X射线光电子能谱技术在高分子材料摩擦化学研究中的应用

X射线光电子能谱技术(XPS)是材料表面分析的重要手段,其近年的快速发展促进了表面化学领域研究的深入.高分子及其复合材料在摩擦学性能方面具有普遍的优势,通过XPS对高分子及其复合材料摩擦表面的分析,可以确定摩擦过程的化学变化,并对改进材料的摩擦学性能起到理论的指导作用.作者主要介绍XPS技术的基本原理,及其在高分子与复合材料摩擦学性能研究中的应用.     

聚ε-己内酯/聚氯乙烯球晶表面的XPS研究

聚合物薄膜在微电子领域中的应用日益增加.聚ε-己内酯/聚氯乙烯（PCL/PVC）是研究得最广泛的聚合物共混薄膜之一.PCL与PVC以一定比例混合时,可以形成环带球晶；同时,体系分为结晶PCL相及PCL/PVC非晶混溶相.用XPS和成象XPS分析技术,对PCL/PVC膜的表面化学组成和元素分布情况进行了研究.观察到PCL在薄膜表面富集.此外,成象XPS表明,PVC在球晶边界处富集,且球晶边界宽度约15 μm.     

X射线光电子能谱仪的开放使用与管理

X射线光电子能谱仪(XPS)是材料表面元素定性和半定量分析的重要手段之一,是表面分析科研工作的必备仪器.为提高测试效率,实施了大型仪器设备开放共享优化,总结了在推动XPS开放过程中管理的经验和体会.     

铅铈和铅钙锡合金阳极腐蚀膜的性能研究

利用叠加交流伏安法、线性电位扫描法、交流阻抗技术和XPS研究了铅铈合金和铅钙锡合金在阳极1.28 V, 4.5 mol/L的硫酸溶液中所形成的阳极腐蚀膜. 结果表明: 稀土铈能抑制阳极膜中高阻抗的Pb(II)化合物的生长, 降低腐蚀膜的阻抗, 并增加膜的孔隙率. 同时可以提高合金的析氢过电位, 有利于电池免维护性能的提高.     

XPS光电子峰和俄歇电子峰峰位表

在长期从事XPS分析测试的经验基础上,搜集了有关文献中的大量数据,编制了XPS光电子峰和俄歇电子峰峰位表,用于正确识别各种样品XPS谱图中的电子峰,达到快速、正确分析各种样品元素组成和化学组成的目的．本峰位表对于从事XPS测试的分析人员和应用XPS的科技人员具有很好的实用价值．     

磁透镜引起的氯化银谱峰异常位移及其在X射线光电子能谱成象分析中的应用

用X射线光电子能谱（XPS）分析了与样品托有良好电接触的银片及其上面的AgCl。观察到在使用样品磁透镜和非单色化X射线源的实验条件下不导电的AgCl的电子峰产生异常大的谱峰位移,还发现这种异常谱峰位移可以应用于XPS成象分析,以提高化学位移很小的元素化学态（如Ag^0和Ag^ )的XPS象的分辨能力。     

钯/聚乙烯醇纤维膜催化水相中的Heck偶联反应

通过静电纺丝和热交联技术、以聚乙烯醇( PVA)作为载体制备了一种电纺纤维膜负载型钯催化剂.利用扫描电镜(SEM)、能谱仪(EDS)和X射线光电子能谱(XPS)对其进行了表征.SEM结果显示:PdCl2的加入导致PVA纤维直径增加、形貌变差,而热交联过程可以减小纤维直径、改善纤维形貌.XPS表征则表明PVA可以还原pd...     

非晶态合金催化剂研究

本文对非晶态合金催化剂的制备及在催化领域中的应用进行了评述.通过骤冷法、化学还原法、浸渍还原法可以得到满足不同催化反应需要的非晶态合金催化剂,并可以通过制备条件的变化调变催化剂的性能.制备过程中焙烧温度、负载量以及不同催化剂载体的选用都会影响所得催化剂的性能.非晶态合金催化剂的非晶态结构、表面形态、活性中心分布等可以通过XRD、EXAFS、DSC、SEM、TEM、XPS等方法进行表征、定性.对于非晶态合金催化剂在含有不饱和基团化合物加氢反应中的研究、应用进行了阐述.     

