非金属矿二级标样配制及其粉末样品的XRF分析方法

针对X射线荧光光谱法(XRF)压片法分析中非金属矿标样不能满足实际工作需要的情况,以四川峨边五渡钾长石矿为例,研究了如何根据非金属矿一级标样配制系列二级标样,以及如何根据二级标样对非金属矿粉末样品进行XRF压片法分析的方法。在采用X射线衍射分析(XRD)和化学分析法研究钾长石矿和一级标样矿物岩石学特征基础上,根据二级标样与待测样品的矿物岩石学特征相同相似原理,确定了非金属矿二级标样配制的基本方法和要求,即二者的矿物种类相同、矿物含量和化学成分相似,并适应待测样品成分的波动及矿物加工的需要,有利于XRF标准工作曲线的绘制;采用实验确定的非金属矿XRF压片法制样条件以及根据二级标样绘制的标准工作曲线,对钾长石矿的SiO2,Al2O3,Fe2O3,TiO2,MgO,CaO,K2O,Na2O等化学成分进行了XRF测试分析,其结果与化学分析法一致,说明本方法准确度较好,能够基本消除矿物效应的影响。     

研究固体微结构的X射线粉末衍射全谱图拟合方法

Ｘ射线粉末衍射全谱图拟合的Ｒｉｅｔｖｅｌｄ方法是一种有效的晶体结构和微结构的分析方法。本文介绍了Ｘ射线粉末衍射全谱图拟合的Ｒｉｅｔｖｅｌｄ方法的基本原理,综述了该方法中的线形分析、校正及其在晶体结构分析、微结构分析、相定量分析和衍射图谱指标化等方面应用的最新进展。文章最后介绍了在实验方案选取方面的新概念     

研究固体微结构的X射线粉末衍射全谱图拟合方法

Ｘ射线粉末衍射全谱图拟合的Ｒｉｅｔｖｅｌｄ方法是一种有效的晶体结构和微结构的分析方法。本文介绍了Ｘ射线粉末衍射全谱图拟合的Ｒｉｅｔｖｅｌｄ方法的基本原理，综述了该方法中的线形分析、校正及其在晶体结构分析、微结构分析、相定量分析和衍射图谱指标化等方面应用的最新进展。文章最后介绍了在实验方案选取方面的新概念     

波长色散X射线荧光光谱法测定黄金饰品含金量

本文提出应用波长色散Ｘ射线荧光光谱仪测定黄金饰品含金量的方法，本法对原有样品盒进行了改造，增设特制窗口和采取样品固定等措施，以系列参考标样建立校准曲线，用经验系数法校正基体效应。比例模拟法校正含量。９个参考标样和１６个金标牌的测定结果表明，在含金量为３７．５０％－９９．９９％的范围内，方法的准确度好：含金量在９９．９９％－９８．９８％范围时，误差为０．０３％－０．１２％，在９８．９８％－３７．５０％范围时，误差为０．０１％－０．５２％，选用含金量不同的５个参考标样为代表，以０．７和１．４的模拟比例，经不同时间多次测定进行统计，相对标准偏差为０．０５％－０．５０％，说明方法的精密度好，本法操作方便，时样品无破坏     

X射线粉末衍射的新起点—Rietveld全谱拟合

Ｒｉｅｔｖｅｌｄ全谱拟合法及高分辨Ｘ射线粉末衍射实验方法的出现与发展,使Ｘ射线粉末衍射进入了一个新阶段,不但提高了分析结果的质量,并且使从头晶体结构测定成为可能。本文扼要介绍了Ｒｉｅｔｖｅｌｄ全谱拟合法的理论;高分辨高准确的粉末衍射装置,从头晶体结构测定方法及多晶材料结构表征的全谱拟合法（包括作物相定性分析、物相定量分析、晶粒大小及点阵畸变的测定等）     

一种可溯源的光谱椭偏仪标定方法

提出了一种用X射线反射术标定光谱椭偏仪的方法.作为一种间接测量方法,光谱椭偏术测得的薄膜厚度依赖于其光学常数,不具有可溯源性.在掠入射条件下,X射线反射术能测得薄膜的物理厚度,测量结果具有亚纳米量级的精密度且与薄膜光学常数无关.在单晶硅基底上制备了厚度分别为2nm,18nm,34nm,61nm及170nm的SiO2薄膜标样,并用强制过零点的直线拟合了两种方法的标样测量结果,拟合直线的斜率为1.013±0.013,表明该方法可在薄膜厚度测量中标定光谱椭偏仪.     

