Improving Fe3Al alloy resistance against high temperature oxidation by pack cementation process

The paper presents the results of oxidation tests of Fe₃Al-based alloys containing additions of Cr, Zr, B, and C, with and without an aluminide coating. The coating was formed by a pack cementation process in which the surface of material got enriched in aluminum. The Al-rich layer was intended to enhance the tendency of Al₂O₃ formation. The slow-growing Al₂O₃ scale provides the best corrosion protection for structural materials at high temperatures. The cyclic oxidation tests were performed in laboratory air at 1373 K. The structure and composition of oxide scales as well as their adherence were evaluated and compared for the materials with and without aluminide coatings. Surface enrichment in aluminum and effect minor addition of Zr on oxidation behavior was discussed.     

Microstructure and mechanical properties of reactive magnetron sputtered Ti-B-C-N nanocomposite coatings

Ti-B-C-N nanocomposite coatings with different C contents were deposited on Si (1 0 0) and high speed steel (W18Cr4V) substrates by closed-field unbalanced reactive magnetron sputtering in the mixture of argon, nitrogen and acetylene gases. These films were subsequently characterized ex situ in terms of their microstructures by X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM), their nanohardness/elastic modulus and facture toughness by nano-indention and Vickers indentation methods, and their surface morphology using atomic force microscopy (AFM). The results indicated that, in the studied composition range, the deposited Ti-B-C-N coatings exhibit nanocomposite based on TiN nanocrystallites. When the C₂H₂ flow rate is small, incorporation of small amount of C promoted crystallization of Ti-B-C-N nanocomposite coatings, which resulted in increase of nano-grain size and mechanical properties of coatings. A maximum grain size of about 8 nm was found at a C₂H₂ flux rate of 1 sccm. However, the hardness, elastic modulus and fracture toughness values were not consistent with the grain size. They got to their maximum of 35.7 GPa, 363.1 GPa and 2.46 MPa m^1/2, respectively, at a C₂H₂ flow rate of 2 sccm (corresponding to about 6 nm in nano-grain size). Further increase of C content dramatically decreased not only grain size but also the mechanical properties of coatings. The presently deposited Ti-B-C-N coatings had a smooth surface. The roughness value was consistent with that of grain size.     

The effect of Al and Cr additions on pack cementation zinc coatings

Zinc is widely used as a protective coating material due to its corrosion resistant properties. The structure and oxidation resistance of Al and Cr mixed zinc coatings, deposited by pack cementation process, is thoroughly examined in this work. The morphology and chemical composition of the as-deposited and oxidized samples was accomplished by electron microscopy while the phase identification was performed by XRD diffraction analysis. The experimental results showed that the addition of aluminum or chromium in the pack mixture forms only Al and Cr rich phases on the surface of the specimens without affecting significantly the phase composition of the rest zinc coatings. In the case of Zn-Al coatings, the overlying layer contains high concentrations of Al together with lower amounts of zinc and iron and in Zn-Cr coatings this layer contains Cr, Fe and Zn atoms and has much smaller thickness. The presence of these additional layers promotes significantly the oxidation resistance of the zinc pack coatings and they preserve most of their initial thickness and chemical content when exposed to an aggressive environment while their oxidation mass gain was measured at low levels during the oxidation tests.     

The structure and tribological behaviors of CrN and Cr-Ti-N coatings

The Cr-Ti-N coatings with different composition were deposited in a medium frequency magnetron sputtering system on Si (1 1 1) substrates. The structures, surface morphology and wear properties were measured. The binary CrN coatings, formed a single-phase fcc structure with nearly random (1 1 1), (2 0 0) and (2 2 0) orientation, while for the Ti was introduced, coatings show a preferred orientation of (2 0 0). Cr-Ti-N coating shows a much smoother surface than CrN coating. Cr-Ti-N coating with 31.75% Ti content shows the best wear behavior. The excellent tribological properties of this composition coating are corresponding to the solid solution nitride structures.     

