X射线荧光光谱理论强度计算中激发因子的选择

激发因子是X射线荧光强度理论计算中的重要参数。对目前常用的四种激发因子算法进行了较为详细的比较,并设计了一种评价激发因子算法的实验方法,即用人工合成试样测定了八对能量接近的X射线特征谱线的强度比,然后根据不同的激发因子算法用理论方法计算出这些谱线对的强度比值,以两者的接近程度来判断这四种激发因子算法的适用性。结果表明,使用NRLXRF程序修改版中的激发因子算法计算出来的理论强度比与实测值之间的相对偏差最小。     

X射线荧光光谱理论强度计算中激发因子的选择

激发因子是X射线荧光强度理论计算中的重要参数。对目前常用的四种激发因子算法进行了较为详细的比较,并设计了一种评价激发因子算法的实验方法,即用人工合成试样测定了八对能量接近的X射线特征谱线的强度比,然后根据不同的激发因子算法用理论方法计算出这些谱线对的强度比值,以两者的接近程度来判断这四种激发因子算法的适用性。结果表明,使用NRLXRF程序修改版中的激发因子算法计算出来的理论强度比与实测值之间的相对偏差最小。     

在能量色散X射线荧光分析中用基本参数法计算合金成份

引言在X射线荧光分析中,基本参数法是校正元素间吸收增强效应的一种数学方法。它是根据样品受激发射荧光X射线的原理在测定了样品中各元素的特征X射线强度以后,利用已知的物理参数,如质量吸收系数,荧光产额,X射线特征谱线的相对强度,入射辐射能谱,几何因子,探测效率等,在给定的初值条件下通过理论计算,用迭代逐步逼近法直接求得样品中各元素的含量。     

X射线荧光光谱法测定Zn镀层质量厚度及计算谱线选择问题研究

用X射线荧光光谱法测定了Fe基上Zn镀层的质量厚度；研究了厚度不同时选用不同谱线计算对测定结果的影响，发现在镀层质量厚度较小时（约〈14mg／cm^2）测量Zn元素的Kα线，质量厚度较大时选择Zn的Kα和Fe的Kα线共同计算，用纯元素和相似标样校正测定结果之间的偏差最小；用纯元素作校正标样测定了3个标准样品的Zn镀层质量厚度，计算结果与标准值符舍得较好。     

能量色散X射线荧光光谱背景扣除方法的探讨

能量色散X射线荧光分析使得特征X射线的全能峰叠加在背景之上,针对能量色散X射线荧光谱线背景扣除算法的研究,简述了剥峰法和小波变换法扣除背景的原理,并将这两种方法用于对实际谱线的处理,取得了良好的效果.同时对两种方法的算法和处理效果进行了对比研究,表明剥峰法相对简单,而小波变换法需要考虑小波基和分解层次等的影响,但是对整个谱线的综合处理效果相对要好一些.     

X射线衍射多谱峰匹配强度比定量相分析方法

提出了1种采用x射线衍射多谱峰匹配强度比进行定量相分析的新方法;该法是利用混合物样品x射线衍射谱图中的多谱峰数据,结合ICDD卡中的各相标准谱峰的相对强度分布数据进行最小二乘法回归分析,求得混合物样品中各相间的多谱峰匹配强度比;以多谱峰匹配强度比取代通常采用的特定单一谱线强度比,用于混合物样品的x射线衍射定量相分析,有利于提高定量相分析的精度;采用多谱峰匹配强度比结合绝热法和基体清洗法X射线衍射定量相分析原理,通过对4组分混合物样品的分析,证实实验结果和理论完全一致。     

