玻璃标样结合硫内标归一定量技术在激光剥蚀-等离子体质谱分析硫化物矿物中的应用

以硬石膏矿物标样中Ca相对于S的灵敏度因子为基准,将玻璃标样中主量和痕量元素相对于Ca的灵敏度因子转换成元素相对于S的灵敏度因子,建立了多玻璃标样结合硫内标归一定量技术分析硫化物单矿物多元素的新方法。利用本方法分析了美国合成多金属硫化物矿物标样MASS-1中20种元素,主量元素分析结果的相对误差小于10%,痕量元素分析结果几乎都落在给定值±不确定度范围内。利用本方法对12个硫化物单矿物分析结果表明,绝大多数主量元素含量测定值的相对误差小于10%,且多数主量元素甚至优于以MASS-1为外标、内标归一定量法及内标校准法分析结果,而痕量元素与MASS-1校准结果较为一致。本方法克服了基体不匹配的问题,能比较准确地定量分析硫化物矿物中的主成分S,可用于定量校准硫化物矿物。     

X射线荧光光谱法测定硅酸盐岩石中主次量成分结果异常时的质量控制北大核心CSCD

硅酸盐岩石样品的主次量成分分析(业内俗称硅酸盐成分全分析)是地质工作的重要内容。通过监测岩石内部成分含量的变化,可以了解相应元素在地壳内的迁移情况和变化规律、元素的集中和分散情况、岩浆的来源及可能出现的矿物相,可进一步解决矿体岩相分带、阐明岩石成因等问题;并且硅酸盐岩石主次量成分的含量是矿物定名时的重要依据[1]。因此,选择能准确测定硅酸盐主次量成分含量的方法非常重要。     

碱熔-标准物质法-电感耦合等离子体发射光谱(ICP-AES)法测定硅酸盐岩中10种主量元素

硅酸盐岩元素的准确测定是其地球化学分析研究的基础,其主量元素含量通常可以采用电感耦合等离子体发射光谱(ICP-AES)法测定,但其测定方法的系统性研究相对缺乏,尤其是样品前处理和基体干扰的有效消除两方面。前处理过程中,考察不同熔剂用量对硅酸盐岩样品的分解能力,发现当熔剂与样品比例达到6:1后,熔珠为纯色透明,经稀硝酸提取后溶液澄清,确定了硅酸盐岩前处理时熔剂与样品的最佳配比。测定过程中,通过考察基体匹配法和标准物质法两种基体干扰消除方法对测定结果的影响,发现当采用与岩性一致或者接近的标准物质绘制校准工作曲线时,基体干扰消除效果更好,更适用于测定硅酸盐岩10种主量元素含量。据此,建立了硅酸盐岩经偏硼酸锂熔融,稀硝酸振荡提取处理,以标准物质法绘制校准工作曲线,采用ICP-AES法同时测定SiO2、Fe2O3、Al2O3、CaO、K2O、MgO、Na2O、TiO2、P2O5、MnO 10种成分含量的方法。对岩石标准物质GBW07107进行分析测定,方法的相对标准偏差(RSD)为0.17%～0.75%,方法检出限为0.001%~0.016%,满足硅酸盐岩样品元素定量分析的要求,而且操作简单快速,环境污染小,适用于大批量样品分析。     

“733”电子探针对造岩矿物定量分析

本文介绍用“733”电子探针,采用Bence和Albee校正法对造岩矿物如长石类、橄榄石类、石榴石类、辉石类、角闪石类、云母类、绿泥石类、沸石类、粘土、碳酸盐类矿物以及榍石、刚玉、红柱石、十字石、沂濛矿、陨铬辉石、磁铁矿、堇青石等矿物进行大批量的测试,还对“733”电子探针定量分析中几个比较重要问题:镀膜技术;对碱金属元素和含水矿物的分析;标样的选择;对分析样品的要求;测试条件的选择进行了分析和讨论。     

激光剥蚀电感耦合等离子体质谱分析硅酸盐矿物基体效应的研究

标样与样品之间基体效应的差异是影响LA-ICP-MS分析结果准确度的重要因素,而元素的相对灵敏度因子(RSF)是基体效应的重要表征.本研究考察了17个玻璃标样中49种常见元素及10个电子探针天然硅酸盐矿物标样中10种主、微量元素RSF的差异,比较了以Ca,Al,Si为内标对基体效应的补偿作用及元素分馏效应的影响.结果表...     

