X射线荧光光谱法表征薄膜进展

X射线荧光光谱法表征薄膜样品以其能同时测定样品的组分和厚度等优点,目前在国内外的研究和应用越来越广泛和深入。文章通过从荧光强度理论计算、基体效应和校正方法、分析误差来源及消除、定量分析软件和实际分析应用等几个方面对X射线荧光光谱法表征薄膜样品的研究作了评述。鉴于薄膜样品制备相似标样比较困难,而基本参数法采用非相似标样表征薄膜的准确度较高,因此基本参数法校正薄膜样品的应用比较广泛。重点介绍了基本参数法的荧光强度理论计算公式的发展、计算误差来源以及分析软件应用。展望了X射线荧光光谱法表征薄膜样品的应用前景和发展方向。     

X射线荧光光谱法测定高纯石墨中的硫

采用X射线荧光光谱法测定出口高纯石墨中的硫，代替传统的化学分析方法。原样品粉末直接压片，标准样品采用国际焦炭样品和淀粉按比例混匀经研磨后压片，采用散射线背景校正法校正基体的影响，效果良好，简便易行。本方法的精与准确度均较好。     

X射线荧光光谱法测定增产丙烯助剂中磷和铁的研究

使用X射线荧光光谱仪,采用人工合成标样,设计合成了一套标准样品,采用数学校正法中的经验系数法校正元素间的互相干扰,样品不经任何处理,粉末直接压片,经验系数法校正基体效应,建立了分析测定增产丙烯助剂中磷和铁含量的方法。讨论了样品制作方法,合适的测量条件,探讨了试样中元素间的相互影响。实验结果表明,该方法重现性好,准确度和精密度较高,测定磷和铁的相对标准偏差为：0.34%和0.59%;测定范围磷为0.01%～2.5%,铁为0.01%～2.5%。分析结果与化学法、等离子发射光谱法测定结果吻合。该方法快速、简便,样品处理简单,可以不分解;分析速度远快于其他分析方法,结果准确,单次测量一个样品只需要5 min,适用范围广,满足了科研和工业生产的需要。     

X射线荧光光谱法直接测定油页岩中微量元素

本文提出用微晶纤维素与GSD等国家一级系列标样按不同比例混合制备标准样品。油页岩样品不经前处理,直接粉末法压片,经验系数法校正元素间效应,直接测定油页岩中V、Co、Ni、Cr、Cu、Zn、Sr、Ba和Rb等元素的X射线荧光光谱法。样品分析结果与ICP-AES法分析结果基本一致,本法具有简单、准确、实用的特点。     

WD-XRF在新疆某地区化探样品上的应用

讨论了波长色散X射线荧光光谱法(WD-XRF)在地质样品分析中的测量条件、适用范围、分析方法的精密度和准确性.本法用经验系数法和散射线内标法校正基体效应,采用粉末压片法制取试样,对新疆某地区化探样品50种元素进行分析,提高了分析精度.重点研究Pb、Zn、Cu、Fe 4种成分.     

加氢催化剂中稀土及钼、钴含量的X-射线荧光光谱测定方法的研究

使用X 射线荧光光谱仪 ,采用人工合成标样 ,粉末直接压片和经验系数校正基体效应的方法 ,建立了加氢催化剂中稀土氧化物及氧化钼、氧化钴含量的测定方法。研究了制样方法、光谱条件 ,讨论了元素间的相互影响。测定范围MoO3:7%～ 13% ,CoO :2 %～ 7% ,RE2 O3:3%～ 6 %。该方法不仅快速、简便 ,而且准确度和精密度较好 ,在上述范围内 ,测定各元素的RSD均小于 2 %。此方法已用于大量样品的分析 ,测定结果与其他方法相符。     

粉末压片法波长色散X射线荧光光谱分析铁矿石样品的矿物效应校正初探

利用10个国内铁矿石标样,对粉末压片法波长色散X射线荧光光谱分析铁矿石样品中主、次量元素时的矿物效应校正进行了初步探讨。文章采用两种方法试图降低由于矿物效应带来的影响。第一种方法(角度校正法)是在测量每个样品 前(包括校正标样以及未知样),对每个待测元素的2θ角度进行实际测量,以校正可能存在的角度偏移;第二种方法(峰面积法)是用峰面积代替峰强度,以校正由于峰形变化所带来的影响。最后用回归分析后的Ｋ因子进行比较。结果表明, 两种方法对矿物效应进行校正都可以不同程度地改善铁矿石中主要元素的校正曲线,尤其是S的校正曲线改善明显。如果在角度校正法或峰面积法的基础上再用基体校正系数,除总Fe外,其他组分均可以满足分析要求,但总Fe仍需要采取 其他措施。     

微束微区X荧光探针分析仪的矿物定量分析

介绍了微束微区X荧光探针分析仪的工作原理,该探针分析仪能够对样品表面约50μm范围内进行多元素定性与定量分析.在定量分析中,建立线性校准方程,采国家标准样品对微束微区X荧光该探针分析仪进行校准曲线的系数标定.以Fe、As和Ti元素所制定的校准曲线为例,定量分析出的元素含量与标准含量相对误差低于9.62％.结果显示微束微区X荧光探针分析仪具有较高的能量的分辨率,可以快速鉴定矿石的物质成分.定量分析结果的准确度低于地质样品分析的误差标准.表明该探针分析仪可以应用于野外条件下矿石微区成分的定性与定量分析.     

