Nanostructured TiCrN thin films by Pulsed Magnetron Sputtering for cutting tool applications

Nanostructured Titanium chromium nitride (TiCrN) thin films at different pulsed frequencies were grown on steels by pulsed reactive DC magnetron sputtering technique. The crystal structure and morphology of the TiCrN films sputtered at different frequencies were characterized. The surface composition and chemical states of each element in TiCrN thin films were studied by ion scattering spectroscopy (ISS) and X-ray photon spectroscopy (XPS).The electrochemical corrosion behavior of the coated steels was monitored by both impedance spectroscopy and potentiodynamic polarization technique in 3.5% NaCl at room temperature. A block on ring wear tester was used to monitor the variation of coefficient of friction with different sputtering frequency. The mechanical applications of TiCrN thin films were studied by fabricating the thin films on micro drill bits and testing it on 1 mm thick steel plates. A superior surface finish, diameter precision of the hole, reduced material build up on the cutting edges and finally increased tool life were obtained with TiCrN coated HSS drill bits. Machining tests were conducted by coating the inserts with TiCrN thin films.     

Comparative study on the corrosion and wear behavior of plasma-sprayed vs. high velocity oxygen fuel-sprayed Al8Si20BN ceramic coatings

Corrosion and wear are common problems encountered in the oil and gas industry. These entail the gradual destruction of materials by mechanical action on the opposite surface, and the chemical and/or electrochemical reaction with their environment. In this research, Al8Si20BN ceramic powder with specific properties against corrosion and wear was selected, and it was sprayed with high velocity oxygen fuel (HVOF) and plasma spray methods onto carbon steel substrates. The coatings were characterized with respect to phase composition, microstructure, microhardness and adhesion strength. Their wear behavior was inspected by applying 5, 10, 15 and 20?N loads by pin-on-disc machine, after which the results of both methods were compared. According to the results, the HVOF-coated models were more durable than the plasma-coated models under different loads in the same condition. In addition, the corrosion deterioration of the coated specimens in both brine (3.5% NaCl) and fossil oil were tested for one month (30 days). Potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) assessment in 3.5% NaCl solution indicated that the HVOF-sprayed specimens had better corrosion protection than the plasma-sprayed specimens. Generally, the HVOF technique facilitated more durable coats with greater corrosion and tribological resistance compared to the plasma coating technique.     

Effect of transition layer on the performance of hydroxyapatite/titanium nitride coating developed on Ti-6Al-4V alloy by magnetron sputtering

A gradient transition multilayer hydroxyapatite/titanium nitride (HA/TiN) coating was prepared on the Ti-6Al-4V alloy by magnetron sputtering. The composition, surface topography, microstructure, adhesion strength and electrochemical properties of the as-deposited coatings were characterized by SEM/EDS, AFM, XRD, FT-IR and electrochemical workstation. The experimental results showed that the single TiN coating deposited at a partial pressure of nitrogen (N₂) of 0.08?Pa had the best internal stress and tribological performance, and its volume loss was only 0.89% of that of Ti-6Al-4V alloy. The introduction of the TiN transition layer greatly improved the wear resistance of the Ti-6Al-4V alloy, and the adhesion strength of the HA layer to the substrate increased from 6.50?±?0.5?N to 11.70?±?1.2?N, an increase of 56%. The HA/TiN coating surface consisted of uniform hemispherical particles with dense structure and invisible defects (micro-cracks and pores). For the HA surface layer, the crystal structure and active hydroxyl (-OH) group was restored after heat treatment. Potentiodynamic polarization experiments indicated that the HA/TiN coating achieved the lowest corrosion current density and the most positive corrosion potential compared to the single TiN layer and Ti-6Al-4V alloy. In summary, it can be conclude that the gradient transition layer can well improve the mechanical properties and electrochemical behavior of the titanium alloy, and largely ensuring the stability of the surface bioactive coating.     