正负压一体式无空气X射线光电子能谱原位转移仓的开发及研制

针对空气敏感材料的表面分析,为了获得更加真实的表面组成与结构信息,需要提供一个可以保护样品从制备完成到分析表征过程中不接触大气环境的装置.通过使用O圈密封和单向密封柱,提出一种简便且有效的设计概念,自主研制了正负压一体式无空气X射线光电子能谱(XPS)原位转移仓,用于空气敏感材料的XPS测试,利用单向密封柱实现不同工作需求下正负压两种模式的任意切换.通过对空气敏感的金属Li片和CuCl粉末进行XPS分析表明,采用XPS原位转移仓正压和负压模式均可有效避免样品表面接触空气,保证测试结果准确可靠,而且采用正压密封方式转移样品可以提供更长的密封时效性.研制的原位转移仓具有设计小巧、操作简便、成本低、密封效果好的特点,适合给有需求的用户开放使用.     

羟基磷灰石中氢键的XPS考察

羟基磷灰石[Ca_(10)(OH)_2(PO_4)_6].是一种具有良好生物活性的人工骨材料.它的结构和其中的氢键已被许多人研究.但对OH~-离子是否以氢键存在和氢键存在的形式仍有争论. 分子中处于不同化学环境的同种原子,其芯能级的电子结合能呈现出不同的化学位移.林安等根据羧基形成氢键时引起C_(1s)结合能的化学位移,用X射线光电子能谱(XPS)研究了聚乙烯接枝丙酸的氢键,表明用XPS并配合IR来研究氢键是可行的.Landis等对包括羟基磷灰石在内的一些磷酸钙矿物进行了较系统的XPS测定,但并未对氢键的存在进行任何讨论. 本文用XPS对几种正磷酸钙盐进行表征,并以IR配合考察羟基磷灰石中的OH~-是否以氢键形式存在和氢键的形式.     

射频等离子沉积聚硅氧烷薄膜的XPS研究

用CVD方法在一台射频放电等离子体聚合实验装置内成功地制备了沉积聚酯薄膜基底有机聚硅氧烷薄膜.该薄膜在有原子氧模拟实验装置内具有抗原子氧剥蚀的良好性能,对航天器等材料表面起到防护作用.有机聚硅氧烷薄膜与等离子体沉积时氧的泄露量有关,且沉积密度经AFM检测有较大的差异.并用XPS较详细考察了不同工艺制备的聚硅氧烷官能团构成和表面状态,以期得到优良的防剥蚀膜.     

Functionalization of Biodegradable Polyester for Tissue Engineering Applications

Summary: Chemical modification of polymer surface may potentially be used to create smart materials that can guide cellular adhesion, proliferation and maintenance of specific expression of molecules. The microbial polyester poly (3-hydroxybutyrate) (PHB) has been attracted attention as promising material for applications in tissue engineering. In this work, a wet-chemical method, base ethylenediamine aminolysis, was performed to improve the adhesion of chondrocytes isolated from human articular cartilage to PHB films. The effects of chemical treatment on PHB films was evaluated by following changes in morphology and surface chemical composition using atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS), respectively. While the effect on cells morphology was studied by scanning electron microscopy (SEM). The treatment with ethylenediamine did not change significantly the morphology of the structures of PHB films surface. However, the roughness of the aminolyzed films was slightly higher. The introduction of nitrogen-containing groups was confirmed by XPS. In vitro experiments indicated that the surface modification did not have toxic effects in cells, since they could adhere and proliferate on modified PHB films. It was observed that long-time treatment improved ability of PHB films to support cell growth, which could be accounted to physicochemical and topological effects.     

