Selective oxidation of dual phase steel after annealing at different dew points

Hot galvanized steels have been extensively used in the automotive industry. Selective oxidation on the steel surface affects the wettability of zinc on steel and the grain orientation of inhibition layer (Fe-Al-Zn alloy) and reduces the iron diffusion to the zinc layer. The aim of this work is to identify and quantify selective oxidation on the surface of a dual phase steel, and an experimental steel with a lower content of manganese, annealed at different dew points. The techniques employed were atomic force microscopy, X-ray photoelectron spectroscopy, and glow discharge optical emission spectroscopy. External selective oxidation was observed for phosphorus on steel surface annealed at 0 °C dp, and for manganese, silicon, and aluminum at a lower dew point. The concentration of manganese was higher on the dual phase steel surface than on the surface of the experimental steel. The concentration of molybdenum on the surface of both steels increased as the depth increased.     

Evolution of steel surface composition with heating in vacuum and in air

X-ray photoelectron spectroscopy (XPS) has been used to investigate the changes in surface composition of three steels as they have undergone heating. The steels were mild steel, and two austenitic stainless steels, commonly designated 304 and 316 stainless steels. XPS measurements were made on the untreated samples, and then following heating for 30 min in vacuo and in a 1 × 10⁻⁶ Torr partial pressure of air, at temperatures between 100 °C and 600 °C.Mild steel behaves differently to the two stainless steels under the heating conditions. In mild steel the iron content of the surface increased, with oxygen and carbon decreasing, as a function of increasing temperature. The chemical state of the iron also changed from oxide at low temperatures, to metallic at temperatures above 450 °C.In both stainless steels the amount of iron present in the surface decreased with increasing temperature. The decrease in iron at the surface was accompanied by an increase in the amount of chromium at the steel surface. At temperatures above 450 °C the iron in both 304 and 316 stainless steels showed significant contributions from metallic iron, whilst the chromium present was in an oxide state. In 316 stainless steel heated to 600 °C there was some metallic chromium present in the surface layer.The surfaces heated in air showed the least variation in composition, with the major change being the loss of carbon from the surfaces following heating above 300 °C. There was also a minor increase in the concentration of chromium present on both the stainless steels heated under these conditions. There was also little change in the oxidation state of the iron and chromium present on the surface of these steels. There was some evidence of the thickening of the surface oxides as seen by the loss of the lower binding energy signal in the iron or chromium core level scans.The surfaces heated in vacuum showed a similar trend in the concentration of carbon on the surfaces, however the overall concentration of oxygen decreased throughout the heating of these steels. There were also significant changes in the oxidation state of the iron and chromium on these surfaces with significant amounts or iron and chromium present in the metallic form following heating up to 600 °C.It appears that the carbon contamination on the surfaces plays an important role in the fate of the surface oxide layer for all of the steels heated in a vacuum environment.     

Microstructure, microhardness, composition, and corrosive properties of stainless steel 304 I. Laser surface alloying with silicon by beam-oscillating method.

Laser surface alloying (LSA) with silicon was conducted on austenitic stainless steel 304. Silicon slurry composed of silicon particle of 5 μm in average diameter was made and a uniform layer was supplied on the substrate stainless steel. The surface was melted with beam-oscillated carbon dioxide laser and then LSA layers of 0.4–1.2 mm in thickness were obtained. When an impinged energy density was adjusted to be equal to or lower than 100 W mm⁻², LSA layers retained rapidly solidified microstructure with dispersed cracks. In these samples, Fe₃Si was detected and the concentration of Si in LSA layer was estimated to be 10.5 wt.% maximum. When the energy density was equal to or greater than 147 W mm⁻², cellular grained structure with no crack was formed. No iron silicate was observed and alpha iron content in LSA layers increased. Si concentration within LSA layers was estimated to be 5 to 9 wt.% on average. Crack-free as-deposited samples exhibited no distinct corrosion resistance. The segregation of Si was confirmed along the grain boundaries and inside the grains. The microstructure of these samples changed with solution-annealing and the corrosion resistance was fairly improved with the time period of solution-annealing. Received: 2 September 1999 / Accepted: 6 September 1999 / Published online: 1 March 2000     

Use of grazing incidence X-ray diffraction for the study of nitrogen implanted stainless steels

The identification of Fe, Ni and Cr nitrides formed by nitrogen-ion implantation (4×10¹⁷ N⁺ cm^-2, 50 keV) in austenitic steels is performed by X-ray diffraction under very low glancing angles (0.00 ⩽ i ⩽ 1.5°). Spectra obtained with increasing angles i permit the investigation of layers with depths varying from 20 to more than 1000 Å. This non-destructive technique allows the surface to be controlled at each step of the treatments. Spectra were recorded on polished steel prior to and after implantation, with or without electrochemical attack. A 100 Å martensitic layer formed during the mechanical polishing is observed on the austenitic substrate. This layer is destroyed by an anodic attack before implantation of the samples. After implantation a CrN or carbonitride overlayer of a few tens of Å in thickness, may be observed. In the subjacent layers several iron and nickel nitrides are present, mainly ϵ-Fe₂N-Fe₃N, ς-Fe₂N and Ni₃N.     

