Corrosion behaviour of galvanized steel and electroplating steel in aqueous solution: AC impedance study and XPS

The efficiency of a new triazole derivative, namely, 2-{(2-hydroxyethyl)[(4-methyl-1H-1,2,3-benzotriazol-1-yl)methyl]amino}ethanol (TTA) has been studied for corrosion inhibition of galvanized steel and electroplating steel in aqueous solution. Corrosion inhibition was studied using electrochemical impedance spectroscopy (EIS). These studies have shown that TTA was a very good inhibitor. Data obtained from EIS show a frequency distribution and therefore a modelling element with frequency dispersion behaviour, a constant phase element (CPE) has been used. The corrosion behaviour of galvanized steel and electroplating steel in aqueous solution was also investigated in the presence of 4-methyl-1H-benzotriazole (TTA unsubstituted) by EIS. These studies have shown that the ability of the molecule to adsorb on the steel surface was dependent on the group in triazole ring substituent. X-ray photoelectron spectroscopy surface analysis with TTA shows that it chemisorbed on surface of galvanized steel and electroplating steel.     

X-ray photoelectron spectroscopy for surface film analysis in corrosion research

Surface films on metals and alloys often protect them from reaction with the environment, and hence a knowledge of their protective properties and composition could be invaluable for predicting their corrosion behaviour. XPS (x-ray photoelectron spectroscopy) could provide a quantitative analysis of the chemical composition, the nature of valence states and elemental distribution within the surface films. The present paper reviews the potential of this technique in corrosion studies. A brief review of the work done on the passivation of iron and iron-chromium alloys and on the inhibition studies on copper base alloys has been given. A few examples of investigations carried out at authors’ laboratory are also included. An attempt has been made to establish a correlation between the compositions of the films formed and corrosion behaviour of carbon steel in 10.5 pH lithium hydroxide solution and of Cu-Ni alloys and sacrificial Al-Zn-Sn alloys in synthetic sea-water.     

First stages of surface steel nitriding: X-ray photoelectron spectroscopy and electrical measurements

Quantitative and qualitative analysis techniques were employed to study the first stages of ultra-high vacuum plasma nitriding of the 42CrMo4 steel. At constant treatment temperature, maintained for all samples at about 360 °C, we have established the influence of treatment time on the chemical composition, thickness and electrical properties of the nitrided layer.In this purpose it was used a stacking atomic layer model describing the sample surface, which takes into account the attenuation depth of photoelectrons by the atomic monolayers. So, we have found that after 2 h of nitriding in laboratory conditions, 70% of the nitrided layer was composed of iron oxide. Also, I–V measurements indicate an influence of the nitride overlayer with increasing treatment time.     

Near surface composition of some alloys by X-ray photoelectron spectroscopy

Chemical compositions of the alloys of CuNi (Cu_0.10Ni_0.90, Cu_0.30Ni_0.70, Cu_0.70Ni_0.30) and BiSb (Bi_0.80Sb_0.20, Bi_0.64Sb_0.34, Bi_0.55Sb_0.45) are determined by X-ray photoelectron spectroscopy. The stoichiometries are determined and are compared with the bulk compositions. Possible sources of systematic errors contributing to the results are discussed. Errors arising out of preferential etching in these alloys have been investigated. It has been inferred from such studies that the preferential etching does not enrich the surface composition with a particular component for the two systems reported here. Quantitative results of CuNi system indicate that the surface regions of the Cu_0.70Ni_0.30 alloy is Cu-rich, although no such evidence is observed in case of BiSb system.     

