Novel plasma nitriding-oxidizing duplex treatment of AISI 316 austenitic stainless steel

In this work, plasma nitriding and plasma nitriding-oxidizing treatment have been performed on AISI 316 austenitic stainless steel. In order to evaluate its response to this treatment, their microstructures and wear resistance have been compared with conventional plasma nitrided. The treatment of plasma nitriding was performed at temperature of 450 °C for 5 h with gas mixture of N₂/H₂:1/3 whereas plasma nitriding-oxidizing was performed with the same parameters of plasma nitriding and temperature of 450 °C with gas mixture of O₂/H₂:1/5 for 15, 30 and 60 min. The structural, mechanical and tribological properties were analyzed using XRD, SEM, microhardness testing and pin-on-disk tribotesting. The results showed that oxidation treatment reduces wear resistance of plasma nitrided sample under high loads. Furthermore the tribological evaluation indicates that by increasing the oxidation time further reduction of wear resistance can be occurred. In addition, it was found that oxidation treatment after plasma nitriding provides an important improvement in the friction coefficient against a AISI 52100 steel pin and reduces surface roughness.     

Determination of the s-phase formation coefficient of plasma nitrided austenitic steel

Plasma nitriding is an effective surface hardening treatment for austenitic stainless steels. During plasma nitriding, s-phase formation takes place which is not only responsible for high hardness and wear resistance but also for good corrosion resistance. In order to estimate the thickness of the s-phase for austenitic stainless steel in a plasma nitriding process, an empirical model is devised. A number of plasma nitriding processes of austenitic stainless steel (304 L) were carried out with varying treatment temperature from 360 °C to 450 °C and process duration ranging from 10 hours to 24 hours with constant pressure, voltage, pulse-to-pause-ratio and gas mixture. A time-temperature dependent s-phase formation coefficient is determined by measuring the thickness of the s-phase using a scanning electron microscope (SEM) and glow discharge optical emission spectroscopy (GDOES). The developed model is verified by three controlled experiments. This model fits the thickness of the s-phase with an error of less than 6 %.     

Effect of high temperature post-oxidizing on tribological and corrosion behavior of plasma nitrided AISI 316 austenitic stainless steel

In this research, the microstructure, tribological and corrosion properties of plasma nitrided-oxidized AISI 316 austenitic stainless steel at high oxidation temperature were studied and compared with conventional plasma nitride. The structural, tribological and corrosion properties were analyzed using XRD, SEM, microhardness testing, pin-on-disk tribotesting and electrochemical polarization. Plasma nitriding was conducted for 5 h at 450 °C with gas mixture of N₂/H₂ = 1/3 to produce the S-phase. The nitrided samples were post-oxidized at 500 °C with gas mixture of O₂/H₂ = 1/5 for 15, 30 and 60 min. X-ray diffraction confirmed the development of CrN, ? and γ′ nitride phases and magnetite (Fe₃O₄) oxide phase under plasma nitriding-oxidizing process. In addition, it was found that oxidation treatment after plasma nitriding provides an important improvement in the friction coefficient and the corrosion resistance. The optimized wear and corrosion resistance of post-oxidized samples were obtained after 15 min of oxidation.     

Nitriding of AISI M2 tool steel in an inductive r.f. plasma

The nitriding of AISI M2 tool steel in an inductive r.f. plasma was investigated. The plasma was sustained with a 27.12 MHz generator in gas mixtures of N₂ and H₂ at a pressure of 10 mbar. The ion nitriding was performed at a net r.f. power of 400 W at substrate temperatures of 450–500 °C. X-ray diffraction studies of the treated samples revealed that the most efficient formation of nitride phases was observed in samples nitrided in a pure N₂ plasma. As a result of the ion nitriding the surface hardness was substantially increased from a Vickers hardness VHN of 290 kgf mm^-2 for untreated samples to a maximum VHN of 1200 kgf mm^-2 for samples treated in a plasma sustained in a gas mixture with N₂:H₂ = 1:1.     

