Accuracy analysis of iron content of galvanized coating using an X-ray fluorescence spectrometer with an L-spectrum

The accuracy(repeatability and reproducibility) of the iron content analysis of galvanized coating using an X-ray fluorescence spectrometer with an L-spectrum is not better than that of flame atomic absorption spectrometry, sometimes it exceeds the quality control limit.Influences, such as current, voltage, equipment(internal circulating water, 10%CH4+90%Ar, and vacuum) checking, instrument monitoring, sample cleaning, and oper-ators, were investigated by means of 6-sigma and lean operations to improve accuracy.

Artificial neural network-based method for discriminating Compton scattering events in high-purity germaniumγ-ray spectrometer

To detect radioactive substances with low activity levels,an anticoincidence detector and a high-purity germanium(HPGe)detector are typically used simultaneously to suppress Compton scattering background,thereby resulting in an extremely low detection limit and improving the measurement accuracy.However,the complex and expensive hardware required does not facilitate the application or promotion of this method.Thus,a method is proposed in this study to discriminate the digital waveform of pulse signals output using an HPGe detector,whereby Compton scattering background is suppressed and a low minimum detectable activity(MDA)is achieved without using an expensive and complex anticoincidence detector and device.The electric-field-strength and energy-deposition distributions of the detector are simulated to determine the relationship between pulse shape and energy-deposition location,as well as the characteristics of energy-deposition distributions for fulland partial-energy deposition events.This relationship is used to develop a pulse-shape-discrimination algorithm based on an artificial neural network for pulse-feature identification.To accurately determine the relationship between the deposited energy of gamma(γ)rays in the detector and the deposition location,we extract four shape parameters from the pulse signals output by the detector.Machine learning is used to input the four shape parameters into the detector.Subsequently,the pulse signals are identified and classified to discriminate between partial-and full-energy deposition events.Some partial-energy deposition events are removed to suppress Compton scattering.The proposed method effectively decreases the MDA of an HPGeγ-energy dispersive spectrometer.Test results show that the Compton suppression factors for energy spectra obtained from measurements on ^(152)Eu,^(137)Cs,and ^(60)Co radioactive sources are 1.13(344 keV),1.11(662 keV),and 1.08(1332 keV),respectively,and that the corresponding MDAs are 1.4%,5.3%,and 21.6%lower,respectively.

Methods for obtaining characteristic γ-ray net peak count from interlaced overlap peak in HPGe γ-ray spectrometer system

For a characteristic c-ray with interlaced overlap peak, and the case where its reliable and credible net count cannot be obtained using the current high-purity germanium(HPGe) multichannel γ-ray spectrum software, two new methods are proposed herein to obtain the γ-ray net peak count from the interlaced overlap peak in the HPGe cray spectrometer system, of which one is the symmetric conversion method based on Gaussian distribution and the other is where the energy average value of two close γ-rays is regarded as the γ-ray energy. The experimental results indicate that the two methods mentioned above are reliable and credible. This study is significant for the development of better γ-ray spectrum processing software for measuring complex γ-ray spectra concerning the nuclear reaction cross section, neutron activation analysis, and analysis of transuranium elements, using an HPGe detector.

Potential Applications of X-ray Fluorescence Core Scanner in Elemental Analyses of the Muddy Sediments on the Coastal Shelves of China and in Ecological Study

Large areas of muddy sediments on the coastal shelves of China provide important samples for studying climate and ecological changes. Analysis of a large number of such samples, which is essential for systematic study on environmental information recorded in mud areas because of complicated sedimentary environment and variable sedimentary rate, requires a fast and economical method. In this study, we investigated the potential of X-ray fluorescence core scanner （XRFS）, a fast analytical instrument for measuring the elemental concentrations of muddy sediments, and observed a significant correlation between the element concentrations of muddy sediments determined by regular X-ray fluorescence spectrometer （XRF） and XRFS, respectively. The correlations are mainly determined by excitation energy of elements, but also influenced by solubility of element ions. Furthermore, we found a striking link between A1 concentrations and marine-originated organic carbon （MOC）, a proxy of marine primary productivity. This indicates that MOC is partly controlled by sedimentary characteristics. Therefore, XRFS method has a good potential in fast analysis of a large number of muddy sediment samples, and it can also be used to calibrate MOC in ecological study of coastal seas.

