准分子激光取样与电感耦合等离子体质谱和光谱联用分析仪器研究进展

将准分子激光剥蚀取样后的产物经由电感耦合等离子质谱与光谱分析,从而获得被激光剥蚀样品的元素与同位素含量信息,是迄今为止适应于表面原位微区分析最为重要的分析科学技术手段之一。基于准分子激光剥蚀取样技术分别与电感耦合等离子体质谱或发射光谱技术联用的分析手段, 已经被广泛应用于地质学、材料学、环境科学,甚至生命科学领域的原位微区分析研究当中, 并且分别体现了各自技术的优势：固体材料表面的原位微区激光剥蚀取样技术既可以获取被分析材料的原位微区信息（满足了需要空间高分辨的微区元素与同位素信息提取的需求）,又避免了样品预处理带来的可能污染问题,同时,脉冲宽度为纳秒或飞秒的深紫外准分子激光具有极高的能量密度,用于剥蚀固体材料表面取样产生的热效应较低,引起的化学元素和同位素分馏效应不明显,其剥蚀取样的产物（气溶胶）可以更为接近代表原被剥蚀固体材料表面的化学元素和同位素组成;电感耦合等离子质谱分析和光谱分析技术已被证明可以高质量地提供被分析样品的元素与同位素信息,激光剥蚀取样技术与电感耦合等离子体质谱分析技术联用已经为固体材料表面的原位微区元素和同位素分析,带来了大量可信的科学分析数据,近年来将质谱分析手段与光谱分析手段联用于等离子体分析,并应用于元素和同位素化学分析,利用质谱分析与光谱分析方法各自的优点,优势互补,旨在提高电感耦合等离子质谱和光谱技术的元素和同位素分析精度,有望成为了一种新的分析科学方案。从应用于原位微区微量元素与同位素化学分析的需求出发,介绍了基于准分子激光剥蚀取样技术和电感耦合等离子体质谱与光谱分析技术同步联用的分析技术方案,并对于研发相关分析仪器的进展进行了概括与展望。     

飞秒激光剥蚀电感耦合等离子体质谱在地球科学中的应用进展

激光剥蚀电感耦合等离子体质谱(LA-ICP-MS)是原位微区元素含量和同位素比值分析测试的主流技术, 已被广泛应用于地球科学等相关领域。飞秒激光剥蚀系统由于其极短的激光脉宽大大降低甚至消除了传统纳秒激光剥蚀产生的热效应导致的元素分馏问题,在非基体匹配分析等方面显示出巨大发展潜力,已成为当前LA-ICP-MS技术的一个新的发展趋势和研究热点。介绍了飞秒激光剥蚀系统的基本特征(飞秒激光及产生原理、当前商用飞秒激光器种类),重点阐述了飞秒激光剥蚀地球科学样品的机理(样品对激光能量的吸收方式、气溶胶的产生和粒度分布特征、剥蚀坑的形貌特征等),评述了飞秒激光剥蚀在改善分析性能方面的独特优势,最后总结了近十几年来它在地球科学样品元素含量和同位素比值分析中的实际应用,并展望了该技术的应用前景。     

液相基质中微量金属元素Pb的激光诱导击穿光谱研究

通过单脉冲激光诱导击穿光谱技术（LIBS）,测定了Pb（NO3）2水溶液中微量重金属元素Pb的LIBS光谱。实验研究溶液中Pb元素的LIBS光谱信号的时间（300ns-1300ns）演化特性,得到了本实验的优化实验条件,光谱探测相对激光的延时为800ns,单脉冲激光能量35mJ。在最佳实验条件下测定Pb微量元素的LIBS定标曲线,计算得到LIBS用于Pb(NO3)2溶液中痕量金属元素分析的检测限为177ppm。     