Effect of surface ZnO coatings on oxidation and thermal stability of zinc films

The effect of thin ZnO coatings grown on Zn films on further oxidation and thermal stability of Zn films deposited on Mo(110) substrate was in situ investigated under ultrahigh vacuum by photoelectron spectrometries and low-energy electron diffraction. The results indicated that ZnO layers formed by oxidizing Zn films had at least a thickness of 3–5 monolayers. Further oxidation of Zn films was confined by as-formed ZnO coatings due to a surface passivation. It was of advantage to explain the difficulty in growing low oxygen-deficient ZnO films. The surface ZnO coatings strongly enhanced the thermal stability of Zn films, which was useful for understanding the underlying application of Zn/ZnO materials, such as Zn/ZnO nanocables with Zn core and ZnO shell.     

Formation of Cr-modified silicide coatings on a Ti-Nb-Si based ultrahigh-temperature alloy by pack cementation process

Cr-modified silicide coatings were prepared on a Ti-Nb-Si based ultrahigh temperature alloy by Si-Cr co-deposition at 1250 °C, 1350 °C and 1400 °C for 5-20 h respectively. It was found that both coating structure and phase constituents changed significantly with increase in the co-deposition temperature and holding time. The outer layers in all coatings prepared at 1250 °C for 5-20 h consisted of (Ti,X)₅Si₃ (X represents Nb, Cr and Hf elements). (Ti,X)₅Si₄ was found as the only phase constituent in the intermediate layers in both coatings prepared at 1250 °C for 5 and 10 h, but the intermediate layers in the coatings prepared at 1250 °C for 15 and 20 h were mainly composed of (Ti,X)₅Si₃ phase that was derived from the decomposition of (Ti,X)₅Si₄ phase. In the coating prepared at 1350 °C for 5 h, single (Ti,X)₅Si₃ phase was found in its outmost layer, the same as that in the outer layers in the coatings prepared at 1250 °C; but in the coatings prepared at 1350 °C for 10-20 h, (Nb_1.95Cr_1.05)Cr₂Si₃ ternary phase was found in the outmost layers besides (Ti,X)₅Si₃ phase. In the coatings prepared at 1400 °C for 5-20 h, (Nb_1.95Cr_1.05)Cr₂Si₃ ternary phase was the single phase constituent in their outmost layers. The phase transformation (Ti,X)₅Si₄ → (Ti,X)₅Si₃ + Si occurred in the intermediate layers of the coatings prepared at 1350 and 1400 °C with prolonging co-deposition time, similar to the situation in the coatings prepared at 1250 °C for 15 and 20 h, but this transformation has been speeded up by increase in the co-deposition temperature. The transitional layers were mainly composed of (Ti,X)₅Si₃ phase in all coatings. The influence of co-deposition temperature on the diffusion ability of Cr atoms was greater than that of Si atoms in the Si-Cr co-deposition processes investigated. The growth of coatings obeyed inverse logarithmic laws at all three co-deposition temperatures. The Si-Cr co-deposition coating prepared at 1350 °C for 10 h showed a good oxidation resistance due to the formation of SiO₂ and Nb, Cr-doped TiO₂ scale after oxidation at 1250 °C for 10 h.     

Microstructure and properties of TiB2-containing coatings prepared by arc spraying

Low cost arc spraying and cored wires were used to deposit composite coatings consisting of TiB₂ and TiB₂/Al₂O₃ hard particles in a Ni(Cr) and stainless steel 304L matrix. Four coatings were prepared namely Ni(Cr)-TiB₂, Ni(Cr)-TiB₂/Al₂O₃, 304L-TiB₂ and 304L-TiB₂/Al₂O₃. The microstructural characteristics of powders and coatings were observed by scanning electron microscopy (SEM). Phase compositions of powders were analyzed by X-ray diffraction (XRD). Although all the analyzed coatings exhibited similar lamella structure, remarkable differences not only in the morphology of hard phase and matrix but also in the size and distribution of hard phases were observed from one coating to another. Tribological behavior of the coatings was analyzed in room temperature dry sliding wear tests (block-on-ring configuration), under 75 N at low velocity (0.5 m/s). The coatings showed far high wear resistance than low carbon steel substrate under same conditions examined. Wear loss of 304L-TiB₂ and Ni(Cr)-TiB₂ coatings were lower nearly 15 times than that of steel substrate. TiB₂ hard phases in coatings bonded well with metal matrix contributed to high wear resistance.     

