Phase relationship of complex multi-component system in chromate cleaner production

The phase relationships of the complex multi-component systems in the liquid-phase oxidization and separation process related with the chromate cleaner production are investigated theoretically and experimentally.The phase diagram of main system Fe- Cr_2O_4-KOH-O_2 of oxidization process and the relationship of its standard Gibbs free energy change with temperature are calculated.A se- ries of phase diagrams of the separation process at different temperatures,such as K(Na)OH-K(Na)_2CrO_4-H_2O,KOH-KAlO_2-H_2O, K(Na)OH-K(Na)_2CO_3-H_2O,K(Na)OH-K(Na)HCO_3-H_2O and K(Na)HCO_3-K(Na)_2CrO_4-H_2O have also been calculated.Some ex- periments are carried out to verify the calculated results.Our results showed that the sub-molten salt media are suitable for the oxidization and separation processes;FeCr_2O_4 can be oxidized across a wide range of temperature;K(Na)_2CrO_4 can be separated from K(Na)AlO_2 system at appropriate temperature and proper concentration;the crystallization of carbonate is easier than that of K(Na)_2CrO_4.     

FeO影响CaO-SiO_2-MgO-Al_2O_3-Cr_2O_3体系中含铬尖晶石晶体析出的热力学分析

不锈钢渣中的铬以尖晶石矿物相状态赋存时不易溶出,有利于钢渣的资源化利用。本文基于熔体非平衡凝固理论,采用热力学数据库FactSage 7.0研究了FeO添加量对CaO-SiO_2-MgO-Al_2O_3-Cr_2O_3不锈钢渣体系中尖晶石晶体析出温度、析出量、化学组成及铬元素赋存状态的影响规律。模拟计算结果表明,尖晶石晶体为高温析出相,主要由MgCr_2O_4和FeCr_2O_4组成;随着FeO添加量不断增多,尖晶石晶体的析出温度逐渐降低,其最终析出量逐渐增加,析出物中FeCr_2O_4所占比例增加而MgCr_2O_4相对减少;铬元素的赋存状态未受FeO添加量变化影响,仍以尖晶石固溶体形式存在。     

Carbothermal reduction process of the Fe-Cr-O system

Understanding the reduction behaviors and characteristics of the end products of Fe-Cr-O systems is very important not only for maximizing the recovery of metals from stainless steel dust but also for the subsequent reuse in metallurgical process. The present work first predicted the possible products thermodynamically when FeCr₂O₄ was reduced by C. The reduction behaviors by graphite of three kinds of Fe-Cr-O systems, i.e., FeCr₂O₄, Fe₂O₃+Cr₂O₃, and Fe+Cr₂O₃, were then investigated in 1350–1550℃. Further, the microstructures of final products and element distribution conditions were examined. The results suggest that, thermodynamically, the mass of products for the carbothermal reduction of FeCr₂O₄ is a strong function of temperature, and the initial carbon content is used. More Fe-Cr-C solution and less residual carbon content are obtained at higher temperatures and lower n_C:n_O ratios (the initial molar ratio of C to O in the sample). Experimental data show that the sample amount tends to affect the reduction rate, and the residual carbon content strongly depends on n_C:n_O. With regard to the phases present in products during the reaction process, metal carbides tend to form in the initial stage, whereas Fe-Cr-C solution forms when the degree of reduction is sufficiently high.     

Formation and transformation of volatile nanoparticles from a diesel engine during exhaust dilution

A classic H 2 SO 4-H 2 O binary homogeneous nucleation model coupled to an aerosol dynamics model,suitable for studying the formation and transformation of volatile nanoparticles (VNPs) during diesel engine exhaust dilution,has been developed.Using the H 2 SO 4-H 2 O binary homogeneous nucleation model,the nucleation ratio and molecular cluster size were calculated.The effect of aerosol dynamic processes on VNP number size distributions was studied.The effects of fuel sulfur content (FSC) and sampling conditions in the laboratory on VNP number size distributions were also calculated.Our simulations demonstrated that nucleation increased the cluster number concentration and that FSC,temperature and humidity significantly affected the nucleation ratio and molecular cluster size.Coagulation promoted the evolution of cluster-particle size distributions from monodisperse to polydisperse.Soot present in the exhaust can suppress the formation of VNPs.FSC and sampling conditions,like the primary dilution temperature,the primary dilution relative humidity,residence time and the primary dilution ratio have significant effects on VNP number size distributions.     