Monitoring Fibre Surfaces with XPS in Papermaking Processes

 Recent instrumental advances have vastly improved the analysis power of X-ray photoelectron spectroscopy (XPS), which has been widely used in applied surface research for decades. In this presentation a set of XPS analysis methods well suited for problems and analytical needs encountered in papermaking technology is presented. The emphasis will be on analysis of pulps and non-coated papers. Examples given describe the use of XPS in quantification of surface lignin and extractives; an alternative approach for evaluating elemental surface distributions via the Tougaard background analysis is also presented. The experimental work and interpretations presented are based on more than two thousand XPS analyses performed at Helsinki University of Technology during 1996–2000. With strictly standardised experimental setup, state-of-the-art instrumentation and a proper combination of analysis methods XPS can yield valuable and consistent information on surface properties of natural fibers.     

Tailoring the surface chemistry of carbon fiber and E‐glass composites for improved adhesion

The main challenges in the manufacture of composite materials are low surface energy and the presence of silicon‐containing contaminants, both of which greatly reduce surface adhesive strength. In this study, carbon fiber (CF) and E‐glass epoxy resin composites were surface treated with the Accelerated Thermo‐molecular adhesion Process (ATmaP). ATmaP is a multiaction surface treatment process where tailored nitrogen and oxygen functionalities are generated on the surface of the sample through the vaporization and atomization of n‐methylpyrrolidone solution, injected via specially designed flame‐treatment equipment. The treated surfaces of the polymer composites were analyzed using XPS, time of flight secondary ion mass spectrometry (ToF‐SIMS), contact angle (CA) analysis and direct adhesion measurements. ATmaP treatment increased the surface concentration of polar functional groups while reducing surface contamination, resulting in increased adhesion strength. XPS and ToF‐SIMS showed a significant decrease in silicon‐containing species on the surface after ATmaP treatment. E‐glass composite showed higher adhesion strength than CF composite, correlating with higher surface energy, higher concentrations of nitrogen and C?O functional groups (from XPS) and higher concentrations of oxygen and nitrogen‐containing functional groups (particularly C₂H₃O⁺ and C₂H₅NO⁺ molecular ions, from ToF‐SIMS). Copyright © 2010 John Wiley & Sons, Ltd.     

Low-temperature transformations of sodium sulfate and sodium selenite in the presence of pre-reduced palladium modifier in graphite furnaces for electrothermal atomic absorption spectrometry

The low-temperature interaction (up to 550°C) of a pre-reduced palladium modifier with sodium sulfate and sodium selenite on the pyrolytic graphite platform was studied using X-ray photoelectron spectroscopy (XPS) and electron microprobe analysis. The equipment applied allowed the introduction of samples heated in an argon flow into the analytical chamber of the XPS spectrometer without contact with the air. Electron microprobe analysis showed that palladium and sulfur preferably occupy different areas on the platform surface. On the contrary, selenium from sodium selenite tends to occupy areas of the graphite surface covered with palladium. The most probable reason for this is the chemisorption of selenium (IV) on the palladium surface at the drying stage. No changes in the XPS spectra of metallic Pd and S⁶⁺ were observed when Na₂SO₄ and Pd were heated together on the graphite platform in the range 100–550°C. The reduction of sodium selenite on the graphite surface already starts during drying. Pre-reduced palladium intensifies this process. The rate of the reduction is proportional to the amount of palladium, and in the presence of palladium at an atomic ratio of Pd/Se=7.5, the transformation of Se⁴⁺ into Se⁰ completes at 250°C.     

Surface and Interface Chemistry in Colloidal Quantum Dots for Solar Applications Studied by X‐Ray Photoelectron Spectroscopy

Control of the surface and interface chemistry of colloidal quantum dots (CQDs) is critical to achieving a product with good air stability and high performing optoelectronic devices. Through various surface passivation treatments, vast improvements have been made in fields such as CQD photovoltaics; however devices have not currently reached commercial standards. We show how X‐ray photoelectron spectroscopy (XPS) can provide a better understanding of exactly how surface treatments act on CQD surfaces, and the effect of surface composition on air stability and device performance.. We illustrate this with PbS‐based CQDs, using XPS to measure oxidation processes, and to quantify the composition of the topmost surface layer after different surface treatments. We also demonstrate the use of synchrotron radiation‐excited depth‐profiling XPS, a powerful technique for determining the surface composition, chemistry and structure of CQDs. This review describes our recent progress in characterization of CQD surfaces using SR‐excited depth profiling XPS and other photoemission techniques.     

