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51.
In this paper, a modified single-index signal regression (mSISR) method is proposed to construct a nonlinear and practical model with high-accuracy. The mSISR method defines the optimal penalty tuning parameter in P-spline signal regression (PSR) as initial tuning parameter and chooses the number of cycles based on minimizing root mean squared error of cross-validation (RMSECV). mSISR is superior to single-index signal regression (SISR) in terms of accuracy, computation time and convergency. And it can provide the character of the non-linearity between spectra and responses in a more precise manner than SISR. Two spectra data sets from basic research experiments, including plant chlorophyll nondestructive measurement and human blood glucose noninvasive measurement, are employed to illustrate the advantages of mSISR. The results indicate that the mSISR method (i) obtains the smooth and helpful regression coefficient vector, (ii) explicitly exhibits the type and amount of the non-linearity, (iii) can take advantage of nonlinear features of the signals to improve prediction performance and (iv) has distinct adaptability for the complex spectra model by comparing with other calibration methods. It is validated that mSISR is a promising nonlinear modeling strategy for multivariate calibration. 相似文献
52.
Richard J.C. Brown Kim E. Jarvis Benoit A. Disch Sharon L. Goddard 《International journal of environmental analytical chemistry》2013,93(3):335-348
Three different types of simple and low-cost calibration material for the measurement of the metals content of ambient particulate matter (PM) on filters using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) have been compared: cellulose ester filters spiked with multi-element calibration solutions, pellets of compressed ambient particulate matter certified reference material (CRM), and powdered ambient particulate matter CRM adhered to a surface. Elements determined were As, Cd, Cr, Cu, Fe, Mn, Ni, Pb, V and Zn, each at approximate levels of 1000?ng per filter. Blank filters spiked with multi-elemental standards were found to be significantly more reproducible and repeatable than materials based on powdered reference materials. However, a comparison of these spiked filters with real samples of ambient PM showed that the analytical sensitivities obtained per mass of analyte were significantly different. It is concluded that the spiked filters could act as very effective quality control standards correcting, to within 1%, drifts in LA-ICP-MS measurements of up to 10%, or as indirect calibration materials supported by additional measurements using traditional wet chemical techniques. 相似文献
53.
We report on an accurate intensity calibration method for low wavenumber Raman spectroscopy. It uses the rotational Raman spectrum of N2. The intensity distributions in the rotational Raman spectra of diatomic molecules are theoretically well established. They can be used as primary intensity standards for intensity calibration. The intensity ratios of the Stokes and anti‐Stokes transitions originating from the same rotational levels are not affected by thermal population. Taking the effect of rotation–vibration interactions appropriately into account, we are able to calculate these intensity ratios theoretically. The comparison between the observed and calculated ratios of the N2 pure rotational spectrum provides an accurate relative sensitivity curve (error ~5 × 10−4) in the wavenumber region of −150 to 150 cm−1. We determine the temperature of water solely from the low wavenumber Raman spectra, using a thus calibrated spectrometer. The Raman temperature shows an excellent agreement with the thermocouple temperature, with only 0.5 K difference. The present calibration technique will be highly useful in many applications of low wavenumber quantitative Raman spectroscopy. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
54.
Kyung Joong Kim 《Surface and interface analysis : SIA》2022,54(4):405-416
Mutual calibration was suggested as a method to determine the absolute thickness of ultrathin oxide films. It was motivated from the large offset values in the reported thicknesses in the Consultative Committee for Amount of Substance (CCQM) pilot study P-38 for the thickness measurement of SiO2 films on Si(100) and Si(111) substrates in 2004. Large offset values from 0.5 to 1.0 nm were reported in the thicknesses by ellipsometry, X-ray reflectometry (XRR), medium-energy ion scattering spectrometry (MEIS), Rutherford backscattering spectroscopy (RBS), nuclear reaction analysis (NRA), and transmission electron microscopy (TEM). However, the offset value for the thicknesses by X-ray photoelectron spectroscopy (XPS) was close to zero (−0.013 nm). From these results, the mutual calibration method was reported for the thickness measurement of SiO2 films on Si(100) by combination of TEM and XPS. The mutual calibration method has been applied for the thickness measurements of hetero oxide films such as Al2O3 and HfO2. Recently, the effect of surface contamination was reported to be critical to the thickness measurement of HfO2 films by XPS. On the other hand, MEIS was proved to be a powerful zero offset method which is not affected by the surface contamination. As a result, the reference thicknesses in the CCQM pilot study P-190 for the thickness measurement of HfO2 films on Si(100) substrate were determined by mutual calibration method from the average XRR data and MEIS analysis. Conclusively, the thicknesses of ultrathin oxide films can be traceably certified by mutual calibration method and most thickness measurement methods can be calibrated from the certified thicknesses. 相似文献
55.
