混合稀土掺杂硬质合金刀具工作表面稀土富集相的能谱分析

在能谱(EDX)分析时,因La的Lβ1与Pr的Lα,Ce的Lβ1与Nd的Lα,La的LIIIab与Pr的Lβ1,Ce的LIIIab与Nd的Lβ1存在谱线重叠现象,而且混合稀土通常以La和Ce为主体元素,在分析混合稀土掺杂合金中含稀土物相时容易出现对Pr、Nd的遗漏。本文介绍La、Ce、Pr、Nd混合稀土掺杂的硬质合金刀具工作表面稀土富集相EDX分析的谱线拟合方法,并对刀具服役过程中La、Ce、Pr、Nd向刀具工作表面的定向迁移进行研究。结果表明,对存在谱线重叠现象的"相似元素"进行EDX分析,应该采用谱线拟合方法判断是否存在"相似元素",以防止出现元素的遗漏与误判;对以La、Ce为主体元素的混合稀土掺杂合金中含稀土物相进行EDX分析时,即使忽视了对Pr、Nd的分析,也不会影响对La、Ce在合金中作用行为规律的判断,但会遗失La、Ce、Pr、Nd在合金中作用行为的整体信息;在对C、S含量适中的金属材料加工过程中,混合稀土掺杂硬质合金工具中的La、Ce、Pr、Nd原子可以定向迁移至工作表面,但这种迁移是非同步的,Ce、Pr、Nd原子具有较La原子高的迁移速度。     

稀土尾矿库周边植物碱蓬对稀土元素的吸收与生物富集作用

为研究稀土尾矿库周边植物碱蓬对4种稀土元素(La、Ce、Pr、Nd)的吸收和富集特征,以广泛分布于稀土尾矿库周边的碱蓬及其根区土壤为研究对象,用ICP-MS法分析土壤中La、Ce、Pr、Nd、Sm、Gd的含量和碱蓬各器官中La、Ce、Pr、Nd的含量,并对土壤进行了污染评价。结果表明,土壤中6种稀土元素的平均含量顺序为:CeLaNdPrSmGd,其数值分别为7826.9 mg/kg、4117.8 mg/kg、2251.0 mg/kg、1393.3 mg/kg、240.1 mg/kg、217.0 mg/kg,且稀土尾矿库周边土壤受到了严重的稀土元素复合污染;碱蓬对La、Ce、Pr、Nd的吸收没有特别的选择性;碱蓬对La、Ce、Pr、Nd的转移能力和耐受力较强,且碱蓬植物体内积累了较多的稀土元素,所以碱蓬在一定意义上可用于该地区稀土元素污染土壤的修复;在采样点GW-1～GW-11中,碱蓬各器官中La、Ce、Pr、Nd的含量水平为根叶茎;在采样点GW-12～GW-18中,碱蓬各器官中La、Ce、Pr、Nd的含量水平为根茎叶,即La、Ce、Pr、Nd主要分布于碱蓬根部;相关性分析表明,碱蓬各器官中的稀土元素大部分来源于其根区土壤;在采样点GW-1～GW-18中,碱蓬对La、Ce、Pr、Nd转移系数的平均值分别为0.976、1.013、0.897、0.944,说明稀土尾矿库周边的碱蓬对稀土元素的转移能力顺序为:CeLaNdPr;碱蓬对La、Ce、Pr、Nd富集系数的平均值分别为0.117、0.153、0.108、0.149,说明稀土尾矿库周边的碱蓬对稀土元素富集能力顺序为:CeNdLaPr。     

稀土离子与钙调素相互作用的研究进展

稀土离子由于配位环境与钙离子具有相似性,能够取代钙离子与钙调素发生作用,对钙调素的结构、构象及生物功能产生影响。各种光谱及生物化学实验研究表明,不同稀土离子与钙调素作用时,在作用力的强弱程度、结合位点、结合序及结合位点的相互作用具有各自的特殊性,本文概述了稀土离子La3+、Ce3+、Pr3+、Nd3+、Sm3+、Eu3+、Gd3+、Tb3+、Ho3+、Er3+和Lu3+等与钙调素的相互作用及对钙调素生物功能产生的影响。     