Magnetron deposition of molybdenum mirrors and micrometer-thick mirror foil with an ordered columnar nanocrystalline structure

The formation of a molybdenum reflecting coating with a columnar nanocrystalline structure is studied under the condition when molybdenum is deposited by dc magnetron sputtering on single-crystalline molybdenum mirrors (substrates). The coating is found to peel off together with a polishing-induced imperfect amorphous surface layer of the substrate. This effect aids in obtaining a free mirror-like molybdenum foil. When the amorphous imperfect layer is removed from the substrate before deposition, the reflecting mirror coating has a good adhesion to the substrate.     

Thermally oxidised rutile-TiO2 coating on stainless steel for tribological properties and corrosion resistance enhancement

In the present work, a novel process has been developed to improve the tribological and corrosion properties of austenitic stainless steels. Efforts have been made to deposit titanium coatings onto AISI 316L stainless steel by magnetron sputtering, and then to partially convert the titanium coatings to titanium oxide by thermal oxidation. The resultant coating has a layered structure, comprising of rutile-TiO₂ layer at the top, an oxygen and nitrogen dissolved α-Ti layer in the middle and a diffuse-type interface. Such a hybrid coating system showed good adhesion with the substrate, improved corrosion resistance, and significantly enhanced surface hardness and tribological properties of the stainless steel in terms of much reduced friction coefficient and increased wear resistance.     

Improvement of hot-dip zinc coating by enriching the inner layers with iron oxide

The performance of hot-dip galvanic coating formed on steel not only depends on the alloy composition of the superficial layer but also significantly, on the composition of the inner alloy layers at the coating/substrate interface. Further, the presence of barrier oxide layers, if any can also improve the performance of galvanic coating. In the present work, the effect of inner iron oxide barrier layer formed prior to hot-dip galvanization was investigated. A continuous and adherent iron oxide layer was formed on steel by anodic oxidation of the steel substrate. Although the wettability of oxide surface by liquid zinc was initially poor, the increase in dipping time and the transition of the oxide layer to unstable form due to the presence of Cl⁻ ion in the flux facilitated localized growth of Fe-Zn alloy phases. The inhibitive nature of the oxide layer was temporary, since the presence of Cl⁻ induces micro cracks on the oxide surface thereby facilitating better zinc diffusion. The modification of the substrate structure during galvanization was found to influence the galvanizing process significantly. The present study predicts scope for application of this process for protection of rusted steel specimens too.     

Laser Nitriding of Iron,Stainless Steel,and Plain Carbon Steel Investigated by Mössbauer Spectroscopy

Nitriding is a common method for improving the hardness, mechanical properties, wear and corrosion resistance of metals. Laser nitriding of metals is an efficient process, where the irradiation of surfaces in air or nitrogen atmospheres with short laser pulses leads to a fast take-up of nitrogen into the irradiated surfaces. This process has been extensively investigated for pure iron, but usually, no tools or functional parts are made of pure iron. Mainly steel or cast iron is used as a base material. Therefore, when looking for technical applicability, also the influence of alloying elements on the laser nitriding process is of great interest. Besides the pure iron various carbon steels and an austenitic stainless steel were studied in laser nitriding experiments in order to investigate the influence of the material itself. Here, the process is investigated via Conversion Electron and X-ray Mössbauer Spectroscopy (CEMS and CXMS), Resonant Nuclear Reaction Analysis (RNRA), and X-Ray Diffraction (XRD). It appears that carbon steels are even better suited for the laser nitriding process than pure iron, and the laser nitriding also works efficiently for the stainless steel which is normally difficult to be nitrided.     

The structure of Mo/Si multilayers prepared in the conditions of ionic assistance

The influence of a negative substrate-applied bias potential on the structure of periodic Mo/Si multilayer compositions has been investigated by means of cross-sectional electron microscopy, small-angle X-ray reflectivity, X-ray diffraction and by modeling the small-angle spectra. It is known that the crystalline structure of molybdenum layers is the main source of interface roughness. In the absence of a bias potential application, the interface roughness tends to develop from the substrate towards the surface of a Mo/Si multilayer composition. A negative bias potential (up to -200 V) applied to a substrate during silicon layer deposition leads to smoother interfaces and improves the layer morphology. After increasing the bias potential over -200 V a considerable growth of an amorphous interlayer transition zone can be observed at Si-on-Mo interfaces. By raising the bias potential during the deposition of Mo layers a development of roughness at Mo-on-Si interfaces as well as growing interlayer thicknesses were found. PACS 61.10.Kw; 68.37.-d; 68.65.Ac     