Alexander G. Shard Ako Miisho Jean-Luc Vorng Rasmus Havelund Ian S. Gilmore Satoka Aoyagi 《Surface and interface analysis : SIA》2022,54(4):363-373
Quantification of the composition of binary mixtures in secondary ion mass spectrometry (SIMS) is required in the analyses of technological materials from organic electronics to drug delivery systems. In some instances, it is found that there is a linear dependence between the composition, expressed as a ratio of component volumes, and the secondary ion intensities, expressed as a ratio of intensities of ions from each component. However, this ideal relationship fails in the presence of matrix effects and linearity is observed only over small compositional ranges, particularly in the dilute limits. In this paper, we assess an empirical method, which introduces a power law dependence between the intensity ratio and the volume fraction ratio. A previously published physical model of the organic matrix effect is employed to test the limits of the method and a mixed system of 3,3′-bis(9-carbazolyl) biphenyl and tris(2-phenylpyridinato)iridium (III) is used to demonstrate the method. This paper introduces a two-point calibration, which determines both the exponent in the power law and the sensitivity factor for the conversion of ion intensity ratio into volume fraction ratio. We demonstrate that this provides significantly improved accuracy, compared with a one-point calibration, over a wide compositional range in SIMS quantification and with a weak dependence on matrix effects. Because the method enables the use of clearly identifiable secondary ions for quantitative purposes and mitigates commonly observed matrix effects in organic materials, the two-point calibration method could be of significant benefit to SIMS analysts. 相似文献
56.
对760nm附近的氧气吸收带,选用植被、枯萎植被、人工地物、沙地和雪地五种典型地表类型,基于模拟数据进行非同步替代光谱定标方法的误差分析,比较不同地表类型得到的光谱定标准确度,为高光谱成像仪的非同步替代光谱定标提供定标图像选择策略.结果表明:运用两种光谱匹配方法——光谱角度匹配和欧氏距离法得到的定标误差基本一致;730~800nm的地表反射率曲线标准差在0.05nm以内时,定标误差集中在±0.5nm范围内;人工地物类型中个别地物如橄榄绿光泽涂料和植被大面积覆盖的图像数据不适合用于非同步替代光谱定标. 相似文献
57.
58.
捷联式惯性导航系统通常采用卫星导航系统的位置、速度信息对惯导解算误差进行校正,但对于水下载体惯性导航系统而言,由于只能获得点位置信息,对惯导的校正精度以及校正参量有限。针对上述问题,提出了基于天文/卫星组合校正捷联式惯导技术,通过卫星精确定位信息和天文快速观测信息,全面修正惯导系统误差、提高导航精度。仿真结果表明,基于天文/卫星组合校正算法对惯导进行校正,相对于传统校正算法精度可提高约50%。 相似文献
59.
综述了近年来烟用香精、香料各组分化合物的定量分析方法的研究进展。面积归一化法、内标法、外标法和标准加入法等常用色谱定量分析方法主要用于烟用香精、香料中目标化合物或单个组分的测定;多标定量法、特征峰-内标定量法和多元校正法能深入剖析烟用香精复杂体系中各组分含量(引用文献48篇)。 相似文献
60.
Theoretical work was performed based on experimental methods described in the literature to simulate and explore feasible routes for the synthesis of energetic octanitrocubane (ONC) and polynitrocubane derivatives. In respective gaseous and liquidous environments, using cubane as the raw material, ONC was successfully synthesized through carboxylation, amination, oxidation and nitration stages, and the related reaction energy barriers were simultaneously acquired. In particular, the polyparametric calibrated gaseous molecular formation enthalpy and the group additivity approach-estimated molecular density were incorporated using the Kamlet-Jacobs equation to evaluate the detonation performance of polynitrocubane derivatives. Some high-energy-density derivatives were found to have superior characteristics as compared with traditional hexagon (RDX) and octagon (HMX) explosives. 相似文献