稀土离子均相电催化氧化处理含酚模拟废水

以不同稀土离子为催化剂,研究了含酚模拟废水的电催化氧化降解.以COD和苯酚的去除情况作为考察指标,确定最佳催化剂及其最佳处理条件;考察了稀土离子与过渡金属离子的投配比对废水处理效果的影响,并对4种稀土催化剂的电化学性能进行了测试.结果表明:所选稀土离子La3+、Ce4+、Pr3+、Nd3+对苯酚的氧化均有良好的电催化性能,其中Pr3+的均相电催化效果最好.在pH =3、电流密度为66.7mA · cm-2条件下,Pr3+投加 量为0.11mmol·L-1能达到最好的降解效果.在此条件下电解废水60min时,COD和苯酚去除率分别达到62.1％和76.3％,比未加催化剂分别提高35.1％和36.6％.Pr3+和Mn2+的协同作用可提高废水的处理效果,当Mn2+与Pr3+的投配比为1∶1时电催化处理效果最好.     

萃取分离轻稀土元素三出口新工艺工业试验全面完成(二)

继去年九月顺利完成轻稀土La、Ce/Pr/Nd三出口工艺工业试验后,北京大学化学系和上海跃龙化工厂继续协作,运用北京大学化学系提出的串级萃取理论关于出口工艺的研究成果,共同设计了La/Ce/Pr—     

轻稀土催化臭氧氧化降解甲基橙模拟废水的研究

采用臭氧催化氧化技术降解人工模拟染料废水。以甲基橙为目标污染物,研究了轻稀土离子(La3+、Ce3+、Pr3+)的投加量对甲基橙去除率的影响,初步探讨了Pr3+催化臭氧氧化降解甲基橙的机理。实验表明,加入一定量的La3+、Ce3+、Pr3+,对甲基橙的去除有促进作用,在初始pH=3,甲基橙溶液浓度为80 mg/L,体积为250mL,臭氧投加量为250 mg/L条件下,La3+、Ce3+、Pr3+的最佳投加量均为0.4 mmol/L,其中Pr3+的催化氧化效果最好。加入Pr3+后能促进臭氧氧化过程中羟基自由基的大量产生,从而加速甲基橙的降解,但Pr3+的加入只能促进510 nm处的吸收峰下降得更快而不能促进200 nm处的吸收峰明显的下降。     

水杨醛缩邻氨基苯酚稀土金属配合物的合成与表征

报道了水杨醛缩邻氨基酚与La3+,Ce4+,Pr3+,Nd3+,Sm3+,Eu3+,Gd3+,Tb3+,Dy3+,Ho3+,Er3+,Tm3+,Yb3+,Lu3+等镧系稀土离子配合物的合成,通过红外光谱、紫外光谱、荧光光谱、摩尔电导、差热以及元素分析等对稀土配合物进行了表征,其组成分别为I:HML2·2H2O(M=La,Ce,Sm,Eu,Gd);II:ML·Y·X:(IIa:Y=H2O,M=Pr,Nd,Lu,X=Cl;M=Tb,X=NO3-。IIb:M=Dy,Ho,Er,Tm,Yb,Y=C2H5OH,X=Cl-),并推测了其可能的结构。还发现La3+和Lu3+对该配体有较强的激活作用,显著地增大了该配合物的荧光强度。     

P204-HCl-H3cit体系分离轻稀土元素的研究

针对高酸度下P204(DEHPA)萃取剂萃取轻稀土氯化物时,La3 、Ce3 、Pr3 、Nd 3 之间分离系数较低的问题,本文研究了含有柠檬酸(H3cit)的P 204-HCl体系中,料液酸度与柠檬酸浓度对轻稀土分离系数的影响,并与P204-HCl体系的萃取结果进行了比较.实验结果表明:在P204-HCl-H3cit体系中,轻稀土分离系数随酸度的增大而降低,随柠檬酸浓度的增加而提高.当料液酸度pH=1.0、柠檬酸浓度=0.25 mol/L时,Ce/La 、Pr/Ce和Nd/Pr的最大分离系数分别为4.10、1.71和1.54,均高于P204-HCl体系下的最大分离系数.     

