Application of PIXE for the determination of transition elements in the grouping study of archaeological clay potteries

Trace element concentrations play an important role in grouping and provenance studies of archaeological artifacts. Particle‐inducedX‐ray emission (PIXE) using low energy proton beams (1.5 and 3 MeV) from a tandem particle accelerator was used to analyze the ancient clay potteries collected from an ancient Buddhist site in India. Concentrations of 13 elements, including eight transition elements, were determined. The concentrations of transition elements were used for the grouping study by statistical cluster analysis according to the similar and dissimilar elemental distribution within the samples. Two International Atomic Energy Agency Reference Materials (RMs) were analyzed to validate the PIXE method. Two samples were analyzed by both PIXE and instrumental neutron activation analysis (INAA) as a part of quality assurance. Grouping results were used for preliminary provenance study. Copyright © 2017 John Wiley & Sons, Ltd.     

含稀土元素的矿渣纳米晶玻璃陶瓷的光谱学研究

利用白云鄂博矿资源废弃物中有价元素以共伴生形成存在的特点制备了高性能的矿渣纳米晶玻璃陶瓷。本文采用电感耦合等离子发射光谱（ICP）、X射线衍射（XRD）、拉曼光谱（Raman）、扫描电子显微镜（SEM）等测试方法对样品的成分和结构进行了深入分析。ICP和XRD、SEM实验结果表明,我们制备的玻璃陶瓷是主晶相为透辉石,晶粒尺寸在45～100nm范围含稀土元素的纳米晶玻璃陶瓷,SEM面扫所显示的元素与ICP成分分析结果较为一致。Raman分析表明,其非晶相主要由具有不同非桥氧键的硅氧四面体结构单元构成的三维网络结构,进一步分析发现稀土微量元素对网络结构有十分明显的影响。我们把矿渣纳米晶玻璃陶瓷与相似成分的玻璃陶瓷的拉曼光谱对比,发现矿渣纳米晶玻璃陶瓷的拉曼谱带普遍比玻璃陶瓷对应的拉曼谱带波数低。相似成分的玻璃陶瓷与矿渣纳米晶玻璃陶瓷的成分差别主要是稀土元素等微量元素。本文的研究方法为研究玻璃陶瓷的成分与结构、性能之间的关系提供了一种研究思路。     

野生中药田基黄中稀土元素含量分析

中药材中的有效成分研究得到了人们的普遍关注。应用ICP-MS分析了中药材田基黄中稀土元素的含量。结果表明田基黄稀土元素La,Ce,Pr,Nd,Sm,Eu,Gd,Tb,Dy,Ho,Er,Yb,Tm,Lu和Y的浓度在6～14 522 ng·g-1的范围之间。在上述稀土元素中,田基黄稀土元素含量超过2 000 ng·g-1的有La(4871.64), Ce(14 522.03)和Nd(2 064.94)。与粮食作物比,田基黄中稀土元素的含量是稻米、小麦、玉米和大麦等粮食的上千倍,这可能是田基黄具有肝病治疗效果的重要因素。稀土元素在田基黄中的分配除了自身的吸收分配特性以外,还要受土壤等环境因素的影响,分配机理还需要进一步研究。     

稀土反射波谱特征及高光谱提取研究进展

稀土是一种重要的战略资源,由于稀土资源的稀缺,近年来对其反射波谱特征与高光谱信息提取的研究较为薄弱。笔者首先从稀土电子层构型和能级跃迁的层面阐述了其光谱机理。稀土由于其特殊的电子构型,它们的4f电子的f-f组态之内容易跃迁,在可见光-近红外有其特有的波谱吸收特征。其次结合自己开展的一些工作,系统总结了15种稀土单元素、稀土矿物(含稀土的氟碳酸盐、磷酸盐、硅酸盐矿物)、稀土溶液的反射波谱特征,可见15种稀土单元素的反射特征差异较大,稀土矿物及溶液的波谱特征是化学组成中优势稀土元素的体现,吸收强弱随着稀土浓度的降低逐渐减弱甚至消失。由于稀土信息提取对高光谱传感器要求较为苛刻,目前的研究主要集中于近距离高光谱传感器探测,航空及航天高光谱遥感探测存在一定困难,根据单元素的波谱吸收特征,近距离高光谱传感器目前可成功提取Nd,Er,Dy,Ho,Sm和Tm等的分布信息;最后文章展望了稀土反射波谱及高光谱稀土找矿研究的难点和重点,旨在为今后研究提供新的思路。     