激光剥蚀电感耦合等离子体质谱小激光斑束线扫描定量分析技术

采用激光剥蚀-扇形磁场电感耦合等离子体质谱(LA-SF-ICP-MS)技术建立了小激光斑束(15μm)线扫描定量分析方法。对比了硅酸盐矿物LA-ICP-MS分析中不同激光进样模式(点剥蚀和线扫描)对于元素信号强度和分馏效应的影响。小激光斑束点剥蚀分析元素信号强度随时间下降明显,并且剥蚀过程中元素深度分馏效应影响明显。深度分馏效应主要是由于各元素倾向于富集在不同粒径颗粒中,而不同大小颗粒在剥蚀坑附近发生冷凝沉淀的几率差异造成。实验结果表明,相对于内标元素Ca,Na、K、Cr、Co、Cd和U等元素富集在更小颗粒中;Cu、Zn、V、Mn、Fe、Ni、Tl、W、Rb、Cs等元素与Ca富集行为相似;Al、Y、Sc、Zr、Nb、Hf、Ta、Th和REE等元素易进入大颗粒中。线扫描分析具有高且稳定的元素信号强度,分析过程中剥蚀行为一致,不受深度剥蚀效应的影响。采用双剥蚀池结构进样系统研究单脉冲激光剥蚀信号结构,不同元素信号强度降低至50%需0.8~1.2 s;降低至20%需1.2~1.6 s;降低至背景值需2~3 s。本研究通过优化仪器参数降低信号叠加作用的影响,在均质和非均质样品(榍石)线扫描分析中,获得了准确的元素含量和元素比值。线扫描定量分析技术可有效降低激光斑束(≤15μm),相对于采用线扫描元素强度分布研究,数据更加直观,可表现元素比值的变化特征。通过调整激光斑束大小和扫描速度可在不同分辨率尺度下全面了解矿物中元素的分布特征。     

稀有元素矿物系统全分析中的铀、钍、稀土元素的纸色层分离和测定

本文用纸色层法分离铀、钍、稀土等元素,用国产色层纸(23×13厘米),用上行法进行条件试验。试验结果表明,试液以硝酸介质,用丁酮-甲基异丁基酮-硝酸-水(45∶45∶5∶5(体积比))作展开剂,分离铀、钍、钪和稀土元素结果良好,Rf值分别为:铀(近于1),钍(0.5),钪(0.16),稀土(0)。温度10—30℃,展开时间2—3小时,铀,钍,稀土元素Rf值变化不大。从20毫克稀土元素中定量分离微克量钍和铀;从4毫克钍中定量分离微克量稀土元素和铀;从10毫克铀中定量分离微克量钍及稀土。解决了铀、钍和稀土元素中大量元素分离微量元素的问题。将分离后的铀、钍、稀土元素色带剪下,视其含量用容量法或比色法测定,相对误差5％左右。拟订了细晶石、褐钇钶矿、黄绿石、黑稀金矿等稀有元素矿物系统全分析中的铀、钍和稀土元素的测定方法。经几年的生产实践和大批样品的分析,结果甚佳。从而简化了稀有元素矿物全分析中铀、钍和稀土元素的分离和测定手续,提高了测定它们的准确度,并缩短分析时间,降低成本。     

