Mechanical and tribological properties of nanocomposite TiSiN coatings

TiSiN coatings with a thickness of 2.5 μm were deposited using a Large Area Filtered Arc Deposition (LAFAD) technique with TiSi targets having different Si content. The influence of the Si content in the coatings on the mechanical properties and tribological behaviors of the TiSiN coatings were systematically studied using nanoindentation and a pin-on-disk tribometer. Nanoindentation results show that the hardness and Young's modulus of the TiSiN coatings increase with increasing Si content in the coatings. Wear test results indicate that the wear rate and friction coefficient of the 440a stainless steel coupons were significantly reduced by deposition of the TiSiN coatings, and the tribological behaviors of the TiSiN coatings are strongly dependent on the Si content in the coatings and the testing ball material. TiSiN coatings exhibit similar friction coefficient when tested against Al₂O₃ and 302 stainless steel balls, but increasing Si content in the coatings causes an increase in the friction coefficient of the TiSiN coatings. With the increase in the Si content in the coatings, the wear rate of the TiSiN coatings decreases when tested against Al₂O₃ balls, but increases significantly when tested against 302 stainless steel balls. The capability of forming a transfer layer on the ball surface contributes to the change in the friction coefficient and wear rate with Si content in the coating and ball materials.     

Mechanical and tribological properties of multilayered TiSiN/CrN coatings synthesized by a cathodic arc deposition process

The monolayered TiSiN and multilayered TiSiN/CrN were synthesized by cathodic arc evaporation. The Ti/Si (80/20 at.%) and chromium targets were used as the cathodic materials. With the different I_[TiSi]/I_[Cr] cathode current ratios of 1.8, 1.0, and 0.55, the multilayered TiSiN/CrN coatings possessed different multilayer periods (Λ) of 8.3 nm, 6.2 nm, and 4.2 nm. From XRD and TEM analyses, both the monolayered TiSiN and multilayered TiSiN/CrN revealed a typical columnar structure and B1-NaCl crystalline, no peaks of crystalline Si₃N₄ were detected. Among the multilayered TiSiN/CrN coatings, the multilayered coating with Λ = 8.3 nm possessed higher hardness of 37 ± 2 GPa, higher elastic modulus of 396 ± 20 GPa and the lower residual stress of − 1.60 GPa than the monolayered (Ti_0.39Si_0.07)N_0.54 coating(− 7.25 GPa). Due to the higher Cr/(Ti +Cr + Si) atomic ratio, the multilayered TiSiN/CrN with Λ = 5.5 nm possessed the lowest friction coefficient. But the lowest of wear rate was obtained by the multilayered TiSiN/CrN with Λ = 8.3 nm, because of higher H³/E^?2 ratio of 0.323 GPa. The monolayered TiSiN possessed the highest wear rate of 2.87 μm²/min. Therefore, the mechanical and tribological property can be improved by the design of multilayered coating.     

Effect of Ti content on the microstructure and mechanical properties of TiAlSiN nanocomposite coatings

TiAlSiN coatings has been proposed and studied because of their desirable properties in hardness and coating-substrate adhesion. Further improvement of their performance can be achieved by better understanding the effect of the concentration of each element on the microstructure and mechanical properties of the coatings. In this paper, the TiAlSiN coatings with different Ti content were deposited by reactive DC magnetron sputtering method. The microstructure and mechanical properties of the coatings were analyzed by energy dispersive spectroscopy, X-ray diffraction, transmission electron microscope, scanning electron microscope, nano-indentor and Rockwell indentation tester. The results reveal that TiAlSiN coatings consisted of amorphous phase and crystalline phase. With a Ti content of 63 at.%, as well as a Si content of 7 at.%, a super-hard TiAlSiN coating with a nanoindentation hardness of 66 GPa was achieved. What is more, in contrast to the well-described super-hard nanocomposite TiAlSiN coatings, another “nanocomposite” microstructure coating with a Ti content of 29 at.% in which the amorphous phase is wrapped in a crystalline phase was identified, with a comparatively low hardness value of 20 GPa. The highest adhesion strengths with a Rockwell indentation classes HF2 was achieved for a coating with a Ti content of 63 or 65 at.%.     

