Fabrication of thin film TiO2 nanotube arrays on Co–28Cr–6Mo alloy by anodization

Titanium oxide (TiO₂) nanotube arrays were prepared by anodization of Ti/Au/Ti trilayer thin film DC sputtered onto forged and cast Co–28Cr–6Mo alloy substrate at 400 °C. Two different types of deposited film structures (Ti/Au/Ti trilayer and Ti monolayer), and two deposition temperatures (room temperature and 400 °C) were compared in this work. The concentrations of ammonium fluoride (NH₄F) and H₂O in glycerol electrolyte were varied to study their effect on the formation of TiO₂ nanotube arrays on a forged and cast Co–28Cr–6Mo alloy. The results show that Ti/Au/Ti trilayer thin film and elevated temperature sputtered films are favorable for the formation of well-ordered nanotube arrays. The optimized electrolyte concentration for the growth of TiO₂ nanotube arrays on forged and cast Co–28Cr–6Mo alloy was obtained. This work contains meaningful results for the application of a TiO₂ nanotube coating to a CoCr alloy implant for potential next-generation orthopedic implant surface coatings with improved osseointegrative capabilities.     

Characterisation of detonation sprayed Mo–Co–Cr–B alloy coatings

Abstract

A novel thermal spray material of Mo–Co–Cr–B with high durability in molten alloys has been developed to utilise for die casting parts and for galvanising bath parts. In the present paper, detonation gun (D gun) spray technique was used to deposit a Mo–Co–Cr–B alloy coating onto 316L stainless steel substrate, and the microstructures and mechanical properties of the coating system were studied using XRD, SEM, tensile test and Vickers microhardness. The results show that the microstructures of the coating consisted of ternary transition metal borides matrix CoMo₂B₂, CoMoB, as well as a little amount of binary borides, MoB and CrB. The ternary borides matrix contained both amorphous phase and nanocrystalline grains with a size of 60±35 nm. The bond strength of the coating decreases with increasing thickness of the as sprayed coatings. The anisotropy in the mechanical properties between the cross-section and plan section of the coatings is examined. Comparing the microhardness and bond strength of detonation sprayed Mo–Co–Cr–B coating with those of HVOF sprayed Mo–Co–Cr–B coating, it can be concluded that the detonation spray process has a better performance than HVOF spray process.     

Coatings and hardfacing alloys for corrosion and wear resistance in diesel engines

Abstract

The potential for surface engineering solutions to increase the corrosion and wear resistance of diesel valves is examined with regard to operation in residual fuel oil combustion products. The environment in which the exhaust valve operates is discussed. The corrosion test is used to sort the 27 coating treatments and 16 hardfacing alloys examined. H ardfacing materials showing the greatest potential are also evaluated in hot wear tests. As reference materials, En 52 steel, Nimonic 80A, and Stellite 6 are included. Corrosion tests over the temperature range 500–700°C have shown that the surface treatments can be ranked in terms of their composition and expected metal surface temperature. Good corrosion resistance to residual fuel oil combustion products reflects primarily the content of the alloy, the base metal (Fe, Ni, or Co) being of secondary importance. Refractory metals (Ti, Nb, Ta, Mo, and W) and other minor alloying additions do not significantly alter the corrosion behaviour, unless they are present in large quantities. Hot wear tests (650°C, 80 MN m^?2 contact pressure) of candidate hardfacing alloys have also demonstrated the importance of the Cr content of the alloy. This probably results from the ease of formation of a protective glaze, lowering the coefficient of friction and therefore the wear rate. Additions of refractory metals were beneficial. Since optimum wear resistant alloys contained high levels of Mo and vv: they were poor in terms of corrosion resistance. It is therefore necessary to balance wear resistance against corrosion resistance in the selection of materials for residual fuel oil service. Two coating systems, vacuum plasma sprayed Ni–50Cr and a chromised diffusion treatment appeared to have potential as valve surface treatments for improved corrosion resistance; and two hardfacing alloys, Tristelle TS2 and Colmonoy 8, offered balanced behaviour as seat materials with acceptable wear resistance and improved corrosion performance. These materials have been evaluated in the engine tests of three different diesel engine manufacturers.