Measurement of GaAs start duration in different solution concentration using infrared images

This paper proposes a new infrared method to measure the start duration of GaAs substrate in chemical etching. When etching starts, the temperature of liquid-film will change because of heat release in the chemical reaction. As a result, the start duration of GaAs can be tested by collecting real-time in-frared thermal images in the course of temperature variation. Both theoretical analysis and experi-mental results show that the line shape liquid film of a 2-mm width is a good monitoring subject. By making use of the grey distribution change of a certain cross section of the line shape liquid film, the start duration of reaction between GaAs and H2SO4-H202-H20 is obtained. The start durations of reac-tion between GaAs substrate and H2SO4： H202： H20 （=5：1：50 and 15：3：50） solution are about 0.2 s and 0.3-0.4 s, respectively. This result and relative method will impulse the research of wet chemical etching technology of GaAs and so on.     

Thermodynamics and density functional theory study of potassium dichromate interaction with galena

The adsorption heat and reaction rate constant of potassium dichromate on the surface of galena were studied. The results indicate that potassium dichromate tends to adsorption on the galena surface. The reaction order is only 0.08385, suggesting that the concentration of potassium dichromate has little influence on its adsorption on the galena surface. In addition, the simulation of CrO₄2? adsorption on the PbS (100) surface in the absence and presence of O₂ was carried out by density functional theory (DFT). The calculated results show that CrO₄2? species adsorb energetically at the Pb-S bond site, and the presence of O₂ can enhance this adsorption.     

Acting mechanism of F,K, and Na in the solid phase sintering reaction of the Baiyunebo iron ore

The effect of F, K, and Na on the solid phase reaction of the Baiyunebo iron ore was investigated by differential thermal analysis (DTA) and X-ray diffraction (XRD). It has been identified that alkaline elements K and Na in the Baiyunebo ore instigate the formation of low melting point compounds Na₂SiO₃ and Na₂O·Fe₂O₃ and the generation of molten state in the solid phase sintering. Element F in the Baiyunebo ore facilitates the formation of cuspidine compound 3CaO·2SiO₂·CaF₂ in the solid phase reaction. The cuspidine compound is kept in solid as one of the final products through the entire sintering process due to its high melting point. In the sintering process, CaF₂ and SiO₂ react with CaO first and form 3CaO·2SiO₂·CaF₂ and 3CaO·2SiO₂, so the formation of ferrites, Na₂O·Fe₂O₃, and 2CaO·Fe₂O₃ is inhibited.     

A thermodynamic model of calculating mass action concentrations for structural units or ion couples in NaClO4-H2O and NaF-H2O binary solutions and NaClO4-NaF-H2O ternary solution

A thermodynamic model of calculating mass action concentrations for structural units or ion couples in NaClO₄-H₂O and NaF-H₂O binary solutions and NaClO₄-NaF-H₂O ternary strong electrolyte aqueous solutions was developed based on the ion and molecule coexistence theory (IMCT). A transformation coefficient was needed to compare the calculated mass action concentration and the reported activity, because they were usually obtained at different standard states and concentration units. The results show that transformation coefficients between the calculated mass action concentrations and the reported activities of the same components change in a very narrow range. The transformed mass action concentrations of structural units or ion couples in NaClO₄-H₂O and NaF-H₂O binary solutions agree well with the reported activities. The transformed mass action concentrations of structural units or ion couples in NaClO₄-NaF-H₂O ternary solution are also in good agreement with the reported activities in a total ionic strength range from 0.1 to 0.9 mol/kg H₂O by the 0.1 mol/kg step with different ionic strength fractions of 0, 0.2, 0.4, 0.5, 0.6, 0.8, and 1, respectively. The results indicate that the developed thermodynamic model can reveal the structural characteristics of binary and ternary strong electrolyte aqueous solutions, and the calculated mass action concentrations of structural units or ion couples also strictly follow the mass action law.     

Oxidation behavior of the Fe-36Al-0.09C-0.09B-0.04Zr alloy at 1250°C

To explore and study the Fe-Al system alloy presenting exceptional oxidation resistance at high temperature, the Fe-36Al-0.09C-0.09B-0.04Zr alloy was designed and developed. The microstructure and hardness of the backing at 1250°C were analyzed and measured. Thermodynamics and kinetics of the oxidation behavior were also analyzed by X-ray diffraction, scanning electron microscopy, and energy-dispersive X-ray spectroscopy techniques. The results show that the microstructure of the Fe-36Al-0.09C-0.09B-0.04Zr alloy is FeAl phase at ambient temperature and is stable at 1250°C. It displays the excellent property of oxidation resistance because the oxide film has only the Al₂O₃ layer, and its oxidation kinetics curve obeys the parabolic law at 1250°C. The oxidation mechanism at 1250°C is presumed that in the early oxidation period, the alloy oxidizes to form a large number of Al₂O₃ and a little Fe₂O₃, then, the enrichment of Al caused by Fe oxidization combines with O to form Al₂O₃.     

