稀土在铁素体不锈钢中的研究现状及发展前景

摘要：铁素体不锈钢具有“节镍资源型”特性及优良的综合性能,被广泛应用于轨道运输、汽车、家电和厨具等行业中。稀土作为战略性资源在不锈钢中的应用已有多年,国内外学者在这方面做了大量研究。归纳和总结了稀土对铁素体不锈钢组织和性能等方面的影响,并对其在钢中的作用机制和影响机制进行了简要分析。大量研究表明,稀土能将钢中不规则状且电子功函数较小的A12O3、MnS夹杂改性为电子功函数较大的球状稀土复合夹杂;此外,稀土能降低钢中晶粒尺寸,净化其晶界,对钢的凝固组织、退火组织等金相组织起到明显的细化作用,提高其耐蚀性能和力学性能。最后展望了稀土在不锈钢中的发展前景。     

Luminescent characterization of rare earth Dy3+ ion doped TiO2 prepared by simple chemical co-precipitation method

Pure and rare-earth ion (Dy³⁺) doped TiO₂ nanomaterials were prepared through a chemical co-precipitation method. The chemical composition, microstructure and optical properties were characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), UV-visible spectroscopy and photoluminescence (PL). XPS analysis reveals that Dy³⁺ ions are preferentially occupied in the TiO₂ crystallite lattices. Both the XRD and TEM analyses confirm that both the pure and Dy doped TiO₂ are in pure anatase phase and in nano size range, respectively. Also it is found that the maximum solubility limit for Dy³⁺ ions is found to be 0.4% in TiO₂ matrix, above which it occupies interstitials and/or crystallite surface of TiO₂ nanocrystals. From the UV-Vis spectroscopy studies it is found that Dy doping induces blue shift in TiO₂. From the PL analysis it is found that doping Dy³⁺ improves the luminescence behavior in comparison with the pure TiO₂ nanoparticles. Overall, doping very low concentrations of Dy³⁺ greatly alters the structural morphology and directly increases the luminescence behavior of TiO₂ suitable for advanced optoelectronic applications.     

Inclusions modification in heat resistant steel containing rare earth elements

Based on the thermodynamic assessment of inclusions evolution, the modification experiments of inclusions containing rare earths were carried out in the Si–Mo furnace from 1600°C to 1500°C. The pure Si and Si–Al alloy were chosen as deoxidants under low and high initial oxygen content, respectively. The field emission scanning electron microscope (FE-SEM) and energy dispersive spectrometer (EDS) were employed to analyse the morphology and chemical compositions of inclusions in the samples. The spherical liquid Ce–Si–Al–O (Ce₄Si₅Al₅O_23.5) inclusions were observed in the steel, which was deoxidised by Si–Al alloy. The evolution mechanisms of inclusions were comprehensively discussed, and models for the formation of oxide inclusions were set up.     

稀土市场回顾及对我国稀土产业发展的建议

对2009~2015年的稀土市场情况进行回顾,结果表明稀土价格分别经历了2009~2011年初处于上升阶段、2011年1季度~2012年3季度处于暴涨暴跌阶段和2012年3季度~2015年末处于下降并持续低位徘徊阶段;稀土价格走势最具波动区间段是2010年第3季度~2013年第1季度,价格呈现倒“V”型态势,在2011年3季度,大部分稀土价格达到2009年的10~15倍;2011年后,稀土价格持续下降,导致大部分产品出口量与创汇额变化呈负相关,如氧化镧从2011年到2014年,出口量增加244.57 %,创汇额却下降80.01 %;2011~2014年稀土出口配额使用率较低,2012年仅为48.33 %,配额制形同虚设.分析表明我国稀土市场持续疲软主要在于我国稀土缺乏定价权和对市场掌控能力偏弱.通过稀土市场情况分析及稀土开发存在的现实困境,提出包括尽快出台资源税和环境税负改革,加快大集团区域化管控稀土资源;促进稀土集团尽快解决现存问题;加快储备政策制定与落实等4方面的建议,为国家对稀土市场的宏观调控建言献策.      

