Surface modification of austenitic stainless steel with plasma nitriding for biomedical applications

In the present study, plasma nitriding of AISI type 303 austenitic stainless steel (SS) specimens was performed using a microwave system. The nitrided layers were characterized by performing scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and a Vickers microhardness test. The antibacterial activities of the nitrided layers were evaluated. XRD and TEM showed that a single γ_N phase was formed by plasma nitriding at the plasma power of 700 W and 450 °C. The analytical results demonstrated that the hardness of type 303 specimens could be enhanced by plasma nitriding because of the formation of the γ_N phase. A bacterial test also demonstrated that the nitrided layer exhibited excellent antibacterial properties.     

The oxidation of Fe-19.6Cr-15.1Mn stainless steel

The oxidation behavior in air of Fe-19.6Cr-15.1Mn was studied from 700 to 1000°C. Pseudoparabolic kinetics were followed, giving an activation energy of 80 kcal/mole. The scale structure varied with temperature, although spinel formation occurred at all temperatures. At both 700 and 800°C, a thin outer layer of -Mn₂O₃ formed. The inner layer at 700°C was (Fe,Cr,Mn)₃O₄, but at 800°C there was an intermediate layer of Fe₂O₃ and an inner layer of Cr₂O₃ + (Fe, Cr,Mn)₃O₄. Oxidation at 900°C produced an outer layer of Fe₃O₄ and an inner layer of Cr₂O₃+(Fe,Cr,Mn)₃O₄. Oxidation at 1000°C caused some internal oxidation of chromium. In addition, a thin layer of Cr₂O₃ formed in some regions with an intermediate layer of Fe₃O₄ and an outer layer of (Fe,Mn)₃O₄. A comparison of rates for Fe₃O₄ formation during oxidation of FeO as well as for the oxidation of various stainless steels, which form spinels, gave good agreement and strongly suggests that spinel growth was rate controlling. The oxidation rate of this alloy (high-Cr) was compared with that of an alloy previously studied, Fe-9.5Cr-17.8Mn (low-Cr) and was less by about a factor of 12 at 1000°C and by about a factor of 100 at 800°C. The marked differences can be ascribed to the destabilization of wustite by the higher chromium alloy. No wustite formation occurred in the high-Cr alloy, whereas, extensive wustite formed in the low-Cr alloy. Scale structures are explained by the use of calculated stability diagrams. The mechanism of oxidation is discussed and compared with that of the low-Cr alloy.     

Spinel coatings for UNS 430 stainless steel interconnects

At the usual temperature of solid oxide fuel cell (SOFC) operation, ferritic stainless steels form electrically insulating or poorly conducting oxide scales, which can cause high internal resistance losses and chromium poisoning. In an effort to avoid this problem, we applied conductive copper manganite and cobalt manganite spinel coatings, with nominal composition MnCo₂O₄ and Cu_1.4Mn_1.6O₄, which were deposited on the surface of UNS 430 stainless steel by electroplating and subsequent air annealing. Microstructural evaluation indicated that the spinel layers inhibited outward diffusion of chromium. Moreover, excellent structural and thermal stability were observed after several thermal cycles at 750 °C and for up to 28 days, and the coating layers showed good adhesion to the substrate.     

Oxidation of high-aluminum austenitic stainless steels

The cyclical oxidation behavior of an austenitic stainless steel (24% Ni, 10% Cr, 5% Al, and balance Fe) has been evaluated in the temperature range 800–1300°C. The effects of trace elements such as S, Y, Zr, and Ti on the oxidation of the austenitic stainless steel have also been evaluated. The results indicate that Fe-Ni-Cr-Al stainless steels exhibit superior oxidation resistance up to 1300°C due to the formation of a very adherent and thin film of -Al₂O₃.     