Vegetation Phenology in Permafrost Regions of Northeastern China Based on MODIS and Solar-induced Chlorophyll Fluorescence

Vegetation phenology is an indicator of vegetation response to natural environmental changes and is of great significance for the study of global climate change and its impact on terrestrial ecosystems.The normalized difference vegetation index(NDVI)and enhanced vegetation index(EVI),extracted from the Moderate Resolution Imaging Spectrometer(MODIS),are widely used to monitor phenology by calculating land surface reflectance.However,the applicability of the vegetation index based on‘greenness'to monitor photosynthetic activity is hindered by poor observation conditions(e.g.,ground shadows,snow,and clouds).Recently,satellite measurements of solar-induced chlorophyll fluorescence(SIF)from OCO-2 sensors have shown great potential for studying vegetation phenology.Here,we tested the feasibility of SIF in extracting phenological metrics in permafrost regions of the northeastern China,exploring the characteristics of SIF in the study of vegetation phenology and the differences between NDVI and EVI.The results show that NDVI has obvious SOS advance and EOS lag,and EVI is closer to SIF.The growing season length based on SIF is often the shortest,while it can represent the true phenology of vegetation because it is closely related to photosynthesis.SIF is more sensitive than the traditional remote sensing indices in monitoring seasonal changes in vegetation phenology and can compensate for the shortcomings of traditional vegetation indices.We also used the time series data of MODIS NDVI and EVI to extract phenological metrics in different permafrost regions.The results show that the length of growing season of vegetation in predominantly continuous permafrost(zone I)is longer than in permafrost with isolated taliks(zone II).Our results have certain significance for understanding the response of ecosystems in cold regions to global climate change.

Application of a Portable XRF Spectrometer for <i>In-Situ</i>and Nondestructive Investigation of Pigments in Two 15th Century Icons

A simple portable X-Ray Fluorescence (XRF) spectrometer was successfully used for in-situ and nondestructive identification of the painting materials in two 15th century icons from the Onufri Museum in Beart, Albania. The spectrometer is based on a low power X-ray tube, a thermoelectrically cooled Si PIN detector and the spectrum acquisition system. It was assembled and adjusted at our laboratory for the investigation of the icons. A small number of pigments were clearly identified by X-Ray Fluorescence (XRF) measurements in both icons. This includes Lead white for the white color, gold and yellow ochre for the yellow color, red lead, cinnabar and red ochre for the red color, as well as cooper based pigments for the green color. At the same time, the investigation raised some new questions that need further investigations by the use of additional analytical techniques. The results show that in both icons are used similar pigments, which are in accordance with the Byzantine icon painting tradition.

能量色散X射线荧光光谱仪在镁砂成分测定中的应用

能量色散X射线荧光光谱仪(X射线能谱仪)具有体积小、价格低、分析速度快等优点而被广泛应用于高分子、陶瓷、混凝土、生物等材料的成分和形态分析,但是在耐火材料行业没有相关方法标准的规定。为了实现X射线能谱仪对镁砂中SiO_(2)、Al_(2)O_(3)、Fe_(2)O_(3)、TiO_(2)、CaO、MgO含量的快速分析,通过优化仪器参数,优选样片制备方法,进行精密度和准确度试验,能谱法和波谱法比对试验。结果表明:以熔铸玻璃片法制取样片,采用X射线能谱仪,可以快速测试镁砂样品中SiO_(2)、Al_(2)O_(3)、Fe_(2)O_(3)、TiO_(2)、CaO、MgO的含量,其相对标准偏差为0.09%~1.85%,具有满意的精密度和准确度。能谱法与波谱法的检测差值满足现用标准GB/T 21114—2019规定的允许差要求,数据可靠。

稳态与瞬态荧光光谱仪在本科教学中的探索实践

大型仪器的高度开发使用与教学工作的有机结合在本科教学中仍旧是一项较有挑战性的工作。为进一步提升学生课程理论知识与分析仪器使用的融合度,本文以稳态与瞬态荧光光谱仪为例,将大型分析仪器与大学中各个阶段学生的学习实践相结合,以提高不同学习阶段的学生稳态与瞬态荧光光谱分析能力,掌握荧光光谱仪使用方法与技能,培养学生利用仪器解决科学问题的能力,提升相关专业的科研素养。