BPMA矿物元素分析工具在含金、含铌钽矿样品分析中的应用

工艺矿物学分析采用自动系统处理后,通常仍有部分精细分析数据需要人工采集,重复劳动工作量大。采用基于扫描电镜(SEM)-X射线能谱(EDS)的BPMA(BGRIMM Process Mineralogy Analyzing System)系统矿物元素分析工具针对目标矿物进行多点EDS元素分析,通过图像特征信息校正保障目标位置精准,通过高计数谱图信息尽量保障后续元素分析的精度。使用工具软件对含金样品进行位置回溯和元素分析统计的测试,并利用工具软件及BPMA系统对某含铌钽矿样品进行工艺矿物学分析测试,实验表明：样品中含量极少的铌钽矿物主要分布在2-5μm,粒度极细,且60%以上被其他矿物包裹,其中,90%的铌分布于褐钇铌矿、铌钙矿;超过80%的钽分布于铌钙矿和铌易解石。工具软件实现的精度可以代替手动操作,批量回找和自动统计显著提高效率;且工具软件对重要矿物元素含量的分析数据则可进一步提高BPMA最终结果数据的精确度。     

激光剥蚀-电感耦合等离子体质谱:双外标结合基体归一定量校准策略

定量校准策略是激光剥蚀电感耦合等离子体质谱(AICP-MS)分析技术的重要组成部分,直接影响分析数据的质量.本研究评估了现有玻璃标准物质定值不确定度的相对大小,并探究了NIST、MPI-DING和USGS系列玻璃标准物质之间的基体效应.结果表明,NIST610的定值不确定度优于其它玻璃标准物质,在本实验条件下,NIST、MPI-DING和USGS系列玻璃标准物质之间的基体效应可忽略不计.在此基础上提出了双外标结合基体归一定量校准策略,外标分别为NIST610和StHs6/80-G.此策略克服了由于NIST610主量成分与地质样品差别大而造成的主量元素准确度差以及StHs6/80-G中某些微量元素含量低、定值不确定度较大等缺点.对比采用3种定量校准策略(单外标NSIT610基体归一法、单外标StHs6/80G基体归一法和双外标基体归一法)校准的ML3B-G数据可知,双外标基体归一法有效避免了单外标基体归一法的不足,并提高了分析数据的准确度.采用双外标结合基体归一定量校准策略校准了BCR-2G、CGSG-2和KL-2G中的主量元素和微量元素.结果表明,绝大多数分析数据在定值不确定度范围内,验证了此校准策略的实用性.同时,本研究得到的主量微量元素数据进一步补充了BCR-2G、CGSG-2和KL-2G的定值数据库.     

氢氟酸直接进样-电感耦合等离子体原子发射光谱法(ICP-AES)测定氧化锆中多种杂质元素

采用氢氟酸微波消解法前处理氧化锆材料,使用氢氟酸进样系统,不需要赶酸直接测定GBW06602氧化锆标准样品中的多元素含量,根据样品情况确定了最佳分析条件和最佳分析谱线。实验结果表明,测定元素线性关系及重复性良好,定量准确,可同时测定氧化锆中的多种金属元素,该方法检出限低,精密度高,分析结果与标准值相吻合,完全满足氧化锆中多元素杂质含量的工业分析要求。     

Performance and limitations of electron probe microanalysis applied to the characterization of coatings and layered structures

Electron probe microanalysis (EPMA) at low electron energies (typically 3-10 keV) has been used to study the composition of coatings with a film thickness of 0.1-1.3 microm ("bulk" analysis). The accuracy of quantification, including the most critical situation of low atomic number elements (boron-oxygen), is about 5% relative by use of pure element or arbitrary compound standards. A special procedure of data processing ("thin film" analysis) enables the simultaneous determination of film thickness and composition, provided that the substrate is known. The film thickness may be in the range of 2 nm to 5 microm. EPMA can be also applied in the mode of "non-destructive in-depth analysis", which is based on the combined evaluation of experiments at different electron energies. The quantitative characterization of layered structures and implantation zones is demonstrated.     