The influence of grain-boundary segregation of Y in Cr2O3 on the oxidation of Cr metal

The oxidation behavior at 900°C of pure Cr and Cr implanted with 2×10¹⁶ Y ions/cm² was studied. The kinetics of oxidation were measured thermogravimetrically and manometrically. The mechanisms of oxide growth were studied using¹⁸O-tracer oxidation experiments, and the composition and microstructure of the oxide scales were characterized by TEM and STEM. Segregation of Y cations at Cr₂O₃ grain boundaries was found to be the critical factor governing changes in the oxidation behavior of Cr upon the addition of Y. In the absence of Y, pure Cr oxidized by the outward diffusion of cations via grain boundaries in the Cr₂O₃ scale. When Y was present at high concentration in the scale, as when Cr implanted with 2×10¹⁰ Y ions/cm² was oxidized, anion diffusion predominated. It is concluded that strain-induced segregation of Y at grain boundaries in the oxide reduced the cation flux along the grain boundaries. The rate of oxidation was reduced because the grain-boundary diffusivity of cations became lower than the grain-boundary diffusivity of the anions, which then controlled the rate of oxidation. Changes in the relative rates of Cr³⁺ and O^2– transport, as well as a solute-drag effect exerted by Y on the oxide grain boundaries, resulted in changes in the microstructure of the oxide.     

Protective effect in sulfuric acid media of alumina and ceria oxide layers electrodeposited on stainless steel

The influence of thin layers of Al₂O₃ and Ce₂O₃-CeO₂, electrodeposited on stainless steel OC4004, on the corrosion behaviour of the systems Al₂O₃/SS, Ce₂O₃-CeO₂/SS and Al₂O₃-Ce₂O₃-CeO₂/SS has been studied in sulfuric acid medium. A pronounced stabilizing effect on the passive state of steel and enhancement of its corrosion resistance has been established both for the samples as deposited and for the thermally treated Ce₂O₃-CeO₂/SS systems. In comparison to them the layers of Al₂O₃ have a substantial impact on the corrosion resistance of the Al₂O₃/SS system only in the cases when the system is not subjected to thermal treatment. The consecutive deposition of Al₂O₃ and Ce₂O₃-CeO₂ films on SS gives as a result an outstanding corrosion-protective effect, whereupon the corrosion potential of the system Al₂O₃/Ce₂O₃-CeO₂/SS is shifted in positive direction with ∼ 0.3 V for the samples as deposited and with ∼ 1 V—for the thermally treated samples. The so established favourable effect has been explained by the increased concentration of chromium oxides in the surface passive film, caused by the presence of cerium oxides, as well as by their action as cathode, effective with respect to the reduction corrosion reaction, shifting strongly the potential (at which this reaction is occurring) in positive direction.     

Improvement in the oxidation behavior of austenitic stainless steels by superficially applied,cerium oxide coatings

The influence of superficially applied CeO₂ coatings on the isothermal-oxidation behavior, preceded by nonisothermal heating, as well as cyclic-oxidation behavior of three grades of austenitic stainless steel (AISI-316, –321, and –304), in dry air is reported. The superficial coating had a thickness of 2.1 m. The linear heating rate employed was 6 K min^–1 up to a maximum temperature of 1423 K, and the isothermal holding temperature was 1273 K. The results clearly depict that CeO₂ coatings not only reduced the rates of scale growth for all three varieties of steel but also imparted improved scale adhesion to the respective alloy substrates, as evident from the fact that the coated steels could withstand a number of thermal cycles without scale rupture. In the bare condition, 321-grade steel exhibited the best performance. However, in the presence of the coating, the improved performances of 316 and 321 grades were almost identical, whereas the 304 variety showed improvement only in the first cycle of exposure. The kinetics results have been substantiated by postoxidation analyses of the alloy/scale combinations by SEM, EDS, EPMA, and XRD techniques to reveal the role of rare-earthoxide coatings on the observed behavior.     