自制开放式荧光光谱仪的搭建、性能测试与实际应用

荧光检测在化学分析、生物检测等多个领域得到广泛应用,因此对本科生进行相关实验教学具有重要意义。本实验成功创制了一套价格低廉、体积小巧的开放式荧光光谱仪,对其性能进行全面评估,并成功应用于实际样品的检测。这有助于培养学生的仪器设计和创制意识,增强他们对自主创制仪器的信心。

手持式XRF在土壤调查修复项目中应用的可靠性分析

为确定手持式X射线荧光光谱仪(XRF)测量精度和准确度是否能够满足土壤环境快速检测要求,以山东省济宁市某地块土壤污染状况调查项目为背景,分别采用XRF快速检测仪检测和实验室检测方法对浅层土层(0.2~0.5 m)和深层土层(1.5~2.0 m)样品中砷(As)、铜(Cu)、铅(Pb)、锌(Zn)和镍(Ni)5种元素浓度进行检测。结果表明:浅层土层重金属As的XRF检测值普遍高于实验室检测值,Cu、Pb、Zn、Ni的XRF检测值普遍低于实验室检测值,误差普遍在±30%以内;浅层土层的重金属元素XRF检测值与实验室检测值普遍相对偏差(RD为−33.82%~23.53%)及总体相对偏差标准差(6.79~19.52)小于深层土层(分别为−30.26%~98.36%、9.53~49.77),相对偏差的离散程度小于深层土层;浅层土层的重金属的决定系数(R^(2)为0.7762~0.9549)普遍高于深层土层(R^(2)为0.7762~0.9549),相关性高于深层土层。野外使用XRF对土壤样品中重金属进行检测时,所取的土壤样品尽量避免大颗粒,对样品待测面进行压实、压平处理,对于含水率高的样品应适当进行干燥处理,以降低检测误差。虽然手持式XRF检测存在一定误差,但在土壤污染状况调查项目中可以较好地反映土壤元素浓度范围,具有较高的可靠性,可以满足项目土壤快速检测需求。

自动双曲面石墨弯晶预衍射X射线荧光光谱法测定后处理工艺样品中的微量铀

为快速、准确、无损检测后处理工艺样品中的微量铀,研制了自动双曲面石墨弯晶预衍射X射线荧光光谱仪,并建立了测定模拟含铀料液中微量铀的分析方法。该仪器在普通能量色散X射线荧光光谱仪的探测器前添加了双曲面石墨弯晶预衍射器,以提高光束的聚焦性,双曲面石墨弯晶参与衍射的有效区域远大于直筒式石墨晶体,大幅降低了铀元素的检出限。测试结果表明,该仪器对铀的检出限为0.033 mg/L,定量限为0.110 mg/L,铀浓度的相对标准偏差优于5%。采用经验系数法对含有锶和钇的模拟含铀料液中的铀元素进行了校正,结果显示,铀回收率在98%~102.3%以上,说明该方法具有较高的准确度。

基于双曲面弯晶技术的X射线荧光光谱仪对塑料快递袋检验分类

目的解决部分塑料快递袋轻元素占比高、元素种类少、常规X射线荧光光谱难以有效区分的缺点。方法利用红外光谱和基于双曲面弯晶技术的X射线荧光光谱仪对7个快递公司,不同地区、不同批次共36个样品进行成分分析和元素含量分析。首先,利用红外光谱对样品基体进行区分,然后再根据元素含量进行组内细分,最后将分类结果作为定类带入梯度提升树模型中,并进行模型稳健性验证。结果样品被红外光谱分为2组,再根据钛元素与硫元素含量将2组细分为5类,梯度提升树模型经过参数优选后准确率为94.2%。结论该方法能够根据样品基体与填料的差异性快速分类并预测所属种类,填补常规X射线荧光光谱检验的空缺,为未知塑料快递袋溯源分类提供了一种新的侦查思路和技术手段。