Polyurethane foam of the polyether type as a solid polymeric extractant for cobalt and iron from thiocyanate media

By combining instrumental and radiochemical neutron activation analysis, up to 47 elements including major, minor, and trace elements, have been determined in lake sediment samples. Instrumental neutron activation involving both short and long irradiations is used to determine 40 elements including most of the environmentally important ones. A radiochemical separation procedure allows the determination of 7 noble metals. The accuracy and precision of the method are 5–10%.     

3D-SIMS analysis of ultra high purity molybdenum and tungsten: a characterisation of different manufacturing techniques and products

Applying a recently developed three dimensional SIMS imaging technique major differences in the distribution of trace elements in ultra high purity Mo and W have been found. In the electron beam melted material severe grain boundary segregation of trace elements have occurred whereas in the hot pressed material trace elements have been present as precipitates with a size of 5–15 m. Guided by the results of the 3D-SIMS images and the advantages of the sintering process a material with homogeneous distribution of trace elements has been developed and characterised. To test the applicability for the microelectronics industry, sputtering targets have been manufactured out of this new material and layers with a thickness of 350 nm have been sputterdeposited on silicon. The quality of these layers, with respect to particle emission and the distribution of trace elements, was evaluated by EPMA and 3D-SIMS imaging. Further improvement of the sintering process led to a material with a completely homogeneous distribution of C, H, N, O and S to minimise the outgassing and diffusion of impurities.Abbreviations BSE Back scattered electron - EPMA Electron probe micro analysis - GAAS Graphite furnace atomic absorption spectrometry - GDMS Glow discharge mass spectrometry - ICP-AES Inductively coupled plasma atomic emission spectrometry - ICP-MS Inductively coupled plasma mass spectrometry - SIMS Secondary ion mass spectrometry - ULSI Ultra large scale integration     

Determination of Precious Metals in Geological Samples from Four Gold Ore Deposits of the North-East of Russia

Compositions of rare mineral phases containing precious metals (PMs) in samples from Natalka, Pavlik, Vetrenskoe, and Degdekan gold ore deposits (North-East of Russia) are studied by scintillation atomic emission spectrometry (SAES) and electron probe microanalysis (scanning electron microscopy and electron probe X-ray microanalysis, SEM–EPMA). The SAES method found dozens and hundreds of particles carrying gold, silver, and all platinum-group elements as native metals, intermetallides and solid solutions, arsenides, antimonites, sulfoarsenides, tellurides, selenides, etc. The variety of the elemental compositions of PM species (mineral phases) found by SAES significantly exceeds the list of minerals found previously by SEM–EPMA because of different natures of optical and X-ray spectra. The sizes of PM particles calculated by the SAES method and measured by SEM–EPMA are similar. The SAES data on the total concentrations of PMs satisfactorily agree with the results of inductively coupled plasma mass spectrometry.     

Evaluation of the analytical performance of inductively coupled plasma mass spectrometry for the simultaneous determination of major and minor elements in basic slags

The application of inductively coupled plasma mass spectrometry to the analysis of basic slags has been studied. A conventional dissolution-fusion procedure and a microwave digestion system were used for sample dissolution. Suitable selection of the analyte isotopes and the use of appropriate instrument settings and of internal standardization makes it possible to determine the major and minor elements in the same test sample dilution. Use of the omnirange device and low-abundance isotopes for the determination of the major elements is evaluated. The influence of the attack reagents is tested and the interferences caused by polyatomic ions are studied and corrected by applying elementary mathematical equations. For the major and minor elements considered, precision was found to be better than 1% (RSD). Results are presented for three basic slag reference materials and the agreement between the certified and found values shows the capacity of the method accurately to determine elemental concentrations in basic slags.     