Structure and wear resistance of the composite layers produced by glow discharge nitriding and PLD method on AISI 316L austenitic stainless steel

The rapid technical development enhances the demands on constructional materials in terms of their resistance to frictional wear, resistance to corrosion and erosion, high hardness, high tensile and fatigue strength. These demands can be satisfied by e.g. applying various surface engineering techniques that permit to modify the microstructure, phase and chemical composition of the surface layers of the treated parts. A prospective line of the development of surface engineering is the production of composite layers by combining various surface engineering methods. The paper presents the results of examinations of the phase composition and frictional wear resistance of the layers produced by hybrid processes, i.e. such that combined glow discharge assisted nitriding performed at 450 °C and 550 °C with a pulsed laser deposition of boron nitride coatings (PLD method). It has been shown that the boron nitride coatings formed on nitrided AISI 316L steel increase its frictional wear resistance.     

A Study on Formation and Growth Mechanism of Nitride Layers During Plasma Nitriding Process of Plastic Injection Mold Steel

Ion nitriding modifies composition of surface layer in steel used in plastic mold application and this consequently improves their lifecycle. In this study, pulsed plasma nitriding technique was used to produce a protecting hard layer on AISI P20 steel at three process temperatures of 450°C, 500°C, and 550°C for durations of 2.5, 5, 7.5, and 10 h at a constant gas mixture of 75% N₂–25% H₂. Surface morphology was studied by optical and scanning electron microscope and the phases formed on the surface layer were determined by X-ray diffraction (XRD). Elemental depth profile was measured by techniques including energy dispersive spectroscopy, wavelength dispersive spectrometer, and glow discharge spectroscopy and for identifying hardness profile, microhardness variations from surface to core of samples were recorded. Results showed that, thickness of compound layer of plastic mold steel AISI P20 was negligible. Moreover in ion nitriding of AISI P20, nitride were formed and grown in some preferred directions and upward diffusion of carbon and downward diffusion of nitrogen occurred during ion nitriding of AISI P20. XRD results showed that, ?-nitride is the dominant phase after plasma nitriding in all strategies. Furthermore, ion nitriding improved hardness of AISI P20 up to three times and as time and temperature increased, hardness and hardness depth of diffusion zone increased considerably.     

Effect of post-oxidizing temperature on tribological and corrosion behavior of plasma nitrided austenitic stainless steel

In this study, the effect of temperature of post-oxidation process on tribological and corrosion behavior of AISI 316 plasma nitrided stainless steel has been studied. Plasma nitriding was carried out at 450 °C for 5 h with gas mixture of N₂/H₂ = 1/3. The plasma nitrided samples were post-oxidized for 1 h with gas mixture of O₂/H₂ = 1/5 at different temperature of 400, 450 and 500 °C. The structural, tribological and corrosion properties were analyzed using XRD, SEM, microhardness testing, pin-on-disk tribotesting and electrochemical polarization. The results indicated that the nitride layer was composed of S-phase. The amount of S-phase decreased as the treatment temperature rose from 400 °C to 500 °C. In addition, it was found that oxidation treatment reduces wear resistance of plasma nitrided sample. It was demonstrated that the corrosion characteristics of the nitrided sample were further improved by post-oxidation treatment. The difference in corrosion resistance is mainly attributed to the thickness of the oxide top layer, which is governed by the post-oxidizing temperature.     

