Formation of Cold-Sprayed Ceramic Titanium Dioxide Layers on Metal Surfaces

Titanium dioxide (TiO₂) coatings have potential applications in biomedical implants or as photo-catalytic functional systems. Cold spraying is a well-established method for metal on metal coatings. In cold spraying, the required heat for bonding is provided by plastic deformation of the impacting ductile particles. In contrast, few authors have investigated the impact phenomena and layer formation process for spraying brittle ceramic materials on ductile metal surfaces. In this study, the formation of TiO₂ coatings on aluminum, copper, titanium, and steel substrates was investigated by SEM, TEM, XRD, and Raman spectroscopy. The results show that the deposition efficiency depends on spray temperature, powder properties, and in particular on substrate ductility, even for impact of ceramic particles during a second pass over already coated areas. Ceramic particles bond to metallic substrates showing evidence of shear instabilities. High-resolution TEM images revealed no crystal growth or phase transitions at the ceramic/metal interfaces.     

Influence of Impact Conditions on Feedstock Deposition Behavior of Cold-Sprayed Fe-Based Metallic Glass

Cold spray is a promising method by which to deposit dense Fe-based metallic glass coatings on conventional metal substrates. Relatively low process temperatures offer the potential to prevent the crystallization of amorphous feedstock powders while still providing adequate particle softening for bonding and coating formation. In this study, Fe₄₈Mo₁₄Cr₁₅Y₂C₁₅B₆ powder was sprayed onto a mild steel substrate, using a variety of process conditions, to investigate the feasibility of forming well-bonded amorphous Fe-based coatings. Particle splat adhesion was examined relative to impact conditions, and the limiting values of temperature and velocity associated with successful softening and adhesion were empirically established. Variability of particle sizes, impact temperatures, and impact velocities resulted in splat morphologies ranging from well-adhered deformed particles to substrate craters formed by rebounded particles and a variety of particle/substrate interface conditions. Transmission electron microscopy studies revealed the presence of a thin oxide layer between well-adhered particles and the substrate, suggesting that bonding is feasible even with an increased oxygen content at the interface. Results indicate that the proper optimization of cold spray process parameters supports the formation of Fe-based metallic glass coatings that successfully retain their amorphous structure, as well as the superior corrosion and wear-resistant properties of the feedstock powder.     

Intermetallic Al-, Fe-, Co- and Ni-Based Thermal Barrier Coatings Prepared by Cold Spray for Applications on Low Heat Rejection Diesel Engines

Conventional thermal barrier coating (TBC) systems consist of a duplex structure with a metallic bond coat and a ceramic heat insulating topcoat. They possess the desired low thermal conductivity, but at the same time they are very brittle and sensitive to thermal shock and thermal cycling due to the inherently low coefficient of thermal expansion. Recent research activities are focused on the developing of multilayer TBC structures obtained using cold spraying and following annealing. Aluminum intermetallics have demonstrated thermal and mechanical properties that allow them to be used as the alternative TBC materials, while the intermetallic layers can be additionally optimized to achieve superior thermal physical properties. One example is the six layer TBC structure in which cold sprayed Al-based intermetallics are synthesized by annealing in nitrogen atmosphere. These multilayer coating systems demonstrated an improved thermal fatigue capability as compared to conventional ceramic TBC. The microstructures and properties of the coatings were characterized by SEM, EDS and mechanical tests to define the TBC material properties and intermetallic formation mechanisms.     

Cold spray of SiC and Al<Subscript>2</Subscript>O<Subscript>3</Subscript> with soft metal incorporation: A technical contribution

Al + SiC, Al + Al₂O₃ composites as well as pure Al, SiC, and Al₂O₃ coatings were prepared on Si substrates by the cold gas dynamic spray process (CGDS or cold spray). The powder composition of metal (Al) and ceramic (SiC, Al₂O₃) was varied into 1:1 and 10:1 wt.%, respectively. The propellant gas was air heated up to 330 °C and the gas pressure was fixed at 0.7 MPa. SiC and Al₂O₃ have been successfully sprayed producing coatings with more than 50 μm in thickness with the incorporation of Al as a binder. Also, hard ceramic particles showed peening effects on the coating surfaces. In the case of pure Al metal coating, there was no crater formation on hard Si substrates. However, when Al mixed with SiC and Al₂O₃, craters were observed and their quantities and sizes depended on the composition, aggregation and size of raw materials.     