Ⅱ－Ⅵ族应变层超晶格的X射线衍射分析

本文报导了用计算机控制的衍射仪（ＣｕＫα辐射）测量的金属有机化学汽相沉淀（ＭＯＣＶＤ）方法生长的Ⅱ－Ⅵ族应变层超晶格的Ｘ射线衍射曲线，观察到了超晶格结构的多级卫星峰，且卫星峰的强度随角度呈周期性变化．对这种卫星峰形成包络的衍射曲线，用Ｘ射线运动学衍射理论进行了分析和讨论，这种讨论有助于理解Ｘ射线衍射曲线中卫星峰的形成．同时用光致发光和包络峰宽度的方法估算了样品的结构参数．     

辉光放电发射光谱氩内标—溅射率校正方法——用于表、逐层定量分析和合金试样分析

本文将自制Grimm型辉光放电源配备在-28中型石英棱镜摄谱仪上,用辉光放电源工作气体氩作内标,试样溅射率作校正项的制作工作曲线方法,以解决表逐层定量分析中的定标问题。为验证氩内标方法的可行性,本文工作中选择包括铁基、铜基、铝基合金在内的部分不同基体和不同牌号的标样,在不同放电条件下进行了实验。实验结果表明,当以氩作内标, 同时考虑溅射率校正的情况下,可以克服基体和第三元素对分析元素谱线强度的影响,同基体不同牌号和不同基体不同牌号的铁、铜、铝基合金标样的工作曲线均能重合在同一直线上。从而表明:当以氩作内标并加溅射率校正时,使用与分析试样成份差别较大的已知成份合金作标样是可行的。这样便扩大了标样的选择范围,一定程度上解决了表,逐层分析过程中,表层和基材成份变化较大时的定标问题。方法的准确度和精密度可以满足表,逐层分析的要求。从而为镀、涂、渗层材料和复合材料的,表层、逐层分析提供了一种新的方法。     

X射线粉末衍射的新起点——Rietveld全谱拟合

Ｒｉｅｔｖｅｌｄ全谱拟合法及高分辨Ｘ射线粉末衍射实验方法的出现与发展，使Ｘ射线粉末衍射进入了一个新阶段，不但提高了分析结果的质量，并且使从头晶体结构测定成为可能。本文扼要介绍了Ｒｉｅｔｖｅｌｄ全谱拟合法的理论；高分辨高准确的粉末衍射装置，从头晶体结构测定方法及多晶材料结构表征的全谱拟合法（包括作物相定性分析、物相定量分析、晶粒大小及点阵畸变的测定等）     

X射线光谱与神经网络中单组分型神经群结构研究

研究、比较了神经群结构与常规神经网络算法的预测性能,考察了过拟合与最佳拟合态等的关系。结果表明,在多元体系中,将神经网络单组分预测模型应用于Ｘ射线荧光光谱分析时,在预测准确度、模型稳定性和外推预测能力方面,神经群结构优于常规神经网络模型。     

Anisotropy enhanced X‐ray scattering from solvated transition metal complexes

Time‐resolved X‐ray scattering patterns from photoexcited molecules in solution are in many cases anisotropic at the ultrafast time scales accessible at X‐ray free‐electron lasers (XFELs). This anisotropy arises from the interaction of a linearly polarized UV–Vis pump laser pulse with the sample, which induces anisotropic structural changes that can be captured by femtosecond X‐ray pulses. In this work, a method for quantitative analysis of the anisotropic scattering signal arising from an ensemble of molecules is described, and it is demonstrated how its use can enhance the structural sensitivity of the time‐resolved X‐ray scattering experiment. This method is applied on time‐resolved X‐ray scattering patterns measured upon photoexcitation of a solvated di‐platinum complex at an XFEL, and the key parameters involved are explored. It is shown that a combined analysis of the anisotropic and isotropic difference scattering signals in this experiment allows a more precise determination of the main photoinduced structural change in the solute, i.e. the change in Pt—Pt bond length, and yields more information on the excitation channels than the analysis of the isotropic scattering only. Finally, it is discussed how the anisotropic transient response of the solvent can enable the determination of key experimental parameters such as the instrument response function.     

