Formation and performance of an Fe-based amorphous-nanocrystalline composite coating by laser cladding and remelting

Abstract

A very important research topic in the area of the surface performance of engineering components, in particular their wear properties, recently has been the application of high quality surface layers on relatively cheap substrates. An Fe-based composite coating with both amorphous and nanocrystalline structures on a mild steel substrate offers a combination of high quality coating and low materials cost, at the same time extending the range of applications of traditional materials. The difficulties posed by preparation of Fe-based amorphous alloys have limited progress for many years. However, the recent development of high power lasers, and of laser material processing technology in general, has made the preparation of a Fe-based amorphous and nanocrystalline composite coatings over a large area a real possibility.     

热喷涂复合涂层不同温度下摩擦磨损特性研究

摘 要: 文中选用等离子喷涂技术在CuCo2Be合金表面制备了Cr3C2-NiCr/NiAl复合涂层。以Al2O3陶瓷球为对偶材料运用UMT-2摩擦磨损试验机对基体和复合涂层进行不同温度下的摩擦磨损试验,并选用三位轮廓仪、扫描电镜、能谱仪、XRD等分析测试手段,详细研究了CuCo2Be合金及喷涂层在不同温度下滑动摩擦磨损后的微观形貌,以及摩擦磨损特性。研究结果表明：等离子喷涂获得的复合涂层致密,涂层为层状结构,物相组成呈现非晶态。通过摩擦磨损试验研究,结果表明500℃时涂层磨损体积远远小于铜合金磨损体积,具有优良的抗摩擦耐磨损性能;在常温时涂层磨损机制以磨粒磨损为主,磨损较小,随着温度的升高涂层磨损机制以氧化磨损和粘着磨损为主。     

Mechanical properties of a FeCuSiB alloy with amorphous and/or crystalline structures

Fe_76.5Cu₁Si_13.5B₉ alloy rods with a diameter of 3 mm were fabricated using the copper mold suction casting method. Structural characterization revealed that different parts of the rods have different microstructures that comprise a complete amorphous structure, an amorphous-crystalline composite structure and a complete crystalline structure. Compression and nanoindentation testing showed that the hardness, strength and elastic modulus of the alloy increase with the crystalline component. High crack propagation rate and narrow shear bands contribute to the local melting and softening for the complete amorphous structure although it exhibits the lowest calculated value of the static elastic energy density.     

Effect of deformation temperature on the deformation behaviors of amorphous/crystalline composites

The amorphous/crystalline composite comprising amorphous particles of Cu54Ni6Zr22Ti18 embedded in the crystalline nickel matrix was produced and its temperature dependence of the plastic deformation behavior was studied in the supercooled liquid region (SLR) of the amorphous alloy. The flow stress of the amorphous alloy was quite sensitive to the testing temperature in the SLR. The deformation of the composites was dominated by the flow stress of the amorphous alloy. The deformation behavior of the composite was analyzed by finite element method (FEM) calculations.     

Microstructure evolution and thermal stability of an Fe-based amorphous alloy powder and thermally sprayed coatings

High velocity oxy-fuel (HVOF) thermal spraying has been used to produce coatings of an Fe–18.9%Cr–16.1%B–4.0%C–2.8%Si–2.4%Mo–1.9%Mn–1.7%W (in at.%) alloy from a commercially available powder (Nanosteel SHS7170). X-ray diffraction (XRD), differential scanning calorimetry (DSC) and scanning electron microscopy (SEM) were employed to investigate the powder, as-sprayed coatings and annealed coatings which had been heated to temperatures in the range of 550–925 °C for times ranging from 60 to 3900 min. Microhardness changes of the coatings were also measured as a function of annealing time and temperature. The powder was found to comprise amorphous and crystalline particles; the former had a maximum diameter of around 22 μm. The coating was composed of splat like regions, arising from rapid solidification of fully molten powder, and near-spherical regions from partially melted powder which had a largely retained its microstructure. The amorphous fraction of the coating was around 50% compared with 18% for the powder. The enthalpies and activation energies for crystallization of the amorphous phase were determined. Crystallization occurred in a two stage process leading to the formation of α-Fe (bcc), Fe_1.1Cr_0.9B_0.9 and M₂₃C₆ phases. DSC measurements showed that the first stage occurred at 650 °C. Annealing the coating gave a hardening response which depended on temperature and time. The as-sprayed coating had a hardness of 9.2 GPa and peak hardnesses of 12.5 and 11.8 GPa were obtained at 650 and 750 °C, respectively. With longer annealing times hardness decreased rapidly from the peak.     