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.     

Cold Spray Coating of Submicronic Ceramic Particles on Poly(vinyl alcohol) in Dry and Hydrogel States

We report an approach using cold spray technology to coat poly(vinyl alcohol) (PVA) in polymer and hydrogel states with hydroxyapatite (HA). Using porous aggregated HA powder, we hypothesized that fragmentation of the powder upon cold spray could lead to formation of a ceramic coating on the surface of the PVA substrate. However, direct spraying of this powder led to complete destruction of the swollen PVA hydrogel substrate. As an alternative, HA coatings were successfully produced by spraying onto dry PVA substrates prior to swelling in water. Dense homogeneous HA coatings composed of submicron particles were obtained using rather low-energy spraying parameters (temperature 200-250 °C, pressure 1-3 MPa). Coated PVA substrates could swell in water without removal of the ceramic layer to form HA-coated hydrogels. Microscopic observations and in situ measurements were used to explain how local heating and impact of sprayed aggregates induced surface roughening and strong binding of HA particles to the molten PVA substrate. Such an approach could lead to design of ceramic coatings whose roughness and crystallinity can be finely adjusted to improve interfacing with biological tissues.     

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.     

Aluminium depletion in NiCrAlY bond coatings by hot corrosion as a function of projection system

Three different projection system are used to prepare NiCrAlY bond coats over metallic substrates: atmospheric plasma spray (APS), high velocity oxyfuel (HVOF) and high frequency pulse detonation (HFPD). These coatings were tested in hot corrosion experiments with sprayed Na₂SO₄ at 1000 °C for 20 and 100 h experiments in air. Coatings surface composition after thermal treatment was characterised by XRD and SEM. Cross section of coatings were analysed by SEM-EDX. A relationship between microstructural characteristics of initial coatings and final performance in hot corrosion was found in terms of porosity percentage: plasma sprayed coatings present higher percentage of porosity compared to HVOF and HFPD projection systems for the same composition and Al is heavily consumed in interparticle oxidation. This Al depletion in turn involves intrinsic chemical failure and surface layer is comprised by a porous spinel of mixed oxides. On the other hand, high energy projection systems produce dense coatings allowing the Al migration to external alumina layer, particularly in the case of HVOF coating.     

冷喷涂技术在生物医学领域中的应用及展望

冷喷涂技术(cold spray technology)是一类赋予材料表面特殊性能的重要手段。概述了冷喷涂技术在制备温度敏感生物材料加工领域的优势,并重点综述了利用冷喷涂技术制备的典型生物材料。目前,冷喷涂沉积永久性植入金属材料,如Ti合金、Fe基合金、Co-Cr合金和可降解金属材料Mg合金等技术相对成熟。近年来随着冷喷涂技术的发展,有效解决和拓展了用于医疗器械表面改性的涂层材料体系,如冷喷涂制备高分子材料超高分子量聚乙烯(UHMWPE)涂层,以及高密度聚乙烯(HDPE)和聚醚醚酮(PEEK)表面冷喷涂制备生物涂层。最值得关注的冷喷涂或真空冷喷涂技术制备陶瓷涂层,如羟基磷灰石(HA)、羟基磷灰石-石墨烯(HA-graphene)以及二氧化钛(Ti O2),在生物医学领域应用具有突破性进展。同时归纳了冷喷涂技术在生物医学领域的研究现状和问题,虽然在针对冷喷涂生物涂层的微观结构、力学行为、腐蚀抗力等方面取得了一定成果,在组织工程、抗菌材料等领域也取得了尝试性突破,但尚缺乏系统的冷喷涂涂层生物学性能表征,涂层与细胞/组织相互作用机理还不明确,相关的临床研究欠缺。最后,在此基础上,展望了未来生物材料朝功能化和个性化医疗方向的发展方向。冷喷涂技术在功能化载药涂层的低温制备和个性化医疗器械增材制造等领域将有更大的应用空间,并给新型生物材料的表面改性带来更多机遇和可能。     

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.     