2,9-二甲基-1,10-菲咯啉的化学发光研究

本文阐明了试剂2,9-二甲基-1,10-菲咯啉(称为新铜灵)在金属离子诸如Cu(Ⅱ)、Pb(Ⅱ)、Fe(Ⅲ)和Ni(Ⅱ)作为催化剂各自存在下,可与过氧化氢在碱性溶液中产生一种绿色的化学发光反应。此化学发光反应的机理已在本文中进行讨论,并认为是由于Cu(Ⅱ)与新铜灵生成之络合物在此过程中进行催化反应而致使过氧化氢生成超氧基离子,而此超氧基离子随即与新铜灵试剂作用产生化学发光。此化学发光反应的产物已用薄层色谱法进行分离,并且分别用紫外、红外和荧光分光光度法进行测定。 此外,这种新的化学发光反应已在我们实验室进行了分析应用试验。用此化学发光体系来做Cu(Ⅱ)的测定也在本文中说明。此法测铜的检测下限为8×10-9克/毫升;线性范围是1×10-8到4×10-7克/毫升。对于0.1ppm之铜的测定而言,除适量的Co(Ⅱ),Mn(Ⅱ)、Ni(Ⅱ)、Cd(Ⅱ)和Cr(Ⅲ)之外,其余外来离子均无干扰。这一分析方法能够满意地用于铝合金中铜的测定。     

基于多谱线内标法的不规则铜合金样品中 Pb元素成分检测研究

原位分析和在线检测是激光诱导击穿光谱(LIBS)技术的一大优势,但是,在野外环境中,人们无法对样品进行统一预处理,面对各种形态的待测样品如何保证LIBS的检测精度是函待解决的一大难题。提出一种多谱线内定标的方法来解决上述问题,即通过求解多条分析谱线的强度和与内标元素谱线的强度比值来建立定标曲线,进而降低光谱信号波动带来的误差,提高线性相关性和检测精度。实验中以铅黄铜合金样品为例,采用LIBS对厚度不一（最大变化值为±2 mm）的铅黄铜样品中的Pb元素进行了定量检测研究,并分别采用传统定标法和多谱线内定标法对这种不规则样品进行校正和建立定标曲线。实验发现,对于不规则样品,传统定标法的检测精度大大降低,定标曲线没有明显的线性关系。当采用单条谱线的内定标方法时,定标曲线线性相关度大大提高,校正决定系数达到0.724 89。而采用多条谱线内标方法（考虑多条分析谱线的相对强度总和）计算发现,当选取5条Pb谱线（Pb 261.42 nm,Pb 280.20 nm,Pb 368.35 nm,Pb 405.78 nm和Pb 520.14 nm）进行计算时,定标曲线线性拟合度达到0.984 6,由此可见该方法消除了样品不规则所带来的光谱强度波动误差,显著提高了测量精度。虽然继续增加分析谱线数目可以进一步提升线性相关度,但是也会增加计算的复杂度,所以选择合适的分析谱线是十分重要的。此外,通过多谱线内标法也能一定程度上消除基体效应和光谱干扰等影响,是一种简单有效且具备普适性的数据处理方法。当然,该方法也存在一定的局限性（如样品成分分布极不均匀、样品表面极不规则致使激光能量低于击穿阈值等）,不过通过调整和优化检测装置方案（例如增大激光能量、增大聚焦光斑、采用长焦距聚焦透镜等）可以更好的发挥该方法的优势。该研究内容可以为LIBS原位检测和在线检测的应用提供一种新思路。     