ICP—AES法测定磷矿中稀土元素及钪

本文研究了磷矿样品的分析方法,选择了同时测定微量稀土及铣的合适条件。此法测定磷矿中十五种稀土元素及钪取得了较满意的结果。     

计算光度法同时测定镧、铈、镨、钕

以二溴一氯-偶氮氯膦(DBC-CPA)为显色剂,并且在显色体系中加入不同量的EDTA-Na2P2O7作为竞争配位剂,使得4组分轻稀土组分间吸收光谱灵敏度的差别加大,从而增加了轻稀土混合物体系组分间吸收光谱的线性独立性,采用数值稳定性强的约束优化算法-可变容差法处理光谱数据,对不同深度比例的4组分轻烯土混合物体系(La^3 ,Ce^3 ,Pr^3 ,Nd^3 )的测定,取得了较为满意的结果.     

离子型稀土矿含量高光谱定量反演研究

运用光谱测量技术来测量土壤、矿物、植物的光谱吸收特征,并将其用于物质成分的分析中,是高光谱遥感技术近些年来的一个新的发展方向,具有速度快、效率高、费用低、损耗少的优点。稀土是战略元素,因具有特殊的物理化学性质,在多个领域都能发挥其独特的作用。近年来对稀土资源需求量的不断增加使得稀土价值不断提高,使得如何快速大面积探测稀土资源,合理对稀土矿进行布设开采成为了当前社会面临解决的重要科学问题。通过对稀土矿物进行光谱采集与分析从而对稀土元素及其化学特征之间的相关性进行研究分析展开了一系列的工作。在研究过程中,实地采集了广西崇左市六汤稀土矿区内的12个稀土矿样,并在实验室控制环境内使用SVC HR1024I便携式地物波谱仪测得其对应的反射光谱数据。对所测得的矿样波谱特征进行了连续统去除处理,并对凸显的特征吸收波段进行相对吸收深度的计算分析,从而运用其波谱特征建立起波谱与矿样稀土总含量、各稀土元素含量间的线性关系。通过实验发现,稀土元素的五个特征吸收波段在可见光和近红外波长分别为370,950,1 400,1 900和2 200 nm。这五个吸收带的强度与总稀土含量呈线性相关,R2达到0.69,同时发现稀土含量值与可见光波段相关性较大,对可见光波段与样本稀土总含量进行相关分析,提取出部分可见光波段中与稀土总含量建模相关性最强的10个波段,分别为340,350,360,370,390,400,420,480,550和760 nm。运用线性回归的方法得到上述波段处的反射率值与样本总稀土含量值的预测模型精度较高,R2大于0.95。运用可见光波段与15种稀土元素含量值也进行了线性建模,相关系数均可以达到0.89以上,表明各单一稀土元素与可见光波段之间的相关性同样较好。通过研究稀土矿样的光谱特性及化学分析,通过5个稀土特征吸收波段和可见光波段与矿样的稀土总含量、15种稀土元素含量进行回归建模,得到了矿样稀土含量的定量预测模型,对稀土矿快速定量-半定量评估具有一定参考价值,同时为进行稀土矿物及其元素高光谱遥感信息提取研究提供了科学启发,为最终实现对稀土资源高效开采的基础上,从源头上降低消耗和生产成本,减少对环境的破坏和污染,为促进中重稀土资源的战略开发和使用提供了科学有效的理论依据。     

卡尔曼滤波ICP－AES法分析稀土元素及其对光谱干扰的校正

本文以卡尔曼（Ｋａｌｍａｎ）滤波ＩＣＰ－ＡＥＳ法进行稀土元素分析，并研究了卡尔曼滤波对其光谱干扰的校正，以及富线基体元素对待测元素、待测元素之间的影响，考察了该方法的检出限、精密度和准确度以及影响滤波的因素。结果表明，该法能有效地消除和校正光谱干扰，减少对分析谱线的选择，改善分析的检出限，分析速度快，结果准确可靠，可适合各种稀土试样（高纯稀土、混合稀土）的日常分析。     

ICP－AES中迭代干扰校正法在稀土配分上的应用

本文采用干扰系数迭代校正法测定稀土氧化物富集样中稀土元素的含量。应用迭代校正程序，计算机可以迅速得出准确结果。为了减少分析波长选择的盲目性，建立了一套扫描峰形图谱库。将ＩＣＰ－ＡＥＳ与微机联用直接选出了各个稀土元素的最优测量条件，综合确定仪器的最佳工作参数。本法的回收率为９０～１０８％，Ｒ．Ｓ．Ｄ小于６％。     

Spin reorientation in (RE)2 (TM)14B alloys (RE = rare earth,TM = transition metal)

Spin reorientation in (RE)₂ (TM)₁₄B alloys has been studied by Moessbauer spectroscopy of oriented and powder samples. The competition of the CEF anisotropy for two rare earth elements with opposite Stevens factors has been investigated in the system Er_2-xDy_xFe₁₄B. The competition between the rare earth and transition metal sublattice anisotropy has been examined in the system Nd₂Co₁₄B doped with 1% Fe⁵⁷ and it has been found that spin reorientation occurs at 550±2K.     

