Surface analytical examinations of welded nickel alloys by XPS, SNMS and SEM/EDX

Tarnish layers are formed in the heat affected zone during the welding of steels and nickel based alloys. They commonly consist of oxides of the alloying elements. The corrosion behaviour of welded components is generally influenced by the thickness and composition of the oxide films. In the following the corrosion behaviour of annealed samples cut from NiMo28 and NiMo16Cr16Ti is investigated, correlating XPS, SNMS and SEM/EDX data to their pitting corrosion potentials.Dedicated to Professor Dr. rer. nat. Dr. h.c. Hubertus Nickel on the occasion of his 65th birthday     

Surface properties of metal alloys used in aviation after plasma treatment

The metal alloys: aluminum AMS 4037, 4041, 4049, carbon steel AMS 5045, titanium alloy AMS 4911 and cadmium steel used in aviation were treated by air and argon plasmas. For their activation, low pressure plasma was used. Surface treatment caused a significant increase of wettability due to the increasing surface roughness and introduction of polar functional groups onto the surface. Changes of surface properties are reflected by the value of electron donor parameter of apparent surface energy. Copyright © 2017 John Wiley & Sons, Ltd.     

XPS study of Cr segregation in a martensitic stainless steel

Cr martensitic steels are promising materials for structural applications in future nuclear fusion reactors. Because the embrittlement after tempering treatments can be a serious problem, the fracture mode of a steel with 10.5 wt% of Cr treated at 700°C for 18 h has been investigated through Charpy tests in the temperature range from −100°C to +150°C. X-ray photoelectron spectroscopy (XPS) analyses carried out on the fracture surfaces evidenced the segregation of Cr in both ductile and brittle (quasicleavage) fields. The unexpected result indicates that Cr segregation weakens the atomic bonds; thus, the fracture path in both the cases corresponds to the zones with higher Cr content.     

Surface analysis of corrosion inhibitor films by XPS and ToFSIMS

In recent years developments in the capabilities of techniques such as XPS and static SIMS have led to wider application of these methods for the characterisation of industrial materials. After a brief discussion of recent key developments of these techniques, this paper presents a selection of results from research work at our laboratory in the characterisation of organic film-forming corrosion inhibitors on a range of metal substrates which illustrate the nature of the information available. The inherent advantage ofsurface sensitivity and the advantages of a multi-technique approach for the evaluation of surface molecular structure from complex organic compounds is discussed. The additional benefits for analysis offered by the latest developments in technique are also demonstrated.     

Effect of phosphorus concentration on the electronic structure of nanocrystalline electrodeposited Ni–P alloys: an XPS and XAES investigation

A surface analysis has been conducted on a series of electrodeposited nickel‐phosphorus (Ni–P) alloys containing from 6 to 29 at.% phosphorus, using X‐ray photoelectron spectroscopy (XPS) and X‐ray excited Auger electron spectroscopy (XAES). No changes in core‐level binding energies, Ni2p3/2 and Ni2p1/2, P2p, P2s, or X‐ray excited NiLMM and PKLL Auger lines were observed regardless of phosphorus concentration. The only systematic differences observed concerned: (i) the binding energy of the Ni2p satellite peak, (ii) the fine structure of the NiLMM Auger lines, (iii) the percentage of the satellite in the total Ni2p3/2 spectrum and (iv) the valence band density of states in the Ni3d electrons region, all related to the electronic structure of the Ni–P alloys. For the first time, it has been possible to describe and rationalise the influence of (phosphorus) ligand concentration on the electronic structure of nickel‐based alloys, using a screening model proposed in the literature for clarifying the role of substituents on the electronic structure of conductor compounds of nickel. As the phosphorus content increases, the number of non‐bonding Ni3d electrons decreases. Thus the d‐type core‐hole screening is less pronounced and the binding energy of the satellite for the final state with a filled Ni4s shell increases. Copyright © 2008 John Wiley & Sons, Ltd.     

Comparative thermodynamic study and characterization of ternary Ag-In-Sn alloys

The results of thermodynamics and characterization of alloys in ternary Ag-In-Sn system is presented in this paper. Thermodynamic properties, in three investigated sections with molar ratio In:Sn=1:1, 1:2 and 1:4, have been calculated at the temperature of 1423 K using different predicting methods (general solution model, Toop, Hillert, Muggianu, Kohler, Redlich-Kister), compared mutually and with literature experimental data. The alloys in investigated sections have been characterized using DTA, XRD, SEM and optic microscopy.     

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。     

XPS study of silicon spheres as a density standard

As density is one of the basic physical properties of materials, an accurate density standard is absolutely essential. To determine density with high accuracy and precision, two 1-kg single-crystal silicon spheres (NMIJ-S4 and NMIJ-S5) are used as the primary standard at the National Metrology Institute of Japan. For the accurate measurement of the mass and volume of the silicon spheres, the effects of the surface layer must be carefully considered. In this work, a surface layer model of NMIJ-S4 and NMIJ-S5 was proposed and the thicknesses of each surface layer were determined using X-ray photoelectron spectroscopy. A detailed uncertainty budget is presented to aid use of the density standard.     