The Influence of the Substrate on the Deposition of Cold-Sprayed Titanium: An Experimental and Numerical Study

The deposition of cold-sprayed titanium on various substrates is studied in this work. A rather coarse powder of titanium (−70 + 45 μm) was sprayed under uniform spraying conditions using a cold spray system onto five different substrates: two aluminum-based alloys (AISI 1050-H16 and AISI 2017-T4), copper, stainless steel AISI 304L, and Ti-6Al-4V. All the spraying experiments were carried out using alternatively nitrogen (N₂) or helium (He) as the process gas. Thick coatings were formed on the various substrates, with the exception of the AISI 2017 substrate. When N₂ was used as the process gas, only a few particles remained adhering to the AISI 2017. The thick pre-existing superficial oxide layer on AISI 2017, which was detected by Electron MicroProbe Analysis (EPMA), appeared to prevent adhesion of cold-sprayed titanium particles. The interaction of the sprayed particles with the various substrates was also studied by means of numerical simulations to better understand the adhesion mechanisms. The microstructure and the characteristics of the coatings were investigated. Deposition efficiency and coating density were found both to be strongly improved by spraying helium as the process gas.     

Effect of Ceramic Particle Velocity on Cold Spray Deposition of Metal-Ceramic Coatings

In this paper, metal-ceramic coatings are cold sprayed taking into account the spray parameters of both metal and ceramic particles. The effect of the ceramic particle velocity on the process of metal-ceramic coating formation and the coating properties is analyzed. Copper and aluminum powders are used as metal components. Two fractions of aluminum oxide and silicon carbide are sprayed in the tests. The ceramic particle velocity is varied by the particle injection into different zones of the gas flow: the subsonic and supersonic parts of the nozzle and the free jet after the nozzle exit. The experiments demonstrated the importance of the ceramic particle velocity for the stability of the process: Ceramic particles accelerated to a high enough velocity penetrate into the coating, while low-velocity ceramic particles rebound from its surface.     

Thin film coatings of WO<Subscript>3</Subscript> by cold gas dynamic spray: A technical note

Dense and adhesive WO₃ films were prepared on a silicon substrate by the cold gas dynamic spray process (or cold spray). In contrast to standard metallic coatings, there was no sizable crater formation and plastic deformation. However, the aggregation of raw powder particles of a relatively large size was found to be destroyed upon impact on the substrate, forming a highly irregular surface with very fine secondary particles and providing good interlocking powder and void reduction among the particles in the coating. High-resolution images of the substrate interface showed that particles at the interface were more densely packed and that good adhesion was obtained. There fore, the particle bombardment onto the first layer of the coating could provide enhanced adhesion to the substrate mechanically and/or chemically.     