纳滤膜处理除铁后浸出液富集铜的研究

采用纳滤膜处理江西德兴铜矿除铁后生物浸出液,通过试验考察操作压力、温度等对渗透通量、铜离子截留率和渗透液电导率的影响.研究结果表明纳滤膜较佳操作条件为：温度30℃,运行压力15bar,流量14L/min;在此条件下浓缩3.7倍时,Cu2＋截留率R为93.1％,浓缩液中Cu浓度为0.764g· L-1.     

巨大芽孢杆菌与稀土离子的相互作用研究

对稀土资源的开采和利用,如稀土微肥的出现,使得稀土与土壤微生物之间产生了相互的影响。为了探明上述两者间的互作机理,对一株能够解磷、解钾的巨大芽孢杆菌对稀土离子的吸附作用进行了考察。结果显示,这株菌对La3+和Ce3+的吸附率分别为29.2%、30.2%,最大吸附量分别为75 mg/L、30 mg/L,而且均能在30 min内进行快速吸附,在60 min内达到吸附平衡。在此菌株最适生长温度范围内的三个温度(25℃、30℃、40℃)下的研究结果表明,吸附温度对吸附过程无明显影响。经载体(海藻酸钠(SA)-硅藻土)固定化后,在160 r/min的转速下该菌株对La3+和Ce3+的吸附率分别提高了20.25%、20.02%。     

织金含稀土磷矿酸法浸出性能及预处理优化工艺试验

硫酸、盐酸、磷酸和硝酸对原生织金磷矿的稀土组分浸出效率不理想,总稀土浸出效率不到36%。采用焙烧活化—硝酸氨水混合预浸出处理织金磷矿,最适宜条件下,CaO和MgO的浸出率分别为24.55%和19.75%,相应的P_2O_5和稀土元素(Y、La、Nd、Ce)损失率为11.25%和3.61%。所得精矿中,Y、La、Nd、Ce和P_2O_5实现了不同程度的富集。预处理精矿的浸出性能较原矿显著改善,硝酸体系下P_2O_5和稀土元素(Y、La、Nd、Ce)浸出效率提高了近40个百分点。     

Luminescence Properties of Rare Earth Ions in Cadmium Metasilicate

The luminescence properties of CdSiO3:RE^3 phosphors doped with various rare earth ions are reported. The series of rare earth ions doped CdSiO3 phosphors are prepared by the conventional high-temperature solid-state method, and characterized by XRD and photoluminescence (PL) spectra. The results of XRD measurement indicate that the products fired under 1050 ~C for 3 h have a good crystallization without any detectable amount of impure phase. The PL spectra measurement results show that CdSiO3 is a novel self-activated luminescent matrix. When rare earth ions such as Y^3 ,La^3 , Gd^3 , Lu^3 , Ce^3 , Nd^3 , Ho^3 , Er^3 , Tm^3 and Yb^3 are introduced into the CdSiO3 host, one broadband centered at about 420 nm resulted from traps can be observed. In the case of other earth ions which show emissions at the visible spectrum region, such as Pr^3 , Sm^3 , Eu^3 , Tb^3 and Dy3 , the mixture of their characteristic line emissions with the ～420 nm strong broadband luminescence results in various emitting colors. As a consequence, different emitting colors can be attairied via introducing certain appropriate active ions into the CdSiO3 matrix. In additional, this kind of phosphors shows good long-lasting properties when excited by UV light. All the results show that CdSiO3 is a potential luminance matrix.     