沉积态铀薄膜表面氧化的X射线光电子能谱

含铀(U)薄膜在激光惯性约束聚变的实验研究中有重要的用途.研究其在不同气氛下的氧化性能可以为微靶制备、储存及物理实验提供关键的实验数据.通过超高真空磁控溅射技术制备了纯U薄膜及金-铀(Au-U)复合平面膜,将其在大气、高纯氩(Ar)气及超高真空度环境中暴露一段时间后,利用X射线光电子能谱仪结合Ar~+束深度剖析技术考察U层中氧(O)元素分布及价态,分析氧化产物及机理.结果显示,初始状态的U薄膜中未检测到O的存在.Au-U复合薄膜中的微观缺陷减弱了Au防护层的屏蔽效果,使其在3周左右时间内严重氧化,产物为U表面致密的氧化膜及缺陷周围的点状腐蚀物,主要成分均为二氧化铀(UO_2).在高纯Ar气中纯U薄膜仅暴露6 h后表面即被严重氧化,生成厚度不均匀的UO_2.在超高真空度环境下保存12 h后,纯U薄膜表面也发生明显氧化,生成厚度不足1 nm的UO_2.Ar~+束对铀氧化物的刻蚀会因择优溅射效应而使UO_2被还原成非化学计量的UO_(2-x),但这种效应受O含量的影响.     

Monolayer vs. multilayer self-assembled alkylphosphonate films: X-ray photoelectron spectroscopy studies

Combining functional organic self-assembled monolayers (SAMs) with conventional semiconductor materials is a key step in the development of integrated electronics-based devices. T-BAG (Tethering by Aggregation and Growth) has been shown to be a simple and reliable method to grow SAMs of alkylphosphonates on oxide surfaces. However, distinguishing SAMs from ultra-thin multilayers is a challenge for most conventional surface characterization techniques.Self-assembled films of octadecylphosphonic acid (ODPA) were deposited on oxide-covered silicon coupons, converted to the corresponding phosphonates, and characterized by high resolution angularly resolved X-ray photoelectron spectroscopy (XPS). It was our goal to distinguish among different bonding configurations for phosphorous in the phosphonate head groups, namely, mono-dentate, bi-dentate or tri-dentate interactions with the oxide surface, as well as to assess quantitatively the near-surface layer composition.We also present an innovative method that allows us to distinguish between monolayer and multilayer films of ODPA on silicon oxide surfaces. This method is based on differential surface charging effects in XPS. It was found that variation in the ODPA film thickness causes differential responses of various spectral characteristics to an electrical bias applied to the sample during XPS measurements. Both positive and negative applied biases were found to affect the carbon core-level (C1s) line-shape and intensity in the case of the multilayer ODPA film, whereas line-shapes and intensities of all XPS lines measured for the monolayer film were unaffected by the application of a dc bias in the ±30 V range.     

X-ray photoelectron spectroscopy study of the growth kinetics of biomimetically grown hydroxyapatite thin-film coatings

Hydroxyapatite (HA) thin-film coatings grown biomimetically using simulated body fluid (SBF) are desirable for a range of applications such as improved fixation of fine- and complex-shaped orthopedic and dental implants, tissue engineering scaffolds and localized and sustained drug delivery. There is a dearth of knowledge on two key aspects of SBF-grown HA coatings: (i) the growth kinetics over short deposition periods, hours rather than weeks; and (ii) possible difference between the coatings deposited with and without periodic SBF replenishment. A study centred on these aspects is reported. X-ray photoelectron spectroscopy (XPS) has been used to study the growth kinetics of SBF-grown HA coatings for deposition periods ranging from 0.5 h to 21 days. The coatings were deposited with and without periodic replenishment of SBF. The XPS studies revealed that: (i) a continuous, stable HA coating fully covered the titanium substrate after a growth period of 13 h without SBF replenishment; (ii) thicker HA coatings about 1 μm in thickness resulted after a growth period of 21 days, both with and without SBF replenishment; and (iii) the Ca/P ratio at the surface of the HA coating was significantly lower than that in its bulk. No significant difference between HA grown with and without periodic replenishment of SBF was found. The coatings were determined to be carbonated, a characteristic desirable for improved implant fixation. The atomic force and scanning electron microscopies results suggested that heterogeneous nucleation and growth are the primary deposition mode for these coatings. Primary osteoblast cell studies demonstrated the biocompatibility of these coatings, i.e., osteoblast colony coverage of approximately 80%, similar to the control substrate (tissue culture polystyrene).     