MST/3157     

微弧氧化处理对多孔Ti-15Mo合金显微结构、耐磨性和耐蚀性的影响

在铝酸盐电解液中对多孔Ti-15Mo合金进行微弧氧化表面改性。利用SEM和XRD研究多孔合金微弧氧化涂层的显微结构和相组成。采用显微硬度计、动电位极化曲线和球-盘摩擦磨损仪分析微弧氧化处理对多孔Ti-15Mo合金硬度、耐蚀性和耐磨性的影响。结果表明,微弧氧化处理未改变多孔Ti-15Mo合金原有的孔隙率和孔径,在合金表面和孔隙内壁呈现典型的粗糙多孔微弧氧化形貌。微弧氧化涂层主要由金红石TiO_2和Al_2TiO_5相组成。经微弧氧化处理后,多孔Ti-15Mo合金的表面显微硬度提高了32%,摩擦系数降低了近50%,磨损率大幅度下降,磨损机制由磨粒磨损转变为粘着磨损。微弧氧化处理后多孔Ti-15Mo合金的耐蚀性较基体提高了近1个数量级,微弧氧化陶瓷涂层的保护效率高达90.78%。     

Influence of Coating Parameter and Sintering Atmosphere on the Corrosion Resistance Behavior of Electrophoretically Deposited Composite Coatings

The purpose of this study is to synthesize and characterize nanosized titania (TiO₂), zinc oxide (ZnO), and its composite coating on Ti–6Al–4V to enhance its corrosion protection behavior in Ringer's solution. Nanosized powders of TiO₂ and ZnO was characterized by Fourier transform infrared spectroscopy (FTIR), powder X-ray diffraction (XRD), and scanning electron microscopy - energy dispersive atomic spectroscopy (SEM-EDAX) analysis. As a result of antibacterial activity, both ZnO and TiO₂/ZnO have produce remarkable inhibition zone on Escherichia coli. The antibacterial activity of composites are due to the combined effect of ZnO on TiO₂. The adherence and surface uniformity of TiO₂/ZnO composite film on titanium implant was examined by optical microscopy and Vickers microhardness test. Corrosion resistant behavior of the coating on titanium implant was investigated by tafel polarization and impedance analysis. The composite coatings on Ti–6Al–4V have produced improved corrosion resistance with a pronounced shift in the anodic corrosion potential (E_corr) with a corresponding less corrosion current density (I_corr) compared to monophase coating. Similar results have been obtained for impedance analysis which indicated a reduction in double layer capacitance (C_dl) and with enhancement in charge transfer resistance (R_ct). These observations suggest improved corrosion resistance property of TiO₂/ZnO composite coating on Ti–6Al–4V.     

Biomimetic growth of apatite on electrolytic TiO2 coatings in simulated body fluid

Titanium and titanium alloys for implants have been widely applied to the orthopaedic and dental fields, due to their excellent corrosion resistance, good mechanical properties and biocompatibility. However, the near bioinert and metallic ions release are still the major problems in the clinical failure. For these reasons, modification of biomaterials surface properties, which support bioactivity and corrosion resistance, should be one of the key objectives in the design of the next generation of orthopaedic/dental implants. Cathodic electrolytic deposition of anatase TiO₂ coating has been successfully deposited on pure titanium substrate. After annealed at 300 °C for 1 h, the coating were further condensed into anatase TiO₂, and gradually transformed into rutile TiO₂ at 500 °C. The dynamic cyclic polarization tests indicated that dense and nanocrystalline anatase TiO₂ coated effectively improved corrosion resistance to avoid aggression of fluoride ion. For immersion tests, the matching structure of anatase TiO₂ and apatite may play an important role in the apatite formation ability. Moreover, the cell culture results also indicated that nanocrystalline anatase TiO₂ not only promoted cells differentiation, but also appeared more bioactive while maintaining non-toxicity. Obviously, the materials characteristics such as crystal structure, surface morphology and corrosion resistance may play an important role in the osteointegration.     

