Elemental composition x-ray fluorescence analysis with a TES-based high-resolution x-ray spectrometer

The accurate analysis of the elemental composition plays a crucial role in the research of functional materials.The emitting characteristic x-ray fluorescence(XRF)photons can be used for precisely discriminating the specified element.The detection accuracy of conventional XRF methodology using semiconductor detector is limited by the energy resolution,thus posing a challenge in accurately scaling the actual energy of each XRF photon.We adopt a novel high-resolution x-ray spectrometer based on the superconducting transition-edge sensor(TES)for the XRF spectroscopy measurement of different elements.Properties including high energy resolution,high detection efficiency and precise linearity of the new spectrometer will bring significant benefits in analyzing elemental composition via XRF.In this paper,we study the Ledge emission line profiles of three adjacent rare earth elements with the evenly mixed sample of their oxide components:terbium,dysprosium and holmium.Two orders of magnitude better energy resolution are obtained compared to a commercial silicon drift detector.With this TES-based spectrometer,the spectral lines overlapped or interfered by background can be clearly distinguished,thus making the chemical component analysis more accurate and quantitative.A database of coefficient values for the line strength of the spectrum can then be constructed thereafter.Equipped with the novel XRF spectrometer and an established coefficient database,a direct analysis of the composition proportion of a certain element in an unknown sample can be achieved with high accuracy.

Quantitative energy-dispersive X-ray fluorescence analysis for unknown samples using full-spectrum least-squares regression

The full-spectrum least-squares(FSLS) method is introduced to perform quantitative energy-dispersive X-ray fluorescence analysis for unknown solid samples.Based on the conventional least-squares principle, this spectrum evaluation method is able to obtain the background-corrected and interference-free net peaks, which is significant for quantization analyses. A variety of analytical parameters and functions to describe the features of the fluorescence spectra of pure elements are used and established, such as the mass absorption coefficient, the Gi factor, and fundamental fluorescence formulas. The FSLS iterative program was compiled in the C language. The content of each component should reach the convergence criterion at the end of the calculations. After a basic theory analysis and experimental preparation, 13 national standard soil samples were detected using a spectrometer to test the feasibility of using the algorithm. The results show that the calculated contents of Ti, Fe, Ni, Cu, and Zn have the same changing tendency as the corresponding standard content in the 13 reference samples. Accuracies of 0.35% and 14.03% are obtained, respectively, for Fe and Ti, whose standard concentrations are 8.82% and 0.578%, respectively. However, the calculated results of trace elements (only tens of lg/g) deviate from the standard values. This may be because of measurement accuracy and mutual effects between the elements.

Geochemical analysis of marine sediments using fused glass disc by X-ray fluorescence spectrometry

A method was developed for content determination of Na, Mg, A1, Si, P,S, C1, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Ga, Nb, Zr, Y, Sr, Rb, Ba, La and Ce etc. covering 26 major, minor, and trace elements in marine sediment samples using fused glass disc by X-ray Fluorescence spectrometry. Calibration was made using marine sediment certified reference materials and the synthetic standard samples prepared by mixing several marine sediments with stream sediment and carbonate standard samples in different proportions. The matrix effect was corrected using theoretical alpha coefficients, experience coefficients and the scattered radiation as the internal standard （for the trace elements）. The accuracy of the method was evaluated by analysis of certified reference materials GBW07314, GBW07334 and GSMS6. The results are in good agreement with the certified values of the standards with RSD less than 2.60%, except for Y, Cr, Ga, Ce, La, Nb, Rb, and V with RSD less than 9.0% （n=12）.

Elemental and proximate analysis of coal by x-ray fluorescence assisted laser-induced breakdown spectroscopy

Although laser-induced breakdown spectroscopy(LIBS),as a fast on-line analysis technology,has great potential and competitiveness in the analysis of chemical composition and proximate analysis results of coal in thermal power plants,the measurement repeatability of LIBS needs to be further improved due to the difficulty in controlling the stability of the generated plasmas at present.In this paper,we propose a novel x-ray fluorescence(XRF) assisted LIBS method for high repeatability analysis of coal quality,which not only inherits the ability of LIBS to directly analyze organic elements such as C and H in coal,but also uses XRF to make up for the lack of stability of LIBS in determining other inorganic ash-forming elements.With the combination of elemental lines in LIBS and XRF spectra,the principal component analysis and the partial least squares are used to establish the prediction model and perform multi-elemental and proximate analysis of coal.Quantitative analysis results show that the relative standard deviation(RSD) of C is 0.15%,the RSDs of other elements are less than 4%,and the standard deviations of calorific value,ash content,sulfur content and volatile matter are 0.11 MJ kg,0.17%,0.79% and 0.41%respectively,indicating that the method has good repeatability in determination of coal quality.This work is helpful to accelerate the development of LIBS in the field of rapid measurement of coal entering the power plant and on-line monitoring of coal entering the furnace.