Microstructure and corrosion resistance behavior of ceramic coatings on biomedical NiTi alloy prepared by micro-arc oxidation

In this paper, ceramic coatings were prepared on biomedical NiTi alloys by micro-arc oxidation (MAO) in constant voltage mode. The current density-time response was recorded during the MAO process. The microstructure, element distribution and phase composition of the coatings prepared at different MAO treatment times were investigated by scanning electron microscopy (SEM), energy dispersive X-ray spectrometer (EDS), thin-film X-ray diffraction (TF-XRD) and X-ray photoelectron spectroscopy (XPS). The corrosion behavior of the coatings in 0.9% NaCl solution was evaluated by the potentiodynamic polarization test. It is found that the coatings become more compact with increasing the MAO treatment time, and the growth rate of coating decreases. The results of TF-XRD, EDS and XPS indicate that the coatings are composed of a large amount of γ-Al₂O₃ and a little α-Al₂O₃, TiO₂ and Ni₂O₃. The Ni content of the coatings is about 3 at.%, which is greatly lower than that of NiTi substrate. The bonding strength of coating-substrate is higher than 40 MPa for all the samples in this study. The corrosion resistance of the coatings is about two orders of magnitude higher than that of the uncoated NiTi alloy.     

Thermal stability, oxidation behavior and magnetic properties of Fe–Co ultrafine particles prepared by hydrogen plasma–metal reaction

Six kinds of Fe–Co ultrafine particles (UFPs) with an average particle size of about 45 nm were prepared by a hydrogen plasma–metal reaction method (HPMR). Particle feature, thermal stability, oxidation and magnetic properties of these UFPs were investigated. Fe–Co UFPs are spherical in shape and have the same crystal structure as bulk samples, but the Co content in Fe–Co UFPs is slightly richer than that in the master samples. Characteristics such as particle shape, mean particle size and specific surface area do not vary remarkably with the Co content. Fe–Co UFPs are stable in Ar and air below 473 K, but oxidize quickly in air above 473 K and simultaneously vary from a spherical shape into acicular shape during oxidation. Although the saturation magnetizations of Fe–Co UFPs both before and after oxidation are smaller than those of bulk samples, they exhibit a composition dependence similar to that of the master alloys. High residual magnetization and coercive force are obtained for Fe–Co UFPs before and after oxidation.     

Significant influence of particle surface oxidation on deposition efficiency, interface microstructure and adhesive strength of cold-sprayed copper coatings

The critical velocity for particle deposition in cold spraying is a key parameter, which depends not only on the material type, but also the particle temperature and oxidation condition. The dependency of deposition efficiency of cold spray Cu particles on the particle temperature and surface oxidation was examined. The effect of particle surface oxide scales on the interfacial microstructure and adhesive strength of the cold-sprayed Cu coatings was investigated. The results show that the deposition efficiency significantly increases with increasing the gas temperature but decreases with augmenting the oxygen content of the starting powder. The oxide inclusions at the interfaces between the deposited particles inhibit the effective bonding of fresh metals and remarkably lower the bond strength of the deposited Cu coatings on steel.     

Corrosion and oxidation properties of NiCr coatings sprayed in presence of gas shroud system

The oxidation of a NiCr bond coat during air plasma spraying was controlled by designing a gas shroud system attached to the plasma torch nozzle. Two nozzles, termed as “normal” and “high-speed” nozzles examined the effect of nozzle internal design on the microstructure and phase structure of coatings. X-ray diffraction and SEM morphologies showed that the shroud system reduced the oxidation of NiCr particles during the spray process. Compared with conventional air plasma spraying, the argon gas shroud reduced the coating hardness because the volume fraction of partially melted particles increased. The high-speed nozzle reduced the oxidation and hardness of NiCr coatings due to the increase of partially melted particles in the coatings.     

