Reactive thermal spray by high velocity ceramic jet and characterization of the coatings

A ceramic jet composed of molten particles in an electrothermally exploded powder spray was identified by the flash, soft x-ray radiography technique. The velocity of the leading edge of the jet was estimated to be 900 m/s. The coating obtained by a ceramic jet of titanium diboride consisted of a mixing layer of the substrate material and sprayed ceramics. A coating, which exhibited no pores or cracks, was formed through the dense deposition and solidification of spray droplets. The successive impacts of the droplets caused melting and stirring of the substrate surface to form a mixing layer. Some of these layers were formed due to capillary movement of the molten substrate material into the fractures of coarse ceramic particles. Thermal spray by chemical reaction between titanium and boron nitride particles resulted in a composite coating of TiN and TiB₂. The character of the mixing layer indicated that the depth profiles depended on the substrate material.     

Plasma Spray Deposition Enhancement of Titanium Nitride Layer Using Nitrogen-Contained Plasma Irradiation of Titanium Substrate as a Pre-spraying Method

Reactive plasma spray of TiN ceramic coating attracts much attention over the years because of its ability to deposit thick layers on various metal surfaces. However, some mechanical properties of the coating such as its hardness should be improved. In this study, initially a thin layer of titanium nitride was prepared on a titanium substrate during irradiation of titanium substrate by a thermal DC nitrogen-contained plasma jet. Then, during reactive plasma spraying, Ti particles were injected into plasma jet, converted to titanium nitride and huddled on to the substrate. This new hybrid method (primary plasma irradiation and post-reactive plasma spraying) for deposition of TiN coatings would combine the advantages of both plasma-enhanced chemical vapor deposition and reactive plasma spraying methods in part. It resulted in a thick and hard layer of titanium nitride film. Sample produced by this method was analyzed with x-ray diffraction confirming titanium nitride production. Vickers hardness was measured using optical microscopy which was around 1319 H_v300g. To study the cross section of the layer, optical microscopy and scanning electron microscopy (SEM) were used.     

热喷涂TiB2-Ni复合涂层组织结构和力学性能

采用团聚烧结方法制备TiB₂-Ni复合粉末喂料,并采用大气等离子喷涂和高速火焰喷涂两种喷涂方法制备了TiB₂-Ni涂层,比较分析了两种涂层的显微组织、物相组成、孔隙率、硬度和断裂韧性.结果表明,与等离子喷涂相比,高速火焰喷涂制备的TiB₂-Ni涂层具有更高的致密度,TiB₂含量,硬度和断裂韧性.两种涂层中TiB₂都没有发生明显的脱硼,氧化,但等离子喷涂过程中TiB₂向金属相中发生了溶解生成了大量脆性Ni₂₀Ti₃B₆相,并降低了涂层中TiB₂的含量,这是涂层硬度和断裂韧性相对较低的主要原因.     

Spraying TiN by a Combined laser and low-pressure plasma spray system

The formation of a TiN-Ti composite coating by thermal spraying of titanium powder with laser processing of the subsequent coating in a low-pressure N₂ atmosphere was examined. A low-pressure plasma spray system was used in combination with a CO₂ laser. First, the coating was plasma sprayed onto a mild steel substrate using a N₂ plasma jet and titanium powder in a controlled low-pressure N2 atmosphere. The coating was then irradiated with a CO₂ laser beam in a N₂ atmosphere, and the coating was heated with a N₂ plasma jet. The amount of TiN formed in the coating was characterized by X-ray diffraction analysis. The influence of plasma spraying conditions such as plasma power, flow of plasma operating gases, chamber pressure, and laser irradiating conditions on the formation of TiN was investigated. The effect of TiN formation in the titanium coating on Vickers hardness of the coatings was examined. It was evident that coating hardness increased with an increase in TiN content in the coating and that a TiN-Ti composite coating with a hardness of more than 1200 H V can be obtained with the use of laser irradiation processing.     