新疆哈密绿松石的矿物学和光谱学特征研究

最近在新疆哈密发现了可规模开采的宝石级绿松石矿床。采用X射线粉晶衍射仪、激光剥蚀电感耦合等离子体质谱仪、扫描电子显微镜、傅里叶变换红外光谱仪、拉曼光谱仪、紫外-可见光谱仪等测试方法,对该地绿松石的化学成分、矿物组成、表面微形貌、红外吸收光谱、拉曼散射光谱、紫外-可见吸收光谱等矿物学和光谱学特征进行了系统对比研究。新疆哈密绿松石的主要化学成分以富Cr (1 617 ppm),V (435 ppm),Ti (428 ppm),贫Ba (99.9 ppm)为特征,随着Fe₂O₃/CuO比值的递减,绿松石的色调由绿变蓝。由磷酸根、羟基和结晶水引起的特征峰出现在该地绿松石的拉曼光谱和红外吸收光谱,其中磷酸根的振动峰位于1 000~1 200和420~650 cm-1,羟基的振动峰出现在3 400~3 600 cm-1,而结晶水引起的振动峰位于3 000~3 300 cm-1。此外,该地绿松石的紫外-可见吸收光谱显示,在600~700和430 nm处分别有由Cu2+和Fe3+引起的吸收峰,这两处的峰强与绿松石的蓝绿色调之间的关系,和新疆哈密绿松石成分中Fe₂O₃/CuO的比值与颜色之间的关系对应一致。     

激光微探针──激光激发离子质量分析器

近年来英国、法国、联邦德国三国又发展了一种新的分析技术,叫做激光微探针──激光激发离子质量分析器.激光微探针有一系列优点:(1)能进行全元素分析.(2)灵敏度高,相对探测极限可到0.1ppm,绝对探测极限可到10-20g.(3)空间分辨好,横向分辨可到1μm,深度分辨可到20nm.(4)质量分辨好,M/△M=500.(5)分析速度快,分析一个点只要100μs,比其他技术快105倍.(6)能分析固体、液体和气体佯品.能分析mm级厚样品和nm级薄的样品,但这种技术的缺点是:(1)定量精度较差,现在达到的最好精度为0.1%.(2)对样品不是无损分析. 激光微探针能进行1μ m3体积的微区…     

纳秒激光诱导紫铜黄铜等离子体特征参数的对比研究(英文)

基于1064nm Nd:YAG激光器,对比研究了紫铜和黄铜等离子的特征参数。洛仑兹函数拟合Cu I 324.75nm得到紫铜和黄铜等离子体的电子密度分别是3.6×1017 cm-3和3.3×1017 cm-3。为了减小谱线自发辐射跃迁几率不确定性和测量误差带来的计算误差,采用改进型迭代玻耳兹曼算法精确求解紫铜等离子体和黄铜等离子体的电子温度分别是6316K和6051K,分析表明,两种等离子体特征参数的差异主要是由于黄铜中的锌元素的电离能(9.39eV)大于铜元素的电离能(7.72eV)而造成的。实验数据证实激光诱导的紫铜和黄铜等离子体满足局部热力学平衡模型和光学薄模型。     

近场光学用于激光解吸飞行时间质谱的亚微米级空间分辨成像

基于激光离子源的飞行时间质谱法作为一门新兴的成像方法,已经被广泛应用于材料、地质、环境、药物和生命科学领域中。但受限于光学衍射极限、聚焦透镜的焦距和数值孔径等因素,使其难以实现亚微米尺寸的高空间分辨率成像。近场技术的引入成功地解决了光学衍射极限的限制,将近场技术与激光电离技术相结合,可以实现对固体样品表面纳米级弹坑的剥蚀。此外,传统的质谱成像技术常常假设样品表面是平整的,忽略其表面形貌的高低起伏,但这往往会导致信号强度不稳定和成像假象。为此,不仅需要获得样品中的化学组成与空间分布,还需同时获得样品表面的形貌信息,才能实现多功能的原位表征。在自行研制的激光解吸/电离飞行时间质谱的基础上,采用近场纳米有孔针尖离子源代替传统的远场激光聚焦,以532 nm波长激光为第一束解析激光,355 nm波长激光为后电离激光,音叉式原子力显微镜控制系统针尖与样品之间的距离维持在近场范围内,对酞菁铜镀层样品表面进行了弹坑剥蚀实验,获得了直径为550～850 nm的弹坑点阵;并对7.5 μm×7.5 μm的标准酞菁铜网格样品进行了铜离子亚微米级的高分辨率成像;此外,纳米有孔针尖离子源作为原子力显微镜的一种变体,还可同时获得成像区域的表面形貌信息,这一结合优势大大拓展了质谱技术在微纳尺度下的原位表征能力。     