X-ray photoelectron and X-ray Auger electron spectroscopy studies of heavy ion irradiated C60 films

The influence of 200 MeV Au ion irradiation on the surface properties of polycrystalline fullerene films has been investigated. The X-ray photoelectron and X-ray Auger electron spectroscopies are employed to study the ion-induced modification of the fullerene, near the surface region. The shift of C 1s core level and decrease in intensity of shake-up satellite were used to investigate the structural changes (like sp² to sp³ conversion) and reduction of π electrons, respectively, under heavy ion irradiation. Further, X-ray Auger electron spectroscopy was employed to investigate hybridization conversion qualitatively as a function of ion fluence.     

Valence band and core level X-ray photoelectron spectroscopy of lead sulfide nanoparticle-polymer composites

Valence band and core level X-ray photoelectron spectroscopy (XPS) were used to probe lead sulfide (PbS) nanoparticle-polymer nanocomposites. Composite materials were prepared by trapping commercially available monodisperse 3 and 10 nm PbS nanoparticles in two polymers, the non-conducting polymer, polystyrene, and the conjugated polymer, poly(2-methoxy-5-(2′-ethyl-hexyloxy)-p-phenylene vinylene (referred to below as MEH-PPV). The nanocomposites prepared from commercial nanoparticles underwent oxidation, mainly to form lead sulfate. However, the narrow size distributions of the commercial nanoparticles allowed observation of distinct changes in the valence band from the 3 to 10 nm nanoparticles. Nanocomposites of 2-5 and 4-7 nm PbS nanoparticles were synthesized by growing the particles in poly(vinyl alcohol) (referred to below as PVA) and MEH-PPV, respectively. These composites both indicated the formation of lead sulfide nanoparticles. Furthermore, the XP spectra for the PVA/PbS composite displayed bonding between the PbS nanoparticles and the polymer while MEH-PPV showed no PbS-polymer bonding. The nanoparticles synthesized in MEH-PPV did not undergo oxidation. The particle size distributions of the synthesized nanoparticles were too broad to display size-dependent changes in the valence band.     

双原子填充式skutterudite化合物的结构及X射线光电子能谱分析

用高温熔融、淬火、扩散退火结合放电等离子烧结(SPS)法合成了Ca和Ce复合填充的单相Ca_mCe_nFe_xCo_4-xSb₁₂(m=0.17—0.27，n=0.05—0.25，x=1.5)化合物，并结合Rietveld结构解析以及X射线光电子能谱(XPS)分析研究了两种原子复合填充skutterudite化合物的结构与填充状态.Rietveld结构解析表明，Ca_mCe_nFe_1.5Co_2.5Sb₁₂化合物具有skutterudite结构，Ca和Ce原子填充到了Sb的二十面体空洞中，填充原子热振动参数B_Ca/Ce远大于框架原子的热振动参数B_Fe/Co和B_Sb.XPS元素窄区谱分析结果表明，Sb原子在结构中有五种化学状态，每种化学状态的相对含量主要由总填充分数决定，填充原子Ca在Sb的二十面体空洞出现概率有三种可能，但在中心位置出现的概率最大. 关键词： skutterudite化合物 双原子复合填充 结构 X射线光电子能谱分析     

Valence-band offset of p-NiO/n-ZnO heterojunction measured by X-ray photoelectron spectroscopy

X-ray photoelectron spectroscopy was used to measure the valence-band offset (VBO) of the NiO/ZnO heterojunction grown on quartz substrate by radio frequency (RF) magnetron sputtering. Core levels of Ni 2p and Zn 2p were used to align the VBO of p-NiO/n-ZnO heterojunction. The valence-band offset (ΔEV) is determined to be 1.47 eV. According to the band gap of 3.7 eV for NiO and 3.37 eV for ZnO, the conduction-band offset (ΔEC) in the structure was calculated to be 1.8 eV, and it has a type-II band alignment.     