Properties of Reactive Plasma Sprayed TiB2-TiC0.3N0.7 Based Composite Coatings with Cr Addition and Laser Surface Treatment

Thick TiB₂-TiC_0.3N_0.7 based composite coatings were deposited by reactive plasma spraying (RPS) successfully in air. The influence to the coating properties (morphology, Vickers microhardness and corrosion resistant property) with Cr addition in the thermal spray powder and TiB₂-TiC_0.3N_0.7 based coatings treated by laser were investigated. The phase composition, structure and properties of composite coatings were studied using XRD, SEM, EDS, Vickers microhardness and electrochemical testers. The results show that the Vickers microhardness values and the density of laser surface treated coatings are improved significantly. The Cr addition in the thermal spray powder can increase the density, improve the wettability of ceramic phases, uniform the phase distribution and enhance the corrosion-resistant property of coatings. However, due to lower microhardness of metal Cr than ceramic phases in coatings, the Vickers microhardness values of plasma sprayed coatings and plasma sprayed coatings with laser surface treatment are a little lower than that of each coating without Cr addition in the thermal spray powder.     

Dominant microstructural feature over photocatalytic activity of high velocity oxy-fuel sprayed TiO2 coating

TiO₂ photocatalytic coatings were deposited through high velocity oxy-fuel spray using anatase powder and rutile powder as feedstock. The as-sprayed TiO₂ coating was composed of anatase phase and rutile phase. The anatase content in the coating was significantly influenced by fuel gas flow and melting condition of spray powder. A high anatase content of 35% was achieved for the coating deposited using rutile powder. The anatase content in the coating deposited using anatase powder reached 55-65%. The as-sprayed TiO₂ coating was photocatalytically reactive for degradation of acetaldehyde in air. The photocatalytic activity was influenced by spray conditions. The surface morphology and phase structure of coatings deposited at different spray conditions were investigated to clarify the relationship between the coating microstructure and activity. It is found that the photocatalytic activity is significantly influenced by anatase content and surface area.     

钛沉积工艺制备TiN/cBN和TiC/金钢石涂层颗粒(英文)

用钛熔盐沉积及热处理工艺分别制备碳化钛涂覆的立方碳化硼颗粒(TiN/cBN)及碳化钛涂覆的金刚石颗粒(TiC/金刚石)。将cBN或金刚石颗粒分别与钛粉和KCl、NaCl和K2TiF6熔盐混合。将所得混合物在Ar气氛中加热至900°C,然后在H2气氛中于1000°C进行热处理。采用扫描电镜、X射线衍射和聚焦离子束技术对所制得颗粒进行表征。结果表明:cBN和金刚石颗粒表面已覆盖了纳米钛层。对Ti/cBN和TiC/金刚石涂层颗粒进行热处理后,颗粒表面沉积的Ti层与cBN和金刚石颗粒发生了原位化学反应,分别转化为钛化合物TiN和TiC。     

Biological,antibacterial activities and electrochemical behavior of borided commercially pure titanium in BSA-containing PBS

The effects of boride coating on the bioactivity, antibacterial activity, and electrochemical behavior of commercially pure titanium (CP-Ti) in phosphate buffer solution (PBS) with bovine serum albumin (BSA) were studied. The grazing incidence X-ray diffraction (GIXRD) pattern confirmed the formation of a TiB/TiB₂ coating via boriding process. Scanning electron microscopy (SEM) observation indicated that the TiB₂ cross-linked particles covered the TiB whiskers. Water contact angle measurements revealed that boriding led to the formation of a surface with intermediate water affinity. Potentiodynamic polarization (PDP) assays demonstrated that the TiB/TiB₂ coating had acceptable passivation behavior in BSA-containing PBS. Electrochemical impedance spectroscopy (EIS) measurements revealed that the passivation behavior of the CP-Ti and the borided samples was improved by increasing exposure time. Based on the Mott-Schottky (M-S) tests, it was realized that the charge carriers of passive films of both samples decreased with increasing exposure time in BSA-containing PBS. The bioactivity test results in a simulated body fluid showed that the TiB/TiB₂ coating switched the CP-Ti from bioinert to bioactive material. Finally, the antibacterial activity test of the TiB/TiB₂ coating against Escherichia coli and Staphylococcus aureus indicated 99% antibacterial activity.     

