不锈钢中铬的X射线荧光光谱分析

以北京钢铁研究院研制的GSB 03-2028系列不锈钢标准物质作为光谱标样,采用基本参数法校正基体效应,建立了X射线荧光光谱测定不锈钢中铬元素的方法.用该方法对标准样品进行分析,分析结果和化学法分析值相吻合,10次制样测量,测定结果的相对标准偏差约为0.14%.     

直流辉光放电质谱法测定多晶硅中关键杂质元素的相对灵敏度因子

采用直流辉光放电质谱(dc-GD-MS)测定多晶硅中关键杂质元素的相对灵敏度因子(RSF).标样制作过程中主要是在连续通入氩气条件下将固定量的非标准多晶硅样品熔化,向硅熔体中均匀掺入浓度范围为1～30 μg/g的关键杂质元素(如B和P),采用快速固化法制成标样;再将制成的标准样品加工成一系列适合GD-MS扁平池(Flat Cell)的片状样品(20 mm×20 mm×2mm).采用二次离子质谱法(SI-MS)对标准样品中关键掺杂元素进行多次定量测定,取平均值作为关键杂质元素的精确含量.优化一系列质谱条件后,运用GD-MS对标样中关键掺杂元素的离子强度进行多次测定,计算平均结果,得到未校正的表观浓度,利用标准曲线法计算出关键杂质元素的相对灵敏度因子.     

X射线荧光光谱分析水基标样替代油基标样的实现

用水基标样替代油基标样,建立X射线荧光光谱测定石油及其产品中微量元素含量的方法。以钒、锰、铁、镍为研究对象,采用乳化技术制备试样,用乳化剂司班80将水基标样和油结合起来,合成油包水型乳状液;采用理论α影响系数法和内标法校准油水差异校正基体效应。实验发现,如果基体组成已知,理论α影响系数法可以校正水基和油基的基体差异,水基标样和油基标样可直接互换;如果基体组成未知,采用内标法校正基体效应,需要将样品合成油水混合液校正才能成功。用原油和燃料油样品进行对比实验,测得结果与标准方法一致。     

辉光放电质谱法测定超高纯铝中痕量杂质元素EI北大核心CSCD

采用辉光放电质谱法(GDMS)分析超高纯铝样品(含铝量≥99.9995%)中B,Mg,Si,P,Cl,Ti等44种主要杂质元素,并且与电感耦合等离子体质谱法(ICPM S)进行对比,主要杂质元素含量检测结果一致。本工作对质谱干扰的排除和预溅射过程时间的确定进行了讨论,采用高纯铝标样对高纯铝中26种主要元素相对灵敏度因子(RSF)进行校正和验证,并考察了检测结果的准确性和精密度。结果表明,GDMS是超高纯铝样品直接测定的最有效手段之一。     

辉光放电质谱法测定超高纯铝中痕量杂质元素

采用辉光放电质谱法(GDMS)分析超高纯铝样品(含铝量≥99.9995%)中B,Mg,Si,P,Cl,Ti等44种主要杂质元素,并且与电感耦合等离子体质谱法(ICPM S)进行对比,主要杂质元素含量检测结果一致。本工作对质谱干扰的排除和预溅射过程时间的确定进行了讨论,采用高纯铝标样对高纯铝中26种主要元素相对灵敏度因子(RSF)进行校正和验证,并考察了检测结果的准确性和精密度。结果表明,GDMS是超高纯铝样品直接测定的最有效手段之一。     

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射线荧光光谱测定中理论α系数的计算及其在硅酸盐类岩石分析中的应用

X射线荧光光谱象其它分析技术一样也存在着元素间的相互影响(基体效应)。人们在理论研究和实验的基础上,提出了多种克服基体效应的数学模式。其中应用最广的是以所谓Lachance方程Wi/Ri=1+∑a_(ii)W_i (1)为代表的一类方程。式中的影响系数a多数是使用标样从实验中求出,故此称之为经验系数法,有的是用二元标样作图求出,也有的如Willy K.de Jongh从基本的理论公式出发考虑x光管的光谱分布用大型计算机算出相对强度R_i进而算出所谓理论a系数。但是这     