Investigation on the Use of the Weakly Basic Polyacrylate AnionExchanger Amberlite IRA-68 for Sorption and Separation of Iminodiacetate Complexes of Rare Earth Elements

Based on the determined affinity series of rare earth element complexes with IMDA for the anion-exchangers, purification of macroquantities of Nd^3 from Y^3 , Sm^3 from Ho^3 , La^3 from Nd^3 and La^3 from Pr^3 on the weakly basic gel anion-exchanger Amberlite IRA-68 was studied. Using the presented method on 1 L of Amberlite IRA-68 in the acetate form, it is possible to obtain about 240 g Nd2O3 purified from Y2O3. Great difference in affinity of La^3 and Nd^3 as well as Pr^3 complexes for this anion-exchanger in the acetate form indicates the possibility of applying this process for purification of lanthanum on the increased scale. On 1 L of Amberihe IRA-68 in the acetate form it is possible to obtain about 1125 g La2O3 purified from Nd2O3. On the basis of these results it can be assumed that unique properties of polyacrylate anion-exchangers enable their application for separation of rare earth elements.     

Stability of Rare Earth Ion-N, N′-bis（2′-Pyridine）methyl-1,10-Phenanthroline-2,9-Dimethanmine Binary Complexes

1 ,10 Phenanthrolinehasbeenextensivelyusedasanazaheterocyclicchelateligandinbothanalyticalandpreparativecoordinationchemistry[1] .Asanim portantligand ,1,10 phenanthrolineunitplaysanim portantroleforthedevelopmentofthesupramolecularchemistry .Manynovelsupramolecularcompoundsin clude 1,10 phenanthrolineunit[2～ 4 ] .Furthermore ,consideringtheuniquecombinationofchemicalstabil ities ,redoxproperties ,luminescenceemissionandex citedstatelifetime ,derivativesof 1,10 phenanthrolinehaveplayedama…     

Biosorption of La^3＋ and Ce^3＋ by Agrobacterium sp.HN1

The Agrobacterium sp.HN1 was isolated from the soil and used to adsorb rare earth ions La3+ and Ce3+.The results showed that the pretreatments of Agrobacterium sp.HN1 did not enhance the adsorption of La3+ and Ce3+.The pH,temperature,time and bacterial age affected the dynamics of adsorption of La3+ and Ce3+.The optimum adsorption conditions for Agrobacterium sp.HN1 were as follows:15 mg/L La3+ of initial concentration,10 mg/L Ce3+,300 mg/L(dry wt.cell) biomass for sorption,6.8 pH,30 oC temperature,150 r/min rotational speed,2 h adsorption time and 28 h bacterial age.The adsorption kinetics of La3+ and Ce3+ for Agrobacterium sp.HN1 followed the pseudo-second order equation.     

氮,氮,氮′,氮′-四辛基-3-氧戊二酰胺色谱柱分离-电感耦合等离子体质谱法测定混合稀土氧化物中重稀土

电感耦合等离子体质谱法(ICP-MS)测定稀土元素时,轻稀土元素Ce、Nd、Sm的氧化物等复合离子严重干扰重稀土元素Tb、Dy、Ho、Er的测定,因此对混合稀土中重稀土元素进行测定前一般需要先对其分离富集。实验在样品溶解后,将N,N,N′,N′-四辛基-3-氧戊二酰胺(TODGA)用硅藻土吸附后装柱,以0.1 mol/L HNO₃为样品溶液介质上柱,通过控制洗脱液的种类、酸度以及洗脱液流速,实现了轻稀土元素La、Ce、Pr、Nd与重稀土元素Tb、Dy、Ho、Er、Tm、Yb、Lu的分离和富集,建立了ICP-MS测定混合稀土氧化物中重稀土元素的方法。实验表明:控制洗脱流速为2.0 mL/min,用pH 2.0的HNO₃淋洗至淋洗体积约为500 mL,继续收集洗脱液,并用ICP-MS检测其中Nd₂O₃含量,直至洗脱液中Nd₂O₃的质量浓度小于200 ng/mL,可将轻稀土元素La、Ce、Pr、Nd及少量Y、Sm、Gd洗脱;再改用350 mL 1 mol/L HCl洗脱重稀土元素,可实现重稀土元素与La、Ce、Pr、Nd及部分Y、Sm、Gd的分离;通过选择¹⁵⁹Tb、¹⁶³Dy、¹⁶⁵Ho、¹⁶⁷Er、¹⁶⁹Tm、¹⁷²Yb、¹⁷⁵Lu为测定同位素可消除质谱干扰。将实验方法应用于混合稀土氧化物中重稀土元素的测定,加标回收率在93%～110%之间,相对标准偏差(RSD,n=8)在1.1%～10%之间。     