Xieite, a new mineral of high-pressure FeCr2O4 polymorph

Xieite, a new mineral, occurs in the shock vein of the Suizhou meteorite. The mineral has an orthorhombic structure and its space group is Bbmm. The cell parameters are a = 9.462（6） A, b = 9.562（9） A, c = 2.916（1）A. The crystal-chemical formula is （Fe0.87Mg0.13Mn0.01）1.01（Cr1.62AI0.25Ti0.08V0.02）1.97O4, or simply formula FeCr2O4. Stronger X-ray diffraction lines are [d （A）, I/Io]： （2.675, 100）, （2.389, 20）, （2.089, 10）, （1.953, 90）, （1.566, 60）, （1.439, 15）, （1.425, 15）, （1.337, 40）. Xieite is a high pressure polymorph of FeCr2O4 and formed by solid-state transformation of chromite under shock-induced high pressure and temperature, in association with other high-pressure minerals including ringwoodite, majorite, lingunite and tuite. The P-Tcondition for the formation of xieite is estimated to be 18--23 GPa and 1800--1950℃, respectively. Xieite has recently been approved by the Commission on New Minerals, Nomenclature and Classification of the International Mineralogical Association （IMA 2007-056）. The mineral name, xieite, is named after Xiande Xie.     

Alkaline digestion behavior and alumina extraction from sodium aluminosilicate generated in pyrometallurgical process

In pyrometallurgical process, Al-and Si-bearing minerals in iron and aluminum ores are easily transformed into sodium aluminosilicates in the presence of Na₂O constituents, which alters the leaching behaviors of Al₂O₃ and SiO₂. It was confirmed that sodium aluminosilicates with different phase compositions synthesized at various roasting conditions were effectively digested in the alkaline digestion process. Under the optimum conditions at temperature of 100-120℃, liquid-to-solid ratio (L/S) of 10:2 mL/g, caustic ratio of 4, and Na₂O concentration of 240 g/L, the actual and relative digestion ratio of Al₂O₃ from the synthesized sodium aluminosilicates reached maximums of about 65% and 95%, respectively, while SiO₂ was barely leached out. To validate the superior digestion property of sodium aluminosilicate generated via an actual process, the Bayer digestion of an Al₂O₃-rich material derived from reductive roasting of bauxite and comprising Na_1.75Al_1.75Si_0.25O₄ was conducted; the relative digestion ratio of Al₂O₃ attained 90% at 200℃.     

Effect of Na+ on xonotlite crystals in hydrothermal synthesis

The effect of Na⁺ ion concentration on the crystalline phase composition and morphology of xonotlite crystals prepared in a CaO-SiO₂-H₂O system via hydrothermal synthesis was analyzed. X-ray diffraction (XRD) and scanning electron microscopy (SEM) results indicate that Na⁺ ion concentration has a significant impact on the composition and morphology of crystalline phases in the products under the initial conditions of a molar ratio of CaO/SiO₂ of 1.0 and a reactant concentration of 0.05 mol·L^?1 at 225°C for 15 h. The main crystalline phase in the products has a phase transition from xonotlite to pectolite, and the morphology changes from fibrous to broomlike shape with the Na⁺ ion concentration increasing. Therefore, the content of Na₂O in the raw material should be less than 5wt% for preparing pure xonotlite crystals via hydrothermal synthesis in a CaO-SiO₂-H₂O system.     