Synthesis,characterization and in vitro studies of polysulfone/graphene oxide composite membranes

The aim of the study was the synthesis of polysulfone (PS)/graphene oxide (GO) composite membranes by phase inversion method as well as their structural, morphological, thermal and mechanical investigation. The performance of composite membranes in terms of distilled water and ethanol fluxes was investigated. The biological activity of mouse mesenchymal stem cells in contact with the new materials was measured. The successful incorporation of GO nanosheets within the PS matrix was confirmed by X-ray diffraction and transmission electron microscopy. Tensile tests indicated a key contribution of GO to the improvement of mechanical performances of PS. Ethanol and water fluxes decrease was remarked with GO addition and was assigned to the stabilization of composite membrane structure. Composite membranes cytotoxicity, cell viability and proliferation potential tests indicated excellent biocompatibility, enhancing cell proliferation and grouping for higher amount of GO within PS matrix.     

Enhancing the mechanical and anticorrosion properties of 316L stainless steel via a cathodic plasma electrolytic nitriding treatment with added PEG

A cathodic plasma electrolytic nitriding(CPEN) treatment with a urea aqueous solution was performed on 316L stainless steel to rapidly improve its surface properties in this work.Test results show that the PEG2000 macromolecules increased the nitriding energy via enhancing the ability to bond the produced gas film to the metal/electrolyte interface.The cross-sectional morphologies indicate that a thick nitrided layer was obtained when the urea concentration was 543 g I~(-1),corresponding to a Vickers hardness 450 HV_(0.1),which was 3.5 times larger than that of the substrate.The nitrided layer mainly contained expanded austenite(γ_N),oxides and iron nitrides(e.g.,Fe_3O_4 and FeN_(0.076)).In terms of its performance,coefficient of friction(COF) of the nitride layer decreased to nearly two-thirds that of the untreated layer,and the passivation current densities of the nitrided sample in a 3.5% NaCl solution decreased by an order of magnitude compared to that of the substrate.Therefore,the approach presented herein provides an attractive way to modify the effect of CPEN in a urea aqueous solution.     

Verschleißschutz und Korrosionsbeständigkeit von austenitischem Stahl durch Plasmadiffusions behandlung

In this paper, we report on a series of experiments designed to study the influence of plasma nitriding on the mechanical properties and the corrosion resistance of austenitic stainless steel. Plasma nitriding experiments were conducted on AISI 304L steel in a temperature range of 375‐475°C using pulsed‐DC plasma with different N ₂‐H ₂ gas mixtures and treatment times. First of all, the formation and the microstructure of the modified layer will be highlighted followed by the results of hardness measurement, adhesion testing, wear resistance and fatigue life tests. In addition the corrosion resistance of the modified layer is described. The microhardness after plasma nitriding is increased by a factor of five compared to the untreated material. The adhesion is examined by Rockwell indentation and scratch test. No delamination of the treated layer could be observed. The wear rate after plasma nitriding is significantly reduced compared to the untreated material. Plasma nitriding produces compressive stress within the modified layer. This treatment improves the fatigue life which can be raised by a factor of ten at a low stress level. The results show that plasma nitriding of austenitic stainless steel is a suitable process for improving the mechanical and the technological properties without significantly effecting the excellent corrosion resistance of this material.     

Enhancing the lifetime and corrosion resistance of gears made of carbon steel

Gears for structural machines require high fatigue strength for high performance. Generally, gears made of carbon steel easily corrode, thus, shortening their fatigue life. The aim of this paper is to improve the fatigue strength of carbon steel gears by means of heat treatment method which was nitriding composed of 95 % nitrogen gas as well as 5 % hydrogen gas, and to investigate its properties after nitriding. Therefore, in order to find the optimum nitriding temperature to increase the hardness and corrosion resistance of gears, the gas nitriding process was conducted at two different tube furnace temperatures: low (550 °C) and high (1150 °C), both for four hours. Microstructural and mechanical property evaluation of the low and high temperature nitrided low-carbon steel BS970-080A15 were studied and the results were compared to identify which gear had better performance in terms of hardness as well as corrosion resistance. The results from Vickers hardness test and weight loss analysis proved that high temperature nitrided carbon steel is harder and more corrosion resistant than the low temperature one.     