The effect of particle size of alumina dispersions on the oxidation resistance of Ni-Cr alloys

The oxidation behavior of Ni-Cr alloys with various chromium concentrations and particle sizes of a dispersion of 10 vol.% Al₂O₃ was observed in 1 atm of oxygen at 1000°C. This study was intended to determine the critical chromium concentration to form a protective Cr₂O₃ oxide layer for different Al₂O₃ particle sizes. The oxidation rate of Ni-Cr alloys containing 10 vol.% Al₂O₃ followed a parabolic rate law and a Cr₂O₃ protective layer continuously formed when the oxidation rate decreased rapidly. Times to form a continuous and protective Cr₂O₃ layer during the initial oxidation shortened as the size of the dispersion decreased. The critical chromium concentration to form a protective Cr₂O₃ layer in the oxide scale was 69 wt.% and was related strongly to the particle size of the Al₂O₃ dispersion.     

Kinetics of the oxidation of metals: Parallel circuit for point defects diffusion

A model is proposed for the oxidation of metals including both bulk crystal lattice diffusion and short-circuit diffusion paths. Assuming local equilibrium between point defects in the bulk and in grain boundaries, we obtain an effective parabolic rate constant k_eff=k_bulk [1+ exp-(H/RT],where H is the enthalpy for the reaction between point defects in the bulk and in short circuits, is the fraction of the short-circuit area, and T is temperature. In the case of the high-temperature oxidation of nickel coated with a thin film of vanadium pentoxide, this model yields to a rate law with a critical oxygen pressure P _c. The nickel vanadium oxide located in the short circuits of the growing oxide NiO is liquid below P_c, leading to a rapid short-circuit diffusion. Above this value, a vanadate precipitates and acts as diffusion blocks for migrating Ni ions.     

The influence of grain-boundary segregation of Y in Cr2O3 on the oxidation of Cr metal. II. Effects of temperature and dopant concentration

The oxidation behavior of pure Cr and Cr implanted with Y was studied as a function of temperature (900 and 1025°C) and ion-implantation dose (1×10¹⁵ and 2×10¹⁶ Y ions/cm²). The microstructures of the Cr₂O₃ scales were affected by both of the variables studied. Yttrium ions segregated at the grain boundaries in the Cr₂O₃ scales formed on the implanted alloys and the concentration of Y at the grain boundaries decreased with a decrease in the dose of implanted Y. The mechanism of growth of the Cr₂O₃ scales was altered by the presence of the Y ions at the Cr₂O₃ grain boundaries only when a critical concentration of Y at the grain boundaries was exceeded.     

The combined effect of refractory coatings containing reactive elements on high temperature oxidation behavior of chromia-forming alloys

The high temperature oxidation behaviors of chromia-forming alloys (F17Ti and Fe-30Cr alloys) have been studied at 1273 K under isothermal conditions and at 1223 K under cyclic conditions, in air under the atmospheric pressure. To extend the oxidation lifetime, coatings have been applied onto the alloy surfaces. Al₂O₃ and Cr₂O₃ films doped with Sm₂O₃ or Nd₂O₃ were prepared via the metal-organic chemical vapor deposition technique. Single Cr₂O₃, Al₂O₃, Nd₂O₃ and codeposited Cr₂O₃-Nd₂O₃, Al₂O₃-Nd₂O₃, Al₂O₃-Sm₂O₃ coatings drastically improved the chromia-forming alloy high temperature oxidation behavior, since they decreased the oxidation rate and enhanced the oxide scale adhesion. Results showed that a critical amount of reactive element (Nd or Sm) in chromia or alumina coatings (11-18 at.%) was needed to observe the most effective effect. The fast precipitation of NdCrO₃ or NdTi₂₁O₃₈ and the segregation of reactive elements at the chromia grain boundaries slowing down outward cation transport and consequently blocking the chromia grain growth, was supposed to be the main reasons of the beneficial effect ascribed to the reactive elements in chromia scales.     

