X-ray photoelectron spectroscopy studies of hard coatings formed by titanium implantation on 304 stainless steel

Titanium ions are implanted (at 30 keV) in 304 stainless steel to a dose of 1.8 × 10¹⁷ ions cm⁻² using 15 μA cm⁻² and 5 μA cm⁻² beam current densities for specimens 2 and 3 respectively. X-ray photoelectron spectroscopy (XPS) measurements are performed at different temperatures. The microhardness of implanted and unimplanted specimens is also measured. In specimen 2 the microhardness does not increase significantly and XPS measurements give evidence of carburized surface alloy formation. At 250°C TiO₂ is detected on the surface and it migrates into the bulk phase above 350°C. In specimen 3 the XPS measurements exhibit an absence of iron owing to the radiation-induced segregation of titanium on the surface. This specimen shows an increase in microhardness. The XPS measurements reveal a layer of (TiC_x-C) on the surface which is suggested to be responsible for the increase in microhardness. Upon heating, TiC_x is seen to move into the bulk phase and the carbon concentration is increased. These changes occuring at higher temperatures are suggested as having an effect on the wear-resistant properties of titanium-implanted 304 stainless steel.     

Preliminary study of anti-infective function of a copper-bearing stainless steel

In this study the copper (Cu)-bearing stainless steel was developed to reduce the incidence of implant-associated infections in clinical areas. A 317L austenitic stainless steel containing 4.5% Cu (317L-Cu SS) was designed and fabricated, and its anti-infective function was preliminarily studied both in vitro and in vivo by means of antibacterial test, confocal laser scanning microscope (CLSM) and scanning electron microscopy (SEM) observations, and animal implantation. The results indicated that the 317L-Cu SS possessed strong antibacterial rates against both Escherichia coli and Staphylococcus aureus, and showed anti-infective ability by inhibiting the formation of bacterial bio-film on surface of the steel due to the release of Cu ions from the steel surface. The microbiological and histological evaluations from animal implantation further proved that the 317L-Cu SS could obviously reduce the happening of bacterial infection, and is potential to be used as a new class of surgical implant material with anti-infective function.     

Laser surface hardening of AISI 420 stainless steel treated by pulsed Nd:YAG laser

The AISI 420 martensitic stainless steel was surface-hardened by a pulsed Nd:YAG laser. The influences of process parameters (laser pulse energy, duration time and travel speed) on the depth and hardness of laser treated area and its corrosion behavior were Investigated. In the optimum process parameters, maximum hardness (490 VHN) in the laser surface treated area was achieved. The pitting corrosion behavior was studied by potentiodynamic polarization technique in 3.5% NaCl solution at 25 °C. Metallographical and electrochemical corrosion studies illustrated beneficial effects of laser surface hardening by refining the microstructure and enhancing the pitting corrosion resistance of the martensitic stainless steel. The pitting corrosion resistance of laser surface treated samples in 3.5% NaCl solution depends on the overlap ratio clearly. The pitting potential (E_pp) decreased significantly by increasing the ratio of pulse overlapping.     

Influence of laser-mechanical treatment on surface topography,erosive wear and contact stiffness

This paper presents the study of surface topography, erosive wear and contact stiffness after the new hybrid method has been applied for the modification of steel surface layer. A combination of laser alloying and the burnishing process, both performed in laser set up, was proposed in order to reduce surface roughness being formed during laser treatment, and to improve contact stiffness. The experiments were conducted on stainless steel, alloyed with Stellite 6, and simultaneously burnished in hot and cold conditions in one operation. The alloying process was performed with continuous laser CO₂ at different parameters. The influence of hybrid treatment parameters on surface topography was examined. This hybrid treatment reconstructed the surface topography and caused an increase in surface smoothness compared to laser alloying. More than a threefold decrease in the average level of roughness, S_a, due to the burnishing process was stated. A good correlation between the parameters of hybrid treatment and roughness was demonstrated. The study shows that laser-mechanical treatment improves erosive wear and contact stiffness compared to laser alloyed and thermal sprayed Stellite 6 layers.     

