A review of in-situ high-temperature characterizations for understanding the processes in metallurgical engineering

For the rational manipulation of the production quality of high-temperature metallurgical engineering,there are many challenges in understanding the processes involved because of the black box chemical/electrochemical reactors.To overcome this issue,various in-situ characterization methods have been recently developed to analyze the interactions between the composition,microstructure,and solid-liquid interface of high-temperature electrochemical electrodes and molten salts.In this review,recent progress of in-situ hightemperature characterization techniques is discussed to summarize the advances in understanding the processes in metallurgical engineering.In-situ high-temperature technologies and analytical methods mainly include synchrotron X-ray diffraction(s-XRD),laser scanning confocal microscopy,and X-ray computed microtomography(X-rayμ-CT),which are important platforms for analyzing the structure and morphology of the electrodes to reveal the complexity and variability of their interfaces.In addition,laser-induced breakdown spectroscopy,high-temperature Raman spectroscopy,and ultraviolet-visible absorption spectroscopy provide microscale characterizations of the composition and structure of molten salts.More importantly,the combination of X-rayμ-CT and s-XRD techniques enables the investigation of the chemical reaction mechanisms at the two-phase interface.Therefore,these in-situ methods are essential for analyzing the chemical/electrochemical kinetics of high-temperature reaction processes and establishing the theoretical principles for the efficient and stable operation of chemical/electrochemical metallurgical processes.

High-temperature thermal stability of C/C−ZrC−SiC composites via region labeling method

To investigate the thermal stability of ceramic-matrix composites,three kinds of C/C−ZrC−SiC composites with different Zr/Si molar ratios were synthesized by reactive melt infiltration.Employing region labeling method,the high-temperature thermal stability of the composites was systematically studied by changing the temperature and holding time of thermal treatment.Results show that the mass loss rate of low Si composites has a growth trend with increasing temperature,and a crystal transformation from β-SiC toα-SiC occurs in the composites.In the calibrated area,SiC phase experiences Ostwald ripening and volume change with location migration,while ZrC phase experiences a re-sintering process with diffusion.Moreover,it is found that increasing temperature has a more obvious effect on the thermal stability than extending holding time,which is mainly attributed to the faster diffusion rate of atoms.

Integrated multi-scale approach combining global homogenization and local refinement for multi-field analysis of high-temperature superconducting composite magnets

Second-generation high-temperature superconducting(HTS)conductors,specifically rare earth-barium-copper-oxide(REBCO)coated conductor(CC)tapes,are promising candidates for high-energy and high-field superconducting applications.With respect to epoxy-impregnated REBCO composite magnets that comprise multilayer components,the thermomechanical characteristics of each component differ considerably under extremely low temperatures and strong electromagnetic fields.Traditional numerical models include homogenized orthotropic models,which simplify overall field calculation but miss detailed multi-physics aspects,and full refinement(FR)ones that are thorough but computationally demanding.Herein,we propose an extended multi-scale approach for analyzing the multi-field characteristics of an epoxy-impregnated composite magnet assembled by HTS pancake coils.This approach combines a global homogenization(GH)scheme based on the homogenized electromagnetic T-A model,a method for solving Maxwell's equations for superconducting materials based on the current vector potential T and the magnetic field vector potential A,and a homogenized orthotropic thermoelastic model to assess the electromagnetic and thermoelastic properties at the macroscopic scale.We then identify“dangerous regions”at the macroscopic scale and obtain finer details using a local refinement(LR)scheme to capture the responses of each component material in the HTS composite tapes at the mesoscopic scale.The results of the present GH-LR multi-scale approach agree well with those of the FR scheme and the experimental data in the literature,indicating that the present approach is accurate and efficient.The proposed GH-LR multi-scale approach can serve as a valuable tool for evaluating the risk of failure in large-scale HTS composite magnets.

Analysis on high-temperature oxidation and growth stress of iron-based alloy using phase field method

High-temperature oxidation is an important property to evaluate thermal protection materials. However, since oxidation is a complex process involving microstructure evolution, its quantitative analysis has always been a challenge. In this work, a phase field method （PFM） based on the thermodynamics theory is developed to simulate the oxidation behavior and oxidation induced growth stress. It involves microstructure evolution and solves the problem of quantitatively computational analysis for the oxidation behavior and growth stress. Employing this method, the diffusion process, oxidation performance, and stress evolution axe predicted for Fe-Cr-A1-Y alloys. The numerical results agree well with the experimental data. The linear relationship between the maximum growth stress and the environment oxygen concentration is found. PFM provides a powerful tool to investigate high-temperature oxidation in complex environments.

