Characterization, Corrosion Resistance, and Cell Response of High-Velocity Flame-Sprayed HA and HA/TiO2 Coatings on 316L SS

The main aim of this study is to evaluate corrosion and biocompatibility behavior of thermal spray hydroxyapatite (HA) and hydroxyapatite/titania bond (HA/TiO₂)-coated 316L stainless steel (316L SS). In HA/TiO₂ coatings, TiO₂ was used as a bond coat between HA top coat and 316L SS substrate. The coatings were characterized by x-ray diffraction and scanning electron microscopy/energy dispersive spectroscopy, and corrosion resistance determined for the uncoated substrate and the two coatings. The biological behavior was investigated by the cell culture studies using osteosarcoma cell line KHOS-NP (R-970-5). The corrosion resistance of the steel was found to increase after the deposition of the HA and HA/TiO₂ bond coatings. Both HA, as well as, HA/TiO₂ coatings exhibit excellent bond strength of 49 and 47?MPa, respectively. The cell culture studies showed that HA-coated 316L SS specimens appeared more biocompatible than the uncoated and HA/TiO₂-coated 316L SS specimens.     

Al2O3–TiO2 composite coatings with enhanced anticorrosion properties for 316L stainless steel

316L stainless steel is used as an important structural material in various industries. However, its service life is limited in the presence of chloride ions due to severe chemical corrosion. Herein, a facile radiofrequency magnetron sputtering process is reported for the synthesis of various Al₂O₃–TiO₂ composite coatings as an anticorrosion layer for 316L stainless steel substrates. The enhanced chemical stability of Al₂O₃–TiO₂ composite coatings was investigated by X-ray photoelectron spectroscopy, electron paramagnetic resonance, and X-ray diffraction measurements. Moreover, the high specific surface area of Al₂O₃–TiO₂ composite coatings displayed better hydrophobic property which can be confirmed by scanning electron microscopy and contact angle measurements. Finally, the direct characterization of anticorrosion properties was carried out using electrochemical tests. All of the above results exhibited the enhanced anticorrosion properties of Al₂O₃ coating after the incorporation of TiO₂. Significantly, the Al₂O₃–TiO₂ composite coatings with 15.56% Ti content provided the best corrosion resistance for 316L stainless steel.     

The examination of corrosion behaviors of hap coated Ti implant materials and 316L SS by sol-gel method

In this research, hydroxyapatite (HAP) coatings have been produced on Ti, Ti6Al4V alloy and 316L stainless steel substrates by sol-gel method. (NH₄) · H₂PO₄ is taken as P precursor and Ca(NO₃)₂ · 4H₂O is taken as Ca precursor to obtain HAP coating. Additionally, three different pretreatment processes (HNO₃, anodic polarization, base-acide (BA)) have been applied to Ti, Ti6Al4V alloy and 316L stainless steel substrates. The corrosion behaviors of bare and HAP coated samples are examined in Ringer and 0.9% NaCl. HAP coated Ti have showed over 87.85% inhibition. HAP coated Ti6Al4V alloys have showed over 87.33% inhibition. In Ringer solution, 99.24% inhibition has been showed in HAP coated anodic pretreatment for 316L stainless steel. All pretreatment processes are effective on clinging of HAP coating to the surface. It is seen that impedance values have increased in HAP coatings (Ti and Ti6Al4V). HAP coatings have raised the corrosion resistance of Ti and Ti6Al4V. The values of polarization resistance in HAP coated samples have increased for 316L stainless steel in 0.9% NaCl and Ringer solutions. It is seen in SEM images that open pores and attachments among pores have been observed in the coating, which increases osteointegration. It is noted in EDX analyses of the surfaces of the HAP coated samples that there is only Ca, O, and P on the surface. Ca/P ratio varies in 1.84–2.00 ranges. As Ca/P ratio increases, the inhibition increases too. It is seen in XRD images of HAP powder that there are HA ate structures. Additionally, it is seen in FTIR analysis, characteristic HA absorption bands have occurred in sintered powders.     