Elastic properties of amorphous and crystalline B1−xCx and boron at low temperatures

We present measurements of the internal friction (Q⁻¹) and speed of sound variation (δ

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₀) of amorphous boron (a-B) and amorphous B₉C (a-B₉C). The elastic properties of these materials, which can only be produced as thin films, are consistent with those of other amorphous solids measured to date and exhibit good agreement with the tunneling model (TM) of amorphous solids. The TM parameter

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γ_t²/ρ

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_t² extracted from the elastic data has the same order of magnitude as that observed for all amorphous solids studied to date; a review will be presented. Using the results from the elastic measurements, we calculate the T² thermal conductivity Λ expected in the TM regime (T≤1 K) for a-B. The predicted thermal conductivity falls within the expected range for amorphous solids and agrees with the thermal conductivity of the crystalline icosahedral boride MB_68-δ (M=Y, Gd), which has been previously shown to exhibit glass-like excitations. We have also measured the internal friction and speed of sound variation of bulk polycrystalline c-B_1−xC_x at low temperatures (0.07 K<T<10 K). The elastic properties evolve towards the behavior characteristics of amorphous solids for increasingly carbon-deficient (x<0.20) specimens. The magnitude of the internal friction for the most carbon-deficient crystalline c-B_1−xC_x sample (x=0.1, c-B₉C) is comparable to that for a-B and a-B₉C, thereby confirming the inherent glass-like vibrational properties of carbon-deficient c-B_1−xC_x. Such behavior supports the glass-like character of carbon-deficient c-B_1−xC_x high temperature (T>50 K) thermal transport reported previously and provides the first experimental evidence for the presence of two-level systems (TLS) in these crystalline solids. However, discrepancies with the tunneling model are present; the data for c-B_1−xC_x bear some similarity to those for amorphous metals in which electronic relaxation channels are active, although details are still unclear. Previous studies have shown that the TM quantity C=Pγ_t²/ρ

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_t² (“tunneling strength”) is essentially independent of the material's shear modulus G=ρ

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_t² over a factor of 17. The elastic data presented in this work now extend the observed independence of the tunneling strength, C, over a factor of 70 in shear modulus.     

Corrosion behaviour of Ni-Zr-Ti-Si-Sn amorphous plasma spray coating

Ni₅₉Zr₂₀Ti₁₆Si₂Sn₃ amorphous material was deposited by a vacuum plasma spraying technique onto steel and copper substrates in order to investigate their behaviour in a corrosive environment. For comparison, the same alloy was prepared as amorphous ribbons by melt spinning. The amorphous nature of the coatings and ribbons was characterized by XRD, DSC and TEM, while XPS and AES analyses were performed to understand the origin of passivation and mode of corrosion. The corrosion behaviour of the coating was studied in H₂SO₄ and HCl solutions open to air at room temperature. Potentiodynamic polarisation and galvanic coupling tests were carried out on the substrate and the coating. It was found that the formation of Zr-, Ti- and Si-rich passive oxide layers provide a high corrosion resistance in H₂SO₄ solution while the breakdown of the passive layer by chloride ion adsorption was responsible for pitting corrosion of the Ni₅₉Zr₂₀Ti₁₆Si₂Sn₃ amorphous ribbons in HCl solution. Galvanic corrosion was the dominant corrosion mechanism for the coating/copper hybrid structure, in contrast to the Ni₅₉Zr₂₀Ti₁₆Si₂Sn₃ amorphous coating, which efficiently protected the steel substrate in the corrosive environment.     