Element migration and phase distribution characteristics during crystallization of rare earth phase in rare earth slag

The crystallization experiment of molten rare earth (RE) slag under different cooling rates was carried out. The characteristics of element migration and phase distribution during RE phase crystallization were studied by using different equipment. The experimental results show that there are two RE phases in the RE slag, namely (Ca, Ce, La)₅(SiO₄)₆F and (Ca,Ce,La,Mg)₃(Ti,Al,Nb)₂O₇. During the cooling crystallization process of molten RE slag, Ca and P elements in the RE phase of (Ca,Ce,La)₅(SiO₄)₆F migrate from inside to outside, and finally gather at the outer edge of the phase to form phase Ca₃(PO₄)₂. The RE phase (Ca,Ce,La)₅(SiO₄)₆F is distributed inside the furnace-cooled slag, and the RE phase (Ca,Ce,La,Mg)₃(Ti,Al,Nb)₂O₇ is distributed in the surface layer of the furnace-cooled slag. And based on the phase distribution characteristics, the central hollowing method is proposed to realize the preliminary enrichment of valuable elements Ti, Nb and RE in RE slag.     

Effect of rare earth and transition metal La-Mn substitution on electrical properties of co-precipitated M-type Ba-ferrites nanoparticles

In the current research work Ba_(1-x)La)xMn)yFe_(12-y)O_(19) hexa-ferrite nanoparticles of different compositions were synthesized using chemical co-precipitation technique. The structural properties were explored using X-ray diffractions(XRD), scanning electron microscopy(SEM) and Fourier transmission infrared spectroscopy(FTIR). XRD indexed pattern confirms the formation of M-type hexagonal phase. The crystallite size of synthesized samples ranges from 13 to 34 ± 2 nm. FTIR peaks observe also confirmed the presence of metaloxygen bond of the desired product. The position of peak at 467 cm~(-1) corresponds to A_2 u vibration for octahedral Fe(4+)-O and peak position E1 u corresponds to vibration of Fe(3+)O4 octahedral bonds. The band v_1 in range(677-559 cm~(-1)) and v_2 in frequency range(356-419 cm~(-1)) are associated to A and B sites.Dielectric properties of all compositions were measured with frequency. The dielectric constant, loss and tangent loss decrease from 26 to 9, 25 to 2 and 0.94 to 0.14, respectively with frequency. DC electrical resistivity is increased with dopant concentration increasing from 2.15 × 10~4 to 1.92 ×10~5 Ω·cm.     

Research progress of rare earth separation methods and technologies

Strategical elements,such as rare earth elements,play a crucial role in the industry,especially in producing high-tech materials.Major global industries have developed a strong dependence on rare earth materials.Every year,there are innovations in industries such as modern technology,green energy,or communications technology,which need more strategic metals to improve investment profitability.This article reviews advances in rare earth separation methods and techniques to guide and recommend the...     

Dissolved rare earth elements estimation of ion-absorption rare earth ores using reflectance spectroscopy in south Jiangxi province,China

Ion-absorption rare earth ores are an important mineral resource in China. Nowadays, the unauthorized mining has become a serious problem, resulting in severe water pollution and the wastage of rare earth elements (REEs). Being able to estimate the concentration of dissolved REEs in water bodies near mines is essential for tackling this environmental problem. Conventionally, quantitative analyses of the contents of dissolved REEs are performed using laboratory-based techniques, which can be time consuming and costly. Spectral reflectance is a rapid and cost-effective means of characterizing the chemical compositions of light-absorbing materials. In this study, reflectance spectroscopy was performed on dissolved REEs, and the correlation between their reflectance characteristics and REE content was determined. A total of 50 aqueous media samples collected in south Jiangxi Province and 25 laboratory-produced aqueous media samples were tested, and their reflectance spectra and REE contents were measured using reflectance spectroscopy and inductively coupled plasma mass spectrometry, respectively. Next, the reflectance, differential reflectance, and absorption depth were analysed based on the REE content. Six diagnostic absorption features related to REEs are recognised in the visible and near-infrared wavelength regions, along with several smaller peaks. It indicates that the results of the absorption depth analysis are in accordance with the absorption spectra characteristics of the REEs, with the R² value being higher than 0.97. The intensity of each of the six absorption bands exhibits a linear correlation to the total REE content. Therefore, linear regression models can be derived for estimating the total concentration of REEs in aqueous media samples. What's more, the detection limit for REEs is determined to be about 30 μg/L. Thus, it can be concluded that reflectance spectroscopy is a suitable technique for estimating the concentration of dissolved REEs.     