Preparation and characterisation of electrophoretically deposited hydroxyapatite coatings on type 316L stainless steel

Hydroxyapatite (HAP) coatings were developed on type 316L stainless steel (SS) by electrophoretic deposition at various deposition potentials from 30 to 90 V using the stoichiometric HAP (Ca/P ratio 1.67) powder in a suspension of isopropyl alcohol. The optimum coating parameters were established at 60 V and 3 min, after vacuum sintering at 800 °C. The phase purity of the coated surface was confirmed by XRD and secondary ion mass spectrometry confirmed the presence of both Ca and P on the coated layers. The electrochemical corrosion parameters E_corr (open circuit potential) and pitting potentials, evaluated in Hank’s solution shifted towards noble direction for the HAP coated specimens in comparison with uncoated type 316L SS. Electrochemical impedance spectroscopic investigations revealed higher polarisation resistance and lower capacitance values after immersing the coated specimens in Hanks solution for 200 h. This indicates the stable nature of the coatings formed.     

Pack Cementation Coatings for High-Temperature Oxidation Resistance of AISI 304 Stainless Steel

Aluminum and titanium are deposited on the surface of steel by the pack cementation method to improve its hot-corrosion and high-temperature oxidation resistance. In this research, coatings of aluminum and titanium and a two-step coating of aluminum and titanium were applied on an AISI 304 stainless steel substrate. The coating layers were examined by carrying out scanning electron microscopy (SEM) and x-ray diffraction (XRD). The SEM results showed that the aluminized coating consisted of two layers with a thickness of 450???m each, the titanized coating consisted of two layers with a thickness of 100???m each, and the two-step coatings of Al and Ti consisted of three layers with a thickness of 200???m each. The XRD investigation of the coatings showed that the aluminized coating consisted of Al₂O₃, AlCr₂, FeAl, and Fe₃Al phases; the titanized layers contained TiO₂, Ni₃Ti, FeNi, and Fe₂TiO₅ phases; and the two-step coating contained AlNi, Ti₃Al, and FeAl phases. The uncoated and coated specimens were subjected to isothermal oxidation at 1050?°C for 100?h. The oxidation results revealed that the application of a coating layer increased the oxidation resistance of the coated AISI 304 samples as opposed to the uncoated ones.     

Enhancing Biocompatibility and Corrosion Resistance of Ti-6Al-4V Alloy by Surface Modification Route

Titanium (Ti) and its alloys are widely used as candidate materials for biomedical implants. Despite their good biocompatibility and corrosion resistance, these materials suffer from corrosion after implantation in biological environments. The aim of this research work is to study the effect of two coatings on biocompatibility and corrosion behavior of Ti-6Al-4V biomedical implant material. Hydroxyapatite (HA) and hydroxyapatite/titanium dioxide (HA/TiO₂) coatings were thermal-sprayed on Ti-6Al-4V substrates. In the latter case, TiO₂ was used as a bond coat between the substrate and HA top coat. The corrosion behavior of coated and un-coated samples in Ringer’s solution was studied by potentiodynamic and linear polarization techniques. Before and after corrosion testing, XRD and SEM/EDS techniques were used for the analysis of phases formed and to investigate microstructure/compositional changes in the coated specimens. The cellular response was analyzed by the MTT (microculture tetrazolium) assay. The results showed that both the HA, as well as, the HA/TiO₂ coatings significantly increased the corrosion resistance of the substrate material. The HA coating was found to be more biocompatible as compared to the un-coated and HA/TiO₂-coated Ti-6Al-4V alloy.     