Vitreous phase coating on glaserite-type alkaline earth silicate blue phosphor BaCa2MgSi2O8:Eu

A simple solid-state reaction was used to apply a vitreous-phase coating onto Eu²⁺-doped BaCa₂MgSi₂O₈ blue-phosphor particles. The vitreous phase was generated by liquid phase sintering at 1200 °C. The coated phosphor exhibited resistant to an acid dispersant. When a small amount of Al and La was added in raw materials, they were incorporated in the vitreous coating phase.     

Characterization of an amorphous–crystalline Mg-based composite

An amorphous–crystalline Mg-based composite with the nominal composition of Mg₆₅Cu₂₀Zn₅Y₁₀ has been formed by casting. X-ray diffractometry, differential scanning calorimetry, backscatter electron imaging, and energy dispersive X-ray analysis were used to characterize the structure of the composite, which is linked to the hardness, modulus, and fracture toughness obtained by Vickers and nanoindentation. Comparisons of the structure–property relationships are also made to composite materials of a similar composition. The effects of the crystalline microstructure on localized deformation through shear banding are discussed and related to the hardness and toughness results.     

Characterizations of cold-sprayed Nickel-Alumina composite coating with relatively large Nickel-coated Alumina powder

Previous studies have shown that the fabrication of metal matrix composites (MMCs) by cold spraying is effective and promising. When light materials, such as SiC and Al₂O₃, were used as reinforcements, it was diffcuclt to obtain a high volume fraction of hard phase in the composite just through the simple powder mixture. Therefore, in this study, a Ni-coated Al₂O₃ powder, which was produced through hydrothermal hydrogen reduction method, was employed aiming at increasing the volume fraction of ceramic particles in the deposited composite coating. It was found that a dense Ni-Al₂O₃ composite coating could be deposited with the Ni-coated Al₂O₃ powder under the present spray conditions. X-ray diffraction analysis indicated that the composite coating had the same phase structures as the feedstock. The volume fraction of Al₂O₃ in the composite was about 29 ± 6 vol.%, which is less than that in the feedstock (nominal: 40-45 vol.%) due to the rebound of some Al₂O₃ particulates upon kinetic impacting. The microhardness of the composite coating was about 173 ± 33Hv_0.2.     

快速冷却和扩散退火对Sn-Bi-X焊料的影响

通过对自行研制的Sn-Bi-X（X=Ag,Cu,Ge,Ce,Sb）无铅焊料进行快速冷却及扩散退火处理,研究其显微观组织和性能的变化。结果表明,冷却速度越大,熔点越低,共晶比例越小。当甩带速度为1 000 r/min时,熔点由190.5℃降低至186.2℃,且Sn-58Bi共晶相完全消失。扩散退火能消除Bi的粗化晶体,使组织均匀,增强焊料的力学性能,并且退火后组织稳定。扩散退火可以作为表面贴装生产工艺流程的一个工序,退火工艺以125℃保温16 h为宜。     

Failure mechanisms of a hydrogenated amorphous carbon coating in load-scanning tests

