Gelling behavior of MgAl2O4 slurries with a common dispersant

MgAl₂O₄ transparent ceramics were shaped by a commonly used polyacrylic acid (PAA), which acted as both dispersant and gelling agent. The spinel slurries were prepared by ball-milling MgAl₂O₄ powder, PAA, and water in an attrition mill. The gelling of slurries happened at room temperature in air atmosphere without any other organic additive. The gelling mechanism was the formation of chelates between Mg²⁺ and carboxyl groups (-COO⁻) of PAA. The frequency-based testing method was applied to investigate the gelling process of the as-prepared slurry. In addition, a novel in situ characterization method based on a modified indentation testing was invented to better understand the strengthening of the wet green body with time and to guide when demolding could be carried out. After sintering, transparent MgAl₂O₄ ceramics with high in-line transmittance were resulted.     

Eco-friendly tape casting of borosilicate glass/Al2O3 sheets for LTCC applications

This work reports the innovative development of a borosilicate glass/Al₂O₃ tape for LTCC applications using an eco-friendly aqueous tape casting slurry. Polyvinylpyrrolidone (PVP) and polyacrylic acid (PAA) were the respective dispersants, while carboxymethyl cellulose (CMC) and styrene acrylic emulsion (SA) were the respective binders. The results showed that PVP was more suitable than PAA as the dispersant for the aqueous casting slurry, and that 1.5 wt% PVP would achieve well dispersion of CABS glass/Al₂O₃ powder in the aqueous slurry. Moreover, a small amount of 2.0 wt% CMC binder could yield smooth CABS glass/Al₂O₃ tapes crack free. A high-quality CABS glass/Al₂O₃ tape with a smooth surface was made from an aqueous slurry containing 1.5 wt% PVP dispersant, 2.0 wt% CMC binder, and 2.0 wt% PEG-400 plasticizer. The density, tensile strength, and surface roughness of the green tape were 2.05 g/cm³, 0.87 MPa, and 148 nm, respectively. The resulting CABS glass/Al₂O₃ composites sintered at 875 °C exhibited a bulk density of 3.14 g/cm³, a dielectric constant of 8.09, a dielectric loss of 1.0 × 10^?3, a flexural strength of 213 MPa, a thermal expansion coefficient of 5.30 ppm/^°C, and a thermal conductivity of 3.2 W m^?1 K^?1, thus demonstrating its broad prospects in LTCC applications.     

Volatilization of fluorine in a CaO–SiO2–CaF2-based system with the substitution of Na2O with K2O

Cuspidine-based systems are used to control the crystallization in mold fluxes, which is enabled by CaF₂ additions. However, excess CaF₂ increases the corrosion of casting machines. Therefore, Na₂O and K₂O are added to the mold flux system to ensure an optimized crystallization and lubrication ability of the flux with the CaF₂ content. This study investigated the effect of substituting Na₂O with K₂O on the volatilization of fluorine in a CaO–SiO₂–CaF₂-based slag system at high temperatures. The substitution of Na₂O with K₂O was performed at 5 mol% intervals. The volatilization was observed by thermogravimetric analysis under several isothermal conditions. The mass loss was measured at a heating rate of 5, 10, and 20 K/min. As the temperature increased, the volatilization of the mixed samples increased. The activation energy was calculated using the Flynn–Wall–Ozawa and Kissinger–Akahira–Sunose methods. A kinetic analysis of the volatilization of fluorine was conducted using the calculated parameters and several known kinetic models. Consequently, the volatilization of the Na-rich sample was controlled by chemical reactions and that of the K-rich sample was identified to be controlled by a phase-boundary-controlled reaction. These results suggest that the addition of mixed alkali oxide promote the volatilization during the early stages of the reaction. From the post-experimental composition analyses, the remaining Na and K in the samples suggested a different mechanism for the Na and K volatilization. The volatilization of Na increased with time, whereas K volatilized easily during the beginning of the reaction.     

Thermodynamic calculation and microstructure characterization of spinel formation in MgO–Al2O3–C refractories

In this paper, by simulating the gas phase conditions inside the MgO–Al₂O₃–C refractories during continuous casting process and combining with thermodynamic analysis, as well as SEM analysis, the gas-gas and gas-solid formation of MA spinel were clarified in carbon containing refractories. Thermodynamic calculations showed that gas partial pressure of CO, O₂ and Mg could meet the formation and stable existence conditions of MA spinel in MgO–Al₂O₃–C refractories under service environment, and nitrogen could not affect the formation of MA spinel at 1550 °C in the thermodynamic condition. The formation processes of MA spinel were analyzed experimentally under embedding carbon atmosphere. The carbon-coated alumina powders in MgO–Al₂O₃–C refractories prevented the direct contact between magnesia and alumina. Mg gas was formed by carbon thermal reaction, then reacted with alumina (gas-solid) and gas containing aluminum (gas-gas) to generate MA spinel. Through gas-gas or gas-solid reaction, the formation of MA spinel was effectively controlled. By means of SEM analysis, a two-layer structure with dense outer spinel layer and loose inner layer was formed in MgO–Al₂O₃–C refractories.     