Parameters for the laser processing of tool and carbon steels

Surface melting of various steel systems, including M2 tool steel and specialty grade carbon steels, by CO₂ lasers was investigated to determine the relative effects of the processing variables such as the laser power P, the spot size d and the interaction time τ (τ = d/v where v is the translation speed of the sample) on the efficiency of the laser melting process. The cross-sectional area A of the laser-melted zone is found to vary linearly with the energy per unit length incident on the surface of the sample (A = P/v). Comparison with the calculated energy required to melt a specified volume of sample provides a means of evaluating the efficiency of a given set of laser processing variables. The area of the melted zone is found to vary proportionately with P/v within certain ranges of conditions, although the power density at the surface is also found to be a critical parameter. The work was made necessary by the need to control the size and geometry of the melted zone to achieve controlled concentrations in a laser alloying experiment, as well as to optimize the conditions for the highest process throughput. The laser processing conditions were 0.45–3.6 kW of laser power, an interaction time of 1–60 ms and a spot size of 0.15–1.25 mm, with power densities ranging from 0.19 to 2.83 MW cm^-2.     

Determination of the surface tension of liquid stainless steel

The surface tensions (σ) and temperature dependencies (dσ/dT) of several commercial 4-series ferritic stainless steels have been measured using the sessile drop technique on an Al₂O₃ plate over the temperature range 1789 to 1883 K in an atmosphere of high purity (P _{O 2} < 10^?19 MPa) argon gas. Precise densities of liquid stainless steels have also been obtained using the modified sessile drop method in order to calculate accurate values of the surface tension. The surface tensions of liquid stainless steels decreased markedly with increasing sulphur concentration in the steels. The variation of surface tensions of liquid stainless steels can be described by the following equation σ = 1790 ? 182 ln (1 + 260a _S) (mN/m) when only S is considered or σ = 1820 ? 304 ln (1 + 383a _O) ? 182ln (1 + 260a _S) (mN/m) when both S and O are considered. The equations apply to the following compositional ranges: mass%O = 0.0022–0.0064, mass%S = 0.0008–0.05. The temperature coefficient of the surface tension (dσ/dT) of liquid stainless steel was found to change from negative to positive at a sulphur concentration of about 30 mass ppm in the steel. Nitrogen was found to have little effect on the surface tension of liquid stainless steel.     

Preparation and antibacterial properties of Ag-containing diamond-like carbon films prepared by a combination of magnetron sputtering and plasma source ion implantation

Ag-containing diamond-like carbon (DLC) films were prepared on austenitic type stainless steel SUS316L and silicon wafer substrates by a process combining reactive magnetron sputtering with plasma source ion implantation (PSII). An Ag disc was used as a target for the sputter source with an RF power of 100 W. A mixture of the gases Ar and C₂H₂ was introduced into the discharge chamber while a negative high voltage pulse was applied to the substrate holder. By changing the gas flow ratios the resulting Ag content of the films could be varied. The prepared films were composed of amorphous carbon with crystalline Ag, as observed by X-ray diffractometry and TEM. Additional sample characterizations were performed by X-ray photoelectron spectroscopy, secondary ion mass spectrometry and Raman spectroscopy. The surface morphology was observed by scanning electron microscopy. The antibacterial activity was determined using Staphylococcus aureus bacteria. All Ag-containing diamond-like carbon films exhibited an antibacterial activity with only small variations depending on the Ag content.     