聚酰亚胺表面化学镀镍-磷合金研究

本文利用甲醛在铜表面的自分解反应成功地在聚酰亚胺表面制备了化学镀镍-磷合金层。采用扫描电子显微镜、光谱仪、四探针法、动电位极化以及电化学阻抗法对制备出的镍-磷合金镀层的微观形貌、反射率、表面电阻以及耐腐蚀性进行了表征,并参照国家标准GBT 5270-2005测试了镀层的结合力。结果表明,聚酰亚胺表面的化学镀镍-磷合金层光滑平整,反射率高达95%以上,表面电阻率10Ω·cm左右,结合力符合国家标准,耐腐蚀性能远优于镀银层。     

The effect of mixture of mercaptobenzimidazole and zinc phosphate on the corrosion protection of epoxy/polyamide coating

The protective performance of solvent-borne epoxy/polyamide coatings formulated with zinc phosphate anticorrosion pigment was improved through the addition of 2-mercaptobenzimidazole as an organic corrosion inhibitor. In addition to determining the optimum percentage of mercaptobenzimidazole, the electrochemical impedance spectroscopy data could show the influence of inhibitor concentration on the epoxy behavior within 35 days of immersion in 3.5 wt% NaCl solution. The improved corrosion protection and adhesion strength in the presence of the pigment and inhibitor were connected to the deposition of a protective layer at the coating/substrate interface which might limit active zones for electrochemical reactions. The precipitation was confirmed using electrochemical impedance spectroscopy, polarization curves and SEM/EDX surface analysis.     

镍磷化学镀层在北方重工业城市雪水中的耐蚀性

为了改善Q235钢在空气污染较为严重的环境中的耐蚀性,以北方重工业城市之一的抚顺望花区的雪水为腐蚀溶液,考察了化学镀镍层在该介质中的耐蚀行为。采用金相显微镜观察了镍磷镀层的表面形貌,通过冷冻-加热循环试验考察了镀层的结合力,借助动电位极化、电化学阻抗谱等方法评价了镀层在雪水中的耐蚀性,测试和观察了浸泡实验的腐蚀速率和表面形貌。结果表明,Ni-P镀层可在Q235钢表面均匀沉积且较为致密,与基体之间有良好的结合力。镀层的自腐蚀电流密度较Q235钢低,电荷转移电阻更大,腐蚀速率是Q235钢的1/3～1/2。Ni-P镀层明显改善了Q235钢在污染较为严重的雪水中的耐蚀性,可作为Q235钢腐蚀防护的一种措施。     

Electrochemical behavior of (Cr,W, Al,Ti, Si)N multilayer coating on nitrided AISI 316L steel in natural seawater

AISI 316L steel is often used in materials applied toward nuclear power but are subjected to pitting corrosion in a marine environment. In this study, (Cr, W, Al, Ti, Si)N multilayer coatings were deposited using multi-arc ion plating on the surface of non-nitrided and nitrided AISI 316L steel. The microstructure and corrosion resistance of four different systems were investigated, namely, (i) untreated AISI 316L steel, (ii) plasma nitrided (PN), (iii) coated on an untreated matrix (coating) only, and (iv) coated on nitrided (hybrid) specimens. The phase structures, morphologies, and compositions of the different specimens were characterized using X-ray diffraction, transmission electron microscope, Atomic Force Microscope, scanning electron microscope, X-ray photoelectron spectroscopy, and energy dispersive x-ray spectroscopy. The results show that a thin CrWAlTiSiN multilayer coating, approximately 2.3 μm in thickness, is deposited on the surface of an ~12 μm nitrided layer. Potentio-dynamic polarization and electrochemical impedance spectroscopy were used to evaluate the assessment of the electrochemical behavior in the natural seawater of China's Yellow Sea. The hybrid specimens exhibited excellent corrosion resistance compared to both the nitrided and coated specimens.     

Electro-deposition and characterizations of nickel coatings on the carbon–polythene composite

Nickel coating on the carbon–polythene composite plate was prepared by electrodeposition in a nickel sulfate solution in this work. The morphology and cross-sectional microstructure of the nickel coating were examined by scanning electron microscope (SEM) and optical microscope (OM), respectively. The influence of bath temperature on the nickel deposition rate was investigated experimentally. The adhesion between the coating and the substrate was evaluated by the pull-off test. The corrosion behavior of the coating in an aqueous solution of NaCl was studied by electrochemical methods. The results showed that the nickel electrodeposition rate could reach up to 0.68 μm min⁻¹ on average under conditions of cathodic current density of 20 mA cm⁻² and bath temperature of 60 °C. It was confirmed that increasing the bath temperature up to 50 °C had a positive effect on the nickel deposit rate, while an adverse effect was observed beyond 60 °C. The adhesion strength between the nickel coating and the substrate can be more than 2.3 MPa. The corrosion potential of the bright coating in the NaCl solution was more positive than that of the dull coating, and the anodic dissolution rate of the bright coating was also far lower at the same polarization potential compared with the dull coating.     