Synthesis and Characterization of Hydroxyapatite/TiO<Subscript>2</Subscript> Coatings on the β-Type Titanium Alloys with Different Sintering Parameters using Sol-Gel Method

In this study, hydroxyapatite (HA) based composite films were successfully syntheses on the β-type Ti29Nb13Ta4.6Zr (TNTZ). The solutionized TNTZ substrates coated with HA and HA/Titania (TiO₂) bioactive composite coatings by sol-gel method under various sintering parameters related to sintering temperatures and heating ramp rates. Microstructural observations of the coatings revealed that apatite was formed on the substrates. The hardness values of the coatings increase with increasing both the sintering temperature and the TiO₂ concentration in the coatings layer. However, it was found that the heating ramp rate of the sintering was not affecting the hardness values so much. Also, the hardness values of the HA/TiO₂ composite coatings at all sintering temperatures were higher than only HA coated TNTZ samples due to the existence TiO₂ phases in the HA matrix. Results indicating that the doping of HA with TiO₂, improve the physical consistency between the coating layer and the substrates and provide a better inter-particle bonding due to the existence TiO₂ phases in the HA.     

The Effect of Water Vapor on the Oxidation Behavior of CVD Iron-Aluminide Coatings

The oxidation behavior of iron-aluminide coatings, Fe₃Al or (Fe,Ni)₃Al, produced by chemical-vapor deposition (CVD) was studied in the temperature range of 700–800°C in air + 10 vol.% H₂O. A typical ferritic steel, Fe–9Cr–1Mo, and an austenitic stainless steel, 304L, were coated. For both substrates, the as-deposited coating consisted of a thin (<5μm), Al-rich outer layer above a thicker (30–50 μm), lower-Al-content inner layer. In addition to coated and uncoated Fe–9Cr–1Mo and 304L, cast Fe–Al model alloys with similar Al contents (13–20 at.%) to the CVD coatings were included in the oxidation exposures for comparison. The specimens were cycled to 1000 1 hr cycles at 700°C and 500 1 hr cycles at 800°C, respectively. The CVD coating specimens showed excellent performance in the water-vapor environment at both temperatures, while the uncoated alloys were severely attacked. These results suggest that an aluminide coating can substantially improve resistance to water-vapor attack under these conditions.     

Corrosion Inhibition of 304 Stainless Steel by Nano-Sized Ti/Silicone Coatings in an Environment Containing NaCl and Water Vapor at 400–600°C

The corrosion behavior of 304 stainless steel (SS) and its corrosion inhibition by brushing nano-sized Ti/silicone coatings on its surface in an environment containing a solid NaCl deposit and water vapor at 400–600°C was studied. Results indicated that water vapor or NaCl, especially water vapor plus NaCl accelerated the corrosion of the steel markedly. The corrosion scales of the uncoated steel had a duplex structure at 400–500°C and internal oxidation occurred for the uncoated steel at 600°C in an environment containing NaCl and water vapor. The corrosion of the 304SS was inhibited efficiently by the coatings at 400–500°C, and the coated steel suffered corrosion to some extent and most of the coatings were destroyed at 600°C. X-ray diffraction (XRD) indicated that the corrosion products of the uncoated steel were mainly Fe₂O₃, Cr₂O₃, NiO or Na₂CrO₄, and the coatings consisted mainly of TiO₂ and SiO₂ after exposure at 400–500°C. The good corrosion resistance of the nano-sized Ti/silicon coatings was attributed to the formation of SiO₂, and TiO₂ that resulted from the decomposition of the organic components in the coating and fast oxidation of nano-Ti powder respectively during the experiments, TiO₂ mixed together with SiO₂ and formed a new coating on the steel surface that played an important role in the protection of the steel.     

Corrosion behaviors of arc spraying single and double layer coatings in simulated Dagang soil solution

Three kinds of single layer coatings of Zn, Zn15Al, 316L stainless steel and two kinds of double layer coatings with inner layer of Zn or Zn15Al and outer layer of 316L stainless steel by arc spraying were developed to protect the metal ends of prestressed high-strength concrete (PHC) pipe piles against soil corrosion. The corrosion behaviors of the coated Q235 steel samples in the simulated Dagang soil solution were investigated by potentiodynamic polarization, electrochemical impedance spectroscopy (EIS) and natural immersion tests. The results show that the corrosion of the matrix Q235 steel is effectively inhibited by Zn, Zn15Al, Zn+316L and Zn15Al+316L coatings. The corrosion rate value of Zn15Al coated samples is negative. The corrosion products on Zn and Zn15Al coated samples are compact and firm. The corrosion resistance indexes of both Zn and Zn15Al coated samples are improved significantly with corrosion time, and the latter are more outstanding than the former. But the corrosion resistance of 316L coated samples is decreased quickly with the increase in immersion time. When the coatings are sealed with epoxy resin, the corrosion resistance of the coatings will be enhanced significantly.     