激光剥蚀电感耦合等离子体质谱法测定碳化硅器件中杂质元素

采用激光剥蚀电感耦合等离子体质谱法(LA-ICP-MS),以NIST玻璃标准物质制作校准曲线,29Si为内标,相对灵敏度因子(RSF)校准标样和样品间的基体效应,对碳化硅陶瓷器件中9种痕量元素(B,Ti,Cr,Mn,Fe和Ni等)进行定量测定。选择线性扫描方式,激光剥蚀孔径为150μm,氦气和氩气流量为0.7 L/min时,信号稳定性和灵敏度最佳。经内标校准后,各元素标准曲线的线性有较大改善,线性相关系数为0.9981~0.9999。以建立的方法对碳化硅标准参考物质(BAM-S003)中的痕量元素进行测定,并与标准参考值进行对比,结果一致,证实了LA-ICP-MS方法应用于碳化硅样品检测的准确性和有效性。采用本方法定量测定碳化硅器件中痕量元素,结果与辉光放电质谱法(GD-MS)测定的结果比较一致。元素B,Ti,Cr,Mn,Fe,Ni,Cu,Sr和La的检出限为0.004~0.08 mg/kg,相对标准偏差(RSD)小于5%。     

铝青铜合金样品的X射线荧光光谱分析

建立了X 射线光谱测定铝青铜系列铜合金中Al、Mn、Fe、Si、Ni、Zn、Sn和Pb 8种元素的方法,探讨电流、电压对荧光强度的影响,基体效应校正采用基本参数法.用该方法对实际样品进行分析,分析结果与化学法分析结果相吻合.各元素测定结果的相对标准偏差为0.10%-5.56%(n=10).     

献血员血清中20种元素的ICP-MS测定

用电感耦合等离子体质谱（ＩＣＰ－ ＭＳ） 测定献血员血清中２０ 种元素, 采用多元素内标法校正基体效应引起的系统误差, 加入内标元素Ｓｃ 、Ｉｎ 和Ｔｌ 分别校正质量数＜ １００ 、１００ ～１８０ 和＞ １８０ 的元素测定, 用牛血清标样ＧＢＷ ０９１３１ 为质控标准物质, 检验方法的可靠性。 测定了献血组和健康对照组血清中微量元素含量, 进行数理统计, 检验其差异性。     

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.     

Elemental fractionation in laser ablation inductively coupled plasma mass spectrometry

The major challenge to the use of laser ablation sample introduction, combined with inductively coupled plasma mass spectrometry, is the problem of calibration. In the geological analysis of minerals, calibration is complicated by the extraordinarily wide variety of sample matrices which may be encountered. While there is a lack of mineral standards with well characterized concentrations near 1 microg/g, the NIST glass reference materials (SRM 610-617) have been demonstrated to be very useful for the analysis of a wide variety of lithophile elements in silicate samples. An internal reference element, for which the concentration is known in the sample, has been widely used to make corrections for the multiplicative effects of volume (or weight) of the sample ablated, instrument drift, and matrix effects. This procedure works extremely well where elements being determined and the internal reference element being used share similar ablation behaviours; i.e., they do not fractionate progressively during the ablation and transport process. In this study, it is demonstrated that, in terms of ablation behaviour, elements fall into several distinct clusters and that the elements within these clusters correlate well with each other during a period of ablation. Thus, elements within a cluster can be determined using an internal reference element from within the same cluster. While a combination of periodic varying properties typifies the clusters, the geochemical classification of elements into lithophile (silicate loving), and chalcophile (sulphide loving) appears to offer the best characterization of the major groups.     

Elemental fractionation in laser ablation inductively coupled plasma mass spectrometry

The major challenge to the use of laser ablation sample introduction, combined with inductively coupled plasma mass spectrometry, is the problem of calibration. In the geological analysis of minerals, calibration is complicated by the extraordinarily wide variety of sample matrices which may be encountered. While there is a lack of mineral standards with well characterized concentrations near 1 g/g, the NIST glass reference materials (SRM 610–617) have been demonstrated to be very useful for the analysis of a wide variety of lithophile elements in silicate samples. An internal reference element, for which the concentration is known in the sample, has been widely used to make corrections for the multiplicative effects of volume (or weight) of the sample ablated, instrument drift, and matrix effects. This procedure works extremely well where elements being determined and the internal reference element being used share similar ablation behaviours; i.e., they do not fractionate progressively during the ablation and transport process. In this study, it is demonstrated that, in terms of ablation behaviour, elements fall into several distinct clusters and that the elements within these clusters correlate well with each other during a period of ablation. Thus, elements within a cluster can be determined using an internal reference element from within the same cluster. While a combination of periodic varying properties typifies the clusters, the geochemical classification of elements into lithophile (silicate loving), and chalcophile (sulphide loving) appears to offer the best characterization of the major groups.     