Characterization of Calcined Kaolin/TiO_2 Composite Particle Material Prepared by Mechano-Chemical Method

Calcined kaolin/TiO2 composite particle material （CK/TCPM） was prepared with TiO2 coating on the surfaces of calcined kaolin particles by the mechano-chemical method. X-ray diffraction （XRD） and scanning electron microscope （SEM） were used to investigate the microstructures and morphologies, respectively. The mechanism of the mechano-chemical reaction between calcined kaolin and TiO2 was studied by infrared spectra （IR）. The results show that TiO2 coats evenly on the surfaces of calcined kaolin particles by Si-O-Ti and Al-O-Ti bonds on their interfaces. The hiding power and whiteness of CK/TCPM are 17.12 g/m^2 and 95.7%, respectively, presenting its similarity to TiO2 in pigment properties.

Effects of ultrasonic impregnation combined with calcination in N_2 atmosphere on the property of Co_3O_4/CeO_2 composites for catalytic methane combustion

CoO/CeOcomposites with high surface areas and ultrafine crystalline sizes for catalytic combustion of methane were firstly prepared by a new sol-gel method which combined ultrasonic impregnation treatment and calcination in Natmosphere. The samples were characterized by various means such as nitrogen adsorption/desorption, X-ray diffraction(XRD), Htemperature-programmed reduction(H-TPR),X-ray photoelectron spectroscopy(XPS) and transmission electron microscopy(TEM). Results showed that the modified catalyst had the mesoporous structure, comparatively higher amount of surface oxygen and larger oxygen vacancies than others. As a result of the structure and surface composition merits, a high methane combustion conversion(50%) could be obtained at a low temperature of 262 °C for the modified CoO/CeOcomposites catalysts. The experimental results demonstrated that ultrasonic impregnation treatment combined with the Nthermal treatment prior to calcination in air had a promising application for preparation of CoO/CeOcomposites catalysts for low-temperature catalytic combustion of methane.

Dissolution-precipitation mechanism of self-propagating high-temperature synthesis of TiC-Cu cermets

The mechanism of self-propagating high-temperature synthesis （SHS） of TiC-Cu cermets was studied using a combustion front quenching method. Microstructural evolution in the quenched sample was observed using scanning electron microscope （SEM） with energy dispersive X-ray （EDX） spectrometry, and the combustion temperature was measured. The results showed that the combustion reaction started with local formation of Ti-Cu melt and could be described with the dissolution-precipitation mechanism, namely, Ti, Cu, and C particles dissolved into the Ti-Cu solution and TiC particles precipitated in the saturated Ti-Cu-C liquid solution. The local formation of Ti-Cu melt resulted from the solid diffusion between Ti and Cu particles.

Spatial Distribution of High-temperature Risk with a Return Period of Different Years in the Yangtze River Delta Urban Agglomeration

Against the background of global warming,research on the spatial distribution of high-temperature risk is of great significance to effectively prevent the adverse effects of high temperatures.By using air temperature data from 1951 to 2018 measured by meteorological stations located in the Yangtze River Delta urban agglomeration,the daily maximum air temperature distribution is interpolated at a resolution of 1 km based on the local thin disk smooth spline function;the high-temperature threshold for return periods of 5,10,20 and 30 yr are then calculated by using the generalized extreme value method.The yearly average high-temperature intensity and high-temperature days are finally calculated as high-temperature danger factors.Socioeconomic statistical data and remotely sensed image data in 2018 are used as the background data to calculate the spatial distribution of high-temperature vulnerability factors and prevention capacity factors,which are then used to compute the high-temperature risk index during different recurrence periods in the Yangtze River Delta urban agglomerations.The results show that the spatial distribution features of high-temperature risk in different return periods are similar.The high-temperature risk index gradually increases from northeast to southwest and from east coast to inland,which has obvious latitude variation characteristics and a relationship with the comprehensive influence of the underlying surface and urban scale.In terms of time variation,the high-temperature risk index and its spatial distribution difference gradually decreases with increasing return period.In different cities,the high-temperature risk in the central area of the city is generally higher than that in the surrounding suburban areas.Jinhua,Hangzhou of Zhejiang Province and Xuancheng of Anhui Province are the top three cities with high-temperature risk in the study area.