TiN及TiSiN涂层在海水环境下的摩擦学行为研究

目的对比研究海水环境下Ti N及Ti Si N涂层与Al2O3对磨的摩擦磨损行为。方法采用多弧离子镀技术在316L不锈钢及单晶硅片上制备Ti N及Ti Si N涂层。利用场发射扫描电子显微镜(SEM)、X射线衍射仪(XRD)及X射线光电子能谱仪(XPS)分析了涂层的截面形貌及化学组织成分。选择纳米压痕仪测量了Ti N及Ti Si N涂层的硬度及弹性模量,使用UMT-3往复式摩擦试验机研究了人工模拟海水环境下Al2O3与Ti N及Ti Si N涂层对磨后的摩擦磨损行为,并采用扫描电镜(SEM)、电子能谱(EDS)及表面轮廓仪来深入分析了磨痕的摩擦磨损情况。结果研究表明,Ti N涂层的硬度为32.5 GPa,当Si元素掺入涂层以后,Ti Si N涂层的硬度提高到了37 GPa。同时,较之于Ti N涂层,Ti Si N涂层的腐蚀电流密度下降了一个数量级。在摩擦实验中,Ti N涂层的摩擦系数和磨损率分别为0.35和5.21×10-6 mm3/(N·m),而Ti Si N涂层的摩擦系数和磨损率均有明显下降,分别为0.24和1.96×10-6 mm3/(N·m)。结论 Si元素掺杂后能显著提高Ti N涂层在海水环境下的摩擦学性能,主要归因于结构的致密,硬度、韧性、抗腐蚀性的提高及润滑相的形成。     

Effect of Micro Arc Oxidation Coatings on Corrosion Resistance of 6061-Al Alloy

In the present study, the corrosion behavior of micro arc oxidation (MAO) coatings deposited at two current densities on 6061-Al alloy has been investigated. Corrosion in particular, simple immersion, and potentiodynamic polarization tests have been carried out in 3.5% NaCl in order to evaluate the corrosion resistance of MAO coatings. The long duration (up to 600 h) immersion tests of coated samples illustrated negligible change in weight as compared to uncoated alloy. The anodic polarization curves were found to exhibit substantially lower corrosion current and more positive corrosion potential for MAO-coated specimens as compared to the uncoated alloy. The electrochemical response was also compared with SS-316 and the hard anodized coatings. The results indicate that the overall corrosion resistance of the MAO coatings is significantly superior as compared to SS316 and comparable to hard anodized coating deposited on 6061 Al alloy.     

Structure and mechanical properties of TiAlSiN/Si3N4 multilayer coatings

TiAlSiN/Si₃N₄ multilayer coatings which have different separate layer thicknesses of TiAlSiN or Si₃N₄ were deposited onto glass sheets, single-crystal silicon wafers and polished WC-Co substrates by reactive magnetron co-sputtering. The morphology, crystalline structure and thickness of the as-prepared multilayer coatings were characterized by TEM, SEM, XRD and film thickness measuring instrument. The mechanical properties of the coatings were evaluated by a nanoindenter. The effects of monolayer thickness on the microstructure and properties of TiAlSiN/Si₃N₄ multilayer coatings were explored. The coatings showed the highest hardness when the thickness of Si₃N₄ and TiAlSiN monolayers was 0.33 nm and 5.8 nm, respectively. The oxidation characteristics of the coatings were studied at temperatures ranging from 700 °C to 900 °C for oxidation time up to 20 h in air. It was found that the coatings displayed good oxidation resistance.     

Mechanical properties of hard AlCrN-based coated substrates

The present investigation has been conducted in order to study three commercially available hard AlCrN-based coated substrates by means of nano- and microindentation, aimed at determining the intrinsic hardness of the films. The results obtained are subsequently discussed taking into consideration the residual stresses and structure (grain size and texture) determined by X-ray diffraction and in the light of published data available in the literature. The study is first carried out with monolithic CrN and AlCrN coatings and it is further extended to the analysis of multilayer AlCrN/TiSiN coatings. Hardness obtained from nanoindentation at low depth and modelling the microindentation data match with values obtained at 22, 30 and 31 GPa for CrN, AlCrN and AlCrN/TiSiN coatings respectively. Residual stresses change from slightly tensile for CrN coating to highly compressive for AlCrN and AlCrN/TiSiN ones while the average grain sizes neglecting microstrains are similar for the three coatings (10-15 nm). AlCrN and AlCrN/TiSiN response similarities result from the low influence played by the stratification as compared to the nanostructure of the polycrystalline sublayers (nanometric grain size).     

