Energy-dispersive X-ray Spectroscopy for the Quantitative Analysis of Pyrite Thin Specimens

To explore ways to improve the accuracy of quantitative analysis of samples in the micrometer to nanometer range of magnitudes,we adopted analytical transmission electron microscopy(AEM/EDS)for qualitative and quantitative analysis of pyrite materials.Additionally,the k factor of pyrite is calculated experimentally.To develop an appropriate non-standard quantitative analysis model for pyrite materials,the experimentally calculated k factor is compared with that estimated from the non-standard quantitative analytical model of the instrument software.The experimental findings demonstrate that the EDS attached to a TEM can be employed for precise quantitative analysis of micro-and nanoscale regions of pyrite materials.Furthermore,it serves as a reference for improving the results of the EDS quantitative analysis of other sulfides.

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.

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.

Identification and analysis of serum samples by surface-enhanced Raman spectroscopy combined with characteristic ratio method and PCA for gastric cancer detection

This study aimed to explore the application of surface-enhanced Raman scattering(SERS)in the rapid diagnosis of gastric cancer.The SERS spectra of 68 serum samples from gastric cancer patients and healthy volunteers were acquired.The characteristic ratio method(CRM)and principal component analysis(PCA)were used to differentiate gastric cancer serum from normal serum.Compared with healthy volunteers,the serum SERS intensity of gastric cancer patients was relatively high at 722 cm^(-1),while it was relatively low at 588,644,861,1008,1235,1397,1445 and 1586 cm^(-1).These results indicated that the relative content of nucleic acids in the serum of gastric cancer patients rises while the relative content of amino acids and carbohydrates decreases.In PCA,the sensitivity and specificity of discriminating gastric cancer were 94.1%and 94.1%,respectively,with the accuracy of 94.1%.Based on the intensity ratios of four characteristic peaks at 722,861,1008 and 1397 cm^(-1),CRM presented the diagnostic sensitivity and specificity of 100%and 97.4%,respectively,and the accuracy of 98.5%.Therefore,the three peak intensity ratios of I_(722)/I_(861),I_(722)/I_(1008)and I_(722)/I_(1397)can be considered as biologicalfingerprint information for gastric cancer diagnosis and can rapidly and directly reflect the physiological and pathological changes associated with gastric cancer development.This study provides an important basis and standards for the early diagnosis of gastric cancer.

Comparison of Calibration Curve Method and Partial Least Square Method in the Laser Induced Breakdown Spectroscopy Quantitative Analysis

The Laser Induced Breakdown Spectroscopy (LIBS) is a fast, non-contact, no sample preparation analytic technology;it is very suitable for on-line analysis of alloy composition. In the copper smelting industry, analysis and control of the copper alloy concentration affect the quality of the products greatly, so LIBS is an efficient quantitative analysis tech- nology in the copper smelting industry. But for the lead brass, the components of Pb, Al and Ni elements are very low and the atomic emission lines are easily submerged under copper complex characteristic spectral lines because of the matrix effects. So it is difficult to get the online quantitative result of these important elements. In this paper, both the partial least squares (PLS) method and the calibration curve (CC) method are used to quantitatively analyze the laser induced breakdown spectroscopy data which is obtained from the standard lead brass alloy samples. Both the major and trace elements were quantitatively analyzed. By comparing the two results of the different calibration method, some useful results were obtained: both for major and trace elements, the PLS method was better than the CC method in quantitative analysis. And the regression coefficient of PLS method is compared with the original spectral data with background interference to explain the advantage of the PLS method in the LIBS quantitative analysis. Results proved that the PLS method used in laser induced breakdown spectroscopy was suitable for simultaneous quantitative analysis of different content elements in copper smelting industry.

