Microstructure and microhardness analysis of the hexagonal oxides formed on the surface of the AISI 304 stainless steel after Nd:YAG pulsed laser surface melting

The laser surface melting (LSM) technique was adopted to modify the surface layer microstructure of the AISI 304 stainless steel in this paper. The results showed that the hexagonal morphologies have been successfully fabricated on the surface after LSM. These hexagons had side lengths of about 0.5-1 μm and were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), field emission scanning electron microscope (FESEM) and high resolution transmission electron microscope (HRTEM). It was proved by the XRD that the stainless steel surface mainly consisted of γ-Fe, Cr₂O₃, Fe₂O₃ and some manganese oxides. The FESEM micrographs showed that the hexagonal oxides were regular hexagons in geometry. The HRTEM micrographs also indicated the presence of the hexagons on the surface of the stainless steel. The spacing values were calculated from the HRTEM micrograph and the SAED pattern, and the hexagonal oxide phases determined by these spacing values were consistent with those verified by the XRD. After LSM, the microhardness of the stainless steel was significantly improved.     

Microstructure and antibacterial properties of microwave plasma nitrided layers on biomedical stainless steels

Nitriding of AISI 303 austenitic stainless steel using microwave plasma system at various temperatures was conducted in the present study. The nitrided layers were characterized via scanning electron microscopy, glancing angle X-ray diffraction, transmission electron microscopy and Vickers microhardness tester. The antibacterial properties of this nitrided layer were evaluated. During nitriding treatment between 350 °C and 550 °C, the phase transformation sequence on the nitrided layers of the alloys was found to be γ → (γ + γ_N) → (γ + α + CrN). The analytical results revealed that the surface hardness of AISI 303 stainless steel could be enhanced with the formation of γ_N phase in nitriding process. Antibacterial test also demonstrated the nitrided layer processed the excellent antibacterial properties. The enhanced surface hardness and antibacterial properties make the nitrided AISI 303 austenitic stainless steel to be one of the essential materials in the biomedical applications.     

Effects of surface nanocrystallization pretreatment on low-temperature ion sulfurization behavior of 1Cr18Ni9Ti stainless steel

A nanocrystalline surface layer of 10 μm thickness was fabricated on 1Cr18Ni9Ti stainless steel by means of supersonic fine particles bombarding (SFPB). The followed low-temperature ion sulfurizing was carried out on the original and the SFPBed (SFPB treated) surface, respectively, forming sulfide layers with certain thickness. X-ray diffraction (XRD) and transmission electron microscopy (TEM) were employed to analyze the phase constituents and grain size of the nanocrystallized surface layer. The surface morphologies and compositions of the sulfide layers were examined by scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). X-ray photoelectron spectroscope (XPS) was used to detect the valence states of the sulfide layers. Elemental distribution with depth was measured by augur energy spectroscopy (AES). The results show that the microstructure of the surface layer is refined to nano-grains with the grain size about 30 nm and random crystallographic orientations by SFPB treatment. The surface nanocrystallization pretreatment can significantly improve the thickness, density, and the FeS content ratio of the sulfide layers. The analysis indicates that, the enhancement in efficiency of the ion sulfurization treatment by SFPB surface nanocrystallization treatment is mainly attributed to the high-density crystal defects and the increase of surface chemical activity.     

Tin oxide nanocrystals embedded in nanopore arrays on stainless steel surface for photocatalytic applications

The immobilization of SnO₂ nanocrystals on solid substrates for practical photocatalytic applications suffers from poor adhesion that will lead to loss of photocatalytic activity and short service life. An efficient hydrothermal synthesis of SnO₂ nanocrystals embedded in nanopore arrays on stainless steel surface was presented in this paper. The morphology, chemical composition and microstructure of the embedded tin oxide nanocrystals were investigated by X-ray diffraction, field-emission scanning electron microscope, X-ray photoelectron spectroscopy and UV-visible diffuse reflectance spectroscopy. The photocatalytic activity and stability of SnO₂ nanocrystals was evaluated by photodegradation of methylene blue. SnO₂ nanocrystals embedded in nanopore arrays on stainless steel surface existed in a tetragonal rutile structure. The increasing of the hydrothermal temperature will lead to the improvement in photocatalytic activity of SnO₂ nanocrystals. The SnO₂ nanocrystals prepared at 220 °C performed the highest photocatalytic activity and good photocatalytic stability, indicating the effective immobilization of SnO₂ nanocrystals on anodized stainless steel.     