The high-temperature oxidation behavior of vanadium-aluminum alloys

The oxidation behavior in air of pure vanadium, V-30Al, V-30Al-10Cr, and V-30Al-10Ti (weight percent) was investigated over the temperature range of 700–1000° C. The oxidation of pure vanadium was characterized by linear kinetics due to the formation of liquid V₂O₅ which dripped from the sample. The oxidation behavior of the alloys was characterized by linear and parabolic kinetics which combined to give an overall time dependence of 0.6–0.8. An empirical relationship of the form: W/A=Bt + Ct^1/2 + D was found to fit the data well, with the linear contribution suspected to be from V₂O₅ formation for V-30Al and V-30Al-10Cr, and a semi-liquid mixture of V₂O₅ and Al₂O₃ for V-30Al-10Ti. The parabolic term is presumed related to the formation of a solid mixture of V₂O₅ and Al₂O₃ for V-30Al and V-30Al-10Cr, and TiO₂ for V-30Al-10TiThe addition of aluminum was found to reduce the oxidation rate of vanadium, but not to the extent predicted by the theory of competing oxide phases proposed by Wang, Gleeson, and Douglass. This was attributed to the formation of a liquid-oxide phase in the initial stages of exposure from which the alloys could not recover. Ternary additions of chromium and titanium were found to decrease the oxidation rate further, with chromium being the most effective. The oxide scales of the alloys were found to be highly porous at 900° C and 1000° C, due to the high vapor pressure of V₂O₅ above 800° C.     

The effect of fe on high temperature oxidation of NiAl

A study was conducted to observe the oxidation of NiAl+3.5at.%Fe alloy inβ-NiAl phase field at air temperatures of 1000, 1200 and 1400°C, and these results were compared with those of pure NiAl alloys. The primary effects of the Fe-addition in NiAl were found to be: 1) decrease in oxidation resistance and adherence of scales during both isothermal and cyclic oxidation tests, 2) enhancement of phase transformation rate from θ toα-AL₂O₃, 3) more rapid formation of characteristically ridgedα-A1₂O₃ scales during initial oxidation stages, and 4) partial sealing of voids formed at the scale-substrate interface and dissolution of Fe inside the alumina scale by the outward diffusion of Fe from the substrate alloy.     

High temperature oxidation of chromium nitrides

Chromium nitride powders oxidized to Cr₂O₃ noticeably above 400°C. Bulk chromium nitrides that were manufactured by sintering were oxidized between 900 and 1100°C in atmospheric air. The Cr₂O₃ layer that formed on bulk chromium nitrides having pores was relatively dense, and grew primarily via the inward transport of oxygen. The Cr₂O₃ layer to some degree deterred the nitrogen evolution from bulk chromium nitrides.     

Super304H奥氏体不锈钢的高温抗氧化性能

对Super304H奥氏体不锈钢在550～800℃进行高温氧化试验,结合氧化动力学规律去研究Super304H奥氏体不锈钢的氧化机理。结果表明,Super304H奥氏体不锈钢在550～800℃氧化质量增加曲线遵循抛物线规律,在750～800℃时60 h以内氧化质量增加趋势最明显,100 h后质量增加高达0.005 mg·mm^-2。在550～750℃逐渐生成致密的氧化膜,主要由Cr₂O₃和Fe_3-xCr_xNiO₄混合氧化物和少量CuCrMnO₄构成。升高温度会促进Cr的选择性氧化,使得Cr₂O₃保护膜开裂,800℃时暴露出的Fe基体与氧原子反应生成瘤状Fe₃O₄,氧化膜厚重并伴有剥落现象。应变速率为3.2×10^-4 s^-1时,不锈钢的抗拉强度随氧化温度升高而降低,600℃的抗拉强度最大,达350 MPa; ...     

Development of cored wires for improving the abrasion wear resistance of austenitic stainless steel

Arc-sprayed coatings are an attractive means to protect components from abrasive wear provided they contain enough hard phases. Because of their hardness and toughness, 316L-TiB₂ cermets were selected as the basis for developing wear-resistant coatings. Cored wires composed of type 304 stainless steel sheaths filled with 10 to 65 wt% TiB₂,1 to 15 wt% additives, and the balance with 316L stainless steel were fabricated and arc-sprayed with air. The arc-sprayed stainless steel-TiB₂ coatings were abrasion tested and the volume loss measured with an optical profiloineter. The volume loss decreased as the proportion of TiB₂ increased. However, large differences in volume loss between coatings that contain about the same volumetric proportion of hard phases cannot be explained by a linear relationship. An inverse rule of mixing was proposed and found useful in determining the influence of different additives. Tin, added in the core as a fugitive liquid transfer agent, was the most powerful additive for improving the wear resistance of stainless steel-base coatings. These advanced arc-sprayed stainless steel-TiB2 coatings exhibit greater wear resistance than those obtained by arc spraying commercial solid and cored wires.     