提高X射线荧光理论计算相对强度准确度的研究

通过与合成标样实测相对强度的比较，研究了影响ＸＲＦ中理论计算相对强度准确２度的主要因素，提出了μ＋τ计算模式的一个混合的质量吸收系数算法。     

X射线荧光光谱法测定镀锌钢板镀层质量

提出了用X射线荧光光谱法测定镀锌钢板镀层(包括锌层、锌铁合金层、钝化层、磷化层和耐指纹层等)的质量。详细叙述了用于上述各层测定所需的系列标准样品的制备方法,分别通过对各不同层的特征组分的荧光强度进行测定,并根据校准曲线计算,分别得到各不同层的单位面积质量(g·m-2)。根据测定各不同组分时谱线荧光强度的强弱,选择不同的测量时间,试验选择直径为30 mm的测量面积。采用与样品相同类型的标准样品作校准曲线,重复10次测定6种镀层样品,其测定值的相对标准偏差在0.10%~0.32%之间。各镀层的测定值与重量法及电感耦合等离子体原子发射光谱法的测定值相比,经t-检验法验证(α=0.05),不存在显著差异。     

基于蒙特卡洛方法的X射线探测器能谱响应研究

为解决X射线荧光测量过程中的仪器刻度和校正难题,通过理论研究并运用蒙特卡洛方法对X射线荧光仪进行建模,得到了X射线探测器能谱响曲线。结果表明:模拟的X射线探测器能谱响应全谱与实测情况基本一致,而主成份谱线则高度一致,特征峰半高宽相对误差均在5%以内。方法为X射线荧光测量的仪器刻度和校正提供重要的研究信息,不仅为元素分析工作节省大量人力物力,也为无标样X射线荧光分析提供了有力的理论支撑。方法也可用于X射线荧光分析过程中的其他研究领域。     

熔融制样–X射线荧光光谱法同时测定铀钼矿中主次成分

采用混合熔剂熔融制样,建立了同时测定铀钼矿中U,Mo,SiO_2,Fe_2O_3,Al_2O_3等的X射线荧光光谱法。以Li_2B_4O_7–LiBO_2作为熔融试剂,NH_4NO_3作为样品的氧化剂,样品与熔剂的质量比为1∶10。除使用铀矿石国家标准物质外,主要选取人工混合校准样品及历年实验室比对的铀钼矿校准样品绘制成工作曲线。采用理论系数法校正样品的基体效应,用Br Kα,Zr Kα,U Lα,Ba Lα,Zn Kα谱线扣除相应元素的谱线重叠干扰。该方法各组分测定结果的相对标准偏差均小于2.0%(n=10);用标准物质验证方法的准确度,测定值相对误差在0.00~8.00%之间,与标准值基本吻合。该法应用于生产实验中,可以满足对铀钼矿准确、快速的测量要求。     

Experimental evaluation of epithermal neutron self-shielding for 96Zr and 98Mo

In a previous work we experimentally tested some neutron self-shielding calculations methods for thermal absorbers, from which the semi-empirical “sigmoid method” gave the most accurate results. In this work we aim at evaluating the accuracy of this method on the epithermal self-shielding phenomena as compared to the analytical “MatSSF method”. Metallic foils of Zr and Mo were compactly stacked together into small cylinders (or disks) of different thickness, allowing for up to 20 % epithermal self-shielding when irradiated on two channels of the BR1 reactor. A 2 % relative difference between calculated and experimental self-shielding factors was obtained from the MatSSF method when a perpendicular source-sample axial configuration was assumed, while the isotropic or the co-axial configuration alternatives gave up to 10 % relative differences. On the other hand, the sigmoid method gave relative differences of up to 6 % that can be reduced to just 2 % by applying the “effective” epithermal absorption cross-sections for ⁹⁸Mo and ⁹⁶Zr proposed in this work.     