微区X射线荧光光谱仪研制及元素生物地球化学动态分布过程研究

微区无损分析可提供物质组成元素的原位分布信息,以揭示物质形成条件、元素动态分布过程与相互作用机理、生物代谢作用等。文章报道了实验室型微区X射线荧光(μXRF)光谱仪的研发和元素生物地球化学动态分布过程研究结果。μXRF光谱仪采用15 μm光斑的聚束毛细管X射线透镜为激发源,选用分辨率为135 eV的硅漂移探测器(SDD),样品和探测器间角度可调,使之可进行异型样品如地质样品的原位分析,利用五轴自控实现样品时空四维元素分布测定。利用该μXRF光谱仪测定了矿物-生物膜间的元素迁移和玉米种发芽过程中的元素分布,发现(1)生物膜可吸附、富集毒性元素铅,是重金属的重要汇集地,最大富集系数1.7。(2)生物膜是金属从固态矿物相经水相进入生态系统的重要途径。(3)在玉米种子中,可检测到K,Ca,Mn,Fe,Cu,Zn和Pb。Zn主要在胚乳中分布,胚中有少量Zn存在;在胚乳和胚中存在微量Fe;胚乳中存在微量Pb,胚中未观测到Pb。(4)经含Pb溶液浸泡发芽后,K在玉米种中胚和胚乳中部分富集,Fe分布在种皮和胚乳中,Cu和Zn主要在胚乳中分布;Pb主要在胚根、胚轴和胚芽中分布,且Pb在新生根中高度富集。研究表明,在种子萌发阶段,Pb等毒性元素可被植物滞留于根部,制约了其向地上部的转移,从而揭示了植物对毒性元素的耐受机制。     

Solutions of the BBGKI equations in the fourth approximation in the temperature

Solutions of the Bogolyubov-Born-Green-Kirkwood-Ivon equations in the fourth approximation in the temperature are given in a class of generalized functions both for van der Waals and ionic crystals in the case of the so-called taking into account of smoothed correlations. A statistical thermodynamics of strongly anharmonic van der Waals and ionic crystals is constructed. Temperature expansions of the correlative distribution functions and thermodynamic quantities are investigated within the framework of the indicated method. The temperature dependence of cubic order is taken into account in the expression of the isochoric specific heat and the Grüneisen parameter of the listed crystals. It is shown that the temperature expansion for the isochoric specific heat of anharmonic crystals converges well for a value of the reduced temperature 0.33 T_m (T_m is the melting temperature).Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 7, pp. 55–59, July, 1981.     

Superconductivity in the t-J model in the large-N limit

Using a 1/N expansion for X-operators the leading contributions to the linearized equation for the superconducting gap of the t-J model are derived and the gap equation solved numerically on a square lattice. We find a strong instability towards superconductivity only in the d-wave (T ₃) channel with T _c/│t│ ～ 0:01 where T _c is the transition temperature and t the nearest-neighbor hopping integral. The underlying effective interaction consists of an attractive, instantaneous term with the band width, and a retarded term due to charge and spin fluctuations with ～ J, as energy scale.     

在稳定中求变在变化中求新——2010年高考浙江省理综(物理)试题评析

1 总体特征 通读2010年高考浙江省理综卷物理试题,给人以耳目一新的感觉.命题者在2010年的命题设计中,做到了三个贴近,即贴近时代、贴近生活、贴近学生.实现了三个有利的原则,即"有利于高等学校选拔新生,有利于中学推行素质教育,有利于激发考生学习科学的兴趣".     

Role of the near-electrode regions in the formation of the volume discharge heterogeneity in nitrogen in the pin-to-plane configuration

The development of streamers and sparks in nitrogen at atmospheric pressure in the pin-to-plane electrode configuration is studied in experiments and theoretical calculations. It is demonstrated that the near-electrode regions play the decisive role in streamer initiation. At a negative pin voltage, a spark is formed in the absence of fast primary streamers. At a positive pin voltage, streamer build-up is initiated by the current spots on the anode that result from the development of the ionization instabilities in the anode region. The calculations show that the formation of the current spot on the anode leads to a redistribution of the electric field in the vicinity of the anode, so that a single avalanche is transformed into a streamer under the conditions when the known criterion for streamer breakdown (the Meek-Raether criterion) is not satisfied. Original Text ? Astro, Ltd., 2006.     

