表面残留有机沾污物的TOF—SIMS及XPS研究

飞行时间次级离子质谱（ＴＯＦ－ＳＩＭＳ）结合Ｘ射线光电子能谱（ＸＰＳ）分析了用化学方法清洗后，银片上残留的未知的有机物，结果显示，有机沾污物主要是一些合１８～３０碳原子，碳链饱和度很高的酮类和酯类化合物；个别有机物可能是硬脂酰胺。这种结构特点使有机物中的Ｃ＝Ｏ基团易于采取氧原子指向基本表面的取向。通过带部分负电荷的氧原子与金属基体镜像力的作用而增强粘附，ＴＯＦ－ＳＩＭＳ－二维离子像显示有机沾污物在     

飞行时间二次离子质谱结合X-射线光电子能谱分析化学清洗后残留的表面有机物

用飞行时间二次离子质谱(TOF-SIMS)结合X射线光电子能谱,分析了用化学方法清洗后银片上残留的未知有机物.TOF-SIMS与XIPS提供的互补的表面信息显示,中分子量以上的有机物主要是几种链长22～27碳原子、碳链饱和度很高的多酮类化合物,可能还有一些多酯类化合物.这些有机物中的C=O基团易于采取氧原子指向金属基体表面的取向,通过带部分负电荷的氧原子与金属基体镜像力的作用而增强粘附.     

XPS和TOF—SIMS在硬盘驱动器（HDD）磁头表面微污染分析中的应用

XPS和TOF－SIMS表面分析仪器联用分析磁头臂焊接位表面有机微污染物成分,找出污染物的来源;XPS能够提供污染物中元素组成及价态信息,而TOF－SIMS能够提供其分子信息。试验证明两者联用是分析表面有机微污染物强有力的手段。     

玻璃表面特性的XPS研究

本文用XPS表征了玻璃表面铜、铅和锡离子的价态,并测定在浮法玻璃底表面锡离子价态的深度分布。对沾锡现象与锡离子价态之间的关系进行了讨论。     

三维编织C/SiC纤维复合块材的XPS研究

用常规XPS、小面积XPS和成象XPS研究了三维编织的C/SiC纤维复合材料.结果表明,在燃气中灼烧后材料表面生成的暗红色反应是由于层中的SiC已氧化成氧化硅,同时反应层中还引入了杂质Fe、Na、Ca和Al;在反应层下Si以元素Si、SiC和氧化硅多种形式存在.块材横截面的多点小面积XPS分析结果表明,元素硅的相对浓度随深度增加而减少, SiC的相对浓度则随深度增加而增加.块材横截面的成象XPS分析清楚地显示了SiC 在纤维束边界间呈大致均匀的分布,在块材两边元素Si的浓度明显偏高.根据XPS象的线性扫描结果估计了纤维束、束间SiC层和块材边缘元素Si富集层的厚度.     

基于UFLC－IT－TOF MS分析技术的妇科再造丸化学成分研究

大品种妇科再造丸由42味中药组成,对多种妇科疾病具有显著疗效。但其组方复杂,化学成分尚未被充分阐明,质量控制水平较低。该研究建立了一种采用超快速液相色谱－离子阱飞行时间质谱联用技术（UFLC－IT－TOF MS）快速鉴定妇科再造丸化学成分的方法,系统研究了其化学物质基础。采用COSMOSIL C18色谱柱（3.0 mm × 150 mm,2.6 μm）进行分离,以0.4%乙酸和乙腈为流动相梯度洗脱;采用电喷雾离子源（ESI）在正负离子模式下采集妇科再造丸MS1、MS2和MS3的碎片信息。通过推导质谱裂解规律,与对照品、文献数据和单味药材图谱比对等方式,共鉴定出155种化学成分,包括萜类成分47个,酚及酚酸类成分43个,黄酮类成分39个,生物碱类成分14个,苯酞类成分8个,其他类成分4个,其中133个成分首次在妇科再造丸中发现。该研究进一步阐明了妇科再造丸的化学成分组成,为其质量标准的提高及药效物质的阐明提供了丰富信息。     

丙二胺缩乙酰丙酮单席夫碱、咪唑金属配合物的XPS与电子结构分析

对6个丙二胺缩乙酰丙酮单席夫碱、咪唑（苯并咪唑）金属配合物进行了XPS分析，得到了配合物在生成过程中金属离子M(Cu^2 、Ni^2 、Co^2 ）的2p轨道、配位体N原子的1s轨道能级的变化道；观察到咪唑或苯并咪唑配位后，其环上另一个非配位的胺N原子向亚胺型N原子状态过渡。     

K-Pb-Tl-O复合氧化物的合成和电子结构的XPS研究

用熔盐阳极电沉积法合成了导电的复合氧化物K-Pb-Tl-O晶体.这些晶体具有纳米尺寸层状结构.用XPS对其进行了表征,并与相关的化合物进行了比较.实验表明,氧化物中的Pb和Tl都以高价态的单一价态存在,但电子结合能比相应的非导电低价化合物的低.该文用原子外弛豫效应解释了复合氧化物中的Pb和Tl的结合能的反常现象.讨论了它们的价电子结构与导电性的关系.     