Impact of Different Grinding Aids on Standard Deviation in X-Ray Fluorescence Analysis of Cement Raw Meal

X-ray fluorescence (XRF) analysis utilizes particle size which is resulted from milling of a material. The milling ensures uniform and fine grained powder. The finer and more uniform the particle size is, the better the result and easier it is for material quality control. To ensure uniformity in particle size and finer powder, a comparative analysis was conducted with different grinding aids and pressed pellet method was used in obtaining analysis results. Pressed pellets of cement raw meal sample milled with different grinding aids (graphite, aspirin and lithium borate) were subjected to XRF. Graphite produced better particle size uniformity with a corresponding standard deviation that made quality control of raw meal easier and better than aspirin and lithium borate.

X-RAY FLUORESCENCE SPECTRA ANALYSIS ON THE STRUCTURE AROUND Ti^(4+) OF BaO-SiO_2-B_2O_3-TiO_2 SYSTEM GLASSES

The structure around Ti^(4+) in Bao-SiO_2 -B_2O_3-TiO_2 had been studied by X-ray fluorescence spectra. The results show that the Ti^(4+) mainly exists in the [TiO_4] and enters the network of [SiO_4]. [TiO_4] has the tendency to change to [TiO_6] with the increase of TiO_2 con-tent. When the TiO_2 content increases to about 20mol% the tendency reaches its maximum.

Determination of Optimum Conditions for X-Ray Fluorescence Analysis Using Coupling Equations

Coupling equations used to calculate the chemical composition of substances by X-ray fluorescence analysis can be classified as empirical, theoretical or semi-empirical based on the method for determining the coefficients of the calibration function. The advantages and disadvantages of each class of equations are discussed. Recommendations for the selecting the optimum conditions for determining empirical correction coefficients and their control during analysis are provided.

Observation and Analysis of VLF Nocturnal Multimode Interference Phenomenon based on Waveguide Mode Theory

Very low frequency(VLF)signals are propagated between the ground-ionosphere.Multimode interference will cause the phase to show oscillatory changes with distance while propagating at night,leading to abnormalities in the received VLF signal.This study uses the VLF signal received in Qingdao City,Shandong Province,from the Russian Alpha navigation system to explore the multimode interference problem of VLF signal propagation.The characteristics of the effect of multimode interference phenomena on the phase are analyzed according to the variation of the phase of the VLF signal.However,the phase of VLF signals will also be affected by the X-ray and energetic particles that are released during the eruption of solar flares,therefore the two phenomena are studied in this work.It is concluded that the X-ray will not affect the phase of VLF signals at night,but the energetic particles will affect the phase change,and the influence of energetic particles should be excluded in the study of multimode interference phenomena.Using VLF signals for navigation positioning in degraded or unavailable GPS conditions is of great practical significance for VLF navigation systems as it can avoid the influence of multimode interference and improve positioning accuracy.

Glancing incidence x-ray fluorescence spectrometry based on a single-bounce parabolic capillary

Glancing incidence x-ray fluorescence spectrometry using a single-bounce parabolic capillary is proposed for the analysis of layered samples.The divergence of the x-ray beam was 0.33 mrad.In this paper,we used this instrumental setup to analyze a Si single crystal and a 50 nm HfO_(2) single-layer film deposited on a Si substrate.

Research progress on fluorescence analysis of antitumor Chinese medicine components

This paper classifies the anti-tumor traditional Chinese medicine's fluorescence analysis and finds that its research content mainly includes two aspects:the application of fluorescence analysis in the determination of the effective component content of anti-tumor traditional Chinese medicine;the study of the combined use of fluorescence imaging technology and the drug.According to literature analysis,it is found that although the research on the fluorescence analysis of anti-tumor Chinese medicine components is in a good state of development,it still needs to explore further in the identification of unknown components and deeper research on known components.Therefore,it can provide a certain basis for clinical guidance of tumor patients.