NiAl/NiCoCrAlY/8YSZ复合喷涂层的微观结构与性能研究

目的提高金属/陶瓷隔热涂层体系在海洋环境下的耐腐蚀性能。方法利用冷喷涂方法制备NiAl复合打底层和Ni CoCrAlY粘结层,与等离子喷涂制备的8YSZ陶瓷层构成适用于海洋环境的多层结构耐蚀隔热涂层体系。利用FE-SEM分别观察喷涂态粘结层和陶瓷层的表面、横截面形貌,通过EDS分析涂层元素分布;利用XRD分析表征涂层的物相组成;借助万能材料试验机,采用拉伸法测试涂层结合强度;利用热循环试验和焰流冲刷试验测试涂层的耐高温性能。结果微观分析表明,冷喷涂制备的NiAl复合打底层和Ni CoCrAlY粘结层形貌致密,涂层材料未发生明显氧化,颗粒变形程度不一,粘结层与基体间的结合强度约为18.4 MPa,粘结层与8YSZ陶瓷层界面结合紧密。陶瓷层物相结构和成分稳定,涂层经12次热震循环和1000个周期的高温焰流冲击后,表面未出现开裂、起皮和脱落。结论采用冷喷涂法和等离子喷涂法联合制备的耐蚀隔热复合涂层体系具备良好的耐热性和耐腐蚀性。冷喷涂制备的金属涂层结构致密,孔隙率低,与陶瓷层结合良好,能够有效提高涂层体系在腐蚀性环境中的耐蚀性能。NiAl复合涂层可以缓解Ni CoCrAlY粘结层和铝合金基材间的热匹配问题,增强涂层的结合性能。     

Effect of Substrate Temperature on Cold-Gas-Sprayed Coatings on Ceramic Substrates

This study focuses on cold-gas-sprayed deposition of metallic coatings onto ceramic substrates for application in power electronics. In order to achieve the required surface activation for bonding, the substrate is heated during spraying. The effects of substrate temperature on bond strength and coating properties are investigated for cold-gas-sprayed coatings of copper and aluminum on Al₂O₃. It is found that the adhesion strengths of the cold-gas-sprayed coatings and that of the single-impacting particles increase with the increasing temperature and roughness of the substrate. Coatings sprayed on heated substrates show relatively low compressive stresses and low hardness, while their electrical conductivity reaches high values of over 90% IACS. Overall, a higher substrate temperature is found to improve the coating properties significantly.     

Fast Regime Fluidized Bed Machining (FR-FBM) of Thermally Sprayed Coatings

Finishing of thermally sprayed metallic, ceramic, and cermet coatings is required to meet tolerances and requirements on surface roughness in most industrial applications. Conventional machining is a costly and time-consuming process, and is difficult to automate. Therefore, this study investigates and develops a new technique highly amenable for automation: fast regime—fluidized bed machining (FR-FBM). Atmospheric plasma sprayed TiO₂, Cr₂O₃, and HVOF-sprayed WC-17%Co and Tribaloy-800 coatings, deposited on AISI 1040 steel substrates, were subjected to FR-FBM treatment. The effects of the leading operational parameters, namely, abrasive size, jet pressure, and processing time, were evaluated on all coatings by using a two/three-levels full factorial design of experiments. The FR-FBM treated surfaces were observed by FE-SEM and their surface finishing was evaluated by contact profilometry. Significant improvements in surface finishing of all the machined thermally sprayed coatings can always be detected, with FR-FBM being able to guarantee the precision and to ensure the closest geometrical tolerances.     

Dependency of fracture toughness of plasma sprayed Al<Subscript>2</Subscript>O<Subscript>3</Subscript> coatings on lamellar structure

The fracture toughness of plasma-sprayed Al₂O₃ coatings in terms of critical strain energy release rate G _Ic was investigated using a tapered double cantilever beam (TDCB) approach. This approach makes the fracture toughness be measured only using the critical fracture load disregarding crack length during test. The Al₂O₃ coatings were deposited under different spray distances and plasma powers to clarify the effect of spray parameters on the G _Ic of the coatings. The fracture surfaces were examined using scanning electron microscope. On the basis of an idealized layer microstructure model for thermal sprayed coatings, the theoretical relationship between the cohesive fracture toughness and microstructure is proposed. The correlation between the calculated fracture toughness and observed value is examined. It was found that the fracture toughness of plasma sprayed Al₂O₃ coatings is not significantly influenced by spray distance up to 110 mm, and further increase in spray distance to 130 mm resulted in large decrease in the fracture toughness of the coatings. The G _Ic value predicted based on the proposed model using lamellar interface mean bonding ratio and the effective surface energy of bulk ceramics agreed well with the observed G _Ic data. Such agreement evidently shows that the fracture toughness of thermally sprayed ceramic coatings at the direction along coating surface is determined by lamellar interface bonding.     