金属有机骨架材料ZIF-8富集黄芩中黄芩苷的新方法

本工作旨在探索MOFs材料高效富集黄芩中黄芩苷的新方法,拓展MOFs在吸附领域的用途.溶剂热法合成了沸石咪唑酯骨架-8（ZIF-8）,并进行了结构表征,以确保其准确合成.研究了ZIF-8对黄芩苷的吸附规律和作用机理：ZIF-8对黄芩苷的吸附符合准二级动力学方程,平衡吸附数据符合Langmuir吸附等温模型.采用响应面法（RSM）得到优化后的最佳吸附参数,在此条件下,ZIF-8对黄芩中黄芩苷的吸附率高达98.22%,且对黄芩中其它成分吸附效果不显著,以pH 6.8的PBS溶液作解吸液,ZIF-8对黄芩苷的解吸率为62.46%,而黄芩苷的纯度由吸附前的21.55%提高到解吸后的64.27%,且ZIF-8在吸附前后稳定性良好,回收率达到83.50%.因此,ZIF-8在吸附纯化黄芩苷方面具有潜在的应用价值.     

氩离子刻蚀还原氧化铜的XPS研究

利用X射线光电子能谱(XPS)及氩离子刻蚀技术,通过改变氩离子枪的刻蚀模式,原位研究氩离子刻蚀对氧化铜的还原情况。结果发现在极其微弱的氩离子束流轰击下,CuO即被还原,刻蚀初期变化较大,之后达到稳恒状态。对Cu2p峰拟合,同时结合俄歇CuLMM峰变化,判定纯CuO经氩离子刻蚀后最终转变为氧化铜、氧化亚铜及少量单质铜的共存状态。研究结果将对氧化铜深度剖析中化学状态的判断具有重要参考价值。     

Interpretation of TOF-SIMS data based on information entropy of spectra

Time-of-flight secondary ion mass spectrometry (TOF-SIMS), when used for the analysis of complex material samples, typically provides data that are complicated and challenging to understand. Therefore, additional data analysis techniques, such as multivariate analysis, are often required to facilitate the interpretation of TOF-SIMS data. In this study, a new method based on the information entropy (Shannon entropy) is proposed as an indicator of the outline characteristics of an unknown sample, such as changes in the material within the sample and mixing conditions. The Shannon entropy values are calculated using the relative intensity of every secondary ion normalized to the total ion count and reflect the diversity of secondary ions in the spectrum. Mixed samples containing two organic electroluminescence materials of different ratios, multilayers of Irganox 1010, and other organic materials were employed to evaluate the utility of Shannon entropy in the analysis of TOF-SIMS data. The findings demonstrate that the Shannon entropy of a spectrum indicates differences in materials and changes in the conditions of a material in a sample without the need for peak identification or the knowledge of specific peaks corresponding to the materials in the sample.     

Study on the effect of collector and inhibitor acid on the floatability of collophane and dolomite in acidic media by TOF-SIMS and XPS

Most of the phosphate ore in southern China is contained within siliceous dolomite phosphate rock, and more than 90% of it is medium and low-grade collophane. Reverse flotation of carbonate gangue minerals (dolomite) from phosphate in acidic media is still the most economical method for the reduction of carbonate in collophane concentrates. It has been recognized that the collophane and dolomite in acidic media affect the surface properties of minerals, thereby affecting their flotation properties. In this paper, HCl and H₃PO₄ were used as regulators or inhibitors to study the flotation behaviour of collophane and dolomite. The inhibition mechanism of collophane and dolomite in two acid media was studied by time-of-flight secondary ion mass spectrometry (TOF-SIMS) and X-ray photoelectron spectroscopy (XPS) analyses. It was found that the addition of an inhibiting acid can partially depress the collophane and improve the flotation of dolomite, thus achieving their flotation separation, and the inhibition effect of H₃PO₄ on collophane is better than that of HCl. And it was found by TOF-SIMS analysis that the increase in acid concentration did not reduce the adsorption concentration of the collector, and the main reason for the inhibition was not the decrease in the adsorption concentration of the collector. The adsorption capacity of collector on dolomite surface with H₃PO₄ is greater than that with HCl. The XPS test indicated that metaphosphate (PO₃⁻¹) is the pivotal ion for depressing collophane under acid conditions.     

