The use of Al-Al2O3 cold spray coatings to improve the surface properties of magnesium alloys

Pure Al and 6061 aluminium alloy based Al₂O₃ particle-reinforced composite coatings were produced on AZ91E substrates using cold spray. The strength of the coating/substrate interface in tension was found to be stronger than the coating itself. The coatings have corrosion resistance similar to that of bulk pure aluminium in both salt spray and electrochemical tests. The wear resistance of the coatings is significantly better than that of the AZ91 Mg substrate, but the significant result is that the wear rate of the coatings is several decades lower than that of various bulk Al alloys tested for comparison. The effect of post-spray heat treatment, the volume fraction of Al₂O₃ within the coating and of the type of Al powder used in the coatings on the corrosion and wear resistance was also discussed.     

Properties of the TiN coatings on previously Ti ion-implanted magnesium alloy substrate

To enhance the mechanical properties of TiN coating on magnesium alloy, metal vapor vacuum arc (MEVVA) ion implantation was performed to modify magnesium alloy substrate before TiN film deposition. Implantation energy was fixed at 45 keV and dose was at 9 × 10¹⁷ cm^− 2. TiN coatings were deposited by magnetically filtered vacuum-arc plasma source on unimplanted and implanted substrate. The microstructure composition distribution and phase structure were analyzed using scanning electron microscopy (SEM) and X-ray diffraction (XRD). The chemical states of some typical elements of the TiN coating were analyzed by means of X-ray photoelectron spectroscopy (XPS). The properties of corrosion resistance of TiN coatings were studied by CS300P electrochemical-corrosion workstation, and the mechanism of the corrosion resistance was also discussed.     

Corrosion protection of AZ31 magnesium alloy by a TiO2 coating prepared by LPD method

TiO₂ layer was prepared as a protective coating for AZ31 magnesium alloy by the liquid phase deposition (LPD) method followed by an annealing treatment. The structural evolution and crystallization of coating brought by annealing were investigated by field emission scanning electron microscopy (FE-SEM) and X-ray diffraction (XRD), respectively. The corrosion protection performance was evaluated in a three-electrode electrochemical examination system. The anatase TiO₂ layer shows evident corrosion resistance. With the increase of the annealing temperature and prolongation of annealing time, the anticorrosion property was improved. The improvements of the anticorrosion properties were related with the structural evolution of the coating brought by the annealing treatment.     

Effect of plasma surface treatment on mechanical and corrosion protection properties of UV-curable sol-gel based GPTS-ZrO2 coatings on mild steel

Hybrid sol-gel based nanocomposite coatings derived from hydrolysis and condensation of a photopolymerizable silane precursor 3-Glycidoxypropyltrimethoxy silane in combination with zirconium-n-propoxide were deposited on mild steel substrates by a dip coating technique. In some cases, substrates were subjected to an atmospheric air-plasma surface pre-treatment prior to coating deposition. The coatings were subsequently densified by exposure to ultraviolet radiation followed by a thermal treatment at 250 °C. Characterization of the coatings with respect to thickness, water contact angle, pencil scratch hardness, adhesion and abrasion resistance was carried out. Corrosion testing was carried out on the coatings for a 1 h exposure to a 3.5% NaCl solution by electrochemical polarization and impedance measurements. The hybrid sol-gel coatings were found to improve the mechanical properties and corrosion resistance of mild steel. Plasma surface pre-treatment was found to improve the adhesion of coatings significantly and decreased the corrosion rate from 0.2652 mpy obtained for coatings without any surface pre-treatment to 0.0015 mpy, which was nearly 600 times lower than that of bare mild steel.     