响应面分析法优化不锈钢激光切割工艺参数

为了获得良好的不锈钢激光切割质量,确定合理的切割工艺参数,本文以3 mm厚304不锈钢为研究对象,采用响应面法进行试验方案的设计和分析,利用超景深显微镜进行了试样表面切缝宽度、表面纹理最大峰值、挂渣量的测量,利用最小二乘法进行数据处理,研究了激光功率(X₁)、切割速度(X₂)、离焦量(X₃)以及辅助气体压力(X₄)对不锈钢切割表面切缝宽度、表面纹理最大峰值、挂渣量的影响规律,并基于响应面法得到了3个响应目标的预测函数.实验结果表明:X₂=2.48 m/min,X₃=-1.05 mm,X₄=1 MPa时,随着激光功率的增加,切缝宽度不断增大;X₁=300 W, X₄=1.2 MPa时,随着切割速度的加快切缝宽度逐渐减小,随着离焦量的增大切缝宽度先减小后增大;X₁=300 W,X₃=0 mm,X₄=1.40 MPa时表面纹理的最大波峰值RZ随着激光功率、离焦量以及切割速度的增大先减小后增大。以切缝宽度最窄、表面纹理最大峰值最小、挂渣量最少为响应目标确定了3 mm厚304不锈钢激光切割的最佳工艺参数为X₁=365.86 W,X₂=2.75 m/min,X₃=0 mm,X₄=1.4 MPa。试验验证发现:切缝宽度、表面纹理最大峰值、挂渣量的预测误差应分别控制在8.4%~12.7%、21%~24.9%、16.7%~19.5%。     

Corrosion behaviour of nanocrystallines 304 stainless steel in simulated secondary side environment

Surface nanocrystallisation (SNC) was prepared on the top-surface layer of 304 stainless steel by ultrasonic surface rolling treatment (USRT). Meanwhile, martensite transformation also occurred during grain refinement, and the surface microhardness increased more than tripled after USRT. The corrosion resistance of nanocrystallines (NC) 304 stainless steel was notably better than that of untreated samples in simulated pressurised water reactor (PWR) secondary water by potentiodynamic polarisation curves, electrochemical impedance spectroscopy and Mott-Schottky curves. Meanwhile, the corrosion mechanism was discussed before and after USRT by X-ray photoelectron spectroscopy (XPS). The main reason is due to the formation of denser Cr(OH)₃ protective film and the reduction of the porous structure Fe₂O₃ content in the NC 304 stainless steel.     

Pits with coloured halos formed on 1Cr18Ni9Ti stainless steel surface after ennoblement in seawater

Micropits surrounded by coloured halos were observed under incident-light microscope on 1Cr18Ni9Ti stainless steel surface after “ennoblement” in seawater. Ennoblement has been attributed to biofilm formation on stainless steel surface in seawater. In this study, the environment in biofilm for ennoblement was simulated by adding H₂O₂ into seawater at concentrations that were reported to detect in marine biofilm [N. Washizu, Y. Katada, T. Kodama, Corros. Sci.46 (2004)1291.]. H₂O₂ increased the passivity of stainless steel in seawater, but this passivation was not uniform. The probability of pitting corrosion was increased after ennoblement. Equal thickness interference on the deposition film around the pits was believed to be the reason for the coloured fringes. It is conceivable that haloed pits on the stainless steel surface are the characteristic morphological indications for pitting corrosion formed under ennoblement condition in seawater. Examinations on the microbial and structural effects of the biofilm were not included in this study.     

Bacterial adhesion reduction on a biocompatible Si+ ion implanted austenitic stainless steel

The colonization of an implant surface by bacteria is an extremely important medical problem, which often leads to the failure of medical devices. Modern surface modification techniques, such as ion implantation, can confer to the surfaces very different properties from those of the bulk underlying material. In this work, austenitic stainless steel 316 LVM has been superficially modified by Si⁺ ion implantation. The effect of surface modification on the biocompatibility and bacterial adhesion to 316 LVM stainless steel has been investigated. To this aim, human mesenchymal stem cells (hMSCs), as precursor of osteoblastic cells, and bacterial strains relevant in infections related to orthopedic implants, i.e., Staphylococcus aureus and Staphylococcus epidermidis, have been assayed. For the understanding of changes in the biological response associated to ion implantation, variations in the chemical surface composition, topography, surface Gibbs energy, isoelectric point and in vitro corrosion behavior have been evaluated. hMSCs adhesion, viability and differentiation to the osteoblastic lineage were unaffected by Si⁺ ion implantation. On the other hand, Si⁺ ion implantation diminished the number of attached bacteria in static conditions and led to smaller adhesion rates and retention strength. The ability of implanted surfaces to reduce the bacterial adhesion was higher for Staphylococcus epidermidis than for Staphylococcus aureus. This study proposes Si⁺ ion implantation as an effective way of reducing bacterial adhesion on 316 LVM stainless steel surfaces without compromising its good biocompatibility.     