Structural phase transitions in yttrium under ultrahigh pressures

X-ray diffraction studies were carried out on the rare earth metal yttrium up to 177?GPa in a diamond anvil cell at room temperature. Yttrium was compressed to 37% of its initial volume at the highest pressure. The rare earth crystal structure sequence hcp?→?Sm?type?→?dhcp?→?mixed(dhcp?+?fcc)?→?distorted fcc (dfcc) is observed in yttrium below 50?GPa. The dfcc (hR24) phase has been observed to persist in the pressure range of 50-95?GPa. A structural transition from dfcc to a low symmetry phase has been observed in yttrium at 99?±?4?GPa with a volume change of -?2.6%. This low symmetry phase has been identified as a monoclinic C2/m phase, which has also been observed in other rare earth elements under high pressures. The appearance of this low symmetry monoclinic phase in yttrium shows that its electronic structure under extreme conditions resembles that of heavy rare earth metals, with a significant increase in d-band character of the valence electrons and possibly some f-electron states near the Fermi level.     

Mössbauer and mineral magnetic studies on archaeological potteries from Adhichanallur, Tamilnadu, India

Megalithic potteries collected from Adhichanallur, Tamilnadu, India (Lat. 8°44′ N; Long. 77°42′ E) have been subjected to various spectroscopic and rock magnetic studies. The type of clay, their origin, level of structural deformation due to firing, firing temperature and atmospheric condition followed during making the potteries are analyzed. The potteries were subjected to Mössbauer and X-ray diffraction studies to analyze the iron phases in them. It is found that the samples were made of local clay (red clay), fired above 600°C under open atmospheric and/or reduced atmospheric conditions and air has been allowed during cooling. The Mössbauer spectra reveal the presence of Fe^3?+?, Fe^2?+? and iron oxides of hematite and magnetite. The firing temperature and firing conditions established from Mössbauer studies are similar to the observation made from FT-IR studies. The magnetic mineral types, the mass fractions and the domain states of the constituent magnetic grains were elucidated from a range of rock magnetic measurements including variation of susceptibility with low field, frequency and temperature, hysteresis parameters and isothermal remanence acquisition data. The magnetic mineralogy of most pottery samples was dominated by magnetite/(titano) magnetite, while magnetic grain size spectrum varies from very fine (super paramagnetic) to fine (stable single domain, pseudo single domain). The reversible thermo magnetic behavior reflects no mineralogical transformations during reheating and all the samples show same Curie temperature 580°C due to magnetite. From the above information it is demonstrated that these samples are suitable for determining the reliable ancient geomagnetic field intensity values existed during that period.     

Performance of lead iodide nuclear radiation detectors with the introduction of rare earth elements

Lead iodide has been recognized as a promising material for room temperature radiation detectors. It has a wide band-gap (∼ 2.3 eV), high atomic numbers (82, 53) and it is environmentally very stable compared to mercuric iodide. Electrical and optical properties of lead iodide grown crystals purified under the influence of selected rare earth elements have been investigated. Photo-luminescence and capacitance-voltage measurements have been performed using different rare earth elements.     

ICP—AES法中稀土元素间的相互干扰研究

稀土元素的谱线较复杂,相互间存在着不同程度的干扰。本文着重研究了ＩＣＰ－ＡＥＳ法中,它们间的干扰情况,并用几种校正方法进行了比较。     

稀土元素的价电子结构和熔点、结合能的关联性

稀土是重要的战略物资资源,有一些已形成产业,在永磁、发光、催化和储氢等方面有着重要的作用. 对稀土及其化合物的研究一直是国内外研究的热点.对稀土原子结构和价电子结构的研究有助于对其的更深刻的理解. 依据固体与分子经验电子理论,对镧系稀土和Sc, Y的价电子结构进行系统地研究, 并以此为基础,对它们的熔点和结合能做进一步分析,分析结果和实验值相符. 研究结果表明:稀土金属的结构与晶格电子和共价电子密切相关,随着晶格电子向共价电子的转换, 稀土金属的熔点趋于增加.稀土的价态变化也是影响电子分布和性能的主因, 如: Sm和Eu的熔点与电子结构的关系不同于其他稀土,外壳层的共价电子之间的转化是其熔点与其他元素之间差别较大的主要原因.稀土的4f电子对结合能的影响大,这是源于其4f电子引发的收缩效应. 此结果揭示了决定稀土熔点和结合能的主要因素是稀土的价电子结构的变化.     