Structure and Bonding in Some Gd(Ⅲ) Metal Complexes Studied by Three-Dimensional X-Ray Analysis and ^(155)Gd Mssbauer Spectroscopy

Some functional lanthanide metal complexes, such as acetylacetonato complexes, ethylenediaminetetraacetato complexes, were successfully applied for diagnostic technique. The authors are interested in investigating the structure and bonding in lanthanide and actinide metal complexes using 166Er, t55Gd, and 237Np Mtissbauer spectroscopies in connection with single-crystal and/or powder X-ray diffraction, making clear the differences on their structures as well as the differences in the participation of 4f and 5f orbitals in the chemical bonds. In this article, the crystal structures of two novel Gd（Ⅲ） acetylacetonato complexes, Gd（pta）3 · 2H2O （pta = 1,1,1 -trifluoro-5,5-dimethy 1-2,4-hexanedione） and Gd（bfa）3 · 2H2O （bfa = 1, 1, 1 -trifluoro-4-phenyl-2-4-butanedione） were reported. Though both of them were dihydrate and had distorted square antiprismatical structure, Gd（pta）3 · 2H2O crystallizes in the P 2 1/n （#14） monoclinic space group and its lattice parameters are a = 1.4141（6） nm, b = 1.0708（3） nm, c =2.2344（4） nm, β =952.4（2）°, and Gd（bfa）3· 2H2O crystallizes in P 212121 orthorhombic space group and its lattice parameters were a = 1.322 （1） nm, b = 2.295 （1） nm, c = 1. 0786（8） nm. In the meantime, the authors had finished a systematic investigation on the ^155Gd Mossbauer isomer shift （δ） of various Gd（Ⅲ） metal complexes having a different coordination number （C.N.） and different ratios coordinating oxygen to nitrogen. A tendency for the 6 value to decrease with an increase in the C.N, and the number of the nitrogen atom coordinating to Gd was confirmed. This indicated that the Gd-O and/or Gd-N bond in the investigated Gd（Ⅲ） metal complexes had a small covalent contribution, which was possible to be deduced from the O and/or N atoms of the lisands donating electrons to 6s, 5d, and 4f orbitals of Gd.

Local Structure Analysis of Lead Zinc Niobate-Barium Titanate Ceramic by X-Ray Absorption Spectroscopy and Density Functional Calculation

The local structure of an alternative Pb（Zn1/3Nb2/3）O3-based perovskite ceramic is investigated. The 0.07BaTiO33-0.93Pb（Zn1/3Nb2/3）O3 ceramic is synthesized using a combination of Zn3Nb2O8 B-site precursor and BaTiO33 perovskite phase stabilizer. Then, x-ray absorption spectroscopy and density functional theory are employed to calculate the local structure configuration and formation energy of the prepared samples. Ba2＋ is found to replace Pb2＋ in AA-site with Zn2＋ occupying BB-site in Pb（Zn1/3Nb2/3）O3, while in the neighboring structure, Ti4＋4＋ replaces Nb5＋5＋ in BB-site with Pb2＋2＋ occupying AA-site. With the substitution of BaTiO33 in Pb（Zn1/3Nb2/3）O3, the bond length between Zn2＋ and Pb2＋ is longer than that of the typical perovskite phase of Pb（Zn1/3Nb2/3）O3. This indicates the key role of BaTiO33 in decreasing the steric hindrance of Pb2＋ lone pair, and the mutual interactions between Pb2＋ lone pair and Zn2＋ and the formation energy is seen to decrease. This finding of the formation energy and local structure configuration relationship can further extend a fundamental understanding of the role of BaTiO33 in stabilizing the perovskite phase in PbZn13Nb23O3-based materials, which in turn will lead to an improved preparation technique for desired electrical properties.

History of the Establishment and Development of X-Ray Analysis Methods in Russia--The USSR. First 20 Years

2012 is a year of celebrate centenary of X-ray discovery information about Laue＇s （Fridrich and Knipping） experiment was This discovery spread quickly in different countries. The history of written in the paper. Also history mention of Laue＇s experiment in Russia was presented. The system group of X-ray diffraction was created in 1919/1920 in Petrograd （A. Ioffe, State Physical Technical Institute） and Moscow. Themes of research results, scientific newness and scientific rate were presented. The organization, political and other reasons which retarded the active progress of the method in 1930 were described. Initial stage of progress of the method in Russia-USSR was studied by historian of science partly. The reasons of it are： closed of scientific community, political system of country, Cyrillic barrier, etc.. This paper acquaints western scientific community with non-famous Russian materials on theme.

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.