Correlated-Electron Systems and High-Temperature Superconductivity

We present recent theoretical results on superconductivity in correlated-electron systems, especially in the two-dimensional Hubbard model and the three-band d-p model. The mechanism of superconductivity in high-temperature superconductors has been extensively studied on the basis of various electronic models and also electron-phonon models. In this study, we investigate the properties of superconductivity in correlated-electron systems by using numerical methods such as the variational Monte Carlo method and the quantum Monte Carlomethod. The Hubbard model is one of basic models for strongly correlated electron systems, and is regarded as the model of cuprate high temperature superconductors. The d-p model is more realistic model for cuprates. The superconducting condensation energy obtained by adopting the Gutzwiller ansatz is in reasonable agreement with the condensation energy estimated for YBa2Cu3O7. We show the phase diagram of the ground state using this method. We have further investigated the stability of striped and checkerboard states in the under-doped region. Holes doped in a half-filled square lattice lead to an incommensurate spin and charge density wave. The relationship of the hole density x and incommensurability δ, δ~x, is satisfied in the lower doping region, as indicated by the variationalMonte Carlocalculations for the two-dimensional Hubbard model. A checkerboard-like charge-density modulation with a roughly period has also been observed by scanning tunneling microscopy experiments in Bi2212 and Na-CCOC compounds. We have performed a variational Monte Carlo simulation on a two-dimensional t-t′-t″- U Hubbard model with a Bi-2212 type band structure and found that the period checkerboard spin modulation, that is characterized by multi Q vectors, is indeed stabilized. We have further performed an investigation by using a quantumMonte Carlomethod, which is a numerical method that can be used to simulate the behavior of correlated electron systems. We present a new algorithm of the quantum Monte Carlo diagonalization that is a method for the evaluation of expectation value without the negative sign problem. We compute pair correlation functions and show that pair correlation is indeed enhanced with hole doping.

Controllable synthesis of CuAlO_(2) via solid-phase method and its catalytic performance for methanol steam reforming to hydrogen

This study explores the controllable synthesis of CuAlO_(2) using copper hydroxide and pseudo-boehmite powders as raw materials via a simple solid-phase ball milling method,along with its catalytic performance investigation in methanol steam reforming(MSR).Various catalysts were prepared under different conditions,such as calcination temperature,calcination atmosphere,and heating rate.Characterization techniques including BET,XRD,XPS,SEM and H2-TPR were employed to analyze the samples.The results revealed significant effects of calcination temperature on the phase compositions,specific surface area,reduction performance,and surface properties of the CA-T catalysts.Based on the findings,a synthesis route of CuAlO_(2) via the solid-phase method was proposed,highlighting the importance of high calcination temperature,nitrogen atmosphere,and low heating rate for CuAlO_(2) formation.Catalytic evaluation data demonstrated that CuAlO_(2) could catalyze MSR without pre-reduction,with the catalytic performance of CA-T catalysts being notably influenced by calcination temperature.Among the prepared catalysts,the CA-1100 catalyst exhibited the highest catalytic activity and stability.The findings of this study might be useful for the further study of the catalytic material for sustained release catalysis,including the synthesis of catalytic materials and the regulation of sustained release catalytic performance.

Influence of Replacement Level of Coal-series Kaolin on Hydration of Ordinary Portland Cement by X-ray Diffraction/Rietveld Method

The influence of replacement level of calcined coal-series kaolin(CCK) on hydration of ordinary Portland cement(OPC) was studied by X-ray diffraction(XRD)/Rietveld method. X-ray diffraction/Rietveld method was used to quantify the crystalline phase composition of the hydrated samples. Additionally, the morphology of hydrated samples was observed by scanning electron microscopy(SEM). The results showed that, calcium hydroxide(CH), ettringite(AFt) and amorphous phase content in hydrated samples decreased as the replacement level of CCK increased, while AFm and str?tlingite increased, which was caused by the combination of dilute, physical and pozzolanic effects. The hydration of anhydrous cement phases was accelerated by physical effect but hindered by the retardation effect of CCK. The role of each effects was discussed in detail to analyze the mechanism of OPC hydration with CCK addition. The SEM images showed that the shortening of AFt at 1 day and the denser texture at 28 days was observed with CCK addition, which was caused by the physical and pozzolanic effects, respectively.