Application and Development Trends of Spectral Analysis in Draft of Non-Ferrous Metal Standards in China

Spectral analysis was a method of identifying substances, determining their chemical composition and calculating their content based on their spectral characteristics. This paper mainly discussed the application of various spectroscopic techniques, mainly including atomic absorption spectrometry (AAS) inductively coupled plasma emission spectrometry (ICP-AES) X-ray fluorescence spectroscopy (XRF) atomic fluorescence spectroscopy (AFS) direct reading spectroscopy (OES) glow discharge emission spectroscopy (GD-OSE) laser-induced breakdown spectroscopy (LIBS), in the formulation of non-ferrous metal standards in China. The AAS method was the most widely used single-element microanalysis method among the non-ferrous metal standards. The ICP-AES method was good at significant advantages in the simultaneous detection of multiple elements. The XRF method was increasingly used in the determination of primary and secondary trace elements due to its simple sample preparation and high efficiency. The AFS was mostly detected by single-element trace analysis. OES GD-OES and LIBS were playing an increasingly important role in the new demand area for non-ferrous metals. This paper discussed matrix elimination, sample digestion, sample preparation, instrument categories and other aspects of some standards, and summarized the advantages of spectral analysis and traditional chemical analysis methods. The new methods of future spectroscopic technology had been illustrated in the process of developing non-ferrous metal standards.

A TOTAL CONTENT X—RAY FLUORESCENCE METHOD FOR COPPER PROSPECTING

A new method is proposed to prospect copper deposits with portable XRF analyzer. The method is based on the close relation between Cu and the chalcophile elements or some other elements in the geochemical anomalies of a Cu deposit. Applications of the technique in Northeast China are presented.

SMONTE CARLO CALCULATION FOR CALIBRATION FUNCTIONS IN TOTAL REFLECTION X-RAY FLUORESCENCE SPECTROMETRY

Simulation approach includes such processes as photon emissions from X-ray tube with a spectral distribution, total reflection on the sample support, photoelectric effect in thin layer sample, as well as characteristic line absorption and detection. The calculation results are in agreement with experimental ones.

Specimen Variation Effects on XRF Analysis by the Monte Carlo Method: Thicknesses, Densities and Particle Sizes

This theoretical study conducted an X-ray fluorescence (XRF) analysis on specimen variation, with emphasis on variations on the thicknesses, density and particle sizes of specimens. The theoretical formula for X-ray fluorescence intensity was derived. These specimen variations were simulated using Monte Carlo Neutron-Particle Transport Code MCNP5. The Cu element X-ray characteristic peak counts were calculated. These variations made a conspicuous impact on the fluorescence intensity X-ray characteristic, in terms of theoretical formulas and calculations. There was a nonlinear relationship between thicknesses and count, except for thin specimens. As the density increased, the count increased in an exponential form for the saturated thick specimens. When the density reached 1 g.cm-3 , the count remained constant. The matrix materials (moisture) could increase the matrix effects. The higher the moisture was, the greater the matrix effect was. Specimen particle size also affects these measurement results. Hence, these specimens must be prepared before measurement. The calculations were consistent with the theoretical formulas.

Structural Analysis of ZnO Film Deposited by Means of Metal Organic Decomposition Method

ZnO films were deposited on glass substrates by means of a metal organic decomposition (MOD) method. We investigated the effect of annealing temperature, time and the number of laminated layers on the film structure on the basis of X-ray diffraction measurements. We found the optimum conditions of the temperature and the time to be 600°C and 40 minutes for the preparation, respectively. In addition, the layer-by-layer forming was not found to degrade the film from viewpoint of X-ray line width.

Timescale Analysis of Spectral Lags

A technique for timescale analysis of spectral lags performed directly in the time domain is developed. Simulation studies are made to compare the time domain technique with the Fourier frequency analysis for spectral time lags. The time domain technique is applied to studying rapid variabilities of X-ray binaries and γ-ray bursts. The results indicate that in comparison with the Fourier analysis the timescale analysis technique is more powerful for the study of spectral lags in rapid variabilities on short time scales and short duration flaring phenomena.