Improvement of quantitative analysis of molybdenum element using PLS-based approaches for laser-induced breakdown spectroscopy in various pressure environments

An experimental setup has been designed and realized in order to optimize the characteristics of laser-induced breakdown spectroscopy system working in various pressure environments. An approach combined the normalization methods with the partial least squares(PLS) method are developed for quantitative analysis of molybdenum(Mo) element in the multi-component alloy,which is the first wall material in the Experimental Advanced Superconducting Tokamak. In this study, the different spectral normalization methods(total spectral area normalization,background normalization, and reference line normalization) are investigated for reducing the uncertainty and improving the accuracy of spectral measurement. The results indicates that the approach of PLS based on inter-element interference is significantly better than the conventional PLS methods as well as the univariate linear methods in the various pressure for molybdenum element analysis.

Development of a Laboratory Cement Quality Analysis Apparatus Based on Laser-Induced Breakdown Spectroscopy

Determination of the chemical composition of cement and ratio values of clinker plays an important role in cement plants as part of the optimal process control and product quality evaluation. In the present paper, a laboratory laser-induced breakdown spectroscopy （LIBS） apparatus mainly comprising a sealed optical module and an analysis chamber has been designed for possible application in cement plants for on-site quality analysis of cement. Emphasis is placed on the structure and operation of the LIBS apparatus, the sealed optical path, the temperature controlled spectrometer, the sample holder, the proper calibration model established for minimizing the matrix effects, and a correction method proposed for overcoming the ＇drift＇ obstacle. Good agreement has been found between the laboratory measurement results from the LIBS method and those from the traditional method. The absolute measurement errors presented here for oxides analysis are within 0.5%, while those of ratio values are in the range of 0.02 to 0.05. According to the obtained results, this laboratory LIBS apparatus is capable of performing reliable and accurate, composition and proximate analysis of cement and is suitable for application in cement plants.

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.

Quantitative analysis modeling for the Chem Cam spectral data based on laser-induced breakdown spectroscopy using convolutional neural network

Laser-induced breakdown spectroscopy(LIBS)has been applied to many fields for the quantitative analysis of diverse materials.Improving the prediction accuracy of LIBS regression models is still of great significance for the Mars exploration in the near future.In this study,we explored the quantitative analysis of LIBS for the one-dimensional Chem Cam(an instrument containing a LIBS spectrometer and a Remote Micro-Imager)spectral data whose spectra are produced by the Chem Cam team using LIBS under the Mars-like atmospheric conditions.We constructed a convolutional neural network(CNN)regression model with unified parameters for all oxides,which is efficient and concise.CNN that has the excellent capability of feature extraction can effectively overcome the chemical matrix effects that impede the prediction accuracy of regression models.Firstly,we explored the effects of four activation functions on the performance of the CNN model.The results show that the CNN model with the hyperbolic tangent(tanh)function outperforms the CNN models with the other activation functions(the rectified linear unit function,the linear function and the Sigmoid function).Secondly,we compared the performance among the CNN models using different optimization methods.The CNN model with the stochastic gradient descent optimization and the initial learning rate?=?0.0005 achieves satisfactory performance compared to the other CNN models.Finally,we compared the performance of the CNN model,the model based on support vector regression(SVR)and the model based on partial least square regression(PLSR).The results exhibit the CNN model is superior to the SVR model and the PLSR model for all oxides.Based on the above analysis,we conclude the CNN regression model can effectively improve the prediction accuracy of LIBS.

Study on Cluster Analysis Used with Laser-Induced Breakdown Spectroscopy

Supervised learning methods（eg.PLS-DA,SVM,etc.） have been widely used with laser-induced breakdown spectroscopy（LIBS） to classify materials;however,it may induce a low correct classification rate if a test sample type is not included in the training dataset.Unsupervised cluster analysis methods（hierarchical clustering analysis,K-means clustering analysis,and iterative self-organizing data analysis technique） are investigated in plastics classification based on the line intensities of LIBS emission in this paper.The results of hierarchical clustering analysis using four different similarity measuring methods（single linkage,complete linkage,unweighted pair-group average,and weighted pair-group average） are compared.In K-means clustering analysis,four kinds of choosing initial centers methods are applied in our case and their results are compared.The classification results of hierarchical clustering analysis,K-means clustering analysis,and ISODATA are analyzed.The experiment results demonstrated cluster analysis methods can be applied to plastics discrimination with LIBS.