Alternative technique for hydroxyapatite coatings

Flame Assisted Chemical Vapor Deposition (FACVD), a novel technique that shows an enormous potential in porous oxides deposition, was employed for the first time aiming to obtain hydroxyapatite (HA) coatings on 316 L stainless steel metallic substrates. Calcium acetate and ammonium phosphate diluted in ethanol were employed as precursor salts. A Ca/P molar ratio of 1.66 was employed in precursor solution, which is equivalent to stoichiometric hydroxyapatite. A porous coating, formed by an open and interconnected network, was observed by scanning electronic microscopy (SEM) and associated with homogenous reactions. Thickness of hydroxyapatite coating was 412 ± 3 μm. X-ray diffraction (XRD) analysis indicated the presence of crystalline coatings, mainly constituted by hydroxyapatite phase and traces of tricalcium phosphate (β-TCP). Carbonate in the hydroxyapatite coatings was identified by Fourier transform-infrared (FTIR) spectroscopy.     

Effects of mechanical properties and layer structure on the cyclic dynamic loading of TiN-based coatings

The cyclic dynamic loading behaviour of a multilayer TiAlSiN coating on M2 steel was systematically investigated using repetitive nano-impact over a wide range of impact load. Its behaviour was compared with a monolayer TiN on the same substrate. When the load was increased to 10 mN and 30 mN for the TiN and TiAlSiN coatings, respectively, cracks started to appear during the tests demonstrated as depth steps in the impact depth curves. The improved crack resistance of TiAlSiN coating is consistent with its higher H/E_r and H³/E_r² measured by nanoindentation. The impact footprints were studied from both top-view and cross-sectional view using a focused ion beam microscope and SEM. Spallation was observed in both coatings at higher impact loads. TiAlSiN coating shows much less spallation due to its multilayer structure. The cross-sectional study discovered that the cracks were initiated within the coating. A simple model has been used to study the power law relationship between the impact volume loss and the impact velocity.     

Effect of C2H2 gas flow rate on synthesis and characteristics of Ti–Si–C–N coating by cathodic arc plasma evaporation

The influences of C₂H₂ gas flow rate on the synthesis, microstructure, and mechanical properties of the Ti–Si–C–N films were investigated. Quaternary Ti–Si–C–N coatings were deposited on WC-Co substrates using Ti and TiSi (80:20 at.%) alloy target on a dual cathodic arc plasma evaporation system. The Ti–Si–C–N coatings were designed with Ti/TiN/TiSiN as an interlayer to enhance the adhesion strength between the top coating and substrate. The Ti–Si–C–N coatings were deposited under the mixture flow of N₂ and C₂H₂. Composition analysis showed that as the C₂H₂ gas flow increased, the Ti, Si and N contents decreased and the carbon content increased in the coatings. The results showed the maximum nanohardness of approximately 40 GPa with a friction coefficient of 0.7 was obtained at the carbon content of 28 at.% (C₂H₂ = 15 sccm). However, as the C₂H₂ gas flow rate increased from 15 to 40 sccm (carbon content from 25.2 to 56.3 at.%), both the hardness and friction coefficient reduced to 20 GPa and 0.3, respectively. Raman analysis indicated the microstructure of the deposited coating transformed from Ti–Si–C–N film to TiSi-containing diamond-like carbon films structure, which was strongly influenced by the C₂H₂ flow rate and is demarcated at a C₂H₂ flow of 20 sccm. The TiSi-containing diamond-like carbon films reveal low-friction and wear-resistant nature with an average friction coefficient between 0.3 and 0.4, lower than both TiSiN and Ti–Si–C–N films.     

TiAl合金表面激光重熔MCrAlY涂层热腐蚀性能

采用等离子喷涂技术在TiAl合金表面制备了MCrAlY涂层,并用激光重熔工艺对涂层进行处理,研究了TiAl合金、等离子喷涂MCrAlY涂层及激光重熔MCrAlY涂层850℃下75%Na₂SO₄+25%NaCl(质量分数)混合盐浸泡热腐蚀性能,分析了不同试样的热腐蚀破坏机理,并讨论了激光重熔处理对涂层热腐蚀性能的影响.结果表明,等离子喷涂MCrAlY涂层能显著提高TiAl合金的耐热腐蚀性能,经过激光重熔后可进一步提高其耐热腐蚀性能.MCrAlY涂层在高温熔盐中的热腐蚀发生的是表面氧化反应和内部硫化反应,主要生成Al₂O₃,Cr₂O₃,NiO,NiCr₂O₄,Ni₃S₂及CrS等腐蚀产物.     