Microstructure and corrosion properties of plasma-sprayed NiCr-Cr3C2 coatings comparison with different post treatment

The effects of laser and plasma arc remelting on the microstructure and properties of plasma-sprayed NiCr-Cr₃C₂ coatings on steel substrates have been investigated. The microstructure of the coatings has been analyzed by X-ray diffraction (XRD) and scanning electron microscope (SEM). It is found that the Cr₃C₂, δ-(Cr,Ni), Cr₇C₃ and Cr₂₃C₆ phases were obtained for both coatings, before and after remelting treatment. The laser remelting was operated in a continuous way with 800 W power in different scan speed, while the plasma arc remelting was operated with a plasma cladding machine under different scan currents. However, the denser microstructure of both remelted coatings can be obtained, especially for the plasma arc remelted coating. The Vickers microhardness measurement showed certain enhancement values for both remelted coatings. The corrosion behavior was evaluated through salt spray corrosion (SSC) method. Energy-dispersive spectroscopy (EDS) showed that the chloride was produced during SSC process. The higher corrosion resistance for plasma arc remelted coating may be due to the more compact microstructure, less porosity rate and tensile residual stress. Compared with laser remelting method, plasma arc remelting is a cheap, convenient and effective remelting method.     

Comparison of electrochemical corrosion behaviour of MgO and ZrO2 coatings on AM50 magnesium alloy formed by plasma electrolytic oxidation

Two types of PEO coatings were produced on AM50 magnesium alloy using pulsed DC plasma electrolytic oxidation process in an alkaline phosphate and acidic fluozirconate electrolytes, respectively. The phase composition and microstructure of these PEO coatings were analyzed by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The corrosion behaviour of the coated samples was evaluated by open circuit potential (OCP) measurements, potentiodynamic polarization tests, and electrochemical impedance spectroscopy (EIS) in neutral 0.1 M NaCl solution. The results showed that PEO coating prepared from alkaline phosphate electrolyte consisted of only MgO and on the other hand the one formed in acidic fluozirconate solution was mainly composed of ZrO₂, MgF₂. Electrochemical corrosion tests indicated that the phase composition of PEO coating has a significant effect on the deterioration process of coated magnesium alloy in this corrosive environment. The PEO coating that was composed of only MgO suffered from localized corrosion in the 50 h exposure studies, whereas the PEO coating with ZrO₂ compounds showed a much superior stability during the corrosion tests and provided an efficient corrosion protection. The results showed that the preparation of PEO coating with higher chemical stability compounds offers an opportunity to produce layers that could provide better corrosion protection to magnesium alloys.     

Characterization of bioactive ceramic coatings prepared on titanium implants by micro-arc oxidation

Micro-arc oxidation （MAO） is an enhanced chemical technology in an electrolyte medium to obtain coating structures on valve-metal surfaces. Titanium oxide films obtained by MAO in the sodium phosphate electrolyte were investigated. The films were composed mainly of TiO2 phases in the form of anatase and mille and enriched with Na and P elements at the surface. Their apafite-inducing ability was evaluated in a simulated body fluid （SBF）. When immersing in SBF for over 30 d, a preferential carbonated-hydroxyapatite was formed on the surfaces of the films, which suggests that the MAO-treated titanium has a promising positive biological response.     

Effect of ZrO2 on corrosion behaviour of chromium coatings

To study the effect of ZrO₂ particles on corrosion behaviour of Cr coating, steel samples were plated in Cr(VI) baths without and with ZrO₂. The corrosion behaviour of plated samples was studied at different exposure times in a solution containing 0.01 mol l⁻¹ H₂SO₄ + 0.5 mol l⁻¹ Na₂SO₄ using cyclic voltammetry and impedance spectroscopy. The equivalent circuit model R_e(Q_cR_pore)(Q_s[OR_s]) was proposed to fit the corrosion process and the parameters Y₀(Q_c),Y₀(Q_s) and R_pore reflecting corrosion behaviour of samples were evaluated. From the results, it was found that samples plated in bath containing ZrO₂ exhibited improved protective properties as a result of the structural characteristics of the coatings obtained; namely, the size and shape of pores.     

Formation of micro-arc oxidation coatings on AZ91HP magnesium alloys

In a neutral solution, coating formation by micro-arc oxidation (MAO) on AZ91HP magnesium alloy was studied. The process involved the substrate dissolution and coating development. During the first 5 s, the sample mass decreased, indicating substrate dissolution dominating the process. After 5 s, the sample mass began to increase and the coating development began to predominate the process. The coating was firstly nucleated on α phase and sparks initially appeared mainly on the edges of the sample. With treating proceeded, the coating was becoming uniform; meanwhile, microscopic pores of anodic coatings increased in size and decreased in number.     