Microstructure and properties of TiC-Fe36Ni cermet coatings by reactive plasma spraying using sucrose as carbonaceous precursor

This study is aimed to introduce an innovative precursor pyrolysis process to prepare Ti-Fe-Ni-C compound powder and to discuss and evaluate the relationship between microstructure and properties of TiC-Fe36Ni cermet coatings in-situ synthesized by reactive plasma spraying (RPS) of these compound powders. The main characteristic of the pyrolysis process is that sucrose (C12H22O11) is used as a source of carbon as well as a binder to bind reactive constituent particles. The compound powder with high bonding strength can avoid the problem that reactive constituent particles are separated during spraying. The TiC-Fe36Ni cermet coatings present typical splat-like morphology of thermally sprayed coatings and consist of two different areas: one is a composite reinforcement area where spherical fine TiC particles (100-500 nm) homogeneously distribute within the Fe36Ni matrix; the other is an area of TiC accumulation. The surface hardness of the coatings reaches about 90 ± 2 (HR15N). The maximum and average microhardness values of the coatings are 1930 HV_0.2 (Vicker Hardness) and 1640 HV_0.2, respectively. The average bonding strength of the coatings is about 62.3 MPa. The wear resistance property of the coatings is much more than that of Ni60 alloys coatings.     

10.6μm激光辐照下光学薄膜的微弱吸收测量

 建立了表面热透镜技术测量光学薄膜微弱吸收的实验装置，对10.6μm CO₂激光辐照下镀制在Ge基底上的不同厚度的单层ZnS，YbF₃薄膜，以及镀制在Ge基底上不同膜系的（YbF₃/ZnSe）多层分光膜的弱吸收进行了测量，并对实验结果作了分析和讨论。实验结果表明，利用本实验系统已测得的待测样品的最低吸收为2.87×10^-4，测量系统的灵敏度为10^-5。     

Microstructure and selected properties of hot-work tool steel with PVD coatings after laser surface treatment

The paper presents the effect of HPD laser treatment on the microstructure and selected properties of the PVD CrN, (Ti,Al) and Ti(C,N) coatings deposited onto hot-work tool steel substrates. The microstructure and surface topography of the investigated samples are characteristic of the diversified morphology connected with the applied laser beam power. Employment of laser beam at 0.7 kW power to the laser treatment of samples with Ti(C,N) coatings causes clear coating adhesion growth because of the diffusive processes induced by heat release. Because of the higher value of the (Ti,Al)N absorption coefficient one can state that the observed substrate materials change and finally coatings destruction in case of those samples is the most noticeable. The moderate effect of the laser beam treatment of the hot-work tool steel with the PVD coating was observed for CrN coatings. However, for laser beam power above 0.5 kW differences in the thermal expansion coefficients of the substrate materials and coatings generate coating crackings.     

Influence of superalloy substrate roughness on adhesion and oxidation behavior of magnetron-sputtered NiCoCrAlY coatings

The present study has been conducted in order to determine the influence of superalloy substrate roughness on adhesion and oxidation behavior of magnetron-sputtered NiCoCrAlY coatings. Six types of coating samples with different substrate roughness were tested. The surface roughness and real surface area of both the substrates and coatings were studied by atomic force microscopy (AFM) techniques. The scratch tests performed at progressive loads were employed to evaluate the adhesion of the coatings. Cyclic oxidation tests were performed at 1100 °C in air for 50 cycles, each cycle consisting of 1 h heating in the tube furnace followed by 15 min cooling in the open air. The AFM measurements exhibit that the surface roughness of the sputtered NiCoCrAlY coating increases with the increasing of the superalloy substrate roughness. The NiCoCrAlY coatings present slightly lower roughness than the corresponding superalloy substrate. The scratch adhesion tests indicate that the coatings on substrates with a smoother surface possess better adhesion than on those with a rougher surface. Both the real surface area and oxidation weight gain of the coatings decrease with the decreasing of the superalloy substrate roughness. The NiCoCrAlY coating sputtered on the superalloy substrate with lower roughness provides relatively higher antioxidant protection than that provided by the coating with rougher substrate.     

The effect of deposition temperature on the surface coverage and morphology of iron-phosphate coatings on low carbon steel

The influence of deposition temperature and concentration of NaNO₂ in the phosphating bath on the surface morphology and coverage of iron-phosphate coatings on low carbon steel was investigated. The phosphate coatings were chemically deposited on steel from phosphate bath at different temperatures (30-70 °C) and with the addition of different amounts of accelerator, NaNO₂ (0.1, 0.5 and 1.0 g dm⁻³). The morphology of phosphate coatings was investigated using scanning electron microscopy (SEM) and atomic force microscopy (AFM). The composition of iron-phosphate coatings was determined using energy dispersive X-ray spectroscopy (EDS) and X-ray diffraction (XRD). Surface coverage was evaluated by the voltammetric anodic dissolution (VAD) technique.It was shown that the increase in temperature of the NaNO₂-free phosphating bath up to 70 °C caused an increase in surface coverage. The addition of NaNO₂ in the phosphating bath significantly increased the surface coverage of phosphate coatings deposited at temperatures lower than 50 °C. The phosphate crystals were of laminated and needle-like structures for deposits obtained at temperatures lower than 50 °C, while at higher temperatures needle-like structure was transformed to laminated structure. The increase in NaNO₂ concentration in the phosphating bath from 0.1 to 1.0 g dm⁻³ did not significantly increase the surface coverage, but decreased the crystals size, consequently favouring the phosphate nucleation and better packing of the crystals.     