Effect of different catalyst supports on the (n,m) selective growth of single-walled carbon nanotube from Co–Mo catalyst

Co–Mo catalysts supported on four different high surface area oxides (SiO₂, Al₂O₃, MgO, and TiO₂) were evaluated to investigate the (n,m) selectivity control in single-walled carbon nanotube (SWCNT) synthesis. Results from Raman spectroscopy and thermogravimetric analysis showed that Co–Mo catalysts supported on SiO₂ and MgO possessed good selectivity toward SWCNTs, while photoluminescence and ultraviolet–visible–near-infrared spectroscopy results indicated that these two catalyst supports induced the same (n,m) selectivity to near-armchair tubes, such as (6,5) and (7,5) tubes. Catalysts supported on TiO₂ produced a mixture of multi-walled carbon nanotubes (MWCNTs) and SWCNTs, whereas catalysts supported on Al₂O₃ mainly grew MWCNTs. Characterization of catalysts by ultraviolet–visible diffuse reflectance spectroscopy suggested that the surface morphology of metal clusters over different supports was not directly responsible for the (n,m) selectivity. Analysis of monometallic (Co or Mo) and bimetallic (Co–Mo) catalysts using temperature program reduction demonstrated that catalyst supports changed the reducibility of metal species. The interaction between supports and Co/Mo metals perturbed the synergistic effect between Co and Mo, leading to the formation of different metal species that are responsible for the observed distinction in SWCNT synthesis.     

Improvement of sulfide-corrosion resistance of gas-turbine blades with sufficient heat resistance by rational alloying

We present the results concerning the influence of alloying elements (Cr, Al, Ti Mo, W, Nb, and Co) on sulfide corrosion resistance in a 75% Na₂SO₄+25% NaCl melt at a temperature of 900°C for 30 h and heat resistance (τ ₂₀₀ ⁹⁰⁰ ) of nickel alloys. To provide high resistance to sulfide corrosion and longterm strength at the level of τ ₂₀₀ ⁹⁰⁰ , nickel-base alloys must contain 14–16% Cr, Ti/Al=0.8–1.5 for ∑Al+Ti=6–7.5%, Cr/Al≥6, , 3–4% Mo, 3–4% W, 4–6% Co, and 1.5–2% Nb. Frantsevych Institute for Problems in Materials Science, Ukrainian Academy of Sciences, Kiev. Translated from Fizyko-Khimichna Mekhanika Materialiv, Vol. 35, No. 4, pp. 79–83, July–August, 1999.     

Effect of microalloying with silicon on high temperature oxidation resistance of novel refractory high-entropy alloy Ta-Mo-Cr-Ti-Al

Abstract

The effect of 1 at.% Si addition to the refractory high-entropy alloy (HEA) Ta–Mo–Cr–Ti–Al on the high temperature oxidation resistance in air between 900 °C and 1100 °C was studied. Due to the formation of protective chromia-rich and alumina scales, the thermogravimetric curves for Ta–Mo–Cr–Ti–Al and Ta–Mo–Cr–Ti–Al–1Si showed small mass changes and low oxidation rates which are on the level of chromia-forming alloys. The oxide scales formed on both alloys at all temperatures are complex and consist of outermost TiO₂, intermediate Al₂O₃, and (Cr, Ta, Ti)-rich oxide at the interface oxide/substrate. The Si addition had a slightly detrimental effect on the oxidation resistance at all temperatures primarily as a result of increased internal corrosion attack observed in the Si-containing HEA. Large Laves phase particles distinctly found in the Si-containing alloy were identified to be responsible for the more rapid internal corrosion.     

