锂辉石-氧化钙烧结法提锂的物相重构与动力学

对锂辉石-氧化钙烧结过程进行热力学分析，绘制了各反应Gibbs自由能与温度的关系图。结果表明，Al₂O₃会优先和Na₂O、Li₂O、K₂O反应，然后与CaO反应生成CaO·Al₂O₃，而且烧结温度需高于1060℃以保证LiAlSi₂O₆能够完成晶形转变。并探讨了锂辉石-氧化钙烧结法提锂的反应机理。考察了不同烧结条件对锂浸出率的影响并对熟料进行X射线衍射（XRD）分析表征。实验结果表明，在配料比为1∶1.25、烧结温度1150℃、烧结时间60min时，锂的浸出率达到92.14%，熟料中的主要物相为Ca₂SiO₄与LiAlO₂。利用XRD和扫描电镜-能谱联用仪（SEM-EDS）对熟料与浸出渣的物相、显微形貌及元素分布情况进行了分析表征。为了确定烧结反应的控制性步骤，在最优烧结条件的基础上对烧结过程进行动力学分析，结果表明，锂辉石-氧化钙烧结体系属于球形颗粒三维界面化学反应控制，烧结过程的动力学拟合方程为\mathrm{1}-{(\mathrm{1}-x)}^{\mathrm{1}/\mathrm{3}}=\mathrm{0.00677}t。     

稀土石膏常压酸化法制备硫酸钙晶须的研究

以含稀土的石膏为原料运用常压酸化法合成硫酸钙晶须,探讨了不同工艺条件对生成的硫酸钙晶须形貌的影响,同时还考察了晶型助长剂的种类和晶型助长剂的含量对硫酸钙晶须生长的影响,利用SEM和XRD分别对硫酸钙晶须的表面形貌、物相特征做了表征分析。实验得到制备硫酸钙晶须的最佳的反应条件：稀土石膏质量浓度为0.22 g/mL、反应时间为25 min、盐酸浓度为2.8 mol/L、反应温度为70 ℃、陈化时间为4 h,在此条件下合成的硫酸钙晶须平均长度为61 μm,平均长径比为30.5;通过对比实验选出了CuCl₂作为促进硫酸钙晶须生长的助长剂,在添加5%（质量分数）的CuCl₂的情况下可使硫酸钙晶须长径比从30.5增至41,长度从61 μm增至81 μm。     

烧结时间对含铅玻璃制备微晶玻璃析晶及性能的影响

以铅玻璃与粉煤灰为原料，通过协同熔炼制备了微晶玻璃。通过XRD和SEM等手段研究了不同烧结时间下微晶玻璃的物相组成及显微结构，测定了微晶玻璃的密度、吸水率、维氏硬度和化学抗性。结果表明: 延长烧结时间对含铅玻璃加入量为40%(FG40)、50%(FG50)样品的晶相类型和晶化程度有影响，而对含铅玻璃加入量为60%(FG60)、70%(FG70)和80%(FG80)样品的影响较小。随着烧结时间延长，样品晶化程度提高，晶体长大，玻璃相减少。适宜的含铅玻璃加入量为50%~70%，对应的FG50、FG60、FG70样品最佳烧结时间分别为4 h、3 h、3 h。     

Low-temperature hot-press sintering of AlN ceramics with MgO–CaO–Al2O3–SiO2 glass additives for ceramic heater applications

Aluminum nitride (AlN) is used a ceramic heater material for the semiconductor industry. Because extremely high temperatures are required to achieve dense AlN components, sintering aids such as Y₂O₃ are typically added to reduce the sintering temperature and time. To further reduce the sintering temperature, in this study, a low-melting-temperature glass (MgO–CaO–Al₂O₃–SiO₂; MCAS) was used as a sintering additive for AlN. With MCAS addition, fully dense AlN was obtained by hot-press sintering at 1500 °C for 3 h at 30 MPa. The mechanical properties, thermal conductivity, and volume resistance of the sintered AlN–MCAS sample were evaluated and compared with those of a reference sample (AlN prepared with 5 wt% Y2O3 sintering aid sintered at 1750 °C for 8 h at 10 MPa). The thermal conductivity of AlN prepared with 0.5 wt% MCAS was 91.2 W/m?K, which was 84.8 W/m?K lower than that of the reference sample at 25 °C; however, the difference in thermal conductivity between the samples was only 14.2 W/m?K at the ceramic-heater operating temperature of 500 °C. The flexural strength of AlN–MCAS was 550 MPa, which was higher than that of the reference sample (425 MPa); this was attributed to the smaller grain size achieved by low-temperature sintering. The volume resistance of AlN–MCAS was lower than that of the reference sample in the range of 200–400 °C. However, the resistivity of the proposed AlN–MCAS sample was higher than that of the reference sample (500 °C) owing to grain-boundary scattering of phonons. In summary, the proposed sintering strategy produces AlN materials for heater applications with low production cost, while achieving the properties required by the semiconductor industry.     

Theoretical kinetic study of the reaction between dimethyl disulfide and OH radicals

The potential energy profile of the reaction between dimethyl disulfide and OH^? radicals is explored by utilizing ab initio and hybrid meta density functional theory methods. Having the energies and structural data of the stationary points, statistical rate theories, such as transition state theory and variable reaction coordinate-transition state theory, are employed to compute the overall rate constants, and discuss the mechanism and product channels. On the basis of the calculations, the overall rate coefficient is predicted to be 2.49?×?10^?10?cm³?molecule^?1?s^?1 at 298?K. It is found that in the most favorable pathway, the reaction proceeds via formation of the relatively unstable intermediate CH₃S^?(OH)SCH₃ decomposing rapidly to yield CH₃S^?+CH₃SOH.     