便携式XRF在农业土壤重金属现场测定中的应用及与实验室分析的比较

研究了便携式X射线荧光光谱仪(p-XRF)在现场测定农业土壤中As、Cu、Cr、Ni、Pb重金属含量的应用,评估了p-XRF的精度、准确度和系统误差,并与常规实验室分析方法进行了比较。实验结果表明,便携式XRF能够快速、准确地测定农业土壤中的多种重金属元素,具有实时、无损、非破坏性和高效等优点。与传统的实验室分析方法相比,便携式XRF的分析结果具有较好的准确性和可靠性,且操作简便、省时省力,能够为农业生产提供及时的重金属污染信息。在土壤样本中,p-XRF测量的As、Cr、Cu、Pb和Ni浓度与实验室分析测量值之间的决定系数均达到0.8,表现出良好的线性关系。实验结果说明便携式XRF在农业土壤重金属现场测定中具有重要的应用价值,为便携式XRF在农业领域的应用提供了有益的参考。

粉末压片-X射线荧光光谱法测定硬质合金混合料中的钴含量

以硼酸为黏结剂,采用粉末压片-X射线荧光光谱法测定硬质合金混合料中的钴含量。考察了研磨时间、黏结剂种类、黏结剂比例等几个关键因素对测定结果的影响,并对标准曲线进行了优化。在仪器最佳工作状态下,选取CoKa谱线作为分析谱线,该方法的线性相关系数R^(2)=0.9999,相对标准偏差(n=11)<0.5%,加标回收率在100%~101%之间。所建立的方法精密度高,结果与化学分析法基本一致,能满足生产中大批量混合料中的钴的快速测定,且测试后的样品通过沸水将压片中的硼酸进行溶解后,样品中的混合料粉末可返还车间进行二次利用。

基于双曲面弯晶技术的便携式X射线荧光光谱仪快速测定土壤中(类)金属元素的含量

为解决常规便携式X射线荧光光谱仪现场检测土壤(类)金属元素时存在的检测元素种类少、部分元素检出限高等缺点,选择GB 15618-2018、GB 36600-2018、农业农村部发布的《第三次全国土壤普查工作方案》包含的重(类)金属元素、金属营养元素以及具有开采价值的(类)金属元素作目标元素,对题示方法的应用可行性(检出限、精密度、准确度)进行了全面考察。土壤样品经烘干、研磨、压实后,用配有双曲面弯晶的便携式X射线荧光重金属分析仪分析,采用快速基本参数法(Fast FP)定量。结果显示:Cd、Hg、As、Cu、Sb、Tl、Mo、Sn、Se、Cs等主要目标元素的检出限为0.2~3 mg·kg^(-1),基本低于环境背景值或上述标准要求的限值(Hg和Se除外)。按照试验方法分析3种水系沉积物成分分析标准物质和两种土壤成分分析标准物质,除测定值在测定下限以下的元素以及Tl、Mg元素外,标准物质中其余主要目标元素测定值的相对标准偏差(n=7)基本低于20%,相对误差的绝对值基本低于35%,Cu、Pb、Cr、Zn和Ni等基础项目元素测定值的相对标准偏差和相对误差符合或接近HJ/T 166-2004对室内平行双样测定精密度和准确度的允许误差要求。利用上述方法分析5种实际土壤样品,所得结果和标准分析方法的基本一致。方法具有快速、准确度高、重现性好,定性、定量元素多的特点,适用于多场合土壤中(类)金属元素的现场测定。

垂直电镀挂具对TO封装陶瓷外壳表面镀镍层厚度均匀性的影响

针对封装陶瓷外壳表面镀层厚度均匀性方面的重要性,利用定制的TO封装陶瓷外壳垂直电镀专用挂具,通过电沉积的方式在TO封装陶瓷外壳的表面电镀镍层。利用X射线荧光(XRF)光谱仪测量研究了TO封装陶瓷外壳相对阳极所在平面与阳极平面间的夹角(θ)对镀镍层厚度均匀性的影响。结果表明,当θ为30°时,在键合指与引线端表面电镀镍层能够实现较好的均匀性,此时的镀层厚度变异系数为24.42%,相比θ为0°和45°时,明显降低了镀镍层厚度的波动范围,有效提升了镀镍层厚度的均匀性。