A diamond-like carbon (DLC) coating with a top layer of pure hydrogenated amorphous carbon (a-C:H) and an interlayer of tungsten-modified hydrogenated amorphous carbon (a-C:H:W) was deposited onto polished cylindrical specimens of a hardened and tempered cold work tool steel. On a load-scanning test rig, tribological–mechanical tests under dry conditions with DLC coated specimens sliding against identical, but uncoated specimens were performed. Additionally, comparative tests with DLC sliding against DLC and tool steel sliding against tool steel were carried out. During each test cycle, the normal load was gradually increased from 13 to 350 N, corresponding to a Hertzian contact pressure of 1.0 to 3.0 GPa. The coefficient of friction was monitored as a function of the normal load, with a significant increase in friction indicating failure of the coating. The tests were repeated and stopped at different total numbers of load cycles. After the tests, a FIB-assisted microscopical analysis in terms of wear and damage of the DLC coating was performed, revealing the (subsurface) failure mechanisms. For DLC sliding against steel, the coating fails within only few load cycles; first tribologically and after that mechanically. Failure is initiated by adherence and subsequent transfer of steel of the counter body. Below adhered steel flakes, tensile cracks form in the a-C:H top layer, with sharp crack edges removing even more steel from the counter body. In following load cycles, coating fragments are being pulled out at these spots, representing the final failure mode. In contrast, for DLC sliding against DLC, no coating failure and also no significant wear are observed, even after a considerably higher number of load cycles.     

Preparation and characterization of hydroxyapatite/titania composite coating on NiTi alloy by electrochemical deposition

NiTi alloy is used as biomaterial due to its unique properties, but the high content of Ni (about 50 at.%) in biomedical NiTi is of concern. Hydroxyapatite/titania composite coating was directly electrodeposited on the surface of NiTi alloy. The coated samples were characterized using X-ray diffraction, scanning electron microscopy, infrared spectroscopy, bonding strength test, polarization and electrochemical impedance spectroscopy (EIS). Results showed that addition of TiO₂ to the electrolyte changed the morphology of hydroxyapatite from thin flake-flower-like crystals to needle-flower-like crystals, and the coating was much denser. Besides, hydroxyapatite crystal grains in the coating were preferentially arranged in the [001] direction, which was perpendicular to the surface of NiTi alloy. The addition of TiO₂ improved the bonding strength between the coating and the substrate. Corrosion resistance of NiTi in the simulated body fluid at 37 °C was significantly improved by more than 50 times by electrodeposition of the hydroxyapatite/titania composite coating.     

非晶态Ni-W-P镀层退火晶化和激光晶化组织结构的演变

用XRD定量分析法并结合扫描电镜形貌观察,研究化学沉积高磷(13.3%)含量的Ni-W-P镀层在不同热处理条件下的晶化程度、晶粒尺寸及晶格应变等组织结构的演变规律。结果表明:高磷非晶态镀层在退火晶化过程中,Ni3P相的体积分数始终高于Ni相的,700℃时,两相的体积分数之差显著增大,镀层仍有残存的非晶相;在400~500℃之间形成的Ni3P的晶粒尺寸大于Ni的;温度为500~700℃时,Ni相的尺寸大于Ni3P的,但均未超过纳米级。镀层晶格应变表现为随退火温度的升高而降低,镀态时晶格应变最大。激光晶化处理的非晶态Ni-W-P镀层的显微结构特征介于400~500℃之间退火的镀层晶化特征。随扫描速度增加,不仅Ni3P晶粒尺寸增大,而且两相的尺寸差变大。     

Influence of fluoride ions on the amorphous phosphating of aluminium alloys

The influence of the F⁻ ions containing compounds: NaF, HBF₄, H₂SiF₆, NH₄F·HF and their concentrations on formation of phosphate coatings on Al in МоО₄²⁻ ions containing solutions, as well as protective properties of the phosphate coatings in a 0.5 M Na₂SO₄ solution have been studied. The studies of film composition by the XPS method have shown, that the phosphate coating consists of the metal phosphates from aluminium alloy and the Mo (IV, V) phosphates, which are formed during reduction of МоО₄²⁻ ions. The mass of phosphate layer and that of etched metal depend on the nature of fluoride ions, which can be arranged in the following order according to the decrease in strength of their influence: H₂SiF₆ > NH₄F·HF > HBF₄ > NaF. Polarization measurements in a 0.5 M Na₂SO₄ solution and the calculated electrochemical parameters testify that phosphated Al samples exhibit a lower corrosion rate and a higher corrosion resistance as compared to non-phosphated Al substrate.     