Hydrolysis-condensation reactions of titanium alkoxides in thin films: A study of the steric hindrance effect by X-ray photoelectron spectroscopy

An original approach based on X-ray photoelectron spectroscopy (XPS) is proposed to study the influence of the surrounding humidity on the hydrolysis-condensation reactions of five titanium alkoxides in thin films. More precisely, the influence of the nature of the ligands (propoxide, butoxide, isopropoxide, phenoxide, and 9H-carbazole-9-yl-ethyl-oxy) on the reaction rate was evidenced. The reaction advancement was evaluated by comparing XPS chemical compositions to theoretical compositions calculated for all the possible rates. XPS chemical environment information allowed validating the reliability of this approach through the evaluation of the condensation state. In both approaches, the influence of the steric hindrance on the reactivity of titanium alkoxides was highlighted to be similar to what has been previously observed in solution. Theses results corroborate the validity of our XPS approach to determine titanium alkoxide hydrolysis-condensation reactions in the specific application of thin films.     

Origin of the surface recombination centers in ZnO nanorods arrays by X-ray photoelectron spectroscopy

The surface composition of as-grown and annealed ZnO nanorods arrays (ZNAs) grown by a two-step chemical bath deposition method has been investigated by X-ray photoelectron spectroscopy (XPS). XPS confirms the presence of OH bonds and specific chemisorbed oxygen on the surface of ZNAs, as well as H bonds on surfaces which has been first time observed in the XPS spectra. The experimental results indicated that the OH and H bonds play the dominant role in facilitating surface recombination but specific chemisorbed oxygen also likely affect the surface recombination. Annealing can largely remove the OH and H bonds and transform the composition of the other chemisorbed oxygen at the surface to more closely resemble that of high temperature grown ZNAs, all of which suppresses surface recombination according to time-resolved photoluminescence measurements.     

Establishment of equivalent circuits from electrochemical impedance spectroscopy study of corrosion inhibition of steel by pyrazine in sulphuric acidic solution

This paper describes the use of the electrochemical impedance spectroscopy technique (EIS) in order to study the corrosion inhibition process of steel in 0.5 M H₂SO₄ solution at the open circuit potential (OCP). Diethyl pyrazine-2,3-dicarboxylate (Prz) as a non-ionic surfactant (NS) inhibitor has been examined. The Nyquist diagrams consisted of a capacitive semicircle at high frequencies followed by a well-defined inductive loop at low frequency values. The impedance measurements were interpreted according to suitable equivalent circuits. The results obtained showed that the Prz is a good inhibitor. The inhibition efficiency increases with an increase in the surfactant concentration to attain 80% at the 5 × 10⁻³M. Prz is adsorbed on the steel surface according to a Langmuir isotherm adsorption model.     

低速高电荷态重离子辐照的GaN晶体表面X射线光电子能谱研究

利用低速高电荷态Xeq+和Pbq+离子对在蓝宝石衬底上生长的GaN晶体膜样品进行辐照,并利用X射线光电子能谱(XPS)对样品表面化学组成和元素化合态进行了分析.结果表明,高电荷态离子对样品表面有显著的刻蚀作用;经高电荷态离子辐照的GaN样品表面氮元素贫乏而镓元素富集;随着入射离子剂量和所携带电荷数的增大,Ga—Ga键相对含量增大;辐照后,GaN样品中Ga—Ga键对应的Ga3d5/2电子的束缚能偏小,晶格损伤使内层轨道电子束缚能向低端方向偏移.     

NiTi合金薄膜厚度对相变温度影响的X射线光电子能谱分析

采用X射线衍射和X射线光电子能谱实验手段对不同厚度的NiTi薄膜相变温度的变化进行了分析.结果表明在相同衬底温度和退火条件下,3?μm厚度的薄膜晶化温度高于18?μm厚度的薄膜.衬底温度越高,薄膜越易晶化,退火后薄膜奥氏体相转变温度As越低.薄膜的表面有TiO₂氧化层形成,氧化层阻止了Ni原子渗出;膜与基片的界面存在Ti₂O₃和NiO.由于表面和界面氧化层的存在,不同厚度的薄膜内层的厚度也不同,因而薄膜越薄,Ni原子的含量就越高.Ni原子的含量的不同会影响薄膜的相变温度. 关键词： NiTi合金薄膜 X射线衍射 相变 X射线光电子能谱     