Mechanical properties and in vitro cellular behavior of zinc-containing nano-bioactive glass doped biphasic calcium phosphate bone substitutes

In the present study, different amounts (0.5–5 wt%) of a sol gel-derived zinc-containing nano-bioactive glass (NBG-Zn) powder were added to biphasic calcium phosphate (BCP). The mixtures were sintered at 1,100–1,300 °C and physical characteristics, mechanical properties, phase composition and morphology of them were studied. The samples were also soaked in human blood plasma for 15 days to evaluate variations in their surface morphologies. Rat calvarium-derived osteoblastic cells were seeded on tops of various samples and cell adhesion, proliferation, and alkaline phosphatase activity were evaluated at different culturing periods. The maximum bending strength (62 MPa) was obtained for BCP containing 0.5 wt% NBG-Zn at temperature 1,200 °C. This value was approximately 80 % higher than that of pure BCP. The bending strength failed when both sintering temperature and amount of added NBG-Zn increased. At 1,100 °C, NBG-Zn additive did not change the phase composition of BCP. At temperatures 1,200 and 1,300 °C, both alpha-tricalcium calcium phosphate (α-TCP) and beta-tricalcium phosphate (β-TCP and) phases were detected. However, adding higher amount of NBG-Zn to BCP resulted in elevation of β-TCP at 1,200 °C and progression of α-TCP at 1,300 °C. Based on the microscopic observations, adding 0.5 wt% NBG-Zn to BCP led to disappearance of grain boundaries, reduction of micropores and formation of a monolithic microstructure. No calcium phosphate precipitation was observed on sample surfaces after soaking in blood plasma, but some pores were produced by phase dissolution. The size and volume of these pores were directly proportional to NBG-Zn content. Based on the cell studies, both BCP and NBG-Zn-added BCP samples supported attachment and proliferation of osteoblasts, but higher alkaline phosphatase enzyme was synthesized within the cells cultured on NBG-Zn-added BCP. Overall, biphasic calcium phosphate materials with improved mechanical and biological properties can be produced by using small quantity of zinc-containing bioactive glass particles.     

Biocompatibility studies of low temperature nitrided and collagen-I coated AISI 316L austenitic stainless steel

The biocompatibility of austenitic stainless steels can be improved by means of surface engineering techniques. In the present research it was investigated if low temperature nitrided AISI 316L austenitic stainless steel may be a suitable substrate for bioactive protein coating consisting of collagen-I. The biocompatibility of surface modified alloy was studied using as experimental model endothelial cells (human umbilical vein endothelial cells) in culture. Low temperature nitriding produces modified surface layers consisting mainly of S phase, the supersaturated interstitial solid solution of nitrogen in the austenite lattice, which allows to enhance surface microhardness and corrosion resistance in PBS solution. The nitriding treatment seems to promote the coating with collagen-I, without chemical coupling agents, in respect of the untreated alloy. For biocompatibility studies, proliferation, lactate dehydrogenase levels and secretion of two metalloproteinases (MMP-2 and MMP-9) were determined. Experimental results suggest that the collagen protection may be favourable for endothelial cell proliferation and for the control of MMP-2 release.     

Einsatz von Sauerstoffmesszellen beim Plasmanitrieren

In plasma nitriding, nitrocarburizing and carburizing in low pressure range 10 – 300 Pa, the gas potentiometric heatable oxygen probes have been technologically proven in a special design. These oxygen measurement cells are also suitable for the exactly measurement of oxygen partial pressure and of the quotient Q_H = p(H₂O)/p(H₂) in process gas for temperatures under 500 °C. The application has been carried out in different special combinations. In plasma nitriding and nitrocarburizing with a cell working‐temperature of 600 °C, an addition of methane up to 3 vol.‐% doesn’t have any influences on the cell voltage signal. The results show a principle suitability of two probes design with air and solid Cu/Cu₂O reference electrode. For the first time it has been managed to create the prerequisites with a newly developed measuring technique for a systematically examination of the influence of oxygen in plasma assisted processes and for low pressures.     