Effect of nitrogen pressure on the microstructure,mechanical and electrochemical properties of CrAlN coatings deposited by filter cathode vacuum arc

CrAlN coatings were prepared on Al–Si alloys using filter cathode vacuum arc deposition technique with nitrogen as the reactive gas and Cr₂₅Al₇₅ alloy target as the arc source. The effect of nitrogen pressure on the microstructure, mechanical properties and electrochemical properties of the coatings had been systematically studied. The results showed that the composition, structure and performance of the CrAlN coating depended on the nitrogen pressure. As the nitrogen pressure increased, the Al and Cr content decreased while the N content increased slowly in the coating. Meanwhile, the phase structure gradually changed from AlN phase to CrN phase. The hardness of the CrAlN coating increased significantly with the increase of nitrogen pressure from 0.04 to 0.06 Pa due to the formation of CrN phase and grain refinement. However, further increasing the nitrogen pressure to 0.07 Pa, the hardness was reduced owing to the deterioration of the surface quality caused by target poisoning. Moreover, the adhesion strength of the coating gradually decreases, and the corrosion resistance of the CrAlN coating first increased and then decreased with increasing the nitrogen pressure. The CrAlN coating deposited at a nitrogen pressure of 0.05 Pa had the best corrosion resistance, with the highest polarization resistance, charge transfer resistance and pore resistance, which was related to the combined effect of great compactness and AlN-dominant phase structure in the coating.     

Effect of pore content and pH on the corrosion behavior of hydrophobic ceramic coatings

In this paper, superhydrophobic ceramic coatings were successfully prepared on stainless steel substrates (S304) by sol–gel method, and the effects of pore content and pH conditions on the corrosion resistance of hydrophobic ceramic coatings were studied. As the porosity increases, the contact angle of the coating increases. Among them, the contact angles of the coatings with 15% and 20% porosity in different pH solutions are all greater than 150°, achieving superhydrophobic surfaces. The contact angle results before and after corrosion show that the solution with a higher pH has a greater damage to the hydrophobicity of the coating. The corrosion resistance of the coatings was evaluated comparatively from polarization curves and electrochemical impedance spectroscopy. As the hydrophobicity improves, the corrosion resistance of the hydrophobic ceramic coating is enhanced. The impedance moduli at .01 Hz of the coating are 1.04 × 10³ times (pH 4), .13 × 10³ times (pH 7), and .74 × 10³ times (pH 10) of the bare steel, respectively. With the increase of pH, the corrosion resistance of hydrophobic ceramic coatings decreases, because OH⁻ in the corrosion solution is more easily adsorbed on the surface of the coating, thereby destroying the long hydrophobic chains.     

Electrochemical and morphological properties of zirconium conversion coating in the presence of nickel ions on galvanized steel

A hexafluorozirconic acid-based conversion coating was applied on a galvanized steel substrate and the influence of nickel ion from nickel sulfate solution (in zirconium solution and in a separate solution) on the corrosion resistance behavior and morphology of zirconium conversion coating was investigated. Electrochemical impedance spectroscopy and DC polarization were conducted in 3.5 wt% NaCl solution in order to optimize practical conditions of zirconium conversion coating and NiSO₄ solution on the galvanized steel substrate. Field emission scanning electron microscopy and X-ray photoelectron spectroscopy were employed to study the morphology and composition of the coated surfaces. Results revealed that the conversion coating obtained from solution containing zirconium and nickel ions (Zr + Ni) did not improve corrosion resistance and uniformity of the coating in comparison with Zr conversion coating in optimized condition. However, a positive effect was obtained from samples coated with separate solutions of zirconium and nickel (Zr–Ni). Improved corrosion resistance and morphology of Zr-based conversion coating were observed in Ni²⁺ concentration, pH, and immersion time of 10 g/L, 6 and 300 s, respectively. Morphology and surface composition analysis proved that two separate layers of conversion coating containing zirconium, zinc, and nickel oxide/hydroxide compounds were formed in the case samples that were treated by separate solutions. This led to better uniformity and higher thickness of the coating. Finally, adhesion strength of epoxy organic coating on galvanized steel with and without conversion coating was investigated by pull-off measurement. Zr–Ni conversion coating in optimum conditions had a positive effect on adhesion of organic coating in comparison with blank sample and samples pretreated with Zr and Zr + Ni conversion coatings through increased surface roughness and physical interlocking.     