Preparing Process of Cerium Acetate and Rare Earth Acetate

Preparing process was presented and the influences of concentration of acetic acid, reaction temperature, the ratio of cerium carbonate and acetic acid, heat preservation time to the yield of cerium acetate were discussed.The crystalline cerium acetate and rare earth acetate such as ( La, Ce, Pr, Nd) (Ac) 3, ( Ce, Pr, Nd) (Ac) 3, ( Pr, Nd, Er,Y) (Ac) 3 and yttrium acetate were prepared under this condition.The shape, structure and composition of the crystals were determined by the methods of SEM, TG-DTA, X-ray diffraction and chemical analysis.The optimum prepared conditions of cerium acetate were described.This prepared process has characteristics such as simple process route, low cost, high yield, good quality, no pollution to environment, etc.     

Rare earth double sulfates from pre-concentrated bastnasite

A mixture of rare earth double sulfates was produced from a Turkish bastnasite-containing pre-concentrate (low grade concentrate) by sulfuric acid baking, subsequent water leaching and precipitation with sodium sulfate. The results of acid baking and leaching indicated that recoveries of rare earth elements up to 90% were readily obtained and the recovery of hydrofluoric acid as a by-product was also possible. Reasonable decontamination of the rare earth double sulfate salt from impurities such as Th, Fe, Al and Mg was possible by rapid precipitation at 50 °C using 1.25 times the stoichiometric amount of Na₂SO_4. The total rare earth double sulfate content (TREDS) was > 90% and analysed 17.3% La, 15.6% Ce, 3.2% Nd, 1.1% Pr, 0.3% Sm, 0.03% Eu, 0.01% Yb and 0.02% Y together with about 0.7% Ca, Fe, Al and other impurities.     

Analysis of Response Surface in the Study of RE(NO_3)_3-HNO_3-P507-Kerosene Extraction System

RE(NO_3)_3-HNO_3-P507-kerosene extraction system(RE=La,Ce,Pr,Nd,Sm,Eu,Gd,Tb,Dy,Ho,Er,Tm,Yb,Lu,Y)was studied by the response surface technique.14 models for extracting single rare earth ele-ment in a broad range of acidity and initial rare earth concentration were obtained by using the stepwiseregression method.Three-dimensional display of the response surface of the model of extracting Er~(3 )wasshowed as an example,which reveals clearly the dependence of distribution ratio upon both initial acidity and ini-tial rare earth concentration.     

Ion imprinted polymer particles of neodymium: synthesis, characterization and selective recognition

Neodymium ion imprinted polymer (Nd3+-IIP) particles for selective solid-phase extraction of Nd3+ were prepared and determined with inductively coupled plasma atomic emission spectrometry (ICP-AES). The unleached Nd3+-IIP particles were prepared by the copolymerization of Nd3+-5,7-dichloroquinoline-8-ol-4-vinylpyridine ternary complex with styrene and divinyl benzene, then Nd3+ was leached to obtain Nd3+-IIP particles. The adsorption capacity of the Nd3+-IIP was 35.18 mg/g. The largest selectivity coefficient for Nd3+ in the presence of competitive ions such as La3+, Ce3+, Pr3+ and Sm3+ was over 110. The proposed method was validated by analyzing two certified reference materials (GBW07301a sediment and GBW07401 soil) and the determined values were in a good agreement with standard values. The method was convenient, selective, sensitive and applicable to the determination of trace Nd3+ in environmental samples with complicated matrix.