Influence of Processing Parameters on the Mechanical Properties of a Plasma Radical Nitrided SCM440 Steel

Plasma radical nitriding was performed to harden the surface of SCM440 steel for 1-10 h at temperature range of 450-550℃. This process involved the use of NH3 gas instead of N2 gas employed for the well-established plasma nitriding method. No compound layer was formed during this process except the experiment carried out at 500℃ for 10 h. The main phase produced in the diffusion zone was identified to be γ＇-Fe4（N, C）. A diffusion depth increased with increasing treatment temperature and time （up to about 250 μm）. The surface hardness of radical nitrided layer was about two times higher than that of the untreated surface. The tensile test was carried out to estimate the mechanical properties of surface-hardened SCM440 steel prepared at various plasma radical nitriding treatment time and temperature. The influence of radical nitriding treatment on the tensile strength of the specimen was found to be insignificant. The highest value of the ultimate tensile strength was obtained in the experiment carried out at 500℃ for 1 h. However, the elongation was greatly affected by the radical nitriding processing parameters. The maximum value of elongation, which is equal to about 18.1%, was also obtained under the condition of 500℃ for 1 h.     

In vitro response of primary rat osteoblasts to titania/hydroxyapatite coatings compared with transformed human osteoblast-like cells

The biocompatibility of titania/hydroxyapatite (TiO₂HA) composite coatings, at different ratio obtained by sol–gel process, was investigated studying the behavior of primary cultures of rat osteoblastic cells, isolated by femoral trabecular bone tissue. Moreover, the results have been compared with the response of human osteoblast-like MG63 cell line. Cytotoxicity of coatings was assessed by lactate dehydrogenase activity (LDH). The cellular behavior was analyzed by the cell proliferation (MTT test), cell morphology (SEM) and the biochemical markers evaluation of osteoblastic phenotype, such as alkaline phosphatase activity (ALP) and osteocalcin production. The results showed that TiO₂/HA coatings have no toxic effects and seemed to be a good support for cell adhesion and proliferation. Moreover, these materials allowed the differentiation of osteoblasts, stimulating the expression of alkaline phosphatase activity. The responses of the primary rat osteoblasts and human osteoblast-like MG63 cell line grown onto these coatings were similar in terms of proliferation and ALP activity. Differences were found considering the osteocalcin production. The results show that these coatings, thanks to their chemical composition and the deposition technique, are very promising for the potential orthopedic and dental applications.     

Influence of the microstructure on the corrosion resistance of plasma‐nitrided austenitic stainless steel 304L and 316L

Austenitic stainless steels are widely used in medical and food industries because of their excellent corrosion resistance. However, they suffer from weak wear resistance due to their low hardness. To improve this, plasma nitriding processes have been successfully applied to austenitic stainless steels, thereby forming a thin and very hard diffusion layer, the so‐called S‐phase. In the present study, the austenitic stainless steels AISI 304L and AISI 316L with different microstructures and surface modifications were used to examine the influence of the steel microstructure on the plasma nitriding behavior and corrosion properties. In a first step, solution annealed steel plates were cold‐rolled with 38% deformation degree. Then, the samples were prepared with three kinds of mechanical surface treatments. The specimens were plasma nitrided for 360 min in a H₂–N₂ atmosphere at 420 °C. X‐ray diffraction measurements confirmed the presence of the S‐phase at the sample surface, austenite and body centered cubic (bcc)‐iron. The specimens were comprehensively characterized by means of optical microscopy, scanning electron microscopy, glow discharge optical emission spectroscopy, X‐ray diffraction, surface roughness and nano‐indentation measurements to provide the formulation of dependencies between microstructure and nitriding behavior. The corrosion behavior was examined by potentio‐dynamic polarization measurements in 0.05 M and 0.5 M sulfuric acid and by salt spray testing.     