Copper-titanium diboride coatings obtained by plasma spraying reactive micropellets

Electrotribological applications require materials with both high electrical conductivity and wear resisance. For this purpose, a copper- base plasma sprayed coating containing titanium diboride particles was developed. The process for fabricating this CU- TiB₂ coating consists of plasma spraying reactive powders that contain a Cu- Ti alloy and boron. The reaction between the copper alloy and boron proceeds in different steps going from solid- state diffusion of titanium and copper to the synthesis of TiB₂ in a liquid below 1083 ‡C. Plasma sprayed copper coatings contain finer TiB₂ crystals than Cu- TiB₂ materials synthesized in a furnace at 1200 ‡C. Coatings with 25 vol% TiB2 have hardnesses that are comparable to Cu- Co- Be and Cu- Ni- Be alloys and to Cu- W and Cu- Mo alloys used in spot welding. Their low electrical resistivity of 52 ΜΩ cm could be increased by lowering the oxygen content with coatings and controlling the formation of TiB₂ clusters, the titanium content in solution in copper remaining low after the synthesis reaction.     

Microstructure and Sliding Wear Performance of Plasma-Sprayed TiB2-Ni Coating Deposited from Agglomerated and Sintered Powder

This work is aimed at developing a route for the deposition of TiB₂-Ni cermet coating. The feedstock was firstly prepared by agglomeration and sintering, which was subsequently subjected to plasma spraying. The microstructures and the phase composition of the powder, as well as the sprayed coating were analyzed by scanning electron microscopy and x-ray diffraction. The microhardness (Hv) and the fracture toughness (K _IC) of the coating were evaluated. A sliding wear test was also performed on the sprayed coating by SRV^® tribo-tester using GCr15 steel as a counterpart. The results showed that the phase of sprayed TiB₂-Ni coatings consisted of TiB₂, Ni, and Ni₂₀Ti₃B₆, whose amount varied depending on the powder calcination temperature and the TiB₂ content in the powder. Both the hardness and the fracture toughness of the coating were also changed with different powders. The Ni₂₀Ti₃B₆ brittle phase was the main factor affecting the fracture toughness of coating, which also had detrimental effect on the sliding wear performance. The 60TiB₂-40Ni coating deposited from the powder calcined at 1250 °C had better sliding wear performance as it presented more dense structure, higher TiB₂ content and less retained Ni₂₀Ti₃B₆ phase in the coating.     

In Situ TiC-Reinforced Ni-Based Composite Coating Prepared by Flame Spraying Using Sucrose as the Source of Carbon

A Ni-Ti-C composite powder for Reactive Thermal Spraying is made by heating a mixture of titanium, nickel, and sucrose to carbonize the sucrose, which is used as the source of carbon. The carbon obtained by pyrolysis of sucrose is a reactive constituent as well as the binder in the composite powder. The titanium and nickel particles are bound by the carbon to form granules of the composite powder. This powder feedstock was used to prepare in situ TiC-reinforced Ni-based composite coating by oxyacetylene flame spraying. The TiC-Ni composite coating is made of TiC, Ni, and some Ni₃Ti. In the coating, a mass of fine TiC particles is uniformly distributed within the metallic matrix. The microhardness and surface hardness of the coating are, respectively, 1433 HV_0.2kg and 62 ± 6 (HR30N). The wear resistance is much better for the TiC-Ni composite coating than for the substrate and Ni60 coating.     

Korrosionseigenschaften dünner Schichten im System Ti?B?N

Corrosion properties of thin coatings in the Ti? B? N system Thin titanium nitride TiN, boride TiB₂ and boronitride Ti(B, N) hard coatings were deposited on titanium substrates by the PVD-process Magnetron-Sputter-Ion-Plating (MSIP). They were characterized by X-ray diffractometry, SEM and WDX-analysis. With increasing B-content the Vickers hardness of the coatings increases. Photoelectron spectroscopic measurements show that all coatings are covered in atmosphere by thin oxid layer. Titanium nitride is electrochemically in 1 N sulphuric acid stable up to 1.3 V (SHE), above 1.3 V it becomes oxidized to titanium oxide TiO₂ and nitrogen N₂. The oxidation products were detected with XPS. Corrosion tests in nitric acid HNO₃ show that the corrosion resistance of titanium nitride is lower than the resistance of titanium. The corrosion of titanium boride and titanium boronitride in sulphuric acid is more intensive compared to titanium nitride. The borides cannot be passivated, but dissolve completely by anodic polarization.     