Change in the sign of the magnetoresistance effect in bilayer superconductor/ferromagnet structures under change in the type of the domain structure in the ferromagnet

The magnetoresistance effects in the bi- and trilayer hybrid planar superconductor/ferromagnet (S/F) structures based on Py (permalloy) and Nb near the superconducting transition temperature T _C are considered. It has been experimentally shown that the sign of the observed magnetoresistance peaks in the bilayer S/F systems changes from negative to positive at the permalloy layer thickness corresponding to the change in the type of domain walls from Néel to Bloch. For the Néel walls at the ferromagnet coercive fields, the negative magnetoresistance effect, which is due to a decrease in the depairing action of the exchange field E _ex, is observed in the S/F bilayers. For the Bloch domain walls, the magnetoresistance of the bilayer S/F structures is determined by the dissipative motion of Abrikosov vortices in the superconducting layer. In the trilayer F/S/F structures, the magnetoresistance is mainly due to the suppression of the superconducting order parameter in the superconducting layer under the action of the accumulation of the spin-polarized carriers near the S/F interfaces.     

Correlation between Variations in the Number of Neutrons in the Atmosphere and in the Intensities of the Atmospheric Ozone Lines

We compare the data on the atmospheric radio emission in two ozone lines with resonance frequencies 96,228 and 101,736 MHz, obtained at the N. I. Lobachevsky State University of Nizhny Novgorod in 1996–2001, with the corresponding results of measuring the number of neutrons in the atmosphere, obtained at the Institute of Terrestrial Magnetism, Ionosphere, and Radio Wave Propagation (Troitsk, Moscow region) using the NM-64 monitor. It is shown that variations in both the optical depth and the intensity ratio of these lines correlate with variations in the number of neutrons. The maximum observed correlation coefficients for the optical-depth decrements of the lines amount to 0.5–0.6, which is about a factor of 1.5 higher than the maximum correlation coefficient for their intensity ratio. We analyze the dependence of the correlation coefficients on the time shift between data series for the ozone line intensity and the number of neutrons in the atmosphere. It is shown that correlation between these data series almost vanishes for a time shift of about 200 h. We discuss the features of the data on the number of neutrons in the atmosphere and the possibility of the solar origin of neutrons.     

Absorption in the final state in reactions and decays in the medium

The role of strong absorption of particles in intermediate and final states has been considered. The range of applicability of phenomenological models of absorption has been studied. This model is nonuniversal. Its applicability depends on the type of interaction Hamiltonian and matrix element used. We also demonstrate that the violation of the unitarity condition can produce a qualitative error in the results. The absorption (decay) in the final state does not tend to suppress the total process probability as well as the probability of the channel corresponding to absorption. This is true for the reactions, decays and nˉ conversion in the medium.     

Metastates in the Hopfield Model in the Replica Symmetric Regime

We study the finite dimensional marginals of the Gibbs measure in the Hopfield model at low temperature when the number of patterns, M, is proportional to the volume with a sufficiently small proportionality constant > 0. It is shown that even when a single pattern is selected (by a magnetic field or by conditioning), the marginals do not converge almost surely, but only in law. The corresponding limiting law is constructed explicitly. We fit our result in the recently proposed language of metastates which we discuss some length. As a byproduct, in a certain regime of the parameters and (the inverse temperature), we also give a simple proof of Talagrands recent result that the replica symmetric solution found by Amit, Gutfreund, and Sompolinsky can be rigorously justified.     

On the analyticity in the potential in classical statistical mechanics

Some general results on strong cluster properties of connected or partially connected correlations, and their links with analyticity properties with respect to the potential or to classes of perturbations of the potential are presented.Equipe de Recherche du C.N.R.S. No. 174