Formation of oxidation-resistant Cu-Mg coatings on (001) Cu for oxide superconducting tapes

The formation of oxidation-resistant buffer layers on (001) oriented Cu for coated high-temperature superconducting tape applications was investigated. The approach employed Cu/Mg multilayer precursor films that were subsequently annealed to form either Mg-doped fcc Cu or intermetallic Cu₂ Mg. The precursor consisted of an Mg/Cu multilayer stack with 5 each of 25 nm thick Mg and 25 nm thick Cu layers which were grown at room temperature by sputter deposition. At annealing temperature of 400 °C, formation of the intermetallic Cu₂ Mg was observed. X-ray diffraction showed that the Cu₂ Mg (100) oriented grains were epitaxial with respect to the underlying Cu film, possessing a cube-on-cube orientation. In order to test oxidation resistance, CeO₂ films were deposited at elevated temperature on Ni/(Cu,Mg)/Cu/MgO structures. In case of the CeO₂ film on Ni/Cu/MgO, significant surface roughness due to the metal oxidation is observed. In contrast, no surface roughness is observed in the SEM images for the CeO₂/Ni/(Cu,Mg)/Cu/MgO structure.     

Investigation on the microstructure and cracking susceptibility of laser-clad V2O5 /NiCrBSiC alloy coatings

The effect of V₂O₅ on the refinement of microstructures and the reduction of cracking susceptibility of laser-clad NiCrBSiC hardfacing coatings are investigated. It is shown that high volume fraction and inhomogeneous distribution of the coarse brittle phases of chromium borides and carbides in NiCrBSiC layer are the dominating origins for hot cracks. The addition of V₂O₅ has an apparent effect on enhancing the toughness, refining the microstructure and reducing the cracking sensitivity of the coating. This is attributed to the generation of vanadium borides and carbides. The vanadium borides generate prior to and consequently inhibit the formation of chromium borides during rapid solidification because of lower standard free energy of formation of the former. They also restrain the growth of chromium carbides and make them distribute homogeneously. The reasons for crack initiation and distribution are discussed based on the microstructures of the cladding layers. It is demonstrated that the generation of cracks is determined by the microstructure of the cladding layers and the occurrence of cracking is governed by heat stress.     

电热爆炸喷涂NiAl-TiB2复合涂层

利用电热爆炸超高速喷涂设备,在镍基高温合金基体上喷涂了含TiB2分别为0、10和20％(质量分数,％)的NiAl复合涂层.分析结果表明涂层均由亚微米晶粒组成,涂层与基体间为冶金结合.加入TiB2显著的提高了NiAl的硬度.在1000℃的等温氧化实验结果表明,NiAl涂层的抗氧化性高于NiAl-TiB2复合涂层.     

Ti-6Al-4V表面ZrO_2/TiO_2微弧氧化复合陶瓷层的生长特性

研究了Ti-6Al-4V表面ZrO2/TiO2复合陶瓷层的生长规律。采用SEM和XRD分析了氧化时间对陶瓷层的厚度、表面和截面形貌、元素分布和相组成的影响。结果表明:膜层呈现出先快后慢最后趋于平稳的生长动力学,最终膜层厚度44μm。陶瓷膜表面分布着富Zr的陶瓷颗粒,这是由于氧化膜外层的火花放电形成的特征结构。膜层由m-ZrO2、Rutile-TiO2和ZrTiO4组成,Zr元素含量最高可达50.47%。随着氧化时间的增长,膜层表面的Zr含量逐渐降低,m-ZrO2逐渐减少而Rutile-TiO2逐渐增多,并且出现了新相Ti2ZrO6。     

Elucidating the microstructural and tribological characteristics of NiCrAlCoCu and NiCrAlCoMo multicomponent alloy clad layers synthesized in situ