Improvement of DLC electrochemical corrosion resistance by addiction of fluorine

The combination of chemical and mechanical properties of diamond-like carbon (DLC) films opens the possibilities for its use in electrochemical applications. DLC electrochemical corrosion behavior is heavily dependent on deposition techniques and precursor gas. Fluorinated-DLC combines the superlative properties of diamond and teflon and becomes one of the most suitable coating for tribological applications. F-DLC was grown over 316L stainless steel using plasma enhanced chemical vapor deposition by varying the ratio of carbon tetrafluoride and methane. The influence of fluorine content on deposition rate, composition, bonding structure, surface energy, hardness, stress, and surface roughness was investigated. Emphasis was placed on the investigation of F-DLC electrochemical corrosion behavior, which was tested by potentiodynamic method. As F content increased, F-DLC films presented lower stress, hardness values and surface free energy. In addition, Raman G-band peak position shifted to higher frequency. The corrosion potential becomes more negative and the anodic and cathodic current densities decreased with the increase of F content, as compared to the pure DLC and the substrates. These results were confirmed by Nyquist plot, which shows a stronger ohmic behavior for F-DLC and Bode plots with different corrosion behaviors. The electrochemical analysis indicated F-DLC films present superior impedance, polarization resistance and breakdown potential as compared to the pure DLC, which indicate they are promising corrosion protective coating in aggressive solutions.     

Effects of different surface cleaning procedures on the superficial morphology and the adhesive strength of epoxy coating on aluminium alloy 1050

This study reports the effects of different cleaning procedures on the surface characteristics of the aluminium alloy 1050 substrates and on the adhesive strength of the epoxy coating to this alloy's surface. The cleaning procedures used in this study were (1) degreasing by acetone, (2) alkaline etching by 5 w/w% NaOH solution and (3) alkaline etching by 5 w/w% NaOH solution followed by acid cleaning by 50 v/v% HNO₃ solution. The surface morphology, chemical composition and topography of the cleaned substrates were investigated by field-emission scanning electron microscope (FE-SEM), energy dispersive spectroscopy (EDS) and atomic force microscope (AFM), respectively. The effectiveness of the cleaning procedures was also studied by polarization test and open circuit potential (OCP) measurements. The surface free energy and work of adhesion were obtained on the cleaned samples using contact angle measuring device. Pull-off test was conducted to evaluate the adhesion strength of the epoxy coating on the aluminium substrates. Results revealed that the surface cleaning of aluminium alloy by alkaline etching followed by acid cleaning method was the most efficient procedure for removing the oxide layer from the surface of aluminium compared to other cleaning procedures. The surface roughness, surface free energy, electrochemical activity and adhesion strength of the epoxy coating to the aluminium surface were significantly increased using this surface cleaning procedure.     

Fault-tolerant hybrid epoxy-silane coating for corrosion protection of magnesium alloy AZ31

In this work, a hybrid epoxy-silane coating was developed for corrosion protection of magnesium alloy AZ31. The average thickness of the film produced by dip-coating procedure was 14 μm. The adhesion strength of the epoxy-silane coating to the Mg substrate was evaluated by pull-off tests and was found to be higher than 16 MPa both in dry and wet conditions. The hybrid epoxy-silane coating showed high corrosion resistance both when intact and when punched through by a needle. The low frequency impedance of intact coating was higher than 1 GΩ cm² after one month of immersion in 3.5% NaCl solution. Both, artificially induced defects and corrosion sites that appeared on the metal surface did not propagate. Their passivation behavior, that we call fault-tolerance, was observed by EIS, SVET-SIET and SEM-EDS. It was ascribed to the good adhesion, high coating integrity and corrosion inhibiting effect provided by diethylenetriamine used as epoxy hardener.     

热浸镀锌层表面偏钒酸盐转化膜

在热浸镀锌试样表面获得了一层均匀、完整的偏钒酸盐转化膜.成膜溶液成分及工艺条件为:NaVO3 5 g/L,pH 1.3,温度30 ℃,时间30 min.对比研究了偏钒酸盐转化膜和铬酸盐转化膜的耐蚀性能.结果表明,偏钒酸盐转化膜由Zn、O、V等元素组成,热浸镀锌层经偏钒酸盐转化处理后电化学阻抗和极化电阻增大,腐蚀电流密度...     

Hard machining performance of PVD AlCrN coated Al2O3/TiCN ceramic inserts as a function of thin film thickness

In the present work, AlCrN coating was deposited on Al₂O₃/TiCN ceramic inserts with varying thin film thickness using physical vapor deposition (PVD) technique. The thickness, surface morphology, chemical composition, hardness and adhesion strength of the coating to the substrate were characterized by field-emission scanning electron microscopy (FESEM), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), micro-indentations and scratch tests respectively. The machining performance of uncoated and coated tools was investigated in hard turning of AISI 52100 steel (62 HRC) under dry environment. The cutting behavior was analyzed in terms of machining forces, tool temperature, wear, friction and chip morphology. Further, a 3D finite element model with hybrid friction criterion has been adopted to support the experimental findings. The results revealed that coating/substrate adhesion and edge radius were the deciding criteria for the machining performance of coated tools with 3 µm coating thickness tool exhibiting best turning performance on Al₂O₃/TiCN mixed ceramic insert.     