Cubic Aluminum Nitride Coating Through Atmospheric Reactive Plasma Nitriding

Aluminum nitride is a promising material for structural and functional applications. Cubic AlN (c-AlN) is expected to have higher thermal conductivity due to their high symmetry; however, its fabrication is difficult. In this study, c-AlN was synthesized by atmospheric plasma spray process through the reaction between Al feedstock powder and nitrogen plasma. Al powders were supplied to the plasma stream by Ar carrier gas and reacted with surrounding N₂ plasma, then deposit onto substrate. The obtained coatings were c-AlN/Al mixture at 150 mm of spray distance, and the nitride content was improved by increasing the spray distance. The coatings almost consist of c-AlN at 300 mm of spray distance. The coatings thickness decreased from 100 to 10 μm with increasing spray distance from 150 to 300 mm. Using carrier gas, N₂ enable to fabricate thick c-AlN coating with hardness 1020 Hv.     

Self-organized nanostructuring of composite coatings at high temperatures for drag reduction and self-cleaning

Coated and nanostructured surfaces gain much importance for improving the efficiency of high temperature applications (e.g. in turbines). By embedding ceramic particles with a negative thermal expansion coefficient (NTEC) into a metallic matrix, a reversible thermal activation of a nanostructured surface can be established.At high temperatures a defined drag reducing surface microstructure (“shark-skin”) is formed in the coating surface, while at low temperatures a self-cleaning effect (in idle periods) is achieved by the reversal of the thermal deformation.A feedstock powder produced by high energy milling and consisting of nanocrystalline yttrium oxide and tungsten oxide particles embedded into a conventional MCrAlY alloy was used for the investigations. By using different thermal spray and cladding techniques the powder is deposited on steel- substrates. In the next step, the coating is implanted with yttrium or xenon in order to induce the formation of Y₂W₃O₁₂. The latter is a ceramic with a strong negative thermal expansion coefficient and is stable up to temperatures above 1373 K. The effects during annealing and the morphology changes are analyzed in detail. Results of the phase transformation, the surface micro-morphology and the microstructured properties of these high-temperature coatings are presented.     

Biocompatible nanostructured high-velocity oxyfuel sprayed titania coating: Deposition, characterization, and mechanical properties

Nanostructured titania (TiO₂) coatings were produced by high-velocity oxyfuel (HVOF) spraying. They were engineered as a possible candidate to replace hydroxyapatite (HA) coatings produced by thermal spray on implants. The HVOF sprayed nanostructured titania coatings exhibited mechanical properties, such as hardness and bond strength, much superior to those of HA thermal spray coatings. In addition to these characteristics, the surface of the nanostructured coatings exhibited regions with nanotextured features originating from the semimolten nanostructured feedstock particles. It is hypothesized that these regions may enhance osteoblast adhesion on the coating by creating a better interaction with adhesion proteins, such as fibronectin, which exhibit dimensions in the order of nanometers. Preliminary osteoblast cell culture demonstrated that this type of HVOF sprayed nanostructured titania coating supported osteoblast cell growth and did not negatively affect cell viability. This article was originally published inBuilding on 100 Years of Success, Proceedings of the 2006 International Thermal Spray Conference (Seattle, WA), May 15–18, 2006, B.R. Marple, M.M. Hyland, Y.-Ch. Lau, R.S. Lima, and J. Voyer, Ed., ASM International, Materials Park, OH, 2006.     

Nanostructured superhard films as typical nanomaterials

The advantages of the use of film samples for nanomaterials science studies are characterized. In particular, nanograined structures are readily obtained in film samples, whereas they are difficult to obtain in bulk samples. The properties of superhard multilayer nitride films, including the deformation of TiN and TiB₂ films during indentation, the effect of an additional external magnetic field on the (TiB₂-B₄C) films' nanostructure and microhardness, as well as galvanomagnetic properties of TiN films are described and discussed in detail. It was found that generally the microhardness of multilayer nitride films increased with the number of layers, except if the two layers mutually dissolved. A microhardness of 78 GPa was achieved in 180 layer TiN/NbN films. TiB₂ films had an inhomogeneous step-like deformation pattern under indentation, in contrast to TiN films, which had a homogeneous deformation pattern, probably due to a slip along columnar grain boundaries. Application of an additional external magnetic field during magnetron sputter deposition increased hardness and smoothness of both crystalline and amorphous (TiB₂-B₄C) films. Decreasing the grain size of TiN films decreased the electron mobility while maintaining the carrier density. The oxygen and carbon distribution can be considered as random in TiN films with the grain size interval of 10-30 nm.     