Oxidation of AISI 304L stainless steel surface with atomic oxygen

Oxidation of stainless steel surface in oxygen atmosphere was investigated by Auger electron spectroscopy (AES) depth profiling. The samples made of AISI 304L stainless steel were exposed to highly non-equilibrium oxygen atmosphere at different temperatures between 300 and 800 K and for different periods between 5 and 600 s. The degree of dissociation of oxygen molecules was of the order of 10%. A thin oxide layer formed on the stainless steel surface consisted of the iron oxide. The thickness depended on the sample temperature. At room temperature it was 7 nm, and it remained the same up to 200 °C. With further increase of temperature, the thickness of the oxide layer increased and reached 40 nm at 450 °C. The thickness was independent of exposure time. The results were explained by two mechanisms of oxide growth. Up to 200 °C the oxidation was run by electro-migration, while at higher temperatures the thermal induced migration prevailed.     

Effect of surface nanocrystallization induced by fast multiple rotation rolling on hardness and corrosion behavior of 316L stainless steel

A nanostructured layer was fabricated by using fast multiple rotation rolling (FMRR) on the surface of 316L stainless steel. The microstructure in the surface was characterized by transmission electron microscopy and X-ray diffraction. The effects of FMRR on the microhardness, surface roughness and corrosion behavior of the stainless steel were investigated by microhardness measurements, surface roughness measurements, potentiodynamic polarization curves and pitting corrosion tests. The surface morphologies of pitting corrosion specimens were characterized by scanning electron microscopy. The results show that FMRR can cause surface nanocrystallization with the grain size ranges from 6 to 24 nm in the top surface layer of the sample. The microhardness of FMRR specimen in the top surface layer remarkably increases from 190 to 530 HV. However, the surface roughness slightly rises after FMRR treatment. The potentiodynamic polarization curves and pitting corrosion tests indicated that the FMRR treated 316L stainless steel with a surface nanocrystallized layer reduced the corrosion resistance in a 3.5% NaCl solution and enhanced the pitting corrosion rate in a FeCl₃ solution. Possible reasons leading to the decrease in corrosion resistance were discussed.     

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.     

Surface microstructures and antimicrobial properties of copper plasma alloyed stainless steel

Bacterial adhesion to stainless steel surfaces is one of the major reason causing the cross-contamination and infection in many practical applications. An approach to solve this problem is to enhance the antibacterial properties on the surface of stainless steel. In this paper, novel antibacterial stainless steel surfaces with different copper content have been prepared by a plasma surface alloying technique at various gas pressures. The microstructure of the alloyed surfaces was investigated using glow discharge optical emission spectroscopy (GDOES) and scanning electron microscopy (SEM). The viability of bacteria attached to the antibacterial surfaces was tested using the spread plate method. The antibacterial mechanism of the alloyed surfaces was studied by X-ray photoelectron spectroscopy (XPS). The results indicate that gas pressure has a great influence on the surface elements concentration and the depth of the alloyed layer. The maximum copper concentration in the alloyed surface obtained at the gas pressure of 60 Pa is about 7.1 wt.%. This alloyed surface exhibited very strong antibacterial ability, and an effective reduction of 98% of Escherichia coli (E. coli) within 1 h was achieved by contact with the alloyed surface. The maximum thickness of the copper alloyed layer obtained at 45 Pa is about 6.5 μm. Although the rate of reduction for E. coli of this alloyed surface was slower than that of the alloyed surface with the copper content about 7.1 wt.% over the first 3 h, few were able to survive more than 12 h and the reduction reached over 99.9%. The XPS analysis results indicated that the copper ions were released when the copper alloyed stainless steel in contact with bacterial solution, which is an important factor for killing bacteria. Based on an overall consideration of bacterial killing rate and durability, the alloyed surface with the copper content of 2.5 wt.% and the thickness of about 6.5 μm obtained at the gas pressure of 45 Pa is expected to be useful as antimicrobial materials that may have a promising future in antimicrobial applications.     

Bacterial adhesion on ion-implanted stainless steel surfaces

Stainless steel disks were implanted with N⁺, O⁺ and SiF₃⁺, respectively at the Surrey Ion Beam Centre. The surface properties of the implanted surfaces were analyzed, including surface chemical composition, surface topography, surface roughness and surface free energy. Bacterial adhesion of Pseudomonas aeruginosa, Staphylococcus epidermidis and Staphylococcus aureus, which frequently cause medical device-associated infections was evaluated under static condition and laminar flow condition. The effect of contact time, growth media and surface properties of the ion-implanted steels on bacterial adhesion was investigated. The experimental results showed that SiF₃⁺-implanted stainless steel performed much better than N⁺-implanted steel, O⁺-implanted steel and untreated stainless steel control on reducing bacterial attachment under identical experimental conditions.     