Absolute line intensities for formic acid and dissociation constant of the dimer

Absolute line intensities in the nu(6) and nu(8) interacting bands of trans-HCOOH, observed near 1105.4 and 1033.5 cm(-1), respectively, and the dissociation constant of the formic acid dimer (HCOOH)(2) have been measured using Fourier transform spectroscopy at a resolution of 0.002 cm(-1). Eleven spectra of formic acid, at 296.0(5) K and pressures ranging from 14.28(25) to 314.0(24) Pa, have been recorded between 600 and 1900 cm(-1) with an absorption path length of 19.7(2) cm. 437 integrated absorption coefficients have been measured for 72 lines in the nu(6) band. Analysis of the pressure dependence yielded the dissociation constant of the formic acid dimer, K(p)=361(45) Pa, and the absolute intensity of the 72 lines of HCOOH. The accuracy of these results was carefully estimated. The absolute intensities of four lines of the weak nu(8) band were also measured. Using an appropriate theory, the integrated intensity of the nu(6) and nu(8) bands was determined to be 3.47 x 10(-17) and 4.68 x 10(-19) cm(-1)(molecule cm(-2)) respectively, at 296 K. Both the dissociation constant and integrated intensities were compared to earlier measurements.     

Line strengths and transition dipole moment of the nu2 fundamental band of the methyl radical

The line strengths of nine Q-branch lines in the nu(2) fundamental band of the methyl radical in its ground electronic state have been measured by diode laser absorption spectroscopy. The vibration-rotation spectrum of methyl was recorded in a microwave discharge in ditertiary butyl peroxide heavily diluted in argon. The absolute concentration of the radical was determined by measuring its kinetic decay when the discharge was extinguished. The translational, rotational, and vibrational temperatures, also required to relate the line strengths to the transition dipole moment, were determined from relative integrated line intensities and from the Doppler widths of the lines after allowing for instrumental factors. The line strengths of the nine Q-branch lines were used to derive a more accurate value of the transition dipole moment of this band, mu(2)=0.215(25) D. Improved accuracy over earlier measurements of mu(2) (derived from line strengths of single lines) was obtained by integrating over the complete line profile instead of measuring the peak absorption and assuming a Doppler linewidth to deduce the concentration. In addition, a more precise value for the rate constant for methyl radical recombination than available earlier was employed. The new value of mu(2) is in very good agreement with high-quality ab initio calculations. Furthermore, the ratio of the transition dipole moments of the nu(2) and nu(3) fundamental bands in the gas phase is now in highly satisfactory agreement with the ratio determined for the condensed phase.     

EDXRF方法在测量含水Fe样中Fe含量的应用

介绍了能量色散X荧光分析方法在含水Fe样品测量中的应用。用ANTG 2000型海底X荧光探测系统对含Fe为10%～60%的Fe样进行测量,建立水分对Fe元素特征Kα射线影响的校正模型。结果表明,通过该模型校正,对含饱和水情况下Fe样品的分析相对误差小于4%,具有良好的分析效果。     

Theoretical and matrix-isolation experimental study of the infrared spectra of 5-azauracil and 6-azauracil

The infrared absorption spectra of 5-azauracil and 6-azauracil isolated in low-temperature Ar and N₂ matrices are reported. Within the limits of accuracy of spectroscopic measurements, both compounds appear to exist, in Ar and N₂ matrices, exclusively in dioxo tautomeric forms. An assignment of the observed infrared absorption bands is proposed based on the comparison of experimental frequencies and intensities with those calculated theoretically at ab initio Hartree-Fock level with 6-31G** basis set. Infrared spectra predicted at this level of theory reproduce the experimental spectra sufficiently accurately to enable a reliable assignment. Basis set dependency (6-31G**, 3–21G) of the theoretical result was also accounted for and it turned out that for accurate prediction of frequencies and intensities the use of basis set augmented with polarization functions is of crucial importance.     

Ab initio calculations and Franck-Condon simulation of the absorption spectra of GeCl2 including anharmonicity.

