析了铝脱氧剂加入后及合金化元素钛加入后的氧、氮气体含量变化及夹杂物特征变化, 并使用FactSage热力学计算软件对Fe-Al-Ti-O夹杂物稳定相图进行计算.研究结果显示, 含钛类氧化物夹杂通常以Al₂O₃类夹杂物作为形核质点, 对其形成包裹状夹杂物.若避免含Ti夹杂物的生成, 当钢中Ti质量分数为0.1%时, 钢中溶解Al质量分数应在0.01%以上.对含钛氧化物的生成及长大流程进行研究, 通过对Al₂O₃夹杂物及Ti₂O₃夹杂物粗化率的计算及附着功的比较可知, Ti₂O₃夹杂物在1600℃时的熟化生长速率较Al₂O₃较大且Ti₂O₃夹杂物与Al₂O₃夹杂物相比不容易相互碰撞融合并从钢液中去除.若提高精炼过程中的氧化物夹杂物去除率, 应严格控制含钛氧化物类夹杂物的生成.      

Investigation of LSM-8YSZ cathode within an all ceramic SOFC. Part I: Chemical interactions

This work focuses on a novel, co-sintered, all-ceramic solid oxide fuel cell (SOFC) concept. The objective is the understanding of interaction and degradation mechanisms of the cathode and current collector layers within the design during co-sintering. Half cells consisting of silicate mechanical support, lanthanum strontium manganite (LSM) current collector, LSM mixed with 8 mol% yttria-stabilized zirconia (8YSZ) composite cathode and 8YSZ electrolyte were co-sintered at 1150 °C < T < 1250 °C. Crystallographically stable LSM compositions within the design were identified. However, the cathode and silicate/electrolyte interacted by interdiffusion of Zn (gas diffusion) and Mn (solid diffusion), and by the formation of several reaction phases (between silicate and cathode only). Introducing silicate poisoning decreased the electrochemical performance of the cell by around 40%. This is likely due to the formation of the Zn- and Mn-rich phase in the cathode, but may also be caused by a higher ohmic resistance of the current collector.     

Temperature- and frequency-dependent hysteresis scaling behaviour and phase transitions in a [001]c 0.73Pb(Mg1/3Nb2/3)O3-0.27PbTiO3 single crystal

The dielectric properties and bipolar polarization-electric field (P-E) and strain-electric field (S-E) dynamic hysteresis of a relaxor [001]_c 0.73Pb(Mg_1/3Nb_2/3)O₃-0.27PbTiO₃ (PMN-0.27PT) single crystal were investigated to reveal more details of the temperature-induced phase transitions. Different linear scaling relations for ferroelectric hysteresis area <A>, coercive field E_c, saturation polarization P_s and remnant polarization P_r versus temperature τ were measured in different temperature regions. For each measurement frequency f, all hysteresis parameters were found to decrease linearly with temperature in the temperature range of the single rhombohedral (R) phase or tetragonal (T) phase, and the rate of decrease in the T phase was observed to be much larger than the corresponding rate in the R phase. In the temperature range near the R-T phase transition, the exponent α in the power law <A>∝f ^α for the R phase was found to be smaller than that for the T phase, and the magnitude of α depended strongly on temperature when the crystal was in the R-T coexisting phase state. Our experimental and theoretical results indicate that the difference in the activation energy and dipole moment in the R and T phases may lead to the observed discrepancy for the P-E and S-E hysteresis behaviour in different temperature regions.