Progress in green and efficient enrichment of rare earth from leaching liquor of ion adsorption type rare earth ores

Ion adsorption type rare earth ores (IATREOs) are a valuable strategic mineral resource in China, which feature a complete composition of fifteen rare earth elements and are rich in medium and heavy rare earth (RE) elements. In the leaching process for recovering rare earth elements from IATREOs, many impurities will be leached together with rare earth elements and enter the leaching liquor. An impurity removal-precipitation enrichment technique is currently applied to selectively recovery rare earth elements from the leaching liquor with the high content of impurities and low concentration of rare earth elements by using ammonium bicarbonate in the industry. However, a high loss of rare earth elements and severe ammonia nitrogen pollution are caused by this process. Therefore, more beneficial impurities removal technologies, mainly for aluminum, and green enrichment technologies with lower pollution are now urgently needed. For this purpose, this paper analyzed two aspects of research progress in recent decades: the green separation of rare earth elements and aluminum from leaching liquor and the green and efficient enrichment of rare earth elements. Finally, an approach for the high-efficiency and green enrichment of rare earth elements from leaching liquor of the IATREOs is proposed in several aspects, including impurity inhibition leaching, neutralization and impurity removal, alkaline calcium and magnesium salt precipitation enrichment, and centrifugal extraction enrichment.     

稀土冶炼中废水的产生与治理

针对包头地区稀土产业，分析概述了稀土湿法冶炼工艺生产工序中废水的产生及其性质。提出稀土废水治理的途径，对促进稀土产业化，控制水环境的污染提供了防治对策。     

Process mineralogy of Weishan rare earth ore by MLA

Mineral liberation analyser (MLA) was applied to quantitatively analyze the rare earth ore from Weishan in Shandong. Mineralogy parameters, such as mineral composition, occurrence states of rare earth elements (REEs) and valuable elements, mineral embedded grain size distribution, mineral association and liberation, are obtained. Results show that the contents of REEs and other valuable elements mainly contained in the ore were La 1.02 wt%, Ce 4.29 wt%, Pr 0.34 wt%, Nd 0.84 wt%, Sr 3.4 wt% and Ba 26.53 wt%, respectively. The REEs mainly occur in bastnaesite and carbocernaite in the form of independent mineral and the contents of bastnaesite and carbocernaite in the ore were 5.96 wt% and 12.30 wt%, respectively. 67.34% of strontium occurs in carbocernaite and the rest occurs in celestobarite and strontianite mineral. 92.71% of barium occurs in barite. Liberation of main rare-earth minerals such as bastnaesite and carbocernaite is more than 80% when the grinding fineness is 78.42% passing 74 μm. The research results could be employed to provide detailed basic theoretical data for further improvement of the beneficiation process flow and the processing index of rare earth ore, the recycling of other valuable minerals and the comprehensive utilization of tailings.     

A review of the recycling of rare earth metals

Although rare earth metals are more abundant than their name would indicate, disruptions of their supplychain have occurred recently, and it is no surprise thatthe US Department of Energy (DOE) and the European Union (EU) Commission have listed several of them as critical for their role as materials essential for a clean society. This paper briefly reviews the major uses for rare earth metals and identifies the potential sources of scrap for recycling. The paper then describes the various processes developed to recycle rare earth-containing scraps, such as spent Ni-metal hydride (MH) batteries, magnets, catalysts, polishing powders and phosphors, with case studies taken from industrial practice and research work. The success of recycling efforts depends not only on adequate technical advancements but also requires the overcoming of non-technical challenges comprising, among others, logistics (collection, transportation), and an appropriate political and legal framework.     

Recent advances in nonlinear optical rare earth structures

Nonlinear optical (NLO) crystals can be employed to expand the laser frequency and thus are of technical importance in advanced laser science. Noncentrosymmetric rare earth compounds keep attracting broad interest as a significant branch of NLO materials because the highly distorted structural motifs centered by rare earth ions could remarkably benefit the second harmonic generation. In this review, we proceed from structure–properties relationship and reveal the role of rare earth element in the optical properties of NLO materials. We believe that this work can deepen the understanding of rare earth-based NLO materials and provide some enlightenment for exploring novel practical NLO crystals.     

Multi-component assembly of luminescent rare earth hybrid materials

This review focuses on the recent research progress in the multi-component assembly of luminescent rare earth hybrid materials, which is based on the luminescent rare earth compounds and two or more other building units, including the other photoactive species. It covers the multi-component luminescent rare earth hybrids which was assembled with different (a) organic-inorganic polymeric units, (b) nanoporous units, (c) nanoparticle composites or (d) other developing special units. Finally, future challenges and opportunities in this field are discussed. Herein it mainly focuses on the work of Yan's group in recent years.     