Interfacial precipitation in hot isostatically pressed diffusion bonds of 17-4 PH stainless steel

Abstract

The embrittlement of hot isostatically pressed (hipped) diffusion bonds manufactured from 17-4 PH stainless steel has been investigated by Auger electron spectroscopy (AES) of in situ fracture specimens. Depth profiling by AES has revealed copper precipitation at the interface of the diffusion bond. This precipitation, up to a few monolayers in thickness, occurs during the ramp up to temperature and pressure of the hot isostatic pressing (hipping) cycle and is not readily removed by subsequent heat treatment. This effect is explained in terms of the metallurgical characteristics of copper within the steel. Results suggest that the extent of the precipitation decreases with increasing process temperature. In the case of PH 13-8 Mo stainless steel, where the precipitation hardening phase is NiAl, the interface is weakened by sulphur segregation and the formation of oxide particles.     

基于复膜金相法的不锈钢构件组织状态无损识别研究

目的 研究在不破坏电力工业用不锈钢构件的前提下应用复膜金相法对其组织状态进行无损识别。方法提出了一种基于复膜金相法的电力工业用不锈钢构件组织状态无损识别方法。使用便携式磨抛设备现场处理不锈钢构件表面,然后在构件的抛光表面用树脂模具构造原位电解池;注入饱和草酸溶液后,通过便携式直流电源对构件进行腐蚀,清洗吹干后,在腐蚀后的表面通过AC膜制备复膜金相,然后将复膜放置到显微镜下进行显微组织观察。结果 试验结果表明,铸态不锈钢中的组织为原始凝固状态,晶内存在明显的二次枝晶臂形态,而锻态不锈钢为多边形等轴晶组织,且晶内存在大量的孪晶组织。SEM、EDS能谱分析和维氏硬度分析结果表明,铸态不锈钢组织在枝晶间存在明显的Mn、Cr元素偏析,枝晶间凝固偏析会造成枝晶内部和枝晶间性能不均匀;锻态不锈钢平均硬度为202.9HV,高于铸态不锈钢的平均硬度（174.3HV）,且锻态不锈钢的硬度分布更均匀。不锈钢构件组织和性能的均匀性会影响其服役性能。结论 提出的基于复膜金相法的电力不锈钢构件组织状态无损识别方法可以为电力工业提供一种安全、高效的构件检测手段。通过复膜金相法可以对电网设备中的不锈钢构件进行无损鉴定...     

A novel method for the growth of ZSM-5 zeolite membrane on the surface of stainless steel

Thin ordered micropore ZSM-5 zeolite membrane has formed on the stainless steel surface. The influence of three different pre-treatment methods for the growth of ZSM-5 zeolite membrane on the stainless steel was studied, including mechanical polishing, soaking in a 20 wt.% sulfuric acid aqueous solution and anodic oxidation treatment. It was found that the anodic oxidation technique was more favorable for the growth of ZSM-5 zeolite membrane on the stainless steel surface compared with the other two methods. By this appropriate pre-treatment process, ordered ZSM-5 zeolite membrane was immobilized on the stainless steel surface and it showed good interaction with the stainless steel. Energy-dispersive X-ray (EDX) spectroscopy result indicates that the ZSM-5 zeolite membrane has a Si/Al ratio of 37. X-ray diffraction (XRD), N₂ adsorption and scanning electron microscopy (SEM) were used to study the crystal structure, specific surface area and morphologies of the ZSM-5 zeolite membrane.     