Experimental and kinetic study on ignition delay times of methane/hydrogen/oxygen/nitrogen mixtures by shock tube

Ignition delay times of methane/hydrogen/oxygen/nitrogen mixtures with hydrogen amount-of-substance fractions ranging from 0–20% were measured in a shock tube facility.The ambient temperature varied from 1422 to 1877 K and the pressure was maintained at 0.4 MPa behind the reflected shock wave.The experiments were conducted at an equivalence ratio of 2.0.The fuel mixtures were diluted with nitrogen gas so that the nitrogen amount-of-substance fraction was 95%.The experimental ignition delay time of the CH4/H2 mixture decreased as the hydrogen amount-of-substance fraction increased.The enhancement of ignition by hydrogen addition was weak when the ambient temperature was >1750 K,and strong when the temperature was <1725 K.The ignition delay time of 20% H2/80% CH4 was only one-third that of 100% CH4 at 1500 K.A modified model based on GRI-Mech 3.0 was proposed and used to calculate the ignition delay times of test mixtures.The calculated results agreed with the experimental ignition delay times.Normalized sensitivity analysis showed that HO·+H2 →H·+H2O was the main reaction for the formation of the H· at 1400 K.As the hydrogen amount-of-substance fraction increased,chain branching was enhanced through the reaction H·+O2→O·+HO·,and this reduced the ignition delay time.At 1800 K,the methyl radical (H3C·) became the key species that influenced the ignition of the CH4/H2/O2/N2 mixtures,and sensitivity coefficients of the chain termination reaction 2H3C·(+M)→C2H6(+M),and chain propagation reaction HO2+H3C·→HO·+CH3O decreased,which reduced the influence of hydrogen addition on the ignition of the CH4/H2 mixtures.     

新疆尉犁蛭石矿蛭石的化学成分研究

对尉犁蛭石矿床的11个蛭石样品和6个金云母样品进行标准X—射线荧光分析得到其化学组成.一般地,蛭石化学组成为:SiO_2>42.49(％),MgO>27.15,Al_2O_3<14.K_2O+Na_2O<8.25;金云母化学组成为:SiO_2<42.01,MgO<26.75,Al_2O_3>14.K_2O+Na_2O>10.07.根据其成分分析结果计算蛭石和金云母的结构式,同时对其主要化学组成之间的关系进行讨论.在由金云母向蛭石的转变过程中,很明显地存在着元素的再分配,Al_2O_3和K_2O含量降低,SiO_2和MgO富集.     

镍基合金CMSX-4在3.5wt.% NaCl溶液中的腐蚀行为

研究二代镍基合金CMSX-4在质量分数为3.5% NaCl溶液中的腐蚀行为,对该类合金在海洋性环境条件下的应用具有深远意义。通过动电位极化方法研究室温条件下镍基合金CMSX-4在3.5 wt.% NaCl溶液中的电化学行为,利用扫描电子显微镜（SEM）、能谱分析仪（EDS）和X射线光电子能谱仪（XPS）对合金表面阳极腐蚀产物进行微观形貌观察及成分分析。研究表明,CMSX-4合金具有一定的钝化能力,钝化区间比较宽广;在镍基合金CMSX-4表面上形成的腐蚀产物可大致分为两层,表层主要由Ni （OH）₂、Cr （OH）₃、Co （OH）₂和Al （OH）₃等氢氧化物组成,内层主要分布着NiO、Al₂O₃、CoO、Cr₂O₃和CrO₃等氧化物及组成合金基体的各种金属;由Ni （OH）₂和Cr （OH）₃等氢氧化物组成的腐蚀产物膜外层能够在腐蚀介质和金属之间产生较好的屏蔽效果;构成腐蚀产物膜内层的NiO、Al₂O₃、Cr₂O₃和CrO₃等氧化物有利于产物膜内层与外层之间建立一定的空间电荷区,对稳定腐蚀产物内层有很大帮助。研究表明CMSX-4合金在海洋性环境中具有一定的耐蚀性能。     

低温电解条件下铝电解用NiFe_2O_4-10NiO基金属陶瓷阳极Fe元素腐蚀行为研究

采用粉末冶金技术制备出铝电解用NiFe2O4-10NiO陶瓷基体和30(40Cu-Ni)/(NiFe2O4-10NiO)金属陶瓷阳极,并在低温电解条件下,对NiFe2O4陶瓷相中Fe元素的腐蚀行为进行研究。结果表明,在烧结过程中,NiFe2O4尖晶石陶瓷基体会在氮气中发生离解,在动态化学腐蚀试验和电解试验中,陶瓷相中的Fe元素更容易进入电解质;电解24h后,铝液中Fe、Ni、Cu的含量分别为0.45%、0.13%和0.03%。     

A novel hydrothermal method for zinc extraction and separation from zinc ferrite and electric arc furnace dust