基体归一定量技术在激光烧蚀-等离子体质谱法锆石原位多元素分析中的应用

探讨了内标法和基体归一法校准的基本原理。基体归一校准法的基本步骤为:先用简单外标法测得样品中尽可能全的主、次、痕量元素含量,氧化物加和后进行100%归一,得到灵敏度校正系数,对所有元素的测定结果进行修正。修正结果的可靠性在很大程度上取决于测定元素是否"完全"。由于锆石的基体元素组成简单且易于测定,很适合用基体归一法校准。在激光剥蚀-电感耦合等离子体质谱法(LA-ICP-MS)微区原位分析中,应用基体归一校准法的最大优点是:可以避免预先用其它微区分析技术对未知样品中的内标元素进行定量。该技术可适用于具有环带结构、难以找到均匀分布的内标元素的地质样品的元素空间分布测定。在高分辨ICP-MS(Element2)和NewWave-UV-213激光系统上,应用基体归一定量技术同时分析了锆石中主、次、痕量共54种元素。对未知锆石样品的分析,基体归一法与内标法结果的一致性令人满意。分析德国蛇纹岩标准玻璃ATHO-G中相对误差<25%的有52个元素,<10%的有36个元素;大多数元素的相对标准偏差<10%。     

X射线荧光光谱法测定催化原料高岭土化学成分的研究

采用LiBO2熔样,X射线荧光光谱仪测定了高岭土的化学组成,结果表明,测定值与化学法及推荐值相符,重复测定高岭土主、次量组分的相对标准偏差小于0.83%,方法简便快捷,分析时间仅为传统湿法化学分析的1/8,应用于高岭土的测定,结果满意。     

电感耦合等离子体原子发射光谱法(ICP-AES)测定硫化物矿石中的14种常微量元素

采用高压消解罐-王水溶样前处理硫化物矿石样品,ICP-AES法测定了硫化物矿GBW07163标准物质中的14种常微量元素的含量,确定了最佳工作条件,选择了最佳分析谱线。实验结果表明,方法线性相关系数良好,可同时测定硫化物矿石中的常微量元素,方法检出限低,精密度高,分析结果与标准值相吻合,可以满足地矿检测的需求。     

Combined EPMA and AES depth profiling of a multilayer Ti-Al-O-N coating

In order to compare thin-film electron probe microanalysis (EPMA) and Auger electron spectroscopy (AES) regarding reliability in quantifying chemical compositions of Ti-Al-O-N coatings with depth, a multilayer was prepared on a silicon wafer by using reactive ionized cluster beam deposition technique. Within a total thickness of about 25 nm the composition of the multilayer varied step by step from Ti-Al-O-N at the bottom to Al-O at the top. AES and, as an innovation, EPMA crater edge profiling was applied to measure the composition with depth. For quantification special thin-film EPMA techniques based on Monte Carlo simulations were applied. The chemical binding states of Al and Ti with depth were analysed using a high resolution energy analyser (MAC 3) for the AES investigations working in the direct mode. According to the deposition procedure the concentration profiles of the components varied with depth for both AES and EPMA measurements. AES provided a better depth resolution than EPMA. To get a true calibration of the depth scale an in-situ measurement method like an optical interferometry will be required. Assuming that the relative sensitivity factors are available AES depth profiling delivers concentration profiles with good accuracy. The new EPMA application provided quantitative depth profiles concerning concentration and coverage. For EPMA crater edge profiling the coating needs to be deposited on a foreign substrate because depth distributions of elements being present in both the layer and the substrate cannot be resolved.The combination of AES-depth profiling with EPMA crater edge profiling techniques is a powerful tool to analyse heterostructures quantitatively.     

ICP-AES测定硫化物矿石中的14种常微量元素

采用高压消解罐王水溶样前处理硫化物矿石样品,ICP-AES法测定了硫化物矿GBW07163标准物质中的14种常微量元素的含量,确定了最佳工作条件,选择了最佳分析谱线。实验结果表明,该方法线性相关系数良好,可同时测定硫化物矿石中的常微量元素,该方法检出限低,精密度高,分析结果与标准值相吻合,可以满足地矿检测的需求。