基体分离-电感耦合等离子体发射光谱法测定赤泥中的稀土氧化物

从赤泥中提取稀土金属,开发高附加值产品,对保护环境特别是提高矿产资源的综合利用率以及实现可持续发展有着重要的意义。赤泥中的稀土元素含量较低(0.001 0%～0.050%),且存在大量的铝和铁等基体元素,如何掩蔽基体元素对稀土元素的干扰是准确定量的关键。传统酸溶法会造成部分元素消解不完全,难以准确定量,回收率低,碱熔法则会由于引入大量的碱熔剂造成严重的基体干扰,同时还会堵塞雾化器。采用氢氧化钠熔融赤泥,熔融物用热水浸取,三乙醇胺溶液掩蔽铝和铁,乙二胺四乙酸二钠溶液络合钙、镁等干扰元素,稀土氢氧化物留存于沉淀中,沉淀经盐酸溶解进入待测液,从而将稀土元素与熔剂和基体元素分离。实验结果表明：标准溶液无需基体匹配,各稀土氧化物校准曲线的线性相关系数均不小于0.999 9,检出限在0.000 2%～0.001 5%之间;按照实验方法分析实际样品中稀土氧化物的含量,测定结果的相对标准偏差(RSD,n=6)为2.5%～7.2%,回收率为85.0%～105.0%;本方法与电感耦合等离子体质谱法(ICP-MS)相比,两种方法的测定结果无显著性差异。ICP-OES实现了赤泥中稀土氧化物的同时测定,为今后分...     

A scientific approach to the attribution problem of renaissance ceramic productions based on chemical and mineralogical markers

Renaissance lustred majolica shards from Gubbio and Deruta (Central Italy) were investigated in order to point out differences in chemical and mineralogical composition between these two very similar Italian potteries and furthermore to find correlations with the local raw clay materials probably used for their production. Chemical and mineralogical analysis on the ceramic body were performed by ICP-OES (inductively coupled plasma optical emission spectroscopy) and XRD (X-ray diffraction), respectively. Investigation of the ceramic body revealed significant differences on calcium content indicating that it could be used as a marker for the two different productions.     

共线双脉冲激光诱导击穿光谱技术检测铝合金中的Cr和Mn

采用两台波长1064 nm的调Q脉冲Nd ∶YAG激光器和多通道小型光纤光栅光谱仪,建立了一套共线双脉冲激光诱导击穿光谱分析装置。与单脉冲激光诱导技术相比,在最佳双脉冲时间延时8 μs时,Mn I 403.07 nm和Cr I 425.43 nm的光谱强度分别增加了14.3倍和17.2倍,以这两条谱线为分析线,铝合金中Mn和Cr的检测限分别由单脉冲时的73和94.5 μg/g降低至双脉冲时的3.76和4.26 μg/g,检测灵敏度提高了约20倍。     

Photon interaction studies using 241Am γ-rays

We have carried out some photon interaction measurements using 59.54 keV γ-rays from a ²⁴¹Am source. These include γ attenuation studies as well as photoelectric absorption studies in various samples. The attenuation studies have been made using leaf and wood samples, samples like sand, sugar etc., which contain particles of varying sizes as well as pellets and aqueous solutions of rare earth compounds. In the case of the leaf and wood samples, we have used the γ-ray attenuation technique for the determination of the water content in fresh and dried samples. The variation of the attenuation coefficient with particle size has been investigated for sand and sugar samples. The attenuation studies as well as the photoelectric studies in the case of rare earth elements have been carried out on samples containing such elements whose K-absorption edge energies lie below and close to the γ-energy used. Suitable compounds of the rare earth elements have been chosen as mixture absorbers in these investigations. A narrow beam good geometry set-up was used for the attenuation measurements. A well-shielded scattering geometry was used for the photoelectric measurements. The mixture rule was invoked to extract the values of the mass attenuation coefficients for the elements from those of the corresponding compounds. The results are consistent with theoretical values derived from the XCOM package.     

稀土氧化物粉末样品的光声光谱研究

利用光声光谱方法对几种常见的稀土氧化物粉末样品在紫外-可见、近红外, 以及中红外波段的光声光谱进行了测量与分析。根据光声光谱图和稀土离子的能级图, 对稀土离子的激发态电子的辐射和无辐射跃迁进行了探讨。与传统的透射谱和吸收谱相比较, 光声光谱具有分辨率高、快速、无损检测等优点, 特别适合于研究不透明、高反射和高散射粉末样品的光学性质。