A novel hydrothermal process was developed to extract zinc from pure zinc ferrite (ZnFe₂O₄) nanopowder and zinc-containing electric arc furnace (EAF) dust using hexahydrated ferric chloride (FeCl₃·6H₂O) as a decomposing agent. The effects of solid FeCl₃·6H₂O to ZnFe₂O₄ ratio by mass (R_F/Z), hydrothermal reaction temperature, and time on zinc extraction were systematically investigated. In the results, when the hydrothermal reaction is conducted at 150℃ for 2 h with R_F/Z of 15:20, the efficiency of zinc extraction from ZnFe₂O₄ reaches 97.2%, and the concentration of ferric ions (Fe3+) in the leaching solution is nearly zero, indicating a high selectivity for zinc. In addition, the zinc extraction efficiency from the EAF dust reaches 94.5% in the case of the hydrothermal reaction performed at 200℃ for 10 h with the solid FeCl₃·6H₂O to EAF dust ratio by mass (R_{F/EAF dust}) of 15:10. Zinc and iron separation is achieved by adjusting the pH value of the leaching solution according to the different precipitation pH values of metal hydroxides.     

Magnetocrystalline anisotropy and spin-wave stiffness in tensile-strained La0.67Ba0.33MnO3 films: An investigation via ferromagnetic resonance

Tensile-strained epitaxial La_0.67Ba_0.33MnO₃ (LBMO) film has been prepared by magnetron sputtering technique on (001) oriented spinel MgAl₂O₄ substrate. The transport and magnetic measurements give an insulator-metal transition and paramagnetic-ferromagnetic transition occurring at ～150 K and 250 K respectively, which implies the phase separation in such a tensile-strained film. By analyzing the angular and temperature dependences of the ferromagnetic resonance (FMR), we determine the magnetocrystalline anisotropy of the film. It is found that the tensile-strained film is dominated by an easy-axis corresponding to the compressive out-of-plane direction, though the magnitudes of anisotropy constants are relatively small and their temperature dependences are some complex. Furthermore, the FMR spectra show additional spin wave resonance (SWR), and the field positions can be indexed to follow a linear dependence on the square of index n. The scaling gives a spin-wave exchange stiffness D of 20.7 meV Ų at low temperature, which is less than half of that in strain-free LBMO films, implying that the double exchange interaction is remarkably suppressed in the tensile-strained LBMO films.     

Effect of slag composition on the cleanliness of 28MnCr5 gear steel in the refining processes

The equilibrium reaction between CaO—Al₂O₃—SiO₂—MgO slag and 28MnCr5 molten steel was calculated to obtain the suitable slag composition which is effective for decreasing the oxygen content in molten steel. The dissolved oxygen content [O] in molten steel under different top slag conditions was calculated using a thermodynamic model and was measured using an electromotive force method in slag–steel equilibrium experiments at 1873 K. The relations among [O], the total oxygen content (T.O), and the composition of the slag were investigated. The experimental results show that both [O] and T.O decrease with decreasing SiO₂ content of the slag and exhibit different trends with the changes in the CaO/Al₂O₃ mass ratio of the slag. Increasing the CaO/Al₂O₃ mass ratio results in a decrease in [O] and an increase in T.O. To ensure that T.O ≤ 20 ppm and [O] ≤ 10 ppm, the SiO₂ content should be controlled to <5wt%, and the CaO/Al₂O₃ mass ratio should be in the range from 1.2 to 1.6.     

Corrosion behavior of ferritic ODS steel prepared by adding YH_2 nanoparticles in supercritical water at 600 °C

The corrosion behavior of the ferritic oxide dispersion strengthened(ODS)steel(14Cr-3Al-2W-0.1Ti)prepared by adding YH_2nanoparticles(NPs)was investigated in supercritical water(SCW)at 600°C for 1500 h.The mass gain of the ODS steel(215.5 mg/dm~2)was lower than that of SUS430 steel(357.2 mg/dm~2).A dual oxide layer generated on the surface of ODS steel after corrosion in SCW.The outer layer was composed of Fe_2O_3and Fe_3O_4,while the inner layer composed of the spinel-type FeCr_2O_4together with Al_2O_3.The generation of Y_2Ti_2O_7NPs in the ODS steel by adding YH_2NPs prohibits the formation of Y-Al-O particles and leaves more Al available to form a continuous protective oxide scale to improve the corrosion resistance.Moreover,the Y_2Ti_2O_7NPs act as efficient barriers to suppress the outward diffusion of metal atoms.This novel ODS steel shows potential applications in supercritical water.