Surface laser alloying of 17-4PH stainless steel steam turbine blades

As a known high-quality precipitation hardening stainless steel with high strength, high antifatigue, excellent corrosion resistance and good weldability, 17-4PH has been widely used to produce steam turbine blades. However, under the impact of high-speed steam and water droplets, the blades are prone to cavitation, which could lead to lower efficiency, shorter life time, and even accidents. In this article, the 17-4PH blade's surface was alloyed using a high power CO₂ laser. The microstructure and microhardness of hardened 17-4PH were tested by scanning electronic microscope (SEM), X-ray diffraction (XRD), energy disperse spectroscopy (EDS) and a microhardness tester. After laser alloying, the surface layer was denser and the grain refined, while the microhardness of the surface (average 610HV_0.2) was about one times higher than that of the substrate material (330HV_0.2). The friction coefficient of the laser-alloyed 17-4PH layer was much lower than that of the substrate.     

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     

Influence of process time on microstructure and properties of 17-4PH steel plasma nitrocarburized with rare earths addition at low temperature

17-4PH stainless steel was plasma nitrocarburized at 430 °C for different time with rare earths (RE) addition. Plasma RE nitrocarburized layers were studied by optical microscope, scanning electron microscope equipped with an energy dispersive X-ray analyzer, X-ray diffraction, microhardness tests, pin-on-disc tribometer and anodic polarization tests. The results show that rare earths atoms can diffuse into the surface of 17-4PH steel. The modified layer depths increase with increasing process time and the layer growth conforms approximately to the parabolic law. The phases in the modified layer are mainly of γ′-Fe₄N, nitrogen and carbon expanded martensite (α′_N) as well as some incipient CrN at short time (2 h). With increasing of process time, the phases of CrN and γ′-Fe₄N increase but α′_N decomposes gradually. Interestingly, the peaks of γ′-Fe₄N display a high (2 0 0) plane preferred orientation. The hardness of the modified specimen is more than 1340 HV, which is about 3.7 times higher than that of untreated one. The friction coefficients and wear rates of specimens can be dramatically decreased by plasma RE nitrocarburizing. The surface hardness and the friction coefficients decrease gradually with increasing process time. The corrosion test shows that the 8 h treated specimen has the best corrosion resistance with the characterization of lower corrosion current density, a higher corrosion potential and a large passive region as compared with those of untreated one.     

Microstructure evolution occurring in the modified surface of 316L stainless steel under high current pulsed electron beam treatment

High current pulsed electron beam (HCPEB) surface treatment of 316L stainless steel (SS) was carried out with a wide spectrum of treating parameters. Microstructure changes occurring in the modified surface were characterized with microscopy, X-ray diffractometry and electron backscatter diffractometry (EBSD) techniques. The evolution regularities of surface craters and microstructure refinement, as well as preferred orientation of (1 1 1) crystal planes were discussed on considering the coupled temperature-stress fields formed in surface layers after an absorption of HCPEB energy.     

Thermal stability of the structural features in the superhydrophobic boehmite films on austenitic stainless steels

Boehmite thin film with 50–100 nm surface flake structure has been synthesized on AISI 316 type austenitic stainless steel by immersing boehmite gel film into boiling water. When further coated with hydrolyzed (heptadecafluoro-1,1,2,2-tetrahydrodecyl) trimethoxysilane (FAS), the boehmite film becomes superhydrophobic with a contact angle for water of 152°. The superhydrophobic property results from both the nanoscale surface flake structure and the low surface energy of the FAS top layer. The topography of such film was revealed by atomic force microscope (AFM) and a set of roughness parameters of such film was discussed. The degradation of superhydrophobicity of the surface was studied as a function of the heat-treatment temperatures. Below 600 °C, the surface remained to be superhydrophobic with the FAS top layer. Above 700 °C, the surface was not superhydrophobic anymore due to a gradual loss in surface roughness which was revealed by field emission scanning electron microscope (FESEM). A phase change from boehmite to γ-Al₂O₃ occurred during the heat-treatments from 700 to 900 °C which was studied by the selected area electron diffraction (SAED) patterns from the transmission electron microscope (TEM) measurement.     

Simple heat treatment for fabrication of carbonaceous layer-coated microelectrodes and conductive stainless steels

A simple heat treatment was used to fabricate carbonaceous layer-coated electrodes: micro-ring electrodes and conductive stainless steel. Substrates of sharpened quartz capillaries or type-316 stainless steel plates were put in an alumina boat with powder of petroleum pitch A240F separately and heated at 1073-1273 K in a flow of nitrogen or argon. By this treatment, both of the substrates were coated with a uniform carbonaceous layer of several hundred nano-meters in thickness. The electric conductivity of the layer was improved by increases in temperature and period of the heating. The quartz glass-capillary covered with the conductive layer was modified to a needle-type microelectrode by coating with an insulating polymer and baring the tip. At least a dozen carbon micro-ring electrodes with an outer radius of about 1 μm were successfully prepared by the simple heat treatment. On the other hand, the carbonaceous layer formed on type-316 stainless steel showed relatively poor conductivity due to the formation of oxides in the layer. However, the conductivity was improved by electroplating of nickel on the substrate before the heating. The carbonaceous layer-coated stainless steel showed good corrosion resistance in sulphuric acid.     