Hot corrosion of two nickel-base superalloys under alkali sulfate deposition conditions

Abstract

The single crystal MD2 (Ni – 8Cr – 5Al –5Co– 2Mo– 8W–6Ta – 1Ti) and the polycrystalline Inconel 792 (Ni –13Cr – 3Al –9Co– 2Mo– 4W–4Ta– 4Ti) were exposed at 850 and 900°C in an severely sulfidising environment comprising synthetic air with 8% water vapour and 2000 ppm SO₂, and a deposit of 20 mol% Na₂SO₄+80 mol% K₂SO₄ applied every 160 hours.

Results were evaluated in terms of mass change, which indicated the existence of an incubation time before the onset of extensive attack, and post-test metallography to evaluate metal loss. Metallographic studies are presented showing the complex external oxide scale formation and internal oxidation and sulfidation.     

激光熔敷钴合金涂层的抗空蚀和冲刷磨损性能

采用激光熔敷方法在20SiMn低合金钢表面制成了Co合金涂层，以两种目前水轮机转用材20SiMn低合金钢和0Cr13Ni5Mo不锈钢作为对比材料，对涂层进行了空蚀，液固两相流冲刷磨损及空蚀和冲刷磨损联合作用实验，采用失重法并结合能谱分析，X射线衍射分析及显微硬度测量等手段研究了涂层的显微结构和在不同形式损伤下涂层的性能并分析了原因。结果表明：在20SiMn低合金钢表面激光熔敷形成的Co合金涂层有良好的抗空蚀性能，这与涂层在空蚀过程中发生的应力诱发马氏体相变密切相关。良好的抗空蚀性能有利于提高涂层抗空蚀和冲刷磨损联合破坏，从而使涂层表现出与0Cr13Ni5Mo不锈钢接近的抗联合损伤性能。     

In vitro biological,chemical and electrochemical evaluation of titania reinforced hydroxyapatite sol–gel coatings on surgical grade 316L SS

Development and characterization of titania (TiO₂)/Hydroxyapatite (HAP) reinforced coating derived by sol–gel dip coating process was studied. Structural, electrochemical and biological behavior of the reinforced coatings were conducted and elaborated in this paper. The bonding between the HAP matrix and TiO₂ reinforcement might have been achieved predominantly through a chemical bond that resulted from the mutual chemical reaction among the components. In vitro electrochemical studies of the reinforced coatings shows good corrosion resistance and minimum leach out of metal ions in the simulated body fluid (Hank's balanced salt solution) environment. The cell culture cytotoxicity studies were also carried out using L929 cell line. Cell culture studies showed that the reinforced coatings were non-cytotoxic to mouse fibroblast cell line. On the basis of these observations, it's concluded that the titania reinforced materials are biocompatible and corrosion resistant and hence are a candidate material for biomedical applications.     

Dry sliding wear behavior and corrosion resistance of NiCrBSi coating deposited by activated combustion-high velocity air fuel spray process

NiCrBSi is a Ni-based superalloy widely used to obtain high wear and corrosion resistant coatings. This Ni-based alloy coating has been deposited onto 0Cr13Ni5Mo stainless steel using the AC-HVAF technique. The structure and morphologies of the Ni-based coatings were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy-dispersive spectrometer (EDS). The wear resistance and corrosion resistance were studied. The tribological behaviors were evaluated using a HT-600 wear test rig. The wear resistance of the Ni-based coating was shown to be higher than that of the 0Cr13Ni5Mo stainless steel because Fe₃B, with high hardness, was distributed in the coating so the dispersion strengthening in the Ni-based coating was obvious and this increased the wear resistance of the Ni-based coating in a dry sliding wear test. Under the same conditions, the worn volume of 0Cr13Ni5Mo stainless steel was 4.1 times greater than that of the Ni-based coating. The wear mechanism is mainly fatigue wear. A series of the electrochemical tests was carried out in a 3.5 wt.% NaCl solution in order to examine the corrosion behavior. The mechanisms for corrosion resistance are discussed.     