Grain Growth Kinetics of SnO_2 Nanocrystals Synthesized by Precipitation Method

Monodispersed spheroidal SnO2 nanocrystals with the grain size of 8-30 nm were synthesized by the precipitation method using SnCl4·5H2O （stannic chloride hydrate） as raw materials.Differential scanning calorimetry/thermogravimetry （DSC/TG）,X-ray diffraction （XRD） and transmission electron microscope （TEM） were used to characterize the structure of SnO2 nanocrystals.The influences of the calcination temperature and time on the lattice constant,the lattice distortion and the grain size of SnO2 nanocrystals were discussed based on the XRD results.The grain growth kinetics of SnO2 nanocrystals during calcination process was simulated with a conventional grain growth model which only took into account of diffusion and with a new isothermal model proposed by our group,which took into account of both diffusion and surface reactions.Using conventional model,the grain growth rate constant of SnO2 crystals is 1.55×104nm5/min with a pre-exponential factor of 5 and an activation energy of 108.62 kJ/mol.Compared with the convention model,the new isothermal model is more realistic in reflecting the grain growth behavior of SnO2 nanocrystals during the calcination process.This indicates that the grain growth of SnO2 nanocrystals is controlled by both diffusion and reaction factors,and the effect of surface reactivity on the grain growth of SnO2 nanocrystals could not be ignored.A combined activation energy estimated with the new isothermal model is 53.46 kJ/mol.

Preparation of Layered Potassium Titanate Whiskers with Large Length-diameter Ratio by KDC Method

Pure K2Ti4O9 whiskers were prepared by KDC（Kneading-Drying-Calcination） method with TiO2 and K2CO3 as raw materials. The influences of TiO2/K2CO3 molar ratio（RT/K）, calcination temperature（TC） and cooling process on phase composition and morphology of the whiskers were investigated by TG-DSC（thermo gravimetric-differential scanning calorimeter）, XRD（X-ray diffraction）, and SEM（scanning electron microscope）. Pure K2Ti4O9 potassium titanate whiskers with large length-diameter ratio（r）（over 250） can be obtained at RT/K = 2.9 and TC = 950 ℃.

Synthesis and microstructure of single-phase BiFeO_3 Powders by Sol-gel Method

The single-phase BiFeO3 powders were prepared by sol-gel method with the starting materials of bismuth nitrate and ferric nitrate, and the effect of the calcined temperature on the phases of BiFeO3 samples was studied. The x-ray diffraction (XRD)showed that the single-phase BiFeO3 powders were obtained with a calcined temperature of 700 ℃. The scanning electron microscope(SEM)analysis indicated that the grain size was around 500 nm in single-phase BiFeO3 powders, and uniform particle size distribution. The FT-IR spectra showed that the BiFeO3 powders began to crystallize at 500℃.

煅烧菱镁矿对油井水泥石综合性能的影响

【目的】解决油井水泥在水化过程中因体积收缩而导致水泥环出现微裂缝、进而出现一系列固井作业安全问题。【方法】以菱镁矿为原料,采取不同的煅烧工艺制备具有不同活性的氧化镁膨胀剂(magnesia expansive agent,MEA),探讨煅烧工艺对MEA的微观结构和活性的影响,研究掺加不同活性MEA的油井水泥石的膨胀性能、抗压强度和渗透率性能。【结果】菱镁矿煅烧温度为900℃、煅烧时间为30 min时,菱镁矿出现欠烧现象,制得的MEA虽然活性较高,但膨胀性能较弱,水泥石的14 d线性体积膨胀率仅为5.37‱;菱镁矿煅烧温度为1200℃、煅烧时间为90 min时生成的MEA活性较低,MEA水化所需诱导时间较长,水泥石体膨胀量较小,水泥石的14 d线性体积膨胀率仅3.26‱。【结论】活性较高且有效成分多的MEA水化产生较大的膨胀力会破环水泥石的内部结构,综合考虑掺MEA水泥石的膨胀性能、力学性能、渗透率性能,菱镁矿最优煅烧方法为煅烧温度1100℃、煅烧时间90 min。

金属有机骨架和g-C_(3)N_(4)共掺杂改性TiO_(2)光催化性能

以钛酸四丁酯、三聚氰胺、二甲基咪唑和Co(NO_(3))_(2)•6H_(2)O为原料,采用溶胶-凝胶法、高温煅烧法,将类石墨相氮化碳(g-C_(3)N_(4))和二甲基咪唑钴(ZIF-67)与TiO_(2)共掺杂,制备了TiO_(2)-g-C_(3)N_(4)-ZIF-67光催化剂。采用XRD、XPS、SEM和紫外-可见漫反射光谱(UV-Vis DRS)对TiO_(2)-g-C_(3)N_(4)-ZIF-67进行了表征,对TiO_(2)-g-C_(3)N_(4)-ZIF-67光催化降解甲基橙的催化活性进行了评价,并对其催化机理进行了推测。结果表明,TiO_(2)-g-C_(3)N_(4)-ZIF-67同时包含锐钛矿及少量金红石相TiO_(2)、g-C_(3)N_(4)及ZIF-67;g-C_(3)N_(4)的加入使TiO_(2)的带隙降至2.45 eV,ZIF-67将带隙进一步降至1.91 eV;g-C_(3)N_(4)和ZIF-67的共掺杂降低了带隙,显著提高了TiO_(2)可见光吸收范围(492~649 nm);TiO_(2)-g-C_(3)N_(4)-ZIF-67形成了Ⅱ型异质结,TiO_(2)-g-C_(3)N_(4)与金属有机骨架的结合增强了TiO_(2)光催化降解甲基橙的能力。Co质量分数21.5%的TiO_(2)-g-C_(3)N_(4)-ZIF-67-2具有最佳的光催化降解甲基橙活性,在可见光照射40 min时,甲基橙降解率可达79.92%,3次循环后甲基橙降解率为58.86%(90 min),光催化反应对ZIF-67的结晶度有所影响,进而影响了循环时的光催化活性。