High-entropy alloys have received considerable attention owing to their unique structures and properties. In this work, two multicomponent alloy clad layers were synthesized from two equimolar powder mixtures of NiCrAlCoCu and NiCrAlCoMo via an in situ reaction on the surface of the AISI 1050 medium carbon steel using the gas tungsten arc welding (GTAW) method. The microstructure, constituent phases and tribological properties of the clad layers were examined under a field-emission scanning electron microscope (FESEM), an X-ray diffractometer (XRD) and a pin-on-disc rotating tribometer. Experimental results indicate that the microstructure of the NiCrAlCoMo clad layer comprises AlFe_0.23Ni_0.77, Co₆Mo₆C₂ and Fe₆₃Mo₃₇. The NiCrAlCoCu clad layer has a simple microstructure that consists of only BCC and FCC solid solution phases, with lattice constants of a = 0.288 nm and a = 0.362 nm, respectively. In the NiCrAlCoMo clad layer, the complex geometric effect caused by the vein-shaped reinforcement results in strong mechanical interlocking, which can prevent detachment of the reinforcement during rubbing. Therefore, the wear performance of the NiCrAlCoMo clad layer greatly exceeds that of the NiCrAlCoCu clad layer.     

Heat treatment effects on the corrosion resistance of some HVOF-sprayed metal alloy coatings

The present study evaluates the effects of a 600 °C, 1 h heat treatment on the corrosion resistance of three High Velocity Oxygen Fuel (HVOF) flame-sprayed alloy coatings: a Co-28Mo-17Cr-3Si (similar to Tribaloy-800) coating, a Ni-20Cr-10W-9Mo-4Cu-1C-1B-1Fe (Diamalloy-4006) coating and a Ni-32Mo-16Cr-3Si-2Co (similar to Tribaloy-700) coating. Electrochemical polarization tests and free corrosion tests were performed in 0.1 M HCl aqueous solution. The corrodkote test (ASTM B380-97R02) was also performed, to evaluate the coatings qualitatively. The heat treatment improves the corrosion resistance of the Co-28Mo-17Cr-3Si coating and of the Ni-20Cr-10W-9Mo-4Cu-1C-1B-1Fe coating by enhancing their passivation ability. The precipitation of sub-micron sized secondary phases after the treatment may produce galvanic microcells at intralamellar scale, but the beneficial contribution provided by the healing of the very small but dangerous interlamellar defects (normally present in thermal spray coatings but not detectable using ordinary scanning electron microscopy) prevails. The effect on Ni-32Mo-16Cr-3Si-2Co coatings is more ambiguous: its sensitivity to crevice corrosion is worsened by the heat treatment.     

Elucidating the microstructure and wear behavior for multicomponent alloy clad layers by in situ synthesis

High-entropy alloys with a wide range of novel microstructures and properties are under extensive development. In this study, two equimolar powder mixtures of NiCrAlCoW and NiCrAlCoSi were prepared as cladding materials. They were clad by gas tungsten arc welding on AISI 1050 medium carbon steel substrate to form an in situ synthesized multicomponent clad layer. The microstructure, chemical composition and constituent phases of the clad layers were characterized by FESEM, EPMA and XRD, respectively. A rotating tribometer was employed to evaluate the tribological properties of the clad layers. Experimental results demonstrate that the NiCrAlCoW clad layer is composed of W (precipitates and residual particles), AlNi and Cr_15.58Fe_7.42C₆. The NiCrAlCoSi clad layer contains only a BCC phase. The two clad layers exhibit high hardness, caused by precipitation hardening with different precipitates. The NiCrAlCoW clad layer exhibits strong mechanical interlocking, which results from the complex phase and microstructure of the NiCrAlCoW clad layer. During rubbing, the in situ phase transformation of the NiCrAlCoSi clad layer induces the softening of the matrix. Therefore, the wear performance of the NiCrAlCoW clad layer is better than that of the NiCrAlCoSi clad layer.     