XPS and ToF‐SIMS characterization of a Finemet surface: effect of cooling

The surface composition of amorphous Finemet, Fe₇₃Si_15.8B_7.2Cu₁Nb₃, was studied by X‐ray photoelectron spectroscopy (XPS) and time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS). The as‐received sample in the original state and after Ar⁺ sputter‐cleaning was analyzed at room temperature as well as after cooling to ? 155 °C. In the cooled state, the surface oxide layer composed of oxides of the alloy constituents was found to become enriched with elemental iron and depleted of elemental silicon, boron, oxygen and carbon as compared to the state at room temperature. Interaction of residual water vapor and hydrogen with the complex oxide layer occurring at low temperatures is believed to be responsible for the enhanced formation of surface hydroxides of the alloy constituents. The processes resulting in the observed redistribution of the elements on the surface of Finemet at low temperatures are discussed. Copyright © 2006 John Wiley & Sons, Ltd.     

镁基储氢合金的表面处理和表面催化

表面处理作为储氢合金性能改善的有效手段，近年来得到了很好的发展和应用，本文简要介绍了镁基储氢合金表面处理的主要方法及其对合金性能的影响。     

Surface characterization of cellulose fibres by XPS and inverse gas chromatography

Inverse gas chromatography (IGC) was used to determine the dispersive component of the free energy as well as the acid-base properties of cellulose fibre surfaces, before and after modification by corona treatment. It was found that the corona treatment increases both the dispersive contribution to surface energy and its acidic character, whereas only a slight increase in its basicity was observed. It was also found that some chemical degradation of the surface occurs at high corona currents. The extent of modification of the surface properties, as revealed by IGC, was correlated to the surface chemical composition deduced from XPS analysis as well as with the electrical conductance and the pH of the water suspensions of the cellulose fibres.     

Surface characteristics of titanium–silver alloys in artificial saliva

Titanium and its alloys are widely used in biomedical and dental fields because of their excellent corrosion resistance and biocompatibility. It is well known that titanium is protected from corrosion because of the stability of the passive film that controls and determines the corrosion resistance and biocompatibility of titanium and its alloys. The purpose of this study was to evaluate the electrochemical properties of titanium–silver alloys and the surface characteristics of passive film in artificial saliva. We designed titanium–silver alloys with silver contents ranging from 0 to 5 at.%, in 1% increments. These alloys were arc‐melted, homogenized, hot‐rolled to 2 mm thickness, and finally solution heat‐treated for 1 h and quenched. Potentiostatic testing was performed, and the open circuit potentials of the alloys were measured in artificial saliva, at 37 °C. The passive films of the titanium–silver alloys were analyzed via XPS. Titanium–silver alloys maintained low current density and showed stable passive region and also had high open circuit potential as compared with pure titanium. The open circuit potential of titanium–silver alloys increased as silver addition increased. With regard to the fraction of oxygen species, a component of over 80% was found to be comprised of oxide. Therefore, the titanium surface mainly consisted of titanium oxide and, on the titanium–silver alloys, this film was composed of TiO₂, Ti₂O₃, and TiO. As silver content increased, the TiO₂ fraction also increased, as did the thickness of the titanium oxide layer formed. Copyright © 2005 John Wiley & Sons, Ltd.     

Surface Fluorination of Carboxylated Nitrile Butadiene Rubber: An XPS Study

Because of their exceptional reactivity, fluorine and fluorinated gases are of primary importance for the modification of the surface properties of materials. This study is devoted to surface treatment of thin nitrile gloves, made of carboxylated nitrile butadiene rubber latex, using either direct fluorination (10% F₂gas diluted in N₂) or plasma-enhanced fluorination in radio-frequency cold plasmas using fluorinated gases (CF₄, CHF₃). Mechanisms of fluorination of these co-elastomers have been proposed on the basis of the assignment of the different components of the XPS spectra. Several mechanisms have been observed depending on the fluorination conditions. Although the modification of nitrile gloves is already effective for fluorination reactions at room temperature, an important activation is observed for experiments carried out at 90°C. When the treatments are carried out at room temperature, a gradual fluorination occurs: in the case of 10% diluted F₂ gas, monofluorinated C—F groups are the species most found at the surface and perfluoro groups CF _n are present in lower amount. An addition reaction takes place at the CH=CH double bonds of the polybutadiene entities, leading to CHF=CHF units. Whatever the fluorination method, thermal activation yields a more massive fluorination of the surface that finally leads to perfluorinated CF₂ groups and terminal —CF₃ groups.     