Cyclic-Oxidation Resistance of Protective Silicide Layers on Titanium

Titanium was powder siliconized and gas nitrided, in order to improve its cyclic-oxidation resistance. Siliconizing was performed in a pure-silicon powder at temperatures in the range of 800–1100° C for 3–48 h. Gas nitriding was carried out in pure N₂ at 1100° C/12 h. Cyclic-oxidation experiments with the siliconized and nitrided samples were conducted in air at 850 and 950° C for up to 560 h. It was found that the siliconized layers grew according to the parabolic law with the activation energy for siliconizing E_S being 47.2 kJ mol^–1. Powder siliconizing at 900–1100° C/3 h produced multi-phase layers, in which Ti₅Si₃ silicide predominated The siliconizing temperature of 800° C/3 h appeared to be insufficient, because it led to a non-uniform surface layer with a slight protective effect. The nitrided layers were composed of titanium nitride TiN and -Ti(N) intestitial solid solution. Measurement of the oxidation kinetics revealed that the titanium siliconized at 900–1100° C/3 h oxidized much more slowly than pure Ti, Ti–6Al–4V alloy and nitrided titanium. Microstructural investigation revealed the complex sub-structure of the scales on the siliconized samples which was composed of rutile+silica, rutile and nitrogen-rich sub-layers. The mechanism of high-temperature cyclic oxidation of the siliconized and nitrided titanium is discussed.     

Cold Spraying of TiO<Subscript>2</Subscript> Photocatalyst Coating With Nitrogen Process Gas

Titanium dioxide (TiO₂) is a promising material for photocatalyst coatings. However, it is difficult to fabricate a TiO₂ coating with anatase phase by conventional thermal spray processes due to a thermal transformation to rutile phase. In this paper, anatase TiO₂ coatings were fabricated by the cold spray process. To understand the influence of process gas conditions on the fabrication of the coatings, the gas nature (helium or nitrogen) and the gas temperature are investigated. It was possible to fabricate TiO₂ coatings with an anatase phase in all spraying conditions. The process gas used is not an important factor to fabricate TiO₂ coatings. The thickness of the coatings increased with the process gas temperature increasing. It indicates that the deposition efficiency of the sprayed particles can be enhanced by controlling the spray conditions. The photocatalytic activity of the coatings is similar or better than the feedstock powder due to the formation of a large reaction area. Concludingly, cold spraying is an ideal process for the fabrication of a TiO₂ photocatalyst coating.     

Microstructure and mechanical properties of B4C reinforced Al-based matrix composite coatings deposited by CGDS and PGDS processes

Coatings of a composite material consisting of an Al-12Si matrix reinforced with 20 wt.% B₄C particles were produced using Cold Gas Dynamic Spray (CGDS) and Pulsed Gas Dynamic Spray (PGDS) processes onto Al-6061 and SS-316L substrates. Two types of composite feedstock powders (mechanically mixed and cryomilled) were used. The influence of the coating process as well as the nature of the feedstock material on the coating microstructure and mechanical properties was studied. The combination of cryomilling to synthesize the feedstock powder and the spray processes provides a unique opportunity to produce hard and dense composite coatings with good cohesion between the deformed particles and good adhesion to the substrate, no phase degradation, very low compressive stresses and high dry sliding wear resistance. The two spray processes have shown almost similar results regarding microstructure and mechanical properties. No effect of the substrate material, Al-6061 and SS-316L, on the coating microstructure and properties was observed.     

自反应电弧喷涂原位合成Ti(C,N)-TiB2-Al2O3复相陶瓷涂层

以Ti+B4C为反应药芯、Al为外皮材料制备反应型喷涂丝材,探讨利用自反应电弧喷涂技术在45钢基体表面制备复相陶瓷涂层的可行性。以X射线衍射仪(XRD)、扫描电子显微镜(SEM)和能谱仪(EDS)等方法分析、观察了涂层的组织与结构,测试了涂层的主要力学性能。结果表明:利用制备的药芯丝材进行喷涂试验,可获得由TiB2、TiB、TiC0.3N0.7、TiN、Al2O3、AlN等多相组成的复相陶瓷涂层。涂层呈典型的层状结构,其连续的基体相内弥散分布着离散的第二、第三相。涂层与基体间的结合强度为18.9MPa,涂层的平均显微硬度与弹性模量分别为735.4HV0.2和461.4GPa,摩擦因数在0.45～0.50之间,耐磨性能较基体材料提高3倍以上。