Porous TiO2 film prepared by micro-arc oxidation and its electrochemical behaviors in Hank's solution

Porous titanium oxide film was prepared by micro-arc oxidation (MAO) method on the surface of titanium alloy in electrolyte containing Ca and P. Surface characterizations of the film were carried out using X-ray diffractometer (XRD), scanning electron microscopy (SEM) and energy dispersive spectrometer (EDS) before and after immersion in Hank's solution. Electrochemical behaviors and corrosion resistance were studied by electrochemical techniques. The film was mainly composed of titania, α-tricalcium phosphate (α-TCP) and amorphous Ca-P compounds. α-TCP and amorphous compounds could transformed into hydroxyapatite (HA) when immersed in Hank's solution. MAO film showed higher corrosion potential and lower corrosion current than the titanium alloy and its chemical stability was slightly changed after formation of HA. Fitted electrochemical impedance spectroscopy (EIS) data indicated that after immersion for 2 weeks the MAO film kept good corrosion resistance. Porous TiO₂ film on titanium alloy by MAO method showed good chemical stability in Hank's solution and the transformation of Ca-P compounds into HA indicated that MAO was an effective method for preparing titanium alloys as bioactive artificial bone substitute even when Ca and P in the tissue environment were not abundant.     

The effect of the substitution of Cu for Ni on magnetoresistance and magnetocaloric properties of Ni50Mn34In16

The effect of the substitution of Cu for Ni on the magnetoresistance behaviour and the magnetocaloric properties of the Ni₅₀Mn₃₄In₁₆ alloy has been investigated. The (Ni-Cu)₅₀Mn₃₄In₁₆ alloys crystallize in the cubic L2₁ structure in austenite phase. While the M_s temperature is about 160 K for the Ni_47.5Cu_2.6Mn_34.0In_15.9 alloy, the martensitic transition is not observed for Ni_45.5Cu_4.6Mn_33.8In_16.1 alloy. To estimate the magnetic entropy change of the Ni_47.5Cu_2.6Mn_34.0In_15.9 alloy, the magnetization measurements as function of magnetic field are performed by continuous and noncontinuous heating methods. The Ni_47.5Cu_2.6Mn_34.0In_15.9 alloy shows the magnetostructural transition whose irreversible ratio is about 50% at 160 K. The magnetocaloric effect strongly depends on the sample history due to the occurrence of the irreversible magnetostructural transition. For the magnetic field change of 2 T, giant magnetoresistance value is about −68% that is rather big among the similar bulk alloys.     

Influence of ZnO content and annealing temperature on the dielectric properties of ZnO/Al2O3 composite coatings

ZnO/Al₂O₃ coatings were prepared by atmospheric plasma spraying (APS) using ZnO powders and Al₂O₃ powders as starting materials. The dielectric properties of these coatings were discussed. Both the real part of permittivity and the energy loss increase greatly with increasing ZnO content over the frequency range 8.2-12.4 GHz, which can be ascribed to orientation polarization and relaxation polarization due to a higher ZnO content. The frequency-dependent maximum of the loss tangent is found to obey Debye theory. In addition, annealing temperature which leads to the change of ZnO content also plays an important role in the dielectric performance.     

MoS2 coated with Al2O3 for Ni-MoS2/Al2O3 composite coatings by pulse electrodeposition

The MoS₂ powders were coated with Al₂O₃ (5 wt.%) through controlling hydrolysis of Al (NO₃)₃·9H₂O. MoS₂ powder coated with Al₂O₃ was written as MoS₂/Al₂O₃ hereinafter. MoS₂/Al₂O₃ powders were put into Ni plating electrolyte bath. Cetyltrimethylammonium bromide (CTAB) — the surfactant was also put into the bath. The experiment proves that MoS₂/Al₂O₃ particles were absorbed onto the Ni plate. The amount of MoS₂/Al₂O₃ deposited on Ni plate rises with the increasing concentration of MoS₂/Al₂O₃ in the bath. The microhardness, micro-surface, phase and the tribological property of the MoS₂/Al₂O₃ multi-plating coating were measured and analyzed. The performances of microhardness and wear resistance of the Ni-MoS₂/Al₂O₃ composite are better than those of Ni-MoS₂ composite.