Corrosion behavior of nitride layer obtained on AISI 316L stainless steel via simple direct nitridation route at low temperature

Newly developed low-temperature nitride synthesis route was used to introduce interstitial nitrogen into the passive layer of as-received and as-polished 316L stainless steel. The new thermochemical route is based on treating the stainless steel samples in potassium nitrate melt in an ultra pure nitrogen atmosphere at 450 °C. Electrochemical impedance spectroscopy (EIS) and dc polarization measurements have been used to evaluate the nitride layer performance in 3.5% NaCl solution. Results showed a marked increase in the corrosion resistance of nitrided stainless steel even after maintaining two weeks in NaCl solution. The effect of the treatment temperature was also studied. Data showed that the as-polished samples nitrided at 450 °C have the highest corrosion resistance. The polarization resistance (R_p) for the as-polished and as-received blank stainless steel samples was estimated by EIS were approximately 4.0 × 10⁴ Ω cm² and 2.0 × 10⁴ Ω cm², respectively. The R_p increased by a factor of 2.5–5 for the nitrided samples. Increasing the nitriding temperature from 450 to 600 °C affects negatively the corrosion resistance of stainless steel in NaCl solution. The R_p of the samples nitrided at 600 °C decreased sharply being almost 1/30 of the R_p of the samples nitrided at 450 °C. Linear polarization measurements showed that the lowest corrosion rates and highest polarization resistances obtained from the as-polished nitrided samples at 450 °C. It has been found from the potentiodynamic measurements that the E_corr of the as-polished nitrided samples at 450 °C is nobler than that measured from the other groups. The surface morphology was analysed by optical microscope and SEM-EDS under different nitriding conditions.     

Effect of the substrate on the electrodeposition of Bi2Te3−ySey thin films

The potentiostatic electrodeposition of n-type Bi₂Te_3−ySe_y thermoelectric films onto stainless steel and gold substrates from nitric acid aqueous solutions has been carried out at room temperature. The cathodic process during the electrodeposition of Bi₂Te_3−ySe_y films was investigated by cyclic voltammetric experiments. The structure and surface morphology of Bi₂Te_3−ySe_y films deposited on both substrates were characterized by X-ray diffraction (XRD) and environment scanning electron microscopy (ESEM) coupled with energy dispersive spectroscopy (EDS). Electrical and thermoelectric properties of as-deposited films were also measured at room temperature. The results show that the reduction process under the same depositing conditions on gold and stainless steel substrates is very different. On gold substrates, H₂SeO₃ in the electrolyte is firstly reduced to elemental Se, and then the deposited Se reacts with HTeO₂⁺ and Bi³⁺ to form Bi₂Te_3−ySe_y alloy. On stainless steel substrates, HTeO₂⁺ in the electrolyte is firstly replaced by elemental Fe to produce elemental Te, and subsequently the generated Te reacts with H₂SeO₃ and Bi³⁺ to form Bi₂Te_3−ySe_y alloy. Analysis of ESEM show that the surface morphology of the films electrodeposited on gold substrates is more compact than that on stainless steel substrates. The XRD patterns indicate that the films electrodeposited on both substrates exhibit preferential orientation along (1 1 0) plane, but the relative peak intensity of (0 1 5) and (2 0 5) planes on stainless steel substrates is stronger than that on gold substrates. The Seebeck coefficient and electrical resistivity of the films deposited on stainless steel substrates are higher than that on gold substrates.     

Resistance upset butt welding of austenitic to martensitic stainless steels

In this research, joining austenitic to martensitic stainless steels and effect of welding power on microstructure and mechanical properties of the joint were investigated. Microstructure of the weld was studied using optical microscopy (OM) and scanning electron microscopy (SEM). Energy dispersive spectroscopy (EDS) linked to SEM was used to determine chemical composition of phases and distribution of chromium (Cr), nickel (Ni) and iron (Fe) at the joint interface. Microhardness and tensile strength tests were performed. Finally fracture surface of samples were studied by SEM. Results showed that an interlayer composed of 80% ferrite and 20% martensite has formed at the joint interface and there were three different zones in the heat affected zone (HAZ) of two steels. Different forms of austenite phase including widmanstatten austenite (W_γ), allotriomorphic austenite (A_γ) and intergranular austenite (I_γ), delta ferrite (δ-ferrite) and chromium carbide (Cr₂₃C₆) have formed in the HAZ of austenitic stainless steel. Fractography of tension samples indicated that in all samples fracture occurred in austenitic stainless steel HAZ. The strength and hardness of the joint increased and HAZ length decreased with increasing of welding power.     