A Mössbauer Study of Austenitic Steel Originating from the Steam Generator of a VVER-440 Type Nuclear Reactor,Paks, Hungary

Real specimens after more than ten years of operation in the steam generator of a VVER-440 type nuclear reactor, Paks, Hungary have been studied. Conversion electron Mössbauer spectroscopy was used for phase analysis of the primary side surfaces of austenitic stainless steel pipes. From the measurements, we concluded that the surface layer of the pipes consisted of a thin (<100 nm) and highly iron depleted oxidic film of nickel and chromium rich compounds. The ratio of the metallic constituents was found to be substantially different from that of the bulk steel to a depth of about 1–1.5 microns as revealed by independent SEM-EDAX studies. These findings may most likely be attributed to the irradiation enhanced diffusion and selective dissolution of iron.The bulk steel was investigated by transmission Mössbauer spectroscopy and X-ray diffraction. The samples originated from different sections of the collector head of the steam generator representing different contact times with steam and liquid water. Besides the paramagnetic peak of austenite, the Mössbauer spectra contained a magnetic sextet of ferrite in various amounts. This difference in phase composition may be attributed to the combination of irradiation effect and different thermal stress.     

Structural changes in austenitic steel in contact with solid oxide electrolyte at 950°C

Changes in the structure and redistribution of alloying elements in 10Kh23N18 austenitic steel after operating at 950°C for 8800 h in contact with La-Sr-Mn-O electrolyte are investigated to establish the reasons for the degrading of the surface layer of a current collector in a solid-oxide fuel cell over long periods of service. It is established that the degradation of the surface layer of steel is associated with the formation of a network of silicon and aluminum oxides along grain boundaries and the considerable discrepancy between the linear thermal expansion coefficients of steel and the solid electrolyte.     

衬底温度对PLD制备的Mo薄膜结构及表面形貌的影响

 运用脉冲激光沉积(PLD)技术在Si(100)基片上沉积了金属Mo薄膜。在激光重复频率2 Hz,能量密度5.2 J/cm²,本底真空10^－6 Pa的条件下,研究Mo薄膜的结构和表面形貌,讨论了衬底温度对薄膜形貌与结构的影响。原子力显微镜(AFM)图像和X射线小角衍射(XRD)分析表明,薄膜表面平整、光滑,均方根粗糙度小于2 nm。沉积温度对Mo薄膜结构和表面形貌影响较大,在373~573 K范围内随着温度升高,薄膜粗糙度变小,结晶程度变好。     

氮化铬过渡层对四面体非晶碳薄膜在高速钢基底上附着特性影响的研究

利用磁过滤阴极电弧与磁控溅射相结合的薄膜沉积技术在高速钢基底上 制备了氮化铬/四面体非晶碳(CrN/ta-C)复合涂层, 通过改变过渡层氮化铬(CrN)的制备工艺, 研究了四面体非晶碳(ta-C)薄膜在钢基底材料上的附着特性的变化. 结果表明, 随着氮气流量的增大, CrN/ta-C复合涂层中的氮化铬经过了Cr-Cr₂N-CrN的相变过程. 同时涂层的附着力也随着氮气流量的增大而增加, 但是当氮气流量超过30 sccm时, 涂层附着力会有所下降; 通过改变基片偏压, 复合涂层中氮化铬的择优取向与晶粒结构发生改变, 随着偏压的增大, 涂层附着力也会大大改善, 但是当偏压超过200 V, 涂层附着特性会略微降低. 通过涂层耐磨性的测试也表明, 在高速钢基底上, CrN涂层能显著提高ta-C薄膜在高速钢基底上的附着力, 同时显著提高耐磨特性. 关键词： 附着力 四面体非晶碳薄膜 X射线衍射 拉曼光谱     

A study of laser surface alloyed steel

Coatings composed of Ni and Co based alloys were prepared by surface alloying of steel substrate. In the study of composition and structure of the coatings, Mössbauer spectroscopy in scattering geometry, X-ray diffraction and energy dispersive X-ray microanalysis were applied. The results, in addition to phase composition data, showed the effect of the thermal history of samples. The contribution of Mössbauer spectroscopy consists in revealing the structure details resulting from rapid cooling of the remelted surface layer.     

Selective growth of carbon nantoubes on SiO2/Si substrate

Three-step raising temperature process was employed to fabricate carbon nanotubes by pyrolysis of ferrocene/melamine mixtures on silica and single crystalline silicon wafers respectively. Then the morphologies, structures and compositions of obtained carbon nanotubes are investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectroscope (EDX) and electron energy-loss spectroscopy (EELS). TEM and SEM observation shows that on silica substrate, high-oriented carbon nanotube can grow compactly to form continuous film on both frontal and cross-section surfaces, but on silicon substrate, only can form on cross-section surface. These carbon nanotubes have much irregular cup-like structure, and with outer diameter varying from 25 nm to 35 nm. At the top end of carbon nanotube there is a catalyst particle. EDX analysis reveals that the particle are iron cluster, and EELS spectrum indicates that the nanotube is composed of pure carbon. Finally, the effect of substrate surface roughness on the growth behavior of carbon nanotubes has been discussed.     