XPS and ISS analysis of Fischer-Tropsch catalysts

Summary The surface compositions of K and Cu containing Fe/Mn oxide catalysts for Fischer-Tropsch synthesis were investigated by XPS and ISS. The surface species after calcination are identified as Fe₂O₃, Mn₂O₃, MnO₂, CuO and most likely KO₂, and after in situ reduction at 723 K Fe⁰, Cu⁰, Fe²⁺ and Fe³⁺ oxides, MnO and KOH. Mn and K are enriched on the surfaces after calcination and reduction; the Cu surface content is approximately equal to the bulk concentration. The K enrichment is especially strong and ISS indicates that potassium is mainly confined to the uppermost layers. The degree of reduction of Fe is strongly dependent on the amount of Cu or K. The change in surface composition during Fischer-Tropsch reaction in the XPS equipment can be correlated to the activity of the catalysts. The pure and Cu containing samples show a constant activity and only a small increase in carbon surface concentration. The K containing catalysts deactivate after a short time and are then totally covered by carbon. On all catalyst surfaces a small amount of carbonate is formed.

---

XPS- and ISS-Analyse von Fischer-Tropsch-Katalysatoren

     

摩擦条件下硫脲对1Cr18不锈钢电化学行为的作用

控制金属材料的腐蚀或磨损有三种方法：１）合理选用耐蚀金属材料（包括开发新材料或对材料进行适宜的表面强化处理;２）改善金属材料服役的介质环境（包括合理使用缓蚀剂）;３）采取电化学保护措施．由于在腐蚀介质中工作的各种摩擦副往往受腐蚀与磨损的协同作用而发生...     

Surface modification of EPDM rubber by plasma treatment

The effect of argon, oxygen, and nitrogen plasma treatment of solvent cast EPDM rubber films has been investigated by means of atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and surface energy measurements. Plasma treatment leads to changes in the surface energy from 25 to 70 mN/m. Treatment conditions influenced both the changes in surface energy and the stability, and it became more difficult to obtain good contact angle measurements after longer (> ca. 4 min) treatment times, probably because of an increasingly uneven surface structure. XPS analyses revealed that up to 20 at. % oxygen can be easily incorporated and that variations of approximately 5% can be controlled by the plasma conditions. Oxygen was mainly found in hydroxyl groups, but also as carbonyl and carboxyl. XPS analyses showed more stable surfaces than expected from contact angles, probably because XPS analysis is less surface sensitive than contact angle measurements. AFM measurements revealed different surface structures with the three gases. The surface roughness increased generally with treatment time, and dramatic changes could be observed at longer times. At short times, surface energy changes were much faster than the changes in surface structure, showing that plasma treatment conditions can be utilized to tailor both surface energies and surface structure of EPDM rubber.     

Application of XPS and ToF-SIMS for surface chemical analysis of DNA microarrays and their substrates

The chemical composition of the functional surfaces of substrates used for microarrays is one of the important parameters that determine the quality of a microarray experiment. In addition to the commonly used contact angle measurements to determine the wettability of functionalized supports, X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) are more specific methods to elucidate details about the chemical surface constitution. XPS yields information about the atomic composition of the surface, whereas from ToF-SIMS, information on the molecular species on the surface can be concluded. Applied on printed DNA microarrays, both techniques provide impressive chemical images down to the micrometer scale and can be utilized for label-free spot detection and characterization. Detailed information about the chemical constitution of single spots of microarrays can be obtained by high-resolution XPS imaging. Figure Eye-catching image for the graphical online abstract