Hydrogen leak detection using laser-induced breakdown spectroscopy

Laser-induced breakdown spectroscopy (LIBS) is investigated as a technique for real-time monitoring of hydrogen gas. Two methodologies were examined: The use of a 100 mJ laser pulse to create a laser-induced breakdown directly in a sample gas stream, and the use of a 55 mJ laser pulse to create a laser-induced plasma on a solid substrate surface, with the expanding plasma sampling the gas stream. Various metals were analyzed as candidate substrate surfaces, including aluminum, copper, molybdenum, stainless steel, titanium, and tungsten. Stainless steel was selected, and a detailed analysis of hydrogen detection in binary mixtures of nitrogen and hydrogen at atmospheric pressure was performed. Both the gaseous plasma and the plasma initiated on the stainless steel surface generated comparable hydrogen emission signals, using the 656.28 Halpha emission line, and exhibited excellent signal linearity. The limit of detection is about 20 ppm (mass) as determined for both methodologies, with the solid-initiated plasma yielding a slightly better value. Overall, LIBS is concluded to be a viable candidate for hydrogen sensing, offering a combination of high sensitivity with a technique that is well suited to implementation in field environments.     

Biofilm inhibition and corrosion resistance of 2205-Cu duplex stainless steel against acid producing bacterium Acetobacter aceti

Acid producing bacterium Acetobacter aceti causes pitting corrosion of stainless steel(SS).This work investigated the enhanced resistance of 2205-Cu duplex stainless steel(DSS) against biocorrosion by A.aceti in comparison with 2205 DSS using electrochemical and surface analysis techniques.With the addition of Cu to 2205 DSS,biofilms on the 2205-Cu DSS surface were inhibited effectively.The largest pit depth on 2205-Cu DSS surface in the presence of A aceti was 2.6 μm,smaller than 5.5 μm for 2205 DSS surface.The i_(corr) was 0.42±0.03 μA cm~(-2) for 2205-Cu DSS in the biotic medium,which was much lower than that for 2205 DSS(3.69±0.65 μA cm~(-2)).All the results indicated that the A aceti biofilm was considerably inhibited by the release of Cu~(2+) ions from the 2205-Cu DSS matrix,resulting in the mitigation of biocorrosion by A aceti.     

Influence of laser surface alloying with chromium and nickel on corrosion resistance of type 304L stainless steel

Abstract

The influence of laser surface alloying (LSA) with Cr and Cr + Ni on the corrosion behaviour of type 304L stainless steel (SS) was investigated using potentiodynamic polarisation and electrochemical impedance spectroscopy (EIS) in chloride (0·5M NaCl) and acidic (1 N H₂SO₄) media. Surface alloying was carried out by laser cladding type 304L SS substrate with premixed powders of AISI type 316L SS and the desired alloying elements. The results indicated that Cr surface alloyed specimen exhibited a duplex (γ + α) microstructure with Cr content of ～24 wt-%, whereas Cr + Ni surface alloyed specimen was associated with austenitic microstructure with Cr and Ni contents of ～22 wt-% each. The potentiodynamic polarisation results in chloride solution indicated that LSA with Cr + Ni considerably enhanced the pitting corrosion resistance compared with LSA with Cr alone. In acidic media, such beneficial effects were not observed. Electrochemical impedance spectroscopy results showed an increase in semicircle arc for both chloride and acidic media for both Cr and Cr + Ni clad samples indicating improvement in the oxide film stability compared with untreated specimen. The polarisation resistance was higher and capacitance values of the laser clad specimen were lower than those in the untreated specimen. The microstructural changes and compositional variations produced by LSA are correlated to the corrosion behaviour.