The background calculation of the filter-fluorescer method

For the measurement of X-ray energy spectrum with filter-fluorescer method,the high energy tail at the rearward of response function is the main source of background.There are,traditionally,two techniques for measuring the background contributions:the same element Z for the fluorescer and filter,or the same element Z?1 for them.Using the formula of fluorescence intensity,and the elemental combinations of cobalt and iron,the backgrounds which the two techniques provide and the real one for measuring black-body radiation at equilibrium temperature of 7×106 K,were calculated.The results show that the Co-Co combination for the filter-fluorescer spectrometer can achieve better effect.A semi-quantitative analysis for the calculation results is discussed.

Spectrofluorimetric Analysis of the Fungicide Carbendazim and Its Metabolite 2-Aminobenzimidazole in Natural Water

A spectrofluorimetric method for the direct analysis of carbendazim [methyl 2-benzimidazole carbamate (MBC)] fungicide and its metabolite 2-aminobenzimidazole (2-AB) in natural waters is described. Very low limit of detection (LOD) and limit of quantification (LOQ) values of 0.002 - 0.06 ng/mL and 0.006 - 0.2 ng/mL, respectively, were determined by spectrofluorimetric method with small relative standard deviation (RSD) values < 1%. This spectrofluorimetric method was applied to the determination of MBC and 2-AB residues in natural waters, with satisfactory recovery values of (88.5% - 119.2%).

核酸提取试剂盒对饲料中牛羊源性成分检测的影响

实时荧光聚合酶链反应法(荧光PCR法)是目前饲料中牛羊源性成分的定性检测中常用方法之一。为了熟练操作和掌握这个方法,使得实验室工作人员在做饲料中牛羊源性成分定性这类检测时能有一个清晰的认识,通过核酸提取试剂盒的选取及平行实验比对,对此进行了阐释。

基于Hsp70基因的绵羊肺炎支原体TaqMan检测方法的建立及其遗传演化分析

热休克蛋白70 (heat shock protein 70,Hsp70)是绵羊肺炎支原体(Mycoplasma ovipneumoniae, Movi)的重要膜蛋白,是机体内高度保守的生物分子,但在种间差异大,可作为分子生物学检测的候选靶区。为建立基于Hsp70基因的Movi通用型TaqMan实时荧光定量PCR(qPCR)检测方法,并进一步了解其遗传变异情况,本研究基于GenBank中Movi的Hsp70基因特征,设计特异性的引物及探针,建立了基于Hsp70基因的绵羊肺炎支原体qPCR检测方法。应用建立的检测方法对88份山羊鼻拭子样品及43份疑似羊支原体性肺炎(Mycoplasmal pneumonia of sheep and goats, MPSG)病料进行检测。将检测结果为Movi阳性的肺组织样品进行分离鉴定,并对分离株Hsp70基因进行序列分析。结果显示,建立的qPCR检测方法其相关系数为1.00,扩增效率为96.0%,斜率为-3.411,Y轴截距为37.29。特异性强,与丝状支原体山羊亚种(Mycoplasma mycoides subsp.capri, Mmc)、山羊支原体山羊肺炎亚种(Mycoplasma capricolum subsp.capripneumoniae, Mccp)、莱氏无胆甾原体(Acholeplasmalaidlawii, AL)、无乳支原体(Mycoplasma agalactiae, Maga)、伪结核棒状杆菌(Corynebacterium pseudotuberculosis, CP)、羊口疮病毒(orf virus, ORFV)、牛支原体(Mycoplasma bovis, Mb)等牛羊常见病原均无交叉反应;敏感性高,最低检测限为5.72 copies·μL^(-1);重复性优,组内变异系数和组间变异系数均小于1.00%。6株Movi分离株Hsp70基因全长均为1 818 bp,与其它Movi参考株核苷酸和氨基酸同源性分别为96.0%~99.4%和98.0%~100.0%;进一步分析发现,山羊源Movi均比绵羊源多1个N-糖基化位点。遗传演化分析表明,其均处于ClusterⅠA亚分支(均为山羊源)。综上,本研究建立了特异性强、敏感性高、重复性优的基于Hsp70基因的Movi的qPCR检测方法。序列分析发现,不同来源Movi的Hsp70基因核苷酸同源性高;遗传演化分析证实,Movi福建株与山羊源分离株遗传关系较近。本研究不仅为Movi临床诊断提供了技术支持,更为进一步了解Movi遗传演化规律提供参考。