Hardystonite improves biocompatibility and strength of electrospun polycaprolactone nanofibers over hydroxyapatite: A comparative study

The aim of this study was to compare physico-chemical and biological properties of hydroxyapatite (HA) and hardystonite (HS) based composite scaffolds. Hardystonite (Ca₂ZnSi₂O₇) powders were synthesized by a sol–gel method while polycaprolactone–hardystonite (PCL–HS) and polycaprolactone–hydroxyapatite (PCL–HA) were fabricated in nanofibrous form by electrospinning. The physico-chemical and biological properties such as tensile strength, cell proliferation, cell infiltration and alkaline phosphatase activity were determined on both kinds of scaffolds. We found that PCL–HS scaffolds had better mechanical strength compared to PCL–HA scaffolds. Addition of HA and HS particles to PCL did not show any inhibitory effect on blood biocompatibility of scaffolds when assessed by hemolysis assay. The in vitro cellular behavior was evaluated by growing murine adipose-tissue-derived stem cells (mE-ASCs) over the scaffolds. Enhanced cell proliferation and improved cellular infiltrations on PCL–HS scaffolds were observed when compared to HA containing scaffolds. PCL–HS scaffolds exhibited a significant increase in alkaline phosphatase (ALP) activity and better mineralization of the matrix in comparison to PCL–HA scaffolds. These results clearly demonstrate the stimulatory role of Zn and Si present in HS based composite scaffolds, suggesting their potential application for bone tissue engineering.     

Silk fibroin protein from mulberry and non-mulberry silkworms: cytotoxicity, biocompatibility and kinetics of L929 murine fibroblast adhesion

Silks fibers and films fabricated from fibroin protein of domesticated mulberry silkworm cocoon have been traditionally utilized as sutures in surgery and recently as biomaterial films respectively. Here, we explore the possibility of application of silk fibroin protein from non-mulberry silkworm cocoon as a potential biomaterial aid. In terms of direct inflammatory potential, fibroin proteins from Antheraea mylitta and Bombyx mori are immunologically inert and invoke minimal immune response. Stimulation of murine peritoneal macrophages and RAW 264.7 murine macrophages by these fibroin proteins both in solution and in the form of films assayed in terms of nitric oxide and TNFalpha production showed comparable stimulation as in collagen. Kinetics of adhesion of L929 murine fibroblasts, for biocompatibility evaluation, monitored every 4 h from seeding and studied over a period of 24 h, reveal A. mylitta fibroin film to be a better substrate in terms of rapid and easier cellularization. Cell viability studies by MTT assay and flow cytometric analyses indicate the ability of fibroin matrices to support cell growth and proliferation comparable to collagen for long-term culture. This matrix may have potential to serve in those injuries where rapid cellularization is essential.     

Plasma nitriding of AISI 52100 ball bearing steel and effect of heat treatment on nitrided layer

In this paper an effort has been made to plasma nitride the ball bearing steel AISI 52100. The difficulty with this specific steel is that its tempering temperature (~170–200°C) is much lower than the standard processing temperature (~460–580°C) needed for the plasma nitriding treatment. To understand the mechanism, effect of heat treatment on the nitrided layer steel is investigated. Experiments are performed on three different types of ball bearing races i.e. annealed, quenched and quench-tempered samples. Different gas compositions and process temperatures are maintained while nitriding these samples. In the quenched and quench-tempered samples, the surface hardness has decreased after plasma nitriding process. Plasma nitriding of annealed sample with argon and nitrogen gas mixture gives higher hardness in comparison to the hydrogen–nitrogen gas mixture. It is reported that the later heat treatment of the plasma nitrided annealed sample has shown improvement in the hardness of this steel. X-ray diffraction analysis shows that the dominant phases in the plasma nitrided annealed sample are ε (Fe_2 − 3N) and γ (Fe₄N), whereas in the plasma nitrided annealed sample with later heat treatment only α-Fe peak occurs.