Role of MgO on densification and mechanical properties in spark plasma sintered Os0.9Re0.1B2 ceramic

To promote the densification and therefore the mechanical properties of boride-based ceramics, MgO was added as sintering aid into Os_0.9Re_0.1B₂ powders for densification by using spark plasma sintering (SPS). The Os_0.9Re_0.1B₂ powders were synthesized by mechanochemical method from powder mixture of Os, Re and amorphous B. The role of MgO on densification, phase composition, microstructure and mechanical properties (hardness, fracture toughness and wear behavior) were studied by using X-ray diffraction (XRD), scanning electron microscope (SEM) with energy-dispersive spectroscopy (EDS), micro indentation and ball-on-disk tribometer. The results show that, with the introduction of MgO as sintering aid, the relative density of the Os_0.9Re_0.1B₂ ceramic samples increased. When the MgO content reached 9 wt%, the as-sintered sample is almost fully dense. No obvious regularity was found from the samples with the addition of different content of MgO. Vickers hardness values of the samples with 0, 3 wt% and 9 wt% MgO are found to be very close with each other within the experimental error (~30 GPa), while the sample with the addition of 6 wt% MgO exhibits the highest hardness of ~35 GPa. The fracture toughness of the samples is decreased slightly with the addition of MgO. The friction coefficient and wear rate of the sample with the addition of 6 wt% MgO was also found to be the lowest among all samples, which indicate best wear resistance. As a whole, with the addition content of 6 wt% MgO, the Os_0.9Re_0.1B₂ ceramic sample performs relatively excellent mechanical properties among four groups of samples.     

Effects of short carbon fiber on the macro-properties,mechanical performance and microstructure of SiSiC composite fabricated by selective laser sintering

Selective laser sintering was combined with reactive melt infiltration to fabricate SiSiC part, and the effects of carbon fiber (C_f) on the properties of the SLS green body, the carbonized and final SiSiC sample were investigated. Results show that the addition of an appropriate amount of C_f (1.59 wt%~2.97 wt%) can increase the bulk density and geometric precision of the sample at all stages, and improve the mechanical properties of green and carbonized samples. The main phases composed of the SiSiC composite were free Si, a-SiC, β-SiC, plus a very small amount of Al–Si alloy. With 1.59 wt% C_f addition, a relatively comprehensive favorable macro-properties of both the green sample and carbonized sample was achieved, and the homogeneous microstructure of the latter favored the decreased free Si content and increased β-SiC content of the final composite. The evolution mechanism of C_f added to the raw material is inferred to be the mutual diffusion of [C] and [Si] that occurred at the C_f/Si melt boundary leading to the formation of the siliconized C_f with relatively large diameter size (24.3 μm) and high aspect ratio (>30). Amorphous C, which derived from the pyrolysis of epoxy resin E12, undergone a dissolution-precipitation mechanism with the formation of fine-grain β-SiC.     

Evolution of properties of parts during MIM and sintering of recycled oxide particles

Metal injection moulding (MIM) is an established process for high volume production of complex shaped metallic parts using commercially available feedstocks. The characteristics of parts after moulding, debinding, and sintering cannot be simply predictable from raw materials because the properties get altered with the process parameters and the corresponding levels of porosity during processing steps. In this study, physical properties, microstructure, and mechanical properties of the MIM parts have been characterised to understand the evolution of strength during various steps in MIM processing. Feedstocks with different binder loading show a considerable difference in physical as well as mechanical characteristics. During sintering of parts which have solid loading of grinding sludge, simultaneous in situ reduction and densification takes place, whereas only densification occurs in carbonyl iron parts. It is, therefore, possible to make complex shaped parts of different levels of porosity from downgraded shop floor metallic waste.     

Preparation of nanocrystalline nickel oxide from nickel hydroxide using spark plasma sintering and inverse Hall-Petch related densification

Nanocrystalline nickel oxide (NiO) was prepared from nickel hydroxide by Spark plasma sintering (SPS) and the mechanisms involved in the densification of NiO were studied. Reverse precipitated nickel hydroxide powders were SPS processed at 400, 600 and 700?°C with 70?MPa pressure. Pure NiO with 12?nm crystallite size formed after 400?°C sintering process. However NiO grains had grown to 18 and 38?nm after 600 and 700?°C sintering respectively. NiO pellets prepared using 600 and 700?°C SPS sintering schedules had relative densities of 83% and 94% respectively. Two displacement rate regimes were observed during densification of NiO in both 600 and 700?°C sintering processes. Decomposition of nickel hydroxide and particle sliding of NiO led to first displacement rate maximum while inverse Hall-Petch based plastic deformation facilitated densification during the constant second displacement rate regime. No densification occurred during sintering holding times indicating the limited role that diffusion played during densification.     

Effects of anion and cation doping on the thermoelectric properties of n-type PbS

The PbCl_xS_1-x and Pb_1-xBi_xS (x? =?0–0.05) bulks were fabricated with a facile method of hydrothermal synthesis and microwave sintering, and the effect of anionic and cationic donors on the thermoelectric performance of PbS was investigated. Although Cl^? and Bi³⁺ both effectively improved the thermoelectric properties of n-type PbS, more excellent thermoelectric performance was obtained from Cl^? doped samples because of higher electrical property and lower thermal conductivity at higher temperature (T? >?600?K). The thermoelectric figure of merit (ZT) reaches 1.04 for PbCl_0.015S_0.985 at 800?K and increases with temperature increasing without sign of saturation, which is probably the highest value ever reported for single-phase polycrystalline n-type PbS. The results also indicate that the hydrothermal synthesis and microwave sintering can realize anion doping as well as cation doping for n-type PbS at low cost, and PbS should be a robust alternative for PbTe thermoelectric materials.