High temperature stability of 2.25Cr-1Mo steel during creep

The creep rapture behaviour of 2.25Cr—1Mo steel in air and in a salt mixture was studied. The salt coating, which can form a liquid phase at the test temperatures, increased the creep rate and reduced the rupture life of the material. The coating reduced the available cross-section of the material by removing the surface layers, thereby resulting in a reduction of the rupture life. Cross-sections of coated samples showed an outer oxide layer comprising oxide of the metal and precipitates of sulphide at the metal/oxide interface. This subsurface penetration of the corrodants was responsible for the early failure of the coated samples. This is typical of hot corrosion mechanisms. The formation of various carbides like M₂₃C₆ and M₆C, as observed by transmission electron microscopy, during creep reduced the creep strength of the material both in air and in the coated state. Increasing temperature enhanced the formation of these carbides with a consequent decrease in creep strength. Applied stress did not seem to play much of a role in the degree of carbide precipitation.     

Effects of Co−Cr corrosion products and corresponding separate metal ions on human osteoblast-like cell cultures

The cytocompatibility of the degradation products of a Co–Cr orthopaedic alloy was investigated with particular focus on the dose-effect of an electrochemically dissolved alloy extract and of the corresponding separate metal ions on human osteogenic bone marrow derived cells. The extract solution contained 15 ppm of Co and 8ppm of Cr as analysed by atomic absorption spectroscopy. Stock salt solutions of CoCl₂·6H₂O, CrCl₃·6H₂O and Na₂CrO₄ at corresponding concentrations were also prepared. Several dilutions of the above metallic solutions were tested for a period of 21 days on cells (third subculture) cultured in -minimal essential medium containing foetal govine serum and supplemented with antibiotics, dexamethasone ascorbic acid and -glycerophosphate. The osteoblast response to the presence of metal ions was evaluated by several biochemical parameters: cell viability (MTT reduction by intracellular enzymes), alkaline phosphatase activity (an osteoblast marker) and protein production (both intracellular and extracellur). Co–Cr corrosion products showed opposite effects to their respective metal salts only on day 1. With time the different metal solutions presented a similar pattern of inhibition. These results suggest that impaired bone formation in vitro can occur in the presence of Co–Cr corrosion products.This paper was accepted for publication after the 1995 Conference of the European Society of Biomaterials, Oporto, Portugal, 10–13 September.     

Oxidation behavior and electrochemical corrosion performance of Ti<Subscript>3</Subscript>Al alloy with TiAl coating

Magnetron-sputter deposition was used to produce a Ti–48Al–8Cr–2Ag (at. %) coating on a Ti–24Al– 17Nb–0.5Mo (at. %) alloy substrate. Oxidation behavior was studied in air at 900–1000°C. The results indicated that the oxidation rate of sputtered Ti–48Al–8Cr–2Ag nanocrystalline coating was lower than that of the Ti₃Al alloy at 900°C. The former formed a scale of merely Al₂O₃, and the latter formed a scale of TiO₂. However, the Ti–48Al–8Cr–2Ag nanocrystalline coating showed a little bit higher oxidation rate than Ti₃Al alloy at 1000°C because the outer TiO₂ scale formed and columnar boundaries of the coating gave a larger actual oxidation area than the original alloy. The electrochemical corrosion behavior was investigated in a 3.5% NaCl solution at room temperature. The coating showed excellent electrochemical corrosion resistance in 3.5% NaCl solution because it exhibited stable passive polarization behavior without any overpassivation phenomena.     

