Bactericidal Performance of Flame-Sprayed Nanostructured Titania-Copper Composite Coatings

A large concern surrounding stainless steel surfaces is the ability of bacteria to grow and attach to them quite easily. One possible solution to destroy these pathogens is to coat surfaces with a biocidal agent. The photocatalytic effect of titanium dioxide (TiO₂) is known to have a bactericidal effect. Coatings of TiO₂ were prepared on 1010 low carbon steel substrates using an oxy-acetylene flame spray torch. TiO₂ coatings containing 5 wt.% copper (Cu) were fabricated to increase the bactericidal effect of the coating. After deposition, the coatings were polished to an average roughness of 1 μm. Solutions of Pseudomonas aeruginosa (PAK) bacteria were placed onto the coating surface for periods of up to 3 h, and the amount of surviving bacteria were counted. Some samples were irradiated with white light and other samples were held in a dark chamber. In coatings of copper-free flame-