Sb掺杂SrTio3透明导电薄膜的光电子能谱研究

用X射线光电子能谱和同步辐射光电子能谱研究了Sb掺杂的钙钛矿型氧化物SrTi1-xSbxO3(x=0.05,0.10,0.15,0.20)薄膜的电子结构.薄膜由紫外脉冲激光淀积在SrTiO3(001)单晶衬底上.该薄膜系列在可见光波段透明,透过率均超过90%.其导电性与掺杂浓度有关,当Sb掺杂浓度x=0.05时,薄膜显示金属型导电性.X射线光电子能谱和同步辐射光电子能谱研究结果表明,Sb掺杂在母化合物SrTiO3的禁带内引入了浅杂质能级和深杂质能级.浅杂质能级上的退局域化电子离化到导带中会产生一定的传导电 关键词： 光电子能谱 光学透过率 脉冲激光沉积薄膜     

X-ray photoelectron spectroscopy study of the passive films formed on thermally sprayed and wrought Inconel 625

There is a well known performance gap in corrosion resistance between thermally sprayed corrosion resistant coatings and the equivalent bulk materials. Interconnected porosity has an important and well known effect, however there are additional relevant microstructural effects. Previous work has shown that a compositional difference exists between the regions of resolidified and non-melted material that exist in the as-sprayed coatings. The resolidified regions are depleted in oxide forming elements due to formation of oxides during coating deposition. Formation of galvanic cells between these different regions is believed to decrease the corrosion resistance of the coating. In order to increase understanding of the details of this effect, this work uses X-ray photoelectron spectroscopy (XPS) to study the passive films formed on thermally sprayed coatings (HVOF) and bulk Inconel 625, a commercially available corrosion resistant Ni-Cr-Mo-Nb alloy. Passive films produced by potentiodynamic scanning to 400 mV in 0.5 M sulphuric acid were compared with air-formed films. The poorer corrosion performance of the thermally sprayed coatings was attributed to Ni(OH)₂, which forms a loose, non-adherent and therefore non-protective film. The good corrosion resistance of wrought Inconel 625 is due to formation of Cr, Mo and Nb oxides.     

X-ray photoelectron spectroscopy characterization of oxidated Si particles formed by pulsed ion-beam ablation

X-ray photoelectron spectroscopy (XPS) is used to probe oxidation states of Si species in particles deposited using a pulsed ion-beam evaporation method. The effects of He ambient gas, ion beam intensity and post-treatments on the oxides composition and oxygen content have been studied. It is found that presence of He ambient gas led to a profound oxidation of Si species as compared to that prepared in vacuum at the same ion-beam ablation energy, i.e. both increase of SiO₂ component and oxygen concentration in the oxides coverage. The deposition in He also resulted in an increase of oxygen concentration even under lower ablation intensity, but a higher Si suboxides concentration. It is revealed that the reaction between Si and O was controlled by the ion beam intensity (temperature of Si plasma) and the gas ambient (collision probability of Si and O species). The difference in structure of oxide layers for samples obtained under various conditions is discussed based on the results of XPS analyses.     

Surface oxidation of NiCo alloy: A comparative X-ray photoelectron spectroscopy study in a wide pressure range

Oxidation of NiCo alloy has been studied under two pressure regimes, 5 × 10⁻¹⁰ and 5 × 10⁻¹ bar, by X-ray photoelectron spectroscopy (XPS). The aim of this work is to investigate the synergetic effect between the two alloy components during the initial stages of oxidation. The results showed that at low oxygen pressure, segregation and preferential oxidation of cobalt takes place, while oxidation of nickel is largely suppressed. The species dominating the surface is CoO but small amount of metallic cobalt still remains even after prolonged oxidation at 670 K. At 0.5 bar O₂ pressure, alloy oxidation was found to be temperature depended. From 420 K to 520 K, cobalt is completely transformed to CoO and the Ni:Co atomic ratio at the surface approaches a minimum, similar to the observations at low pressure regime. However, at higher temperatures (from 520 K to 720 K), nickel is re-segregated on the surface, in the expense of cobalt, while CoO is further oxidized to Co₃O₄. At this temperature range formation of mixed Ni-Co-O spinel-like oxides is probable as supported by the characteristic modifications of the Ni 2p_3/2 photoelectron peak and the increase of the Ni:Co atomic ratio.