Geometrical parameters, vibrational frequencies and relative electronic energies of the X1A1, ?3B1 and A1B1 states of GeCl2 have been calculated at the CCSD(T) and/or CASSCF/MRCI level with basis sets of up to aug-cc-pV5Z quality. Core electron correlation and relativistic contributions were also investigated. RCCSD(T)/ aug-cc-pVQZ potential energy functions (PEFs) of the X1A1 and ?3B, states, and a CASSCF/MRCl/aug-cc-pVQZ PEF of the A1B1 state of GeCl2 are reported. Anharmonic vibrational wavefunctions of these electronic states of GeCl2, obtained variationally using the computed PEFs, are employed to calculate the Franck-Condon factors (FCFs) of the ?-X and A-X transitions of GeCl2. Simulated absorption spectra of these transitions based on the computed FCFs are compared with the corresponding experimental laser-induced fluorescence (LIF) spectra of Karolczak et al. [J. Chem. Phys. 1993, 98, 60-70]. Excellent agreement is obtained between the simulated absorption spectrum and observed LIF spectrum of the ?-X transition of GeCl2, which confirms the molecular carrier, the electronic states involved and the vibrational assignments of the LIF spectrum. However, comparison between the simulated absorption spectrum and experimental LIF spectrum of the A-X transition of GeCl2 leads to a revision of vibrational assignments of the LIF spectrum and suggests that the X1A1 state of GeCl2 was prepared in the experimental work, with a non-Boltzmann vibrational population distribution. The X(0,0,1) level is populated over 4000 times more than expected from a Boltzmann distribution at 60 K, which is appropriate for the relative population of the other low-lying vibrational levels, such as the X(1,0,0) and X(0,1,0) levels.     

Structure of Nano‐sized CeO2 Materials: Combined Scattering and Spectroscopic Investigations

The structure of several nano‐sized ceria, CeO₂, systems was investigated using neutron and X‐ray diffraction and X‐ray absorption spectroscopy. Whilst both diffraction and total pair distribution functions (PDFs) revealed that in all of the samples the occupancy of both Ce⁴⁺ and O^2? are very close to the ideal stoichiometry, the analysis using Reverse Monte Carlo technique revealed significant disorder around oxygen atoms in the nano‐sized ceria samples in comparison to the highly crystalline NIST standard. In addition, the analysis revealed that the main differences observed in the pair correlations from various X‐ray and neutron diffraction techniques were attributable to the particle size of the CeO₂ prepared by the reported three methods. Furthermore, detailed analysis of the Ce L₃‐ and K‐edge EXAFS data support this finding; in particular the decrease in higher shell coordination numbers with respect to the NIST standard, is attributed to differences in particle size.     

Solvent dependence of conformational stability and analysis of vibrational spectra of 2,2,3,3,3-pentafluoro-1-propanol

The conformational stability of 2,2,3,3,3-pentafluoro-1-propanol was investigated by the DFT-B3LYP/6-311+G** and the ab initio MP2/6-311+G** calculations. The calculated potential energy curves of 2,2,3,3,3-pentafluoro-1-propanol at both levels of theory were consistent with three distinct minima that correspond to Trans-gauche-gauche (Tgg), trans-trans-gauche (Ttg) and trans-gauche-gauche(-) (Tgg1) conformers in the order of decreasing relative stability. The equilibrium constants for the conformational interconversion of 2,2,3,3,3-pentafluoro-1-propanol were calculated and found to correspond to an equilibrium mixture of about 46% Tgg, 43% Ttg and 11% Tgg1 conformations at 298.15K. The calculated (%Ttg/%Tgg) ratio of 0.93 is consistent with the 0.85 ratio of the observed intensities of the 772 and 794 cm(-1) lines in the Raman spectrum of the liquid. The nature of the high energy Ttg conformation was verified by solvent experiments using formamide (epsilon = 109.5) and acetonitrile (epsilon = 37). The vibrational frequencies of the molecule in its stable forms were computed at B3LYP level and complete vibrational assignments were made based on normal coordinate calculations and comparison with experimental data of the molecule.     

x-射线荧光光谱法测定重整催化剂中铂、铕、铈

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 ,建立了重整催化剂中铂、铕、铈含量的测定方法。测定铂、铕、铈的相对标准偏差依次为 :0 .5 9%、0 .72 %、0 .75 %。