Amorphous carbon coated stainless separator for PEFCs

An SUS316L stainless steel separator was coated with amorphous carbon by using an electron cyclotron resonance (ECR) plasma sputtering technique, and used in a polymer electrolyte fuel cell (PEFC). Characteristics of this carbon film were investigated with Raman spectroscopy and XPS. Quantitative depth profiles and chemical depth profiles of the deposited carbon layer were measured with GD-OES and XPS, respectively. The contact resistivity between a carbon paper and the carbon coated SUS316L steel was also measured. The performance of PEFC single cells assembled with carbon coated SUS316L separators, uncoated SUS316L separators, and conventional carbon separators were compared. The results revealed that an assembled PEFC having carbon coated SUS316L separators provided better performance than one having uncoated SUS316L, and the PEFC showed comparable performance to one having conventional carbon separators.     

大气等离子喷涂TiB2-316L不锈钢基复合涂层及其耐磨性能

分别采用高能球磨制备了TiB2含量(质量分数)为10%的316L不锈钢基复合粉,高能球磨与喷雾干燥造粒工艺制备了TiB2含量(质量分数)为40%的316L不锈钢基复合粉,大气等离子喷涂制备相应的TiB2-316L不锈钢基金属陶瓷涂层与316L不锈钢涂层.室温下采用高速环块磨损试验研究TiB2-316L不锈钢基金属陶瓷涂层的磨损特性.采用X射线衍射分析涂层物相,扫描电镜分析喷涂粉末、涂层结构和摩擦副磨损表面形貌.结果表明,大气等离子喷涂两种制粉工艺获得的316L不锈钢基TiB2复合粉能获得较耐磨的316L不锈钢基TiB2复合涂层,耐磨性高于316L不锈钢涂层,且TiB2在复合涂层中增强涂层耐磨性的原因是TiB2颗粒在涂层316L韧性基体中充当强化相,且TiB2在摩擦接触处摩擦氧化形成的氧化产物具有自润滑特性,能减少涂层的磨损量.     

In vitro electrochemical evaluation and phase purity of natural hydroxyapatite coating on medical grade 316L stainless steel

Natural hydroxyapatite (HA) has been electrophoretically deposited on the surface of medical grade 316L stainless steel (SS). Deposition was performed at various applied voltages of 30, 60, and 90 V for 3 min. After deposition the samples were dried at room temperature and sintered in a vacuum furnace (10⁻⁴–10⁻⁵ Torr) at 800 ^°C for 1 h. In vitro electrochemical studies were performed in the Hank's solution. The results showed that corrosion potential and breakdown potential of the coated samples shifted toward nobler potential compared with the uncoated 316L SS. Electrochemical impedance spectroscopy investigations revealed a higher polarization resistance, total impedance, and lower capacitance values for the coated samples compared to the bare one which indicated the improvement of corrosion resistance of the coated samples. The surface morphology of the samples was studied by a scanning electron microscope, and also phase purity and crystallinity of the coating material were investigated by X-ray diffraction. Deposition at 60 V for 3 min was found to be an optimum coating condition which led to the uniform, continuous, and crack-free coatings. The crystallinity of the coating materials was measured to be high, and quantitative analysis of the coatings after sintering showed some partial decomposition of natural HA to tricalcium phosphate.     