The effect of aluminum as an alloying addition or as an implant on the high-temperature oxidation of Ni-25Cr

The oxidation behavior of aluminum-implanted Ni-25Cr and Ni-25Cr containing 1 wt.% Al has been studied at 1000°C and 1100°C in oxygen. As did Y alloying addition or Y-implantation, 1 wt.% Al added to Ni-25Cr prevented nodular formation of Ni-containing oxides, improved spalling resistance of the scale upon cooling to a similar degree, and eliminated the formation of large voids between the alloy and the scale at the oxidation temperature. However, the Al addition did not alter the rate of growth of the Cr₂O₃ scale, nor did it change the growth direction. Al-implantation produced no effect even when the maximum concentration and depth of penetration were adjusted to be identical with those of the yttrium in the Y-implanted alloy. The implications of these results concerning the reactive element effect are discussed.     

309SMOD奥氏体耐热不锈钢的高温氧化行为

采用增重法分析了309SMOD奥氏体不锈钢板材在不同温度下的氧化行为,获得了该钢高温氧化的抛物线动力学曲线,利用SEM、EDS及XRD对氧化物的形貌和物相进行了分析。结果表明,800 ℃氧化物形貌为板状和块状,900 ℃、1000 ℃的氧化物主要为尖晶石颗粒。309SMOD奥氏体不锈钢表面由于高温氧化生成具有3层结构的混合氧化物膜,最外层结构为MnCr₂O₄和FeCr₂O₄,次外层结构的氧化物为Cr₂O₃,最内层结构的氧化物为SiO₂,这种结构的氧化膜使得309SMOD奥氏体不锈钢具有良好的抗高温氧化性能。     

An experimental setup for the study of gas-solid reequilibration phenomena

The effect of Y additions on the oxidation mechanism of NiAl at 1270 K has been investigated. Mass transport in the alumina scale was examined with¹⁸O tracers. Proton activation analysis (¹⁸O(p, )¹⁵N) and SIMS were used to measure the¹⁸O distribution in the scale. On pure NiAl and low-doped (0.07% Y) NiAl mainly outward scale growth was observed. Addition of 0.5% Y induces oxide formation at both interfaces of the scale. Larger quantities of Y added to the alloy (>0.5%) do not dissolve completely in the NiAl, but form Y-rich segregates. Internal oxidation of these intergranular segregates was observed. The relation between the modification of the scale-growth mechanism and the improved adherence of the scale to the alloy due to the addition of Y is discussed.     

The effects of deformation variables on hot workability of austenitic stainless steel

The torsion tests of 304 stainless steel were performed in the temperature range of 900~1100°C and strain rate range of 5.0 × 10^-2~5.0 × 10°/sec to study the high temperature softening behavior. The flow curves and microstructures showed the behavior of dynamic recrystallization (DRX). The dependence of temperature(T) and the stain rate(ɛ) on the flow stress was expressed by the hyperbolic sine law, ɛ=2.75 × 10 (sinh 0.076σ)^5.26 exp(-379000 J/mol/RT). The dynamically recrystallized grain size(d_DRX) was related to the value of the Zener-Hollomon parameter Z. Under the Z value of 10¹⁷, it was found that the grain size ranged from 10 to 20 μm. The relationship between the dynamically recrystallized grain size and Z parameter was found as follows: d_DRX=l 39.48-7.33 log Z and the calculated grain sizes were well matched with the experimental values. To determine the optimum condition of plastic deformation, the deformation map was made from the efficiency of power dissipation. The maximum efficiency was 0.41 at the condition of 1100°C, 0.5/sec, 100%.