X射线荧光光谱粉末直接压片法测定哈默斯雷铁矿中的主次元素含量

本方法采用塑料环作镶圈，粉末直接压片，用X射线荧光光谱法测定哈默斯雷铁矿中的TFe、SiO2、Al2O3、P、S、Cu、MgO和Na2O的含量，试验结果表明：基体影响无需进行校正，方法的准确度和精密度均较高，结果令人满意。     

X荧光光谱分析软件的开发与应用

本文介绍了在能量色散X荧光分析仪上开发的文件资料管理系统，多元线性回归、快速半定量分析、镀层厚度分析和多功能Lucas-tooth强度校正等应用软件。这些软件的应用提高了分析水平、管理效率和科研开发能力。     

微波消解ICP-OES快速测定难溶钒钛磁铁矿中铁、钛、钒

建立了添加络合剂A进行微波消解难溶钒钛磁铁矿,电感耦合等离子体发射光谱(ICP-OES)测定其中铁、钛、钒的方法。通过正交实验确定的最优消解条件是:0.1g钒钛磁铁矿;12mL浓盐酸;0.04g络合剂A;消解时间10min;微波功率385W。用新建立的方法对攀枝花钢铁研究院的钒钛磁铁矿(GBW07226)进行消解,用ICP-OES法对Fe,Ti,V进行测定,测定的相对误差和相对标准偏差均达到分析化学的要求。新建立的方法中,添加络合剂与溶解出的金属离子络合,使得试样与溶解介质盐酸的接触面不断更新,显著加速了矿物的溶解,用ICP-OES法测定消解液,实现了多种主量、微量元素同时测定。该法试剂用量少、经济;样品消解、测定迅速;对环境友好;适合大批量样品快速测定。建立的方法对国家商检部门、相关分析测试单位等具备实际应用价值。     

X射线荧光光谱法测定钒钛磁铁矿成分

试样经熔融制成玻璃样片,用X射线荧光光谱法测定钒钛磁铁矿主要成分,实验确定最佳熔融条件和测定条件,测量结果与标样值、未知试样化学分析值对照表明,本法快速、简便、准确、可靠。     

钢铁中钒、钛元素的激光诱导击穿光谱定量检测

采用激光诱导击穿光谱(LIBS)技术测量钢铁中钒、钛元素的含量。选取V Ⅰ 440.85 nm和Ti Ⅰ 334.19 nm作为定量分析谱线、基体元素谱线Fe Ⅰ 438.35 nm作为内标谱线,分别建立了基本定标法和内定标法的钢铁样品中V和Ti含量的光谱分析定标曲线,并将它们用于检验样品的定量分析。研究表明,V和Ti基本定标曲线的拟合相关系数R2分别为0.987 5和0.990 9,对检验样品中V和Ti元素的测定相对误差最大分别为11.1%和4.0%;而采用内定标法时,V和Ti的拟合相关系数R2分别达到0.995 2和0.992 1,对检测样品中V和Ti元素的测定相对误差均可降低到4.0%以下。结果证明,采用内定标的激光诱导击穿光谱分析方法更适于钢铁样品中钒、钛含量的测定。     

A study of propylene polymerization over bimetallic titanium–vanadium catalysts

New bimetallic catalysts based on microspherical TiCl₃ modified with vanadium trichloride to obtain its different concentrations on the TiCl₃ surface were synthesized. The presence of a VCl₃ crystalline phase in the catalyst was confirmed by X-ray analysis. The synthesized catalysts were applied to studying propylene polymerization in a liquid monomer medium. The kinetics of the polymerization process was determined, and the structure and properties of the synthesized isotactic polypropylene (IPP) were established. It was demonstrated that the PPI samples synthesized over the developed titanium–vanadium catalysts has enhanced freeze resistance as compared to IPP sample obtained over conventional titanium catalysts.     