Corrosion behaviour of single (Ti) and duplex (Ti–TiO2) coating on 304L stainless steel in nitric acid medium

Sputter deposited single titanium (Ti) layer, and duplex Ti–TiO₂ coating on austenitic type 304L stainless steel (SS) was prepared, and the corrosion performance was evaluated in nitric acid medium using surface morphological and electrochemical techniques. Morphological analysis using atomic force microscope of the duplex Ti–TiO₂ coated surface showed minimization of structural heterogeneities as compared to single Ti layer coating. The electrochemical corrosion results revealed that, titanium coated 304L SS showed moderate to marginal improvement in corrosion resistance in 1 M, and 8 M nitric acid, respectively. Duplex Ti–TiO₂ coated 304L SS specimens showed improved corrosion resistance as compared to Ti coating from dilute (1 M) to concentrated medium (8 M). The percentage of protection efficiency for base material increases significantly for duplex Ti–TiO₂ coating as compared to single Ti layer coating. The oxidizing ability of nitric acid on both the coatings as well as factors responsible for improvement in protection efficiency are discussed and highlighted in this paper.     

Corrosion behavior in SBF for titania coatings on Mg–Ca alloy

TiO₂ coating was obtained by sol–gel method to improve the corrosion resistance of Mg–Ca alloy in human body environment. The corrosion behavior of Mg–1.0 Ca alloy with TiO₂ coating was investigated by electrochemical tests and immersion tests in simulated body fluid (SBF). Bare Mg–1.0 Ca alloy suffered serious attack after immersed in simulated body fluid only for 48 h. While for the Mg–1.0 Ca alloy with TiO₂ coating, the surface almost maintained intact with only several collapses after immersed in SBF for 168 h. The electrochemical test results showed that the free corrosion current (i _corr) of Mg–1.0 Ca alloy substrate was 3.3275e−2A/cm², while the i _corr of TiO₂ coating was only 1.58549e−5A/cm². Therefore, TiO₂ coating significantly improved the corrosion resistance of Mg–1.0 Ca alloy in SBF. This enhances the potential of Mg–Ca alloy used as biodegradable orthopedic material.     

含H2S的NaCl溶液中溶解氧对PH13-8Mo钢腐蚀性能的影响

为研究新型马氏体沉淀硬化不锈钢PH13-8Mo在含饱和H_2S的NaCl溶液中的腐蚀行为,利用极化曲线、电化学阻抗谱等电化学测试和浸泡实验相结合的方法,通过扫描电子显微镜(SEM)和X射线光电子能谱分析技术(XPS),观察了该高强钢在含H_2S的除氧和不除氧的NaCl溶液中的腐蚀形貌,并对其腐蚀产物的成分进行了分析.结果表明:在除氧的NaCl溶液中,阳极极化曲线的形状发生了明显的变化,电化学阻抗谱的容抗弧的幅值也较未除氧的溶液中变小;在除氧的NaCl溶液中浸泡7 d后,由于H_2S水解后的S~(2-)或HS~-离子侵入到钝化膜的内部,并与钝化膜或金属基体发生反应,使得试样表面发生全面腐蚀,腐蚀产物主要为Fe、Cr、Ni、Mo的氧化物和硫化物;而在未除氧的NaCl溶液中浸泡后,试样表面仅发生局部腐蚀.     

Mechanical and thermal properties of HVOF sprayed Ni based alloys with carbide

The objective of the present study is to develop multi-functioned coating to the components, which are made of copper with electroplated Ni and are widely used for steel making industry. In this paper, we report the mechanical and thermal properties of Ni based superalloys with carbide sprayed by high velocity oxygen fuel (HVOF), and the detailed effects of sprayed material, spraying conditions, and initial powder structure on these properties. It was found that, among commercial Ni self-fluxing alloys (without fusing treatment), coating with a carbon content of 0.58 mass% had the most preferable properties, with a good balance of the hardness, strength, and thermal shock resistance. The thermal shock resistance depended not only on the strength of the coating but also on the volume contraction when tested at high temperatures. For the several developed Ni based superalloys with carbide, Ni20Cr8Mo5Fe–WC and Ni16Cr15Mo3–WC demonstrated the prominent adhesion strength and thermal shock resistance with high Galvanic corrosion resistance through optimized spraying condition. Also, 20 mass% NiCr–Cr₃C₂ coating sprayed by using employed relatively small primary particle succeeded in achieving the multi-superior properties; high adhesion strength, high corrosion resistance and thermal shock resistance.