Effects of carbon fiber surface treatment on the tribological properties of 2D woven carbon fabric/polyimide composites

Polyacrylonitrile (PAN)-based carbon fabric (CF) was modified with strong HNO₃ oxidation and then introduced into polyimide (PI) composites. The friction and wear properties of the carbon fabric reinforced polyimide composites (CFRP), sliding against GCr15 stainless steel rings, were investigated on an M-2000 model ring-on-block test rig under dry sliding. Experimental results revealed that the carbon fiber surface treatment largely reduced the friction and wear of the CFRP. Compared with the untreated ones, the surface-modified CF can enhance the tribological properties of CFRP efficiently due to the improved adhesion between the CF and the PI matrix. Scanning electron microscope (SEM) and X-ray photoelectron spectroscopy (XPS) study of the carbon fiber surface showed that the fiber surface became rougher and the oxygen concentration increased greatly after surface treatment, which improved the adhesion between the fiber and the PI matrix and improved the friction-reduction and anti-wear properties of the CFRP. An erratum to this article can be found at     

Characterization of oxide layers and interface layers of ferrite stainless steel (SUS430) by57Fe CEMS

The oxide layers on stainless steel formed by heating at various high temperatures and by dipping in LiF + BeF₂ molten (Flibe) bath at 600 °C were characterized by CEMS. Hematite was a major iron product at 600 °C and fine oxides with paramagnetic Fe(III) species were produced at the higher temperatures than 700 °C. The interface of stainless steel beneath oxide films was characterized as the hyperfine field distributions. Paramagnetic Fe(III) species were produced on Cr depleted layers in the Flibe bath. CEMS is effective for simultaneous characterization of both oxide surface and interface layers of the ferritic stainless steel.     

Ultrasonic butt welding of aluminum,aluminum alloy and stainless steel plate specimens

Welding characteristics of aluminum, aluminum alloy and stainless steel plate specimens of 6.0 mm thickness by a 15 kHz ultrasonic butt welding system were studied. There are no detailed welding condition data of these specimens although the joining of these materials are required due to anticorrosive and high strength characteristics for not only large specimens but small electronic parts especially. These specimens of 6.0 mm thickness were welded end to end using a 15 kHz ultrasonic butt welding equipment with a vibration source using eight bolt-clamped Langevin type PZT transducers and a 50 kW static induction thyristor power amplifier. The stainless steel plate specimens electrolytically polished were joined with welding strength almost equal to the material strength under rather large vibration amplitude of 25 microm (peak-to-zero value), static pressure 70 MPa and welding time of 1.0-3.0 s. The hardness of stainless steel specimen adjacent to a welding surface increased about 20% by ultrasonic vibration.     

Analysis of oxide formation induced by UV laser coloration of stainless steel

Laser-induced coloration on metal surfaces has important applications in product identification, enhancing styles and aesthetics. The color generation is the result of controlled surface oxidation during laser beam interaction with the metal surfaces. In this study, we aim to obtain in-depth understanding of the oxide formation process when an UV laser beam interacts with stainless steel in air. The oxide layer is analysed by means of optical microscopy, scanning electron microscopy (SEM) and time-of-flight secondary ion mass spectrometer (TOF-SIMS). TOF-SIMS results clearly show the formation of duplex oxide structures. The duplex structure includes an inner layer of Cr oxide solution and an outer layer of Fe oxide solution. The oxide layer thickness increased as the results of Fe diffusion to surface during multiple laser scanning passes.     

Formation of nano-crystalline and amorphous phases on the surface of stainless steel by Nd:YAG pulsed laser irradiation

Thin surface layers consisting of nano-crystalline and amorphous phases on the surface of stainless steel have been attained under the Nd:YAG pulsed laser irradiation. The phases and microstructures were investigated by X-ray diffraction (XRD) and high resolution transmission electron microscope (HRTEM). The phase compositions of the surface determined by XRD were α-Fe (ferrite) and γ-Fe (austenite) or only γ-Fe in the near surface region on the bases of the different laser power densities. The nano-crystalline grains with sizes of 4-100 nm could result from high cooling rate and crystallization in amorphous region by homogeneous and heterogeneous nucleation. The formation of the amorphous phase was attributed to the higher cooling rates.