Plasma Spray Physical Vapor Deposition of La1−x Sr x Co y Fe1−y O3−δ Thin-Film Oxygen Transport Membrane on Porous Metallic Supports

Plasma spray physical vapor deposition (PS-PVD) is a very promising route to manufacture ceramic coatings, combining the efficiency of thermal spray processes and characteristic features of thin PVD coatings. Recently, this technique has been investigated to effectively deposit dense thin films of perovskites particularly with the composition of La_0.58Sr_0.4Co_0.2Fe_0.8O_3?δ (LSCF) for application in gas separation membranes. Furthermore, asymmetric type of membranes with porous metallic supports has also attracted research attention due to the advantage of good mechanical properties suitable for use at high temperatures and high permeation rates. In this work, both approaches are combined to manufacture oxygen transport membranes made of gastight LSCF thin film by PS-PVD on porous NiCoCrAlY metallic supports. The deposition of homogenous dense thin film is challenged by the tendency of LSCF to decompose during thermal spray processes, irregular surface profile of the porous metallic substrate and crack and pore-formation in typical ceramic thermal spray coatings. Microstructure formation and coating build-up during PS-PVD as well as the annealing behavior at different temperatures of LSCF thin films were investigated. Finally, measurements of leak rates and oxygen permeation rates at elevated temperatures show promising results for the optimized membranes.     

A comparative study of tribological behavior of plasma and D-gun sprayed coatings under different wear modes

In recent years, thermal sprayed protective coatings have gained widespread acceptance for a variety of industrial applications. A vast majority of these applications involve the use of thermal sprayed coatings to combat wear. While plasma spraying is the most versatile variant of all the thermal spray processes, the detonation gun (D-gun) coatings have been a novelty until recently because of their proprietary nature. The present study is aimed at comparing the tribological behavior of coatings deposited using the two above techniques by focusing on some popular coating materials that are widely adopted for wear resistant applications, namely, WC-12% Co, A1₂O₃, and Cr₃C₂-MCr. To enable a comprehensive comparison of the above indicated thermal spray techniques as well as coating materials, the deposited coatings were extensively characterized employing microstructural evaluation, microhardness measurements, and XRD analysis for phase constitution. The behavior of these coatings under different wear modes was also evaluated by determining their tribological performance when subjected to solid particle erosion tests, rubber wheel sand abrasion tests, and pin-on-disk sliding wear tests. The results from the above tests are discussed here. It is evident that the D-gun sprayed coatings consistently exhibit denser microstructures and higher hardness values than their plasma sprayed counterparts. The D-gun coatings are also found to unfailingly exhibit superior tribological performance superior to the corresponding plasma sprayed coatings in all wear tests. Among all the coating materials studied, D-gun sprayed WC-12%Co, in general, yields the best performance under different modes of wear, whereas plasma sprayed Al₂O₃ shows least wear resistance to every wear mode.     

Factors affecting the microstructure of platinum-modified aluminide coatings during a vapor phase aluminizing process

Platinum (Pt)-modified aluminide coatings were developed by electroplating a thin layer of Pt followed by an industrial vapor phase aluminizing process. The goal of this work was to systematically investigate the effect of critical coating process parameters (such as the electroplated Pt thicknesses, Al contents in Cr-Al nuggets, diffusion heat treatments) and substrates on the final Pt-modified aluminide coatings. Surface morphology and cross-section microstructure of the developed coatings were inspected and compared by using Optical Microscope, Scanning Electron Microscope (SEM) equipped with energy dispersive spectroscopy (EDS). Experimental results showed that the Al and/or Pt increase shall favor the formation of ξ-PtAl₂ phase; transformation of ξ-PtAl₂ into β-(Ni,Pt)Al phase can be obtained via a heat treatment process; Cr, Co elements in the studied Ni-base superalloy substrates did not show significant influence on coating outer layer microstructure; while substrate elements affect the microstructure of the coating interdiffusion layer.