Figure of merit for the quality of ZrO2 coatings on stainless steel and nickel-based alloy surfaces

A figure of merit (FOM) has been developed to define the quality of ceramic (e.g., ZrO₂) coatings on metal and alloy [Type 304SS and Alloy 600] surfaces. Zirconia (ZrO₂) coatings were developed as a means of protecting the metal/alloy surfaces from stress corrosion cracking (SCC) in boiling water reactor (BWR) primary heat transport circuits, by inhibiting the cathodic reaction (reduction of oxygen and hydrogen peroxide) on the surface external to the crack. The distribution of pores in the coating plays an important role in corrosion prevention, such that the lower the porosity of the coating, the better the protection afforded to the system against SCC. Since the reactors operate at high temperature (e.g., at 288 °C under full power conditions), the temperature dependence of the FOM was investigated. The figure of merit (FOM) was developed by measuring impedance data over a wide range of frequency (10 mHz-5 kHz) at temperatures of 25, 100, 200, and 288 °C in hydrogenated, buffered solutions, with the hydrogen electrode reaction (HER) being used as a “fast” redox couple. An “equivalent circuit” analog was first developed from the bare surface impedance data and this analog was then employed in a second step to model the pore bottom in defining the pore distribution on the coated surface. A lognormal distribution (LND) of the pores was assumed and the parameters of the LND were determined using a constrained optimization technique to fit the model to the experimental data for the coated surface at different temperatures. The results suggest that, as temperature increases, the coating becomes more porous, making the substrate more susceptible to corrosion cracking. At 288 °C, 87% of the SS and 85% of the Ni-alloy surfaces become porous with the pore radius varying from 0.0001 cm to 0.01 cm.     

The effects of a CeO2 coating on the corrosion parameters of type 304 stainless steel

Coatings of CeO₂ derived from inorganic sol-gel dispersions were applied to type 304 bright annealed stainless steel (British Standard 1449 type 304S31) coupons and subjected to heat treatments at 450 and 550 °C. The coatings, 0.5 μm thick, were transparent, adherent, and stable. The aqueous corrosion properties of the coated coupons in 1 molar NaCl were then studied by potentiodynamic polarization measurements and electrochemical impedance spectroscopy. The derived corrosion parameters were then compared with similarly heat-treated, uncoated 304SS coupons. The results indicate that the application of a CeO₂ coating, heat treated at 550 °C, improves the corrosion rate as compared to an uncoated heat-treated coupon. The polarization curve for the 450 °C heat-treated, coated coupon showed passive behavior compared to transpassive for the uncoated specimen. The impedance spectrum data for the uncoated, as-received coupon could be modeled using a resistor in series with a parallel capacitor resistor combination “Randles” equivalent circuit. A coated coupon, heat treated at 550 °C, could be modeled using a more complex equivalent circuit involving a constant phase element, due to the CeO₂ coating. Modeling of the impedance characteristics for the oxidized coupons required the addition of a second series element consisting of a parallel resistor capacitor combination to give a Chi square statistic fit of X² < 5 X 10^-4.     

Hot corrosion behavior of detonation gun sprayed Cr3C2–NiCr coatings on Ni and Fe-based superalloys in Na2SO4–60% V2O5 environment at 900 °C

The present work investigates the hot corrosion resistance of detonation gun sprayed (D-gun) Cr₃C₂–NiCr coatings on Superni 75, Superni 718 and Superfer 800 H superalloys. The deposited coatings on these superalloy substrates exhibit nearly uniform, adherent and dense microstructure with porosity less than 0.8%. Thermogravimetry technique is used to study the high temperature hot corrosion behavior of bare and Cr₃C₂–NiCr coated superalloys in molten salt environment (Na₂SO₄–60% V₂O₅) at high temperature 900 °C for 100 cycles. The corrosion products of the detonation gun sprayed Cr₃C₂–NiCr coatings on superalloys are analyzed by using XRD, SEM, and FE-SEM/EDAX to reveal their microstructural and compositional features for elucidating the corrosion mechanisms. It is shown that the Cr₃C₂–NiCr coatings on Ni- and Fe-based superalloy substrates are found to be very effective in decreasing the corrosion rate in the given molten salt environment at 900 °C. Particularly, the coating deposited on Superfer 800 H showed a better hot corrosion protection as compared to Superni 75 and Superni 718. The coatings serve as an effective diffusion barrier to preclude the diffusion of oxygen from the environment into the substrate superalloys. It is concluded that the hot corrosion resistance of the D-gun sprayed Cr₃C₂–NiCr coating is due to the formation of desirable microstructural features such as very low porosity, uniform fine grains, and the flat splat structures in the coating.     