Disintegration of a coarse-grained vanadium monoxide VO<Subscript><Emphasis Type="Italic">y</Emphasis></Subscript> powder

A coarse-grained powder of nonstoichiometric cubic vanadium monoxide VO _y is disintegrated in a Retch PM 200 planetary ball mill. Milling of the coarse-grained vanadium monoxide powder VO _y at a rate of rotation of 500 rpm for 2 h significantly broadens diffraction lines, and the crystal structure of vanadium monoxide VO_1.00 after milling remains the same. High-resolution scanning electron microscopy and X-ray diffraction studies of the microstructure of vanadium monoxide demonstrate that high-energy milling can produce vanadium monoxide powders with an average crystallite size of 23 ± 10 nm. The vanadium monoxide produced by milling has a crystallite size that is half the crystallite size in the titanium monoxide produced by severe plastic deformation.     

A spectroscopic study of uranium(VI) interaction with magnetite

The uranium sorbed onto commercial magnetite has been characterized by using two different spectroscopic techniques such as X-ray photoelectron spectroscopy (XPS), and extended X-ray absorption fine structure (EXAFS). Magnetite samples have been put in contact with uranium(VI) solutions in conditions in which a high uranium uptake is expected. After several days, the magnetite surface has been analysed by XPS and EXAFS. The XPS results obtained are not conclusive regarding the uranium oxidation state in the magnetite surface. On the other hand, the results obtained with the EXAFS technique show that the uranium-magnetite sample spectrum has characteristics from both the UO₂ and schoepite spectra, e.g. a relatively high coordination number of equatorial oxygens and two axial oxygens, respectively. These results would indicate that the uranium sorbed onto magnetite would be a mixture of uranium(IV) and uranium(VI).     

Electron structure and chemical binding in the titanium and vanadium compounds

Electron structure of octahedral clusters of carbides, nitrides and oxides of titanium and vanadium is calculated by the Xα method. Self-consistent method to determine a cluster charge is offered in terms of which the value and direction of the charge transfer at forming of the chemical bond may be obtained. The calculation results are compared with the data obtained experimentally by the X-ray photoelectron and emission spectroscopy.     

Studies on the Preparation of Magnetic Photocatalysts

A crystalline titanium dioxide coating was deposited onto silica insulated magnetite particles to prepare a stable magnetic photocatalyst. The direct deposition of crystalline titanium dioxide was conducted by aging dispersions of insulated magnetite particles in a titanium sol–gel precursor mixture at 60–90°C. The coating process was found to be influenced by pH, alkoxide precursor concentration, aging time and reaction temperature. A mechanism for the formation of the titanium dioxide coating has been proposed. The photocatalytic performance of the prepared particles was found to be related to the preparation conditions.     

Iron oxide nanoparticles modified with oleic acid: Vibrational and phase determination

A simple path methodology to detect the phase composition of iron oxide nanoparticles modified with oleic acid based on vibrational spectroscopy is present here and applied on three different nanoparticles prepared by co-precipitation method. Firstly, the phase composition, magnetite, maghemite, and hematite, is determined using a reference intensity ratio methodology on X-ray diffraction pattern. Also, the size of each sample was calculated by Scherrer equation. Scanning, transmission electron microscopy, microanalysis and electron diffraction show a core magnetite particles size of around 10 nm for all particles. Based on lattice vibrations, we find a concentration of around 80% of magnetite and a hematite phase lower than 5%. Whereas, the magnetite composition from X-ray diffraction shows 76%. We also investigate the metal-organic interaction and disorder degree of organic molecule conformation by infrared and Raman spectroscopy analysis. Hematite lattice vibrations show more alterations as it interacts with the organic acid. Finally, magnetic measurements at room temperature of the modified particles, suggest a superparamagnetic behavior and high saturation magnetization.     

Hydrogen adsorption on activated carbon nanotubes with an atomic-sized vanadium catalyst investigated by electrical resistance measurements

Activated multi-walled carbon nanotubes were prepared with appended vanadium as a hydrogen storage medium. The pore structure was significantly improved by an activation process that was studied using Raman spectroscopy, field emission transmission electron microscopy and pore analysis techniques. X-ray photoelectron spectroscopy and X-ray diffraction results reveal that the vanadium catalyst was introduced into the carbon nanotubes in controlled proportions, forming V₈C₇. The improved pore structure functioned as a path through the carbon nanotubes that encouraged hydrogen molecule adsorption, and the introduced vanadium catalyst led to high levels of hydrogen storage through the dissociation of hydrogen molecules via the spill-over phenomenon. The hydrogen storage behavior was investigated by electrical resistance measurements for the hydrogen adsorbed on a prepared sample. The proposed mechanism of hydrogen storage suggests that the vanadium catalyst increases not only the amount of hydrogen that is stored but also the speed at which it is stored. A hydrogen storage capacity of 2.26 wt.% was achieved with the activation effects and the vanadium catalyst at 30 °C and 10 MPa.