Finite element modelling of the thermo-mechanical behavior of coatings under extreme contact loading in dry machining

During metal cutting processes, intensive friction and high temperature generated at the tool chip interface affect the cutting zone of the tool, by inducing damage and wear. To improve the cutting tool's life, thin hard coatings, synthesized by physical or chemical vapor deposition (PVD or CVD) techniques, are often used as protective layers. In this work, numerical/theoretical analysis of dry machining has been performed to study the impact of different coating layers on the machining process. Four cases are considered: an uncoated tool made of tungsten carbide (WC-Co) and coated tungsten carbides in three different configurations. The first one is made of one layer namely TiN, the second one (hypothetical carbide insert) is composed of two layers (Al₂O₃ and TiN), and the last one has three layers (TiCN, Al₂O₃ and TiN). The workpiece material is an AISI 316L stainless steel. All cutting conditions are fixed in order to highlight the effect of coatings independently from others influencing parameters. The analysis has shown the impact of the different configurations of coatings on the temperature level inside the tool and on its surface, on the pressure and also on the cutting and feed forces.     

Behaviour in hot ammonia atmosphere of SiO2-coated stainless steels produced by a sol-gel procedure

AISI 304 stainless steel coated with silica films obtained by a sol-gel procedure was tested together with uncoated 304 and 316 samples in anhydrous ammonia at high temperature. The highest rate of attack was experienced by all uncoated samples; the ammonia attack develops a nitride scale that embrittles the metal. After 115 h of testing at 500°C uncoated samples were completely degraded, while the coated 304 samples were lightly attacked. The SiO₂ coating is a good barrier against ammonia corrosion. The multilayer coatings provide lower corrosion protection than single-layer coatings.     

Sol-gel derived HA/TiO2 double coatings on Ti scaffolds for orthopaedic applications

Hydroxyapatite/titania （HA/TiO2） double layers were coated onto Ti scaffolds throughout for orthopaedic applications by sol-gel method. Differential scanning calorimetry （DSC）, thermogravimetric analysis （TG） and X-ray diffractometry （XRD） were used for the characterisation of the phase transformations of the dried gels and coated surface structures. Scanning electron microscope （SEM） equipped with energy dispersive spectrometry （EDS） was used for the observation and evaluation of the morphology and phases of the surface layers and for the assessment of the in vitro tests. The in vitro assessments were performed by soaking the HA/TiO2 double coated samples into the simulated body fluid （SBF） for various periods. The TiO2 layer was coated by a dipping-coating method at a speed of 12 cm/min, followed by a heat treatment at 600 ℃ for 20 min. The HA layer was subsequently dipping-coated on the outer surface at the same speed and then heat-treated at difference temperatures. The results indicat that the HA phase begins to crystallize after a heat treatment at 560 ℃. The crystallinity increases obviously at 760 ℃. SEM observations find no delamination or crack at the interfaces of HA/TiO2 and TiO2/Ti. The HA/TiO2 coated Ti scaffolds displays excellent bone-like apatite forming ability when it is soaked into SBF. Ti scaffolds after HA/TiO2 double coatings can be anticipated as promising implant materials for orthopaedic applications     

316L表面激光熔覆复合等离子体电解氧化制备多孔陶瓷涂层及其生物应用（英文）

为了提高316L不锈钢的生物活性,采用激光熔覆(LC)技术在316L不锈钢表面制备钛层,然后利用等离子体电解氧化(PEO)技术在钛层上形成多孔陶瓷涂层。采用三维表面轮廓仪、SEM、EDS、XRD和XPS等测试方法对涂层试样的形貌、微观结构和组成进行表征。通过动电位极化曲线和模拟体液(SBF)浸泡试验,分别对涂层的耐腐蚀性和生物活性进行评价。结果表明,多孔陶瓷涂层主要由锐钛矿和金红石组成,并检测到高结晶HA。陶瓷涂层的主要元素为Ca、P、Ti和O。在模拟体液中,LC+PEO复合生物涂层比316L基质具有更优异的耐腐蚀性,并且复合涂层能有效提高316L不锈钢的生物活性。     

Improvement in corrosion resistance of CrN coated stainless steel by conformal TiO2 deposition

A conformal titanium dioxide (TiO₂) layer was deposited onto chromium nitride (CrN) coated stainless steel by atomic layer deposition technique, and the electrochemical corrosion test on the CrN single-layer and TiO₂/CrN double-layer coated sample was carried out. The equilibrium corrosion potential of the double-layer coated sample shifted positively compare to that of the single-layer coated one. Moreover, the corrosion current density decreased significantly with the TiO₂ deposition, revealing that better corrosion resistance was obtained after the deposition of the TiO₂ layer. The improvement in corrosion resistance after the TiO₂ deposition was attributed to the blocking of the through-thickness cracks or pinholes in the CrN layer.     