X射线衍射光谱和X光电子能谱研究直接甲醇燃料电池阳极催化剂

利用Ｘ射线衍射光谱和Ｘ光电子能谱研究了甲醇电催化氧化的Ｐｔ－Ｍｏ／Ｃ催化剂,发现该内化剂主要以０价态的Ｐｔ和氧化态的Ｍｏ存在,分析了甲醇在该催化剂的活化机理。     

A simple calibration procedure of polycapillary based portable micro‐XRF spectrometers for reliable quantitative analysis of cultural heritage materials

Portable micro‐X‐ray fluorescence (micro‐XRF) spectrometers mostly utilize a polycapillary X‐ray lens along the excitation channel to collect, propagate and focus down to few tens of micrometers the X‐ray tube radiation. However, the polycapillary X‐ray lens increases the complexity of the quantification of micro‐XRF data because its transmission efficiency is strongly dependent on the lens specifications and the propagated X‐ray energy. This feature results to a significant and not easily predicted modification of the energy distribution of the primary X‐ray tube spectrum. In the present work, we propose a simple calibration procedure of the X‐ray lens transmission efficiency based on the fundamental parameters approach in XRF analysis. This analytical methodology is best suited for compact commercial and portable micro‐XRF spectrometers. The developed calibration procedure is validated through the quantitative analysis of a broad range of samples with archeological relevance such as glasses, historical copper alloys, silver and gold alloys offering an overall accuracy of less than 10%–15%. Copyright © 2015 John Wiley & Sons, Ltd.     

Atomistic modeling of ternary additions to NiTi and quaternary additions to Ni–Ti–Pd,Ni–Ti–Pt and Ni–Ti–Hf shape memory alloys

The behavior of ternary and quaternary additions to NiTi shape memory alloys is investigated using a quantum approximate method for the energetics. Ternary additions X to NiTi and quaternary additions to Ni–Ti–Pd, Ni–Ti–Pt, and Ni–Ti–Hf alloys, for X=Au, Pt, Ir, Os, Re, W, Ta,Ag, Pd, Rh, Ru, Tc, Mo, Nb, Zr, Zn, Cu, Co, Fe, Mn, V, Sc, Si, Al and Mg are considered. Bulk properties such as lattice parameter, energy of formation, and bulk modulus of the B2 alloys are studied for variations due to the presence of one or two simultaneous additives.     

硅铁合金中硅的间接测定

通过对样品的Ｘ光物相分析,探明硅铁合金的成分,经分光光度法测定铁的含量。从而间接地得到非单质硅的含量。本方法快速准确,为硅铁中有效硅的含量分析提供了一条捷径。     

Use of the CEARXRF GUI‐Based Monte Carlo–Library Least‐Squares (MCLLS) Code for the Micro‐Focused EDXRF analyzer

The CEARXRF GUI‐Based Monte Carlo–Library Least‐Squares (MCLLS) Code is demonstrated with results from a micro‐focused EDXRF analyzer, which can be used to calculate elemental weight fractions in metal alloys or rock samples accurately by library least‐squares regression of the measured X‐ray spectrum with computer‐generated elemental library spectra. An elemental stratified sampling variance reduction technique has been implemented in the CEARXRF5 code, which equalizes the statistical precision of the elemental libraries within the measured sample independent of the relative elemental amounts that are present. Also, an improved Si(Li) detector response function (DRF) has been obtained for micro‐focused X‐ray fluorescence (XRF) analyzers, and the DRF parameters are obtained based on regression from pure elemental experimental spectra. It is demonstrated that the resulting MCLLS approach can greatly improve the accuracy of elemental XRF analysis results. Copyright © 2011 John Wiley & Sons, Ltd.     