The kinetics of copper corrosion in nitric acid

The strategy for the permanent disposal of high-level nuclear waste in Canada involves sealing it in a copper-coated steel container and burying it in a deep geologic repository. During the early emplacement period, the container could be exposed to warm humid air, which could result in the condensation of nitric acid, produced by the radiolysis of the humid air, on the copper surface. Previous studies have suggested that both nitrate and oxygen reduction will drive copper corrosion, with the nitrate reduction kinetics being dependent on the concentration of soluble copper(I) produced by the anodic dissolution of copper in the reaction with oxygen. This study focused on determining the kinetics of nitrate and oxygen reduction and elucidating the synergistic relationship between the two processes. This was investigated using corrosion potential and polarization measurements in conjunction with scanning electron microscopy and X-ray photoelectron spectroscopy. Oxygen reduction was shown to be the dominant cathodic reaction with the oxidation of copper(I) to copper(II) by nitrate, promoting the catalytic cycle involving the reaction of copper(II) with copper to reproduce copper(I).     

汽车加油口双色注射模设计

分析了汽车加油口塑件结构,确定了注射成型方案、进胶方式,并介绍了通过滑块与开模动作配合实现塑件脱模的过程。     

Achieving fabrication of highly transparent Y2O3 ceramics via air pre-sintering by deionization treatment of suspension

An easy albeit quite effective deionization suspension treatment was adopted to alleviate the detrimental effects related to the hydrolysis of Y₂O₃ in an aqueous medium. Fabrication of highly transparent Y₂O₃ ceramics with a fine grain size via air pre-sintering and post–hot isostatic pressing (HIP) treatment without using any sintering additive was achieved using the treated suspensions. The hydrolysis issue of Y₂O₃ powder in an aqueous medium was effectively alleviated by using deionization treatment, and a well-dispersed suspension with a low concentration of dissolved Y³⁺ species was obtained. The dispersed suspensions were consolidated by the centrifugal casting method, and the green bodies derived from the suspension of 35.0 vol% solid loading showed an improved homogeneity with a relative density of 52.1%. Fully dense Y₂O₃ transparent ceramic with high transparency was obtained by pre-sintering consolidated green compacts at a low temperature of 1400°C for 16 h in air followed by a post-HIP treatment at 1550°C for 2 h under 200 MPa pressure. The sample had a fine average grain size of 690 nm. The in-line transmittance of the sample reached 83.3% and 81.8% at 1100 nm and 800 nm, respectively, very close to the theoretical values of Y₂O₃.     

磁性硅铁载铜吸附Hg0动力学机制及密度泛函研究

采用粉末冶金法将纳米单质铜(Cu⁰)、硅铁(FeSi)、四氧化三铁硅涂层(Fe₃O₄@SiO₂)混合煅烧并制备出新型磁性硅铁载铜吸附剂MagFeSi-Cu⁰。实验研究不同烟气温度下MagFeSi-Cu⁰的汞吸附能力基础上,结合颗粒内扩散模型、准二阶动力学模型、Elovich模型及Bangham模型分析了MagFeSi-Cu⁰吸附Hg⁰过程的主要控制步骤。在此基础上,依据密度泛函理论(DFT)研究了不同反应温度下FeSi表面Cu⁰原子与Hg⁰原子的汞齐作用机制。研究结果表明,Bangham模型的拟合值与MagFeSi-Cu⁰汞吸附实验值拟合度最高,MagFeSi-Cu⁰表面痕量Hg⁰吸附由汞的外扩散和表面铜汞齐吸附共同控制;通过密度泛函计算,发现Cu⁰颗粒表面Cu-Hg齐吸附能为-0.534 eV,当烟气温度从80℃上升至200℃时,Hg⁰原子与单质Cu原子的吸附自由能从-22.47 kJ/mol下降至-13.96 kJ/mol,这些结果为深入了解Hg⁰在Cu(111)表面的反应机理提供了理论基础。     

Anisotropic strength and fracture resistance of epoxy-ceramic composite materials produced by ultrasound freeze-casting

The anisotropic mechanical properties of ultrasound freeze cast epoxy-ceramic composite materials were studied by measuring flexural strength and fracture resistance curves (R-curves) using both unnotched and notched three-point beam bending experiments, respectively, cut in three different orientations relative to the directional freezing axis. Three ultrasound frequencies of 0.699, 1.39 and 2.097 MHz were used in order to introduce different length scales into the microstructure, with 0 MHz used as the control samples. For all cases, the composites showed higher strength and fracture resistance when the crack plane cut across the direction of ice growth (denoted as the YX orientation). The anisotropic properties were more evident for the material produced without ultrasound (0 MHz) where the flexural strength was approximately 160% higher for the YX orientation compared to two orthogonal orientations. Most of the fracture resistance increase was found to occur within a crack extension, Δa, of ～0.5 mm. Comparing the fracture resistance at Δa = 0.5 mm for the highly anisotropic 0 MHz samples showed that the YX orientation was approximately 86% tougher than the two orthogonal orientations. When the ultrasound operation frequencies of 0.699, 1.39 and 2.097 MHz were applied, the amount of anisotropy in the strength and fracture resistance gradually decreased as the operating frequency increased. The high strength and fracture resistance for the YX orientation was attributed to the alignment of the ceramic particles along the freeze front direction creating a barrier for crack propagation. Ultrasound modifies the material microstructure, introducing relatively dense ceramic layers perpendicular to the freezing front direction that act as an additional, orthogonal barrier to crack propagation. The addition of the denser layers acts to improve the mechanical properties in the weaker orientations and reduce the overall anisotropy.