XPS and ToF‐SIMS characterization of a Finemet surface: effect of heating

X‐ray photoelectron spectroscopy (XPS) and time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) were used to study the surface composition and electronic structure of Finemet, Fe₇₃Si_15.8B_7.2Cu₁Nb₃, in the original amorphous state and after gradual heating in vacuum to a temperature of 400 °C and cooling back to room temperature. It was found that relaxation processes occurring during heat treatment well below the crystallization onset caused the physico‐chemical state of Finemet surface to change irreversibly. In the relaxed alloy, the surface originally covered with the native air‐formed oxide was significantly enriched with elemental iron and depleted of other alloy constituents compared with the original state. Yet in the as‐quenched state, clustering of copper atoms on the Finemet surface was detected which was enhanced by heating. The thermal treatment resulted in the selective reduction of iron oxides and caused noticeable changes in the valence band structure and the Fe L₃VV Auger spectrum associated with atomic redistribution. Copyright © 2009 John Wiley & Sons, Ltd.     

Surface composition of alloys

The practical importance of alloy surfaces in catalysis, corrosion andother aspects of materials performance is widely recognized. What is needed now is sufficient knowledge of the relationship between externally controllable factors — alloy composition, temperature, environment — and surface properties — composition, structure, chemical activity — to control materials performance in these applications. Our purpose here is to review progress in determining and predicting the relationship between one surface property, composition, and certain externally controllable variables: overall composition, temperature, environment and physical form.We find that theoretical treatments of metal alloy surface composition now include essentially all significant physical effects and can predict values for most parameters of interest. Though improvements are still possible, the accuracy of predictions is more often limited by uncertainties or absence of the basic data for the calculations (e.g., thermochemical values) than by the models themselves.Alloy surface composition can now be measured well. The first monolayercomposition of large alloy slabs can be determined quantitatively over a wide temperature range in ultra-high vacuum. Difficulties with specimens of practical interest still challenge experimentalists. Among these are supported catalysts, surfaces under chemisorbed layers and composition of layers below the first. Significant progress is being made and we expect the next few years will see success.     

XPS investigation of the composition of the external surface of concrete after demoulding,cleaning and carbonation

X‐ray photoelectron spectroscopy (XPS) coupled with ion beam etching allows the measurements of concentrations gradients at the external surface of concrete. The chemical modifications, caused by the moulding and cleaning operations and due to carbonation, are efficiently investigated. Based on the detection of specific elements (such as chlorine, carbon and silicon), the presence of formworks residues is established on the concrete surface. Similarly, aliphatic (C –(C,H) and carbonaceous (C –O) residues of the demoulding agent can be detected. The concentration gradients show the presence of moulding residues is mainly superficial and decreases rapidly according to the depth. However, certain of these contaminants (and especially polydimethylsiloxane residues) could alter the wetting of aqueous‐based coatings. The sandblasting process can partially remove the moulding residues, but the decontamination remains incomplete in spite of the high increase of the roughness of the samples. On the contrary, the concentrations in aliphatic and carbonaceous residues increase after cleaning with solvents, which can be trapped in the pores of concrete to contaminate the surface. The carbonation process is also investigated by XPS. The concentration gradient of the carbonate component of the C 1 s peak shows a front of carbonation progressing as a function of the time after demoulding. Copyright © 2012 John Wiley & Sons, Ltd.     

Oxygen states during thermal decomposition of Ag2O: XPS and UPS study

Using photoemission XPS and UPS methods, we have studied the oxygen states in the silver metal lattice during the thermal decomposition of Ag₂O. It has been shown that one half of the lattice oxygen inside subsurface layers of Ag₂O is transformed to subsurface oxygen in metallic silver characterized by a quasimolecular structure. Thermal annealing up to 1000 K did not result in the removal of the residual subsurface oxygen.     

Surface film formation on a graphite electrode in Li‐ion batteries: AFM and XPS study

The formation of a passivation film (solid electrolyte interphase, SEI) at the surface of the negative electrode of full LiCoO₂/graphite lithium‐ion cells using LiPF₆ (1M ) in carbonate solvents as electrolyte was investigated by means of x‐ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). The analyses were carried out at different potentials of the first and the fifth cycles, showing the potential‐dependent character of the surface‐film species formation. These species were mainly identified as Li₂CO₃ up to 3.8 V and LiF up to 4.2 V. This study shows the formation of the SEI during charging and its partial dissolution during discharge. Copyright © 2005 John Wiley & Sons, Ltd.     

Segregation of Sn in the binary CuSn and ternary CuSnSb alloy systems

Progression studies have been followed from Cu(111)‐ and Cu(100)Sn binaries to Cu(111)‐ and Cu(100)SnSb ternary‐alloy systems under the same experimental conditions. The segregation behaviour of Sn in the two orientations are explained. It is found that the kinetic segregation profiles of Sn in the ternary alloys shift to lower temperatures as compared to that in the binary. The Sn profile shift is mainly due to the decrease in the activation energy of Sn in the ternary systems. For a particular Cu orientation, the other segregation parameters that the Sn profiles depend on, like the pre‐exponential factor, segregation energy and the interaction coefficient, are found to be the same in the two systems. There is also a change in the equilibrium segregation profiles of Sn. In the ternary system, site competition between Sn and Sb causes the Sn to suffer exponential desegregation and eventual displacement from the surface. Copyright © 2006 John Wiley & Sons, Ltd.