Thickness and composition of gold and silver alloys determined by combining EDXRF‐analysis and transmission measurements

Energy‐dispersive X‐ray fluorescence (EDXRF)‐analysis is a technique which in the case of metals analyzes thin surface layers. For example, when gold and silver alloys are analyzed, it typically interests a depth of microns up to a maximum of tens of microns. Therefore, it can give wrong results or be affected by a large indetermination when the sample composition is altered because of surface processes, as often happens when silver alloys are oxidated, and sometimes in the case of gold alloys rich on copper or silver. A complementary technique was therefore developed, of bulk analysis, which uses the same equipment employed for EDXRF‐analysis; the X‐ray beam from the X‐ray tube is monochromatized by means of a tin secondary target, which K lines bracket the silver‐K discontinuity. The sample to be analyzed is positioned between the secondary target and the detector. This technique is able to determine (by measuring the attenuation of tin‐K rays) thickness and/or composition of gold and silver alloys having a thickness of less than about 120 µm for gold and about 0.7 mm for silver. The method was tested with Au–Ag–Cu alloys of known composition and thickness and then applied to gold and silver artifacts from the tomb of the Lady of Cao, which belongs to the Moche pre‐hispanic culture from the North of Peru, and dates about 300 A.D. Copyright © 2014 John Wiley & Sons, Ltd.     

X射线荧光光谱法测定样品中镁的不确定度

对X射线荧光光谱熔融法测定土壤样品中的镁含量的不确定度进行了评定.通过对试验过程的分析,测量结果的不确定度的来源有以下几个方面,仪器的综和稳定性,制样,标准物质,校准曲线回归分析,重复测量.在得到各不确定度分量后,通过合成得到测量结果的标准不确定度,再乘以扩展因子2（95％置信概率）,得到测量结果的扩展不确定度.     

Density functional theory study of structural,electronic,and thermal properties of Pt,Pd, Rh,Ir, Os and PtPdX(X= Ir,Os, and Rh) alloys

The structural, electronic, mechanical, and thermal properties of Pt, Pd, Rh, Ir, Os metals and their alloys Pt Pd X(X= Ir, Os and Rh) are studied systematically using ab initio density functional theory. The groundstate properties such as lattice constant and bulk modulus are calculated to find the equilibrium atomic position for stable alloys. The electronic band structure and density of states are calculated to study the electronic behavior of metals on making their alloys. The electronic properties substantiate the metallic behavior for all studied materials. The firstprinciples density functional perturbation theory as implemented in quasi-harmonic approximation is used for the calculations of thermal properties.We have calculated the thermal properties such as the Debye temperature, vibrational energy, entropy and constant-volume specific heat. The calculated properties are compared with the previously reported experimental and theoretical data for metals and are found to be in good agreement. Calculated results for alloys could not be compared because there is no data available in the literature with such alloy composition.     

Insight into growth of Au–Pt bimetallic nanoparticles: an in situ XAS study

Au–Pt bimetallic nanoparticles have been synthesized through a one‐pot synthesis route from their respective chloride precursors using block copolymer as a stabilizer. Growth of the nanoparticles has been studied by simultaneous in situ measurement of X‐ray absorption spectroscopy (XAS) and UV–Vis spectroscopy at the energy‐dispersive EXAFS beamline (BL‐08) at Indus‐2 SRS at RRCAT, Indore, India. In situ XAS spectra, comprising both X‐ray near‐edge structure (XANES) and extended X‐ray absorption fine‐structure (EXAFS) parts, have been measured simultaneously at the Au and Pt L₃‐edges. While the XANES spectra of the precursors provide real‐time information on the reduction process, the EXAFS spectra reveal the structure of the clusters formed in the intermediate stages of growth. This insight into the formation process throws light on how the difference in the reduction potential of the two precursors could be used to obtain the core–shell‐type configuration of a bimetallic alloy in a one‐pot synthesis method. The core–shell‐type structure of the nanoparticles has also been confirmed by ex situ energy‐dispersive spectroscopy line‐scan and X‐ray photoelectron spectroscopy measurements with in situ ion etching on fully formed nanoparticles.