SEM/EDS investigation of one-step flame sprayed and fused Ni-based self-fluxing alloy coatings on steel substrates

Abstract

This study presents the results of light optical and scanning electron microscopy as well as energy dispersive spectroscopy investigation of the Ni-based self-fluxing alloys (NiCrBSi, NiCrWBSi and NiCrBSi + WC) deposited on steel substrates (heat treated carbon steel C45, heat treated low-alloyed steel 42CrMo4 and austenitic stainless steel X6CrNiMo18-10-2) by one-step flame spraying and fusing process. The microstructure of coatings and coating/substrate interface but also the effects of deposition technology on the heat-treated steel substrates which have frequently been used in practice were investigated. The influence of the sample size on the microstructure was also discussed. A proof is given of the change in the structure of coating, coating/substrate interface and substrate due to high fusing temperature, depending on type of steel substrate (and relating thermal properties), coating thickness but also on dimensions of the sample.     

A micro-spectroscopy study on the influence of chemical residues from nanofabrication on the nitridation chemistry of Al nanopatterns

We applied spatially resolved photoelectron spectroscopy implemented with an X-ray photoemission electron microscopy (XPEEM) using soft X-ray synchrotron radiation to identify the compositional and morphological inhomogeneities of a SiO₂/Si substrate surface nanopatterned with Al before and after nitridation. The nanofabrication was conducted by a polymethylmethacrylate (PMMA)-based e-beam lithography and a fluorine-based reactive ion etching (RIE), followed by Al metalization and acetone lift-off. Three types of chemical residues were identified before nitridation: (1) fluorocarbons produced and accumulated mainly during RIE process on the sidewalls of the nanopatterns; (2) a thick Al-bearing PMMA layer and/or (3) a thin PMMA residue layer owing to unsuccessful or partial lift-off of the e-beam unexposed PMMA between the nanopatterns. The fluorocarbons actively influenced the surface chemical composition of the nanopatterns by forming AlF compounds. After nitridation, in the PMMA residue-free area, the AlF compounds on the sidewalls were decomposed and transformed to AlN. The PMMA residues between the nanopatterns had no obvious influence on the surface chemical composition and nitridation properties of the Al nanopatterns. They were only partially decomposed by the nitridation. The regional surface morphology of the nanopatterns revealed by the secondary electron XPEEM was consistent with the scanning electron microscopy results.     

Electron spectroscopic study of passive oxide layer formation on Fe-19Cr-18Ni-1Al-TiC austenitic stainless steel

Surface oxidation of a TiC-enriched austenitic stainless steel alloy was investigated at 50 °C by X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS). It was found that a passive oxide layer started to form on the alloy surface after 5 L of oxygen exposure. Further oxidation of the alloy was suppressed after 500 L of oxygen exposure when a stable passive layer was formed. It was found also that Ti and Ni did not oxidize and Ti remained in a carbide form during whole oxidation. The oxidation kinetics of different metals were investigated as well.     

Is a coating part of the substrate? The case of vanadium carbide on steel

Metallic surfaces, especially that of steel, are generally protected by various types of coatings. This paper presents some of the results of CEMS studies currently being made on mild steel substrate coated with a thin layer of vanadium carbide (VC). CEMS studies were done before and after coating. The internal magnetic field was found to be oriented at an angle of 48 degrees with respect to the transverse surface of the steel sample. After coating with VC at 950 °C, this value was reduced to 39 degrees. Molecular orbital calculations indicated that the electron density along the surface of the steel is significantly changed when the VC layer is formed, which leads to the changes in the magnetic field directions that are observed. The experimental data therefore reveal that vanadium from the coating diffuses into the iron substrate.     

P110钢CO2腐蚀产物膜的XPS分析

为了确定CO2腐蚀产物膜的组成及不同层次结构中成分和含量的差异,采用P110钢在高温高压腐蚀静态釜中制备CO2腐蚀产物膜,利用SEM观察了腐蚀产物膜的表面和断面形貌,结合XRD分析结果,通过XPS研究了两层结构膜的化学组成差异。结果表明,腐蚀产物膜断面呈现双层结构;膜层的主要成分是FeCO3,还有少量的CaCO3和铁的氧化物,但内层CaCO3较多且夹杂着Fe3C和单质Fe,外层氧化物稍多;通过内外层Ca^2＋含量差异推断出内层腐蚀膜优先形成。