Analysis of solids by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS)—II. Matching with a pressed pellet

The possibility of quantitative elemental analysis of solids by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) has been investigated. The solids were mixed with binder material in a ratio of 1:10 and pressed into a pellet in order to obtain a similar matrix composition (matrix matching), and further so that an internal standard could be added. The binder material used was a 1:1 mixture of graphite and cellulose, the latter being impregnated with an aqueous palladium standard solution.

The method was applied to various types of reference materials, including organic materials (leaves and grass), coal, fly ash and several geological materials. Though with the internal standard a precision of 3–6% relative could be obtained, matrix matching was not completely satisfactory. For all the reference materials, results were generally within a factor of 5 of the reference values. This proved to be independent of the mode of the laser (free-running or Q-switched), the elements studied (over 50) and the sample materials investigated.

The detection limits obtained ranged from mg/kg levels for the lower mass elements to 1–100 μg/kg for the higher mass elements. However, the experimental set-up was subject to large memory effects. Detection limits estimated to be ultimately attainable if the memory effects can be overcome are a factor of 10–100 better.     

Sandwich‐Structured Graphene–Nickel Silicate–Nickel Ternary Composites as Superior Anode Materials for Lithium‐Ion Batteries

We report the synthesis of sandwich‐structured graphene–nickel silicate–Ni ternary composites by using the solvothermal method followed by a simple in situ reduction procedure. The composites show an interesting structure with graphene sandwiched between two layers of well‐dispersed Ni nanoparticles (NPs) anchored on ultrathin nickel silicate nanosheets. These ternary composites exhibit enhanced performance as anode materials owing to the synergistic effect between the graphene matrix and electrochemically inert Ni nanoparticles, an effect that holds promise for the design and fabrication of other advanced electrode materials.     

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灰岩中14种主次量元素

采用X射线荧光光谱法对灰岩中的Ca,Mg,Si,K,Na,Fe,Al,Ti,P,S,Mn,Sr,Ba,Cl等14种元素进行同时测定,采用硼酸镶边垫底的粉末压样法,优化了测量条件。对比较轻的元素,采用经验影响系数法校正基体效应,对于较重的元素,采用理论α影响系数法校正基体效应。分析标准参考物质GBW 07132,各元素的精密度(RSD)为0.1%~5.9%,分析标准参考物质GBW 07130,各元素的测定值与标准值相符,该方法对各元素的测定范围宽、速度快。     

Assessment of the homogeneity of the synthesized beryllium-bearing silicate glass for its use as a quality control material in the X-ray electron probe microanalysis of silicates

Results of assessment of the stability and homogeneity of the Be?Mg?Al?silicate glass synthesized by the authors and possibilities of its use as a quality control material (QCM) in the X-ray electron probe microanalysis (EPMA) of Be-bearing silicate materials, i.e., crystals and quenched melts (glasses), and also silicates and oxides are presented. The homogeneity of the samples was studied at the macro- (10–100 μm) and microlevels (1–10 μm) and assessed according to the scheme of dispersion analysis. A possibility of using the Be–silicate glass as a certified reference material for the determination of the concentrations of Mg, Al, Si was estimated using international reference materials of glasses and QCM of minerals of the known composition. The metrological performance of the experimental data obtained suggest that the studied glass can be used as a QCM in the EPMA of Be-bearing silicate materials, silicates, and oxides. The use of the Be-silicate glass as a certified reference material of composition in EPMA ensures acquisition of satisfactory data on the composition of minerals including cordierite and beryllium cordierite, beryllium indialite, beryl and also of metastable phases of chrysoberyl and compounds with the structure of β-quartz and petalite.     

电感耦合等离子体质谱法对GSS系列土壤及沉积物标准物质中多种元素的定值

介绍对10种GSS系列土壤及沉积物标准物质中多种元素进行定值的方法和结果，采用模拟土壤元素天然组成比值的校正溶液，对元素间的基体干扰具有明显的抑制作用，利用115In-103Rh双内标元素校正系统，可有效地抑制分析信号的动态漂移，建立了电感耦合等离子体质谱法对土壤及沉积物标准的物质中多种元素定值的方法，用该方法对GSS－4，GSS－5，GSS－8及GSD－9共4种土壤标准物质进行测定，绝大部分元素的测定结果与标准值的相对误差小于10％，相对标准偏差小于10％，对GSS－10－GSS－16，AMS－1，BEM及DMS－1共10种土壤及沉积物待定值标准物质进行定值，绝大部分元素测定结果的相对标准偏差小于10％。