Corrosion behavior of TiN coated type 316 stainless steel in simulated PEMFC environments

The corrosion behavior of TiN coated type 316 stainless steel (SS) was investigated in simulated proton exchange membrane fuel cell environments, i.e. 0.01 M HCl + 0.01 M Na₂SO₄ solutions bubbled with pure oxygen and hydrogen gases, respectively, by using electrochemical measurement techniques. 316SS substrate can passivate spontaneously in simulated cathode environment, while it is in active state at the corrosion potential in simulated anode environment. TiN coatings have much better corrosion resistance and passivity under both simulated conditions. No significant degradation takes place in TiN coatings under the typical load conditions of fuel cell for 4 h. The loss of small part of coatings occurs during the immersion tests of TiN coatings in the oxygen environment for 1000 h and in the hydrogen environment for 240 h, respectively, but the exposed substrate areas are passivated in both environments. The results reveal that TiN coating can offer 316SS higher corrosion resistance and electric conductivity, and that further effort to improve the coating quality and to evaluate the long-term stability of 316SS/TiN coating systems under simulated conditions are deserved. In addition, the characteristics of corrosion process for TiN coatings on passivatable substrate were discussed in detail.     

Influence of an oxidation protective coating upon hot corrosion and mechanical behaviour of Ti–48Al–2Cr–2Nb alloy

48-2-2 specimens were coated with Au using electrochemically process and vacuum heat treatment. Au diffused and the coating was composed of TiAlAu₂ and TiAlAu layers from the surface to the bulk alloy. A transition zone between the coating and the sound alloy composed of Au-enriched TiAl is also formed. The oxidation and NaCl salt corrosion behaviours of the coated specimen were investigated through cyclic tests and the effects of coating on mechanical properties of TiAl were assessed by means of creep properties. Au coating was effective in improving the oxidation and NaCl salt corrosion resistances of the coated specimens at 800 °C and 600 °C respectively. This good resistance is attributable to the formation of an Al₂O₃ scale on the surface of the coated specimen. During oxidation, or NaCl salt corrosion, the upper TiAlAu₂ layer of the coating transformed in an Al₂O₃ layer on a TiAu₂ layer. The slightly lower creep properties exhibited by the coated specimens are presumably linked to Cr-enriched phases that segregate at grains boundaries during the vacuum heat treatment. The degradation of creep properties after coating and corrosion is believed to be brought about either by the formation of the brittle TiAu₂ phase or by corrosion or oxygen diffusion through the upper scale.     

Tribological properties of titanium aluminides coatings produced on pure Ti by laser surface alloying

Titanium aluminides coatings were in-situ synthesized on a pure Ti substrate with a preplaced Al powder layer by laser surface alloying. The friction and wear properties of the titanium aluminides coatings at different normal loads and sliding speeds were investigated. It was found that the hardness of the titanium aluminides coatings was in the following order: Ti₃Al coating > TiAl coating > TiAl₃ coating. Friction and wear tests revealed that, at a given sliding speed of 0.10 m/s, the wear volume of pure Ti and the titanium aluminum coatings all increased with increasing normal load. At a given normal load of 2 N, for pure Ti, its wear volume increased with increasing sliding speed; for the titanium aluminides coatings, the wear volume of Ti₃Al coating and TiAl coating first increased and then decreased, while the wear volume of TiAl₃ coating first decreased and then increased with increasing sliding speed. In addition, the friction coefficients of pure Ti and the titanium aluminides coating decreased drastically with increasing sliding speed. Under the same dry sliding test conditions, the wear resistance of the titanium aluminium coatings was in the following order: Ti₃Al coating > TiAl coating > TiAl₃ coating.     

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.     

电弧离子镀制备 TiSiN 纳米复合涂层

目的在SiH4气氛下制备Si掺杂的TiSiN纳米复合涂层,为SiH4用于工业化TiSiN涂层生产提供依据。方法采用电弧离子镀技术,在SiH4气氛下,于单晶硅和硬质合金衬底上制备Si掺杂的TiSiN纳米复合涂层,研究SiH4流量对TiSiN涂层化学组分、微观结构、硬度和耐磨性能的影响。结果 SiH4流量对TiSiN纳米复合涂层的微观结构、硬度及摩擦系数的影响明显。随着SiH4流量的增加,TiSiN涂层由柱状晶生长的晶体结构逐渐转变为纳米晶镶嵌于非晶基体的复合结构。Si在涂层中以Si3N4非晶相存在,随着涂层中Si含量逐渐增加,TiN晶粒尺寸逐渐减小,Si3N4起到细化晶粒的作用。在42 m L/min的SiH4流量下,涂层硬度高达4100HV0.025。在对磨材料为硬质合金的条件下,TiSiN涂层摩擦系数小于0.6。结论 SiH4气氛下可以制备出Ti N纳米晶镶嵌于Si3N4非晶相结构的TiSiN纳米复合涂层,涂层的显微硬度较高。SiH4可以作为Si源用于TiSiN纳米复合涂层的工业化生产。