硼砂煅制工艺优化及质量评价

目的 优化硼砂煅制工艺,并对其进行质量评价。方法 以铺设厚度、煅制温度、煅制时间为影响因素,失水率、蓬松度、粉碎率、四硼酸钠含量为评价指标,星点设计-效应面法优化硼砂煅制工艺。采用扫描电镜(SEM)、热重分析(TG)、拉曼光谱、X射线衍射(XRD),比较硼砂煅制前后质量差异。结果 最佳条件为铺设厚度2 cm,煅制温度365℃,煅制时间100 min。煅制后,硼砂微观形态、成分组成、晶型结构发生变化,失去全部结晶水而转变为非晶体状态。结论 该方法稳定可行,可用于工业大批量生产煅硼砂。

Mo-Sn相互作用对Mo1Sn2催化剂二甲醚低温氧化性能的影响

采用两步水热法制备了一系列Mo-Sn催化剂,通过改变锡氧化物焙烧温度,考察钼氧化物与不同性质锡氧化物之间的作用方式对二甲醚(DME)低温氧化制甲酸甲酯(MF)性能的影响。结果表明,催化剂的性能与处理条件密切相关,当80℃焙烧Sn氧化物,与Mo进行水热作用,通过500℃焙烧得到的MolSn2-80 Sn-500催化剂表现出较好的活性,110℃反应温度下,MF选择性达97.7%,二甲醚转化率为14.7%。通过XRD、Raman、FT-IR、低温ESR、NH_(3)-TPD、CO_(2)-TPD及H_(2)-TPR对催化剂的表面物理化学性质以及钼物种的配位结构进行了表征。结果表明,Sn氧化物焙烧温度的改变影响了钼氧化物在SnO_(2)表面的存在形式,较低温度处理Sn氧化物后,催化剂中MoO_(3)与MoO_(x)共存,且Mo-Sn界面处Mo^(5+)配位结构增多,催化剂表面较多的酸量有利于DME氧化反应进行,强碱不利于MF生成。

磁性ZnO/CoFe_(2)O_(4)复合材料的制备及其光催化性能

为了解决纳米光催化材料在使用后难以回收的问题,采用低温煅烧法制备了磁性ZnO/CoFe_(2)O_(4)复合材料。通过扫描电镜、X射线衍射、红外及紫外-可见漫反射等方法对材料进行了表征,并探讨了ZnO和CoFe_(2)O_(4)不同复合比对材料光催化活性的影响。结果表明,当ZnO与CoFe_(2)O_(4)复合质量比为12∶1时,所得材料的光催化活性最好;在500W氙灯照射下,其对甲基橙的光催化降解活性优于商业P25。光催化捕获实验表明,·OH是降解过程中的最主要活性物种,在重复使用5次后仍有较高的光催化活性,且易于在外部磁场作用下分离回收。

α-MoO_(3)的结构形貌与其催化合成季戊四醇正辛酸酯的构效关系研究

通过溶胶-凝胶法制备一种用于季戊四醇(PER)和正辛酸(OTA)酯化合成季戊四醇正辛酸酯(POE)的α-MoO_(3)催化剂.采用XRD、SEM、XPS和FITR分析手段对α-MoO_(3)粉体进行了表征.结果表明,焙烧温度对α-MoO_(3)的晶相结构、表观形貌及催化性能的影响显著.当焙烧温度达到450℃时,催化剂为正交晶面结构(021)和(110)同时择优取向的α-MoO_(3),样品表面光洁平整、大小均匀、分散性好,同时表现出较高的催化活性.在适宜的反应条件下(T=200℃, t=4 h,酸醇摩尔比n(OTA)∶n(PER)=4.0∶1,催化剂用量n(α-MoO_(3)-450)∶n(PER)=0.005),PER转化率可达98.8%, POE的选择性可达100%.