Effects of pulsed bias duty ratio on microstructure and mechanical properties of TiN/TiAlN multilayer coatings

TiN/TiAlN multilayer coatings were deposited on M2 high speed steel by a pulsed bias arc ion plating system. The effect of pulsed bias duty ratio on the microstructure, mechanical and wear properties was investigated. The amount of macroparticles reduced with the increase of the duty ratio. The surface roughness was 0.0858 μm at duty ratio of 50%. TiN/TiAlN multilayer coatings were crystallized with orientations in the (1 1 1), (2 0 0) (2 2 2) and (3 1 1) crystallographic planes and the microstructure strengthened at (1 1 1) preferred orientation. At duty ratio of 20%, the hardness of TiN/TiAlN multilayer coatings reached a maximum of 3004 HV, which was 3.2 times that of the substrate. The adhesion strength reached a maximum of 77 N at 50% duty ratio. Friction and wear analyses were carried out by pin-on-disc tester at room temperature. Compared with the substrate, all the specimens coated with TiN/TiAlN multilayer coatings exhibited better tribological properties.     

Electroless Ni-P/Ni-B duplex coatings for improving the hardness and the corrosion resistance of AZ91D magnesium alloy

The Ni-P/Ni-B duplex coatings were deposited on AZ91D magnesium alloy by electroless plating process and their structure, morphology, microhardness and corrosion resistance were evaluated. The duplex coatings were prepared using dual baths (acidic hypophosphite- and alkaline borohydride-reduced electroless nickel baths) with Ni-P as the inner layer. The coatings were amorphous in as-plated condition and crystallized and produced nickel borides upon heat-treatment. SEM observations showed that the duplex interface on the magnesium alloy was uniform and the compatibility between the layers was good. The Ni-P/Ni-B coatings microhardness and corrosion resistance of having Ni-B coating as the outer layer was higher than Ni-P coatings. The Ni-P/Ni-B duplex coatings on AZ91D magnesium alloy with high hardness and good corrosion resistance properties would expand their scope of applications.     

Oxidation and reduction of thin Ru films by gas plasma

The oxidation and reduction of Ru thin films grown on a Si(1 0 0) surface were studied by X-ray photoemission spectroscopy (XPS). Ru thin films were oxidized with O₂ plasma generated by an rf discharge, and their XPS spectra were measured. The spectra were decomposed into several components for Ru suboxides attributable to different stages of oxidation. After sufficient exposure to oxygen, a stoichiometric rutile RuO₂ layer was found to have formed near the surface. Thermal annealing at 500 K resulted in a thicker RuO₂ layer. Experiments demonstrated that the Ru oxide layer can be removed by H(D) atoms via the desorption of water molecules.     

磁场辅助激光熔覆制备Ni60CuMoW复合涂层

采用磁场辅助激光熔覆技术,在Q235钢表面制备了Ni60CuMoW复合涂层,借助SEM,EDS 和XRD 等表征手段对涂层进行了微观组织和物相分析,利用维氏硬度计测试了复合涂层截面的显微硬度分布,通过摩擦磨损实验和电化学测试系统研究了复合涂层的磨损性能和耐腐蚀性能。研究结果表明：涂层主要由-Ni,Cu）固溶体、硅化物和硼化物组成,Cr3Si晶粒细化且均匀致密;磁场辅助作用下,激光熔覆涂层平均显微硬度达到913HV0.5,为无磁场辅助涂层的1.5 倍,磨损失重仅为无磁场涂层的36%,自腐蚀电位上升了100 mV,腐蚀电流密度降低了70%,耐磨耐蚀性能得到了显著改善。