相对流速对316L钢焊缝在液态铅铋合金中腐蚀行为的影响

在核工业领域,316L不锈钢因其优异的性能常被作为核用钢种,液态铅铋合金常作为加速器次临界驱动系统(ADS)的冷却剂,高速流动的液态铅铋合金(LBE)会对316L不锈钢焊缝造成氧化腐蚀,同时氧化腐蚀后的产物也会对液态LBE造成污染,所以研究316L不锈钢焊缝在液态铅铋合金中的腐蚀行为具有重要意义. 文中对比研究了使用母材作为焊丝进行TIG焊的316L不锈钢焊缝在550 ℃动态(相对流速为1.70,2.31,2.98 m/s)液态LBE中的耐腐蚀性能,试验时间为1 500 h. 结果表明,三组试样都生成了双氧化层,外氧化层主要为Fe₃O₄,内氧化层主要为FeCr₂O₄,内氧化层相对于外氧化层较致密;随着流速的提高,元素的传质过程变快,氧化腐蚀加剧,内氧化层增厚.     

Erosion-corrosion behavior of nano-particle-reinforced Ni matrix composite alloying layer by duplex surface treatment in aqueous slurry environment

The present study concerns a duplex surface treatment of AISI 316L stainless steel to enhance the erosion-corrosion resistance. The duplex surface treatment consisted of Ni/nano-SiC and Ni/nano-SiO₂ predeposited by brush plating and a subsequent surface alloying with Ni-Cr-Mo-Cu by double glow process of the substrate. Results showed that under alloying temperature (1000 °C) condition, the amorphous nano-SiO₂ particles still kept the amorphous structure, whereas the nano-SiC particles had been completely decomposed and Ni, Cr reacted with SiC to form Cr_6.5Ni_2.5Si and Cr₂₃C₆. The electrochemical corrosion behaviors of composite alloying layers compared with the single alloying layer and 316L stainless steel were measured under a range of hydrodynamic conditions by recording the current response, open circuit potential, potentiodynamic polarization curves and electrochemical impedance spectroscopy (EIS). Results showed that the increase of the impact velocity had significant influence on the current density of composite alloying layer with brush plating Ni/nano-SiC particles interlayer obtained under flowing condition at a potential of 200 mV, whereas there were only small fluctuations occurred at current response of composite alloying layer with brush plating Ni/nano-SiO₂ particles interlayer. The results of potentiodynamic polarization indicated that, with increasing impact velocity under slurry flow conditions, the corrosion potentials of test materials decreased and the corrosion current densities of test materials increased. The corrosion resistance of composite alloying layer with brush plating Ni/nano-SiO₂ particles interlayer was prominently superior to that of single alloying layer under slurry flow conditions; the corrosion resistance of composite alloying layer with brush plating Ni/nano-SiC particles interlayer was evidently lower than that of single alloying layer, but higher than that of 316L stainless steel under slurry flow conditions. The results of EIS indicated that, with respect to the R_tot obtained in sand-free flow, the impacts of sand particles dramatically decreased the R_tot values of composite alloying layer with brush plating Ni/nano-SiC particles interlayer, single alloying layer and 316L stainless steel, whereas the impact action slightly decreased that of composite alloying layer with brush plating Ni/nano-SiO₂ particles interlayer. The weight loss rate studies suggested that the highly dispersive nano-SiO₂ particles were helpful to improve the erosion-corrosion resistance of composite alloying layer, whereas the carbides and silicide phase were deleterious to that of composite alloying layer due to the fact that preferential removal of matrix around the precipitated phase takes place by the chemical attack of aggressive medium.