Industrial Food Quality Analysis Using New k-Nearest-Neighbour methods

The problem of predicting continuous scalar outcomes from functional predictors has received high levels of interest in recent years in many fields,especially in the food industry.The k-nearest neighbor(k-NN)method of Near-Infrared Reflectance(NIR)analysis is practical,relatively easy to implement,and becoming one of the most popular methods for conducting food quality based on NIR data.The k-NN is often named k nearest neighbor classifier when it is used for classifying categorical variables,while it is called k-nearest neighbor regression when it is applied for predicting noncategorical variables.The objective of this paper is to use the functional Near-Infrared Reflectance(NIR)spectroscopy approach to predict some chemical components with some modern statistical models based on the kernel and k-Nearest Neighbour procedures.In this paper,three NIR spectroscopy datasets are used as examples,namely Cookie dough,sugar,and tecator data.Specifically,we propose three models for this kind of data which are Functional Nonparametric Regression,Functional Robust Regression,and Functional Relative Error Regression,with both kernel and k-NN approaches to compare between them.The experimental result shows the higher efficiency of k-NN predictor over the kernel predictor.The predictive power of the k-NN method was compared with that of the kernel method,and several real data sets were used to determine the predictive power of both methods.

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.

Study of Inner-Shell Excitation and Relaxation Processes in Atomic and Ionic Neon by Means of Soft X-Ray Spectroscopy

By using soft X-ray spectroscopy, we investigate the inner-shell excitation and relaxation processes in atomic and ionic neon targets. Resonant X-ray emission spectroscopy was applied to neutral neon atom in the regions of the [1s]np （n = 3, 4,…, ε） excited states and [1s2p]3pmp （m = 3,4） doubly excited states to obtain the spectroscopic information on the [2p]np and [2p^2]3prnp final electronic states, where square brackets indicate hole states. The energy levels of the [2p^2]3prnp （m = 3,4） electronic states were spectroscopically measured for the first time. As for the ionic neon target, on the other hand, the photoion yield spectroscopy was adopted to survey the 1s→ np （n = 2, 3） resonant excitation and subsequent Auger decay processes for Ne^＋ target-ions. The observed Ne^2＋ photoion yield spectrum is successflllly explained by the theoretical calculations based on the nmlticonfiguration Dirac-Fock method

Fluorine Assessment of Igneous Rocks by Neutron Activation Analysis

The main goal of the current study was to determine the fluorine in the rock samples coal (SARM-18, SARM-19, and SARM-20), opal glass NBS91 and phosphate rock NBS694 using neutron activation analysis. Neutrons energy of 14 MeV used for irradiation was produced by bombardment of a water-cooled titanium tri-tide target with a beam of deuterons accelerated to a potential of 350 KV to develop a neutron flux (108 n⋅cm-2⋅s-1) on the sample at the neutron generator in the ECN (Netherlands Energy Research Foundation) Petten. This new approach contributes to the existing knowledge of fluorine measurement by the coincidence channels investigation of the positron energy with respect to decay time for each radionuclide element. The present study was designed to determine the fluorine by fast neutron through the reaction of F19 (n, 2n) F18. Interference was treated by irradiating the standard of these elements and reasonable selection of the decay time between the end of irradiation and beginning of counting time. The results of this method indicate that the concentration of fluorine is agreed fairly with literatures.

硼砂煅制工艺优化及质量评价

目的 优化硼砂煅制工艺,并对其进行质量评价。方法 以铺设厚度、煅制温度、煅制时间为影响因素,失水率、蓬松度、粉碎率、四硼酸钠含量为评价指标,星点设计-效应面法优化硼砂煅制工艺。采用扫描电镜(SEM)、热重分析(TG)、拉曼光谱、X射线衍射(XRD),比较硼砂煅制前后质量差异。结果 最佳条件为铺设厚度2 cm,煅制温度365℃,煅制时间100 min。煅制后,硼砂微观形态、成分组成、晶型结构发生变化,失去全部结晶水而转变为非晶体状态。结论 该方法稳定可行,可用于工业大批量生产煅硼砂。