Influence of Basicity on the Formation of Cluster Ions/Adduct Ions for Organic Ammonium Halides by Positive Secondary Ion Mass Spectrometry

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XPS investigations of the electrochemical double layer on silver in alkaline chloride solutions

The electrochemical double layer on Ag in alkaline NaCl solutions was examined ex situ with X-ray photoelectron spectroscopy (XPS). The specimens were removed from the electrolyte with hydrophobic surfaces and under potential control. The potential dependent surface concentrations of the adsorbed anions (Cl⁻, OH⁻), cations (Na⁺), the surface excess charge and the amount of adsorbed water were determined and compared to the results obtained for acidic NaCl solutions. The distinct differeness found between both electrolytes were discussed in terms of a specific adsorption of hydroxide ions in the basic Cl⁻-electrolyte; i.e., the OH⁻-surface concentration has to be considered for a proper determination of the cationic excess charge and the potential of zero charge. In addition, the initial stages of silver (1) oxide formation were examined with XPS.     

In situ XPS and SIMS analysis of O2+ beam‐induced silicon oxidation

The chemical composition variation of silicon under 4 keV O₂⁺ ion beam bombardment at different incident angles was studied by in situ small‐area XPS. The changes in secondary ion profile (³⁰Si⁺, ⁴⁴SiO⁺, ⁵⁶Si₂⁺, ⁶⁰SiO₂⁺) during oxygen ion beam bombardment also have been monitored. We present a direct correlation of the changes in secondary ion depth profile with surface composition during sputtering. Evolution of the secondary ion profile obtained from SIMS shows similar trends with variation of oxygen concentration in the crater surface measured by XPS. It is shown that when the oxygen ion beam incidence angle is < 40° silicon dioxide is the dominant species on the crater surface and the matrix ion species ratio (MISR) value for ⁴⁴SiO⁺/⁵⁶Si₂⁺ is higher than for ³⁰Si⁺/⁵⁶Si₂⁺. For incidence angles of >40°, the formation of sub‐oxide is favoured and thus the MISR value for ⁴⁴SiO⁺/⁵⁶Si₂⁺ is lower than for ³⁰Si⁺/⁵⁶Si₂. At 40° bombardment there are similar amounts of SiO₂ and sub‐oxides present on the crater surface and the MISR values for ⁴⁴SiO⁺/⁵⁶Si₂⁺ and ³⁰Si⁺/⁵⁶Si₂⁺ are also similar. Copyright © 2004 John Wiley & Sons, Ltd.     

Characterization of bidentate phosphoryl compounds on soil particulates using SIMS

The presence of organic compounds as surface contaminants on particles can provide valuable data about the particles environment, but identification can be analytically challenging. This is true particularly for compounds that have the potential for strong surface binding, such as compounds capable of multidentate attachment. Direct analysis using time‐of‐flight secondary ion mass spectrometry was evaluated for characterization of soil particles contaminated with low concentrations of two bidentate organophosphoryl compounds, diphenyl‐N,N‐di‐n‐butylcarbamoylmethylphosphine oxide and tetraphenylmethylene diphosphine dioxide. Molecular ions were formed by cationization with H⁺ and alkali elements Na⁺ and K⁺ that are indigenous to the particle surface chemistry. Spectra generated from a contaminated calcareous soil were dominated by K⁺‐containing ions, whereas spectra from a sandy loam had more abundant Na⁺‐species. Cation‐bound dimers were also formed which favored incorporation of K⁺, and a unique aluminosilicate‐phosphoryl conjugate cation was also formed when the diphosphoryl ligand was present on the surface. The phosphoryl ligands also underwent fragmentation reactions, the course of which varied depending on the cation that was bound. Minimum detectable surface concentrations were evaluated and were in the 0.04–0.2 monolayer range, depending on the compound and soil particle matrix they was bound to. The ion signature was detected on soil particle surfaces for time periods exceeding six months, suggesting that the characterization approach could be used for environmental exposure history at times well beyond initial exposure. Copyright © 2009 John Wiley & Sons, Ltd.     

Probing the surface chemical structure of some novel poly(ortho esters) prepared with N-methyl and N-phenyl ethanolamine by time-of-flight secondary ion mass spectrometry (ToF-SIMS)

The surface chemical structures of a series of novel poly(ortho ester) homopolymer and copolymer films prepared using N-methyl- and N-phenyl-ethanolamine (MDE and PDE) have been investigated using time-of-flight secondary ion mass spectrometry (ToF-SIMS). Systematic fragmentation patterns were observed within the ToF-SIMS spectra up to m/z = 1600, which were readily interpreted in terms of the polymer structures. Cations were detected which could be assigned to structures arising from the diols, the ortho ester species and diads, triads etc. of the monomer, from both the homopolymer and the random portion of the copolymer chains. The analysis of the proposed ion structures suggested two major mechanisms of fragmentation based on the cleavage of the ortho ester bonds involving either the exocyclic or the endocyclic alkoxy group. The Tof-SIMS peak area ratios for ions diagnostic of the diols and the ortho ester species reflected the bulk copolymer composition in a semi-quantitative fashion. The observation of such relationships for high mass cations (up to m/z = 500) is particularly noteworthy and has not been reported previously. These studies allow a dramatic insight into the surface chemical structure of these poly(ortho esters), information which has formed the foundation of current investigations on the mechanisms of the acid-catalysed surface degradation of these polymers.