Scratch resistance and electrochemical corrosion behavior of hydroxyapatite coatings on Ti6Al4V in simulated physiological media

Using an electrochemical process, needle-like hydroxyapatite crystals with Ca/P ratio of 1.67 were synthesized on Ti₆Al₄V without the formation of any precursor. In vitro dissolution/precipitation process was investigated by immersion of the coated substrate into Hank??s solution up to 14?days. Physical and chemical characterizations were performed by scanning electron microscope coupled with energy dispersive X-ray spectroscopy and by X-ray diffraction. In particular, through a sequence of reactions including dissolution, precipitation, and ions exchange during immersion tests, a precipitated bone-like apatite coating homogenous and less porous was formed. Further, the corrosion behavior of the untreated and HA-coated specimens in simulated body fluid was evaluated using potentiodynamic polarization and electrochemical impedance spectroscopy. The results showed that the corrosion rates of the samples with HA layer before and after immersion tests were 72 and 80?% lower than that of the bare titanium alloy. At last, the adhesion of the HA layer was determined through the use of scratch tests. A particular tribological behavior and a strong link to the substrate were revealed.     

Effect of steel microfibers on corrosion of steel reinforcing bars

Steel microfiber reinforcement was previously found to be successful in mitigating alkali silica reaction in concrete, an expansive phenomenon. The use of steel microfibers to mitigate rebar corrosion, another expansive reaction, was investigated. Mortar specimens with and without steel microfiber reinforcement were exposed to a corrosive environment. All specimens were prepared with water/cement ratios of both 0.40 and 0.55, cured for 28 days, and then submerged in aerated 3.5% NaCl solution. The corrosion behavior of the specimens was monitored via electrochemical measurements. Three types of electrochemical tests were performed: corrosion potential measurements, potentiodynamic polarization, and electrochemical impedance spectroscopy. Chloride concentration measurements and microscopic analysis were performed as well. The polarization curves, Tafel, and polarization resistance measurements indicate that the steel rebar in the microfiber-reinforced mortars are more resistant to corrosion than the rebar in the control mortars, despite higher chloride concentrations. Furthermore, the steel microfiber-reinforced cement based materials have a lower electrolytic resistance. This is not indicative of a higher corrosion rate, which would be the case if it had been observed in standard mortar specimens.     

Preparation and corrosion behavior studies of chemically bonded phosphate ceramic coating reinforced with modified multi-walled carbon nanotubes (MWCNTs)

To improve the corrosion resistance of the chemically bonded phosphate ceramic coating, the MWCNTs are selected as the reinforcement after the modification. Through the analysis of TEM, Raman, XRD, and FTIR, it can be shown that MWCNTs are modified with carboxyl groups and the surfactant after treatment, and show good dispersion. In addition, the electrochemical experiments were carried out with 3.5 wt% NaCl solution to investigate the corrosion behavior of the coatings. The results suggest that the corrosion resistance of coatings is improved with the introduction of MWCNTs and the corrosion resistance increases with the increase in MWCNTs. Besides, the corrosion mechanism of MWCNTs reinforced coating corrosion resistance was also investigated based on the corrosion behavior and microstructural characterizations. The gel strength is improved with the addition of MWCNTs because of its strong strength, which can prevent crack occurring and form the bridge when crack happens. Therefore, H₂O, O_2, and Cl⁻ can be prevented from reaching to the substrate, which leads to good corrosion resistance.     

Effects of hydrogen on the corrosion of pure magnesium

Electrochemical measurements and capacitance measurements were performed for better understanding of the effects of hydrogen on the corrosion of pure magnesium. Anodic polarization curves, activation energy (E_a), pitting initiation time and electrochemical noise (EN) were carried out, which showed that hydrogen had a strong influence on the corrosion of magnesium. There existed a highest corrosion resistance of magnesium, when a series of cathodic charging current density were applied to the specimens due to the optimum hydrogen concentration in the hydride coating (MgH₂) on the surface. Mott-Schottky results confirmed that there was a hydride coating on the charged magnesium. Hydrogen ionized as H⁻ and depleted donor/electron, which induced the inversion of semi-conductivity from N-type to P-type.