Discrepancies in the morphology and physical properties of amorphous and crystalline sprayed lanthanum nickel oxide films

Amorphous LaNiO₃ (a-LNO) and crystalline LaNiO₃ (c-LNO) films were prepared by spraying an aqueous precursor solution of lanthanum and nickel chlorides on hot (450 °C) fused silica substrates followed by annealing at high temperatures (550–850 °C). Thermal analysis of a dried precursor indicated that a stable oxide phase is formed at 560 °C with no distinct crystallization peak. Scanning electron microscopy (SEM) powered with energy-dispersive X-ray spectroscopy (EDX) of as-sprayed films showed rough surfaces with particulate-like deposits and incomplete pyrolysis chloride composition. No chloride contents were detected in annealed films. X-ray diffraction showed that films annealed at 550 °C and 650 °C were a-LNO and those annealed at 750 °C and 850 °C were c-LNO. The c-LNO phase was indexed as a single-phase perovskite structure with (1 1 0) orientation. SEM/EDX showed that a-LNO films have rough surfaces and c-LNO films have uniform crack-free smooth surfaces. Electrical properties measurements showed that c-LNO films have lower resistivity than a-LNO films and both types of LNO films have semiconductor resistant temperature dependence. The activation energy of electric conduction of a-LNO films was found to be much higher than that of c-LNO films. The optical transmittance and reflectance of the films were studied in the UV–visible–near IR range. The optical constants were obtained by modeling the measured transmission and reflection spectra. Because of the discrepancies in the morphology and in the physical properties of a-LNO and c-LNO films, the best fit modeling of transmission and reflection spectra was obtained by using different theoretical models and different geometrical configurations. While the Drude model accounting for larger carrier density was found to be significant for c-LNO, using the Bruggmann model and a configuration of a rough layer on top of a compact film was found to be significant for a-LNO.     

Formation, properties and microstructure of amorphous/crystalline composite Ag20Cu30Ti50 alloy using miscibility gap

The aim of the work was to produce the amorphous/crystalline composite with uniform distribution of fine crystalline soft phase. Silver–copper–titanium Ag₂₀Cu₃₀Ti₅₀ alloy was prepared using 99.95 wt% Ag, 99.95 wt% Cu, 99.95 wt% Ti that were arc-melted in argon atmosphere. Then the alloy was melt spun on a copper wheel with linear velocity of 33 m/s. Investigation of the microstructure for both arc-melt massive sample and melt-spun ribbons was performed with use of scanning electron microscope (SEM) with EDS, light microscope (LM) and X-ray diffraction. The thermal stability was evaluated by differential scanning calorimetry (DSC). The properties such as Young modulus and Vickers hardness number before and after crystallization of the amorphous matrix were measured with use of nanoindenter. The microstructure was investigated by transmission electron microscope (TEM). It was found, that the alloy has a tendency for separation within the liquid state due to the miscibility gap which resulted in segregation into Ti–Cu–Ag matrix and Ag-base spherical particles after arc-melting. During rapid cooling through the melt spinning the Ag₂₀Cu₃₀Ti₅₀ alloy formed an amorphous/crystalline composite of fcc silver-rich spherical particles within the amorphous Ti–Cu–Ag matrix.     

Characterizations of cold sprayed TiN particle reinforced Al2319 composite coating

In this study, a dense Al2319/TiN composite coating was successfully prepared using cold spraying with mechanically blended powders. TiN particles were uniformly dispersed in the coating matrix with a volume fraction of 38.7 vol.%, which is higher than that of 32.7 vol.% in the powder blend. Compared with the pure Al2319 coating, the Al2319/TiN composite coating exhibits a significantly increased adhesive strength. The incorporation of the TiN particles increases the coating hardness from 106 ± 7.8 to 154.5 ± 18.9 Hv_0.2. In addition, compared with the pure Al2319 coating, the composite coating exhibits a significantly improved tribological performance. The results obtained in this work indicated that cold spraying is a promising process to fabricate Al alloy-based composite coatings.