武钢高性能建筑结构用钢的开发与展望

简述建筑结构用钢的特点,介绍武钢高性能建筑结构用钢的开发成果及产品在国内外重大工程上的应用业绩,着重介绍耐火耐候建筑结构用钢的创新点,描述国内外建筑结构用钢的发展趋势。     

离子型稀土萃取分离工艺技术现状及发展方向

对我国离子型稀土萃取分离工艺中,现有的模糊联动萃取新技术的概念及基本技术经济特征;洗液、反液共用新技术的优势及在工艺设计中应采取的有效措施;稀土皂技术使用的目的及控制好稀土皂饱和度的关键技术;有机相各种皂化技术的技术经济特点;有机相溶料技术的特点及适用范围;C272+P507双溶剂萃取技术特点等进行了系统的分析讨论.对进一步加强稀土萃取分离工艺优化研究;稀土分离产品高纯化、物理性能优良化的指标控制技术的研发;提高萃取过程的装备和自动化水平;节能减排、环境保护、实现清洁生产等方面提出了今后努力的方向.     

Research progress of rare earth Ce on improvement of microstructure and homogeneity of as- cast steel

The thermodynamic behavior of Ce and its compounds in molten steel was summarized, and the types of stable compounds after Ce added to molten steel and its variation were predicted. The mechanisms and rules of Ce compounds and dissolves Ce refining solidification structure of as- cast steel were summarized respectively. The improvement of homogenous by Ce was analyzed and the reason of decrease of element segregation was summarized. At last, some problems were pointed out which had not been solved in the research of rare earth Ce to improve the microstructure and homogeneity of steel, and put forward the main directions of the future research in this field.     

Luminescence and low temperature trap centers in mixed rare earth borate crystal

The single crystal of this compound has been grown from melt by using a conventional Czochralski technique. The temperature dependent luminescence spectra were measured using a 265 nm laser as an exciting source in the range of 10–300 K. The scintillation decay time profile was measured and found to have three components. The influence of the trap centers on the luminescence properties was studied by means of thermoluminescence (TL) glow peak analysis. Low temperature TL glow peaks were measured in the temperature range of 10–300 K at the heating rate of 0.1 K/s for X-ray irradiated sample. The TL glow peak consists of two dominant peaks at 88 and 109 K. Several glow peaks with a complex nature causes the decrease in the light yield at temperatures below 250 K, and along with long scintillation decay components were observed. The trap parameters such as activation energy (E), frequency factor (s) and order of kinetics (b) were calculated using various standard methods such as peak shape (PS), variable heating rate (VHR), initial rise (IR) and computerized glow curve deconvolution (CGCD).     

Kinetics model for leaching of ion-adsorption type rare earth ores

This paper aims to establish a mathematical model that can analyze the whole leaching kinetics process of ion-adsorption type rare earth ores. This leaching process is composed of three steps: (1) ammonium ions arrive at the ore particle surface through the diffusion layer; (2) ammonium ions exchange with rare earth ions; and (3) rare earth ions enter into the external solution through the diffusion layer. In the leaching process, it is hypothesized that the ore particle size remains constant. The process of ammonium ions and rare earth ions passing through the diffusion layer was described by the Fick law, and the reversible ion exchange process between ammonium ions and rare earth ions was described by the Kerr model. A leaching kinetics model of rare earth ions by ammonium ions was constructed. Accuracy of this kinetics model was verified with laboratory tests. It is found that the correlation coefficients of all data are greater than 0.9000. The proposed kinetics model is therefore feasible for kinetics analysis throughout the leaching process.     

Effect of roasting activation of rare earth molten salt slag on extraction of rare earth,lithium and fluorine

A new process was proposed to extract rare earth elements(REEs),Li and F from electrolytic slag of rare earth molten salt by synergistic roasting and acid leaching.Firstly,the thermodynamic analysis of roasting reaction was carried out,then the effects of roasting factors on leaching REEs,Li and F in slag were investigated.In additions,the mineral phase and morphology of molten salt slag,roasting slag and acid leaching slag were characterized,and the migration mechanism of REES,Li and F minerals...