便携式单波长激发能量色散X射线荧光光谱法在土壤重金属速测中的应用

应用便携式单波长激发能量色散X射线荧光光谱(SW-PXRF)法测定国家土壤标准物质(GSS-1a~GSS-8a)及安徽铜陵农田重金属污染土壤中Cr、Ni、Cu、Zn、Pb、As和Cd 7种元素的含量,将农田污染土样的测试结果与电感耦合等离子体质谱(ICP-MS)法进行对比,分析该方法对各元素的检出限、精密度及准确度。进一步探究土壤含水量和粒径对测定结果的影响,并通过实验确定现场测试时的最佳前处理条件。结果表明:SW-PXRF法对土壤中各元素检出限均低于1.3 mg/kg,其中Cd的检出限可低至0.07 mg/kg。除Cd的精密度略差外,其余元素相对标准偏差基本小于5%。除As和Cd外,其余元素相对误差的平均值均可控制在-10%~10%。SW-PXRF法与ICP-MS法的测定结果相关性较好,除Cr、Ni外,其余元素决定系数均高于0.95。土壤含水量和粒径对测定结果存在一定影响,现场测试时只要将土样在200℃下烘干6 min并研磨60 s,就能在最短时间内削弱含水量和粒径的影响。

XRF和PXRF测定土壤中10种重金属元素方法研究

本文采用台式X射线荧光光谱仪(台式XRF)和便携式X射线荧光分析仪(PXRF)分别对土壤中Cu、Cr、Pb、Zn、Ni、As、Co、V、Mn和Ti等10种元素进行监测分析。采用台式XRF分析这10种元素在各自相应的范围内线性良好,r=0.9990~0.9999,检出限为0.8 mg/kg~5.5 mg/kg,平行测定3次的RSD<2%;而采用PXRF测定,RSD<10%,准确度明显低于台式XRF,对土壤中Cr、Zn、Ni、As、Co、V和Mn等部分元素仅可进行半定量分析。X射线荧光光谱法简化了土壤样品分析,解决了传统的检测分析方法,耗时长,前处理复杂,强酸的使用易导致环境的二次污染等问题,在土壤重金属分析中具有明显的优势。

粉末压片-X-射线荧光光谱法分析砂岩型铀矿制样中粘结剂用量的探讨

由于砂岩型铀矿的成矿特性,样品粉末的内聚力小,采用直接压片法有时难以成型,样片表面常见裂纹,上机测量易碎裂。混合压片法适应性强,制样成功率高,但常见的问题是样品经粘结剂稀释会影响元素的检出限及结果的准确性。通过对粉末压片-X射线荧光光谱法测定砂岩型铀矿地质样品时前期制样中添加粘结剂的比例进行研究,按照不同比例在铀矿石标准物质GBW04101、GBW04102中添加粘结剂,在扫描电子显微镜下观察到随着粘结剂用量的增加,样片表面的光滑度及致密度都呈上升趋势,在X-射线荧光光谱仪上对主量元素进行测定后发现X射线强度在粘结剂添加量大于0.2 g时明显下降,经与GBW04101、GBW04102标准值进行对比后,优选出粘结剂与样品的最佳比例为1∶20,在此比例下制成的样片光滑平整,不易碎裂,用粉末压片-X射线荧光光谱法进行测定,标准物质测定结果的相对误差为0.56%~6.76%,相对标准偏差(RSD,n=12)为0.013%~7.7%,均达到了《地质矿产实验室测试质量管理规范》DZ/T 0130—2006的要求。为粉末压片-X射线荧光光谱法分析砂岩型铀矿地质样品提供了可靠的实验参考依据。

液相色谱-原子荧光联用仪泵流量和最小检测量测定结果的不确定度评定

本文依据JJF 1059.1—2012、JJG 1151—2018建立了液相色谱-原子荧光联用仪泵流量和最小检测量测定结果的不确定度评定的数学模型,阐述了测量结果的不确定度评定方法,确定测量过程中不确定度的来源,并对不确定度进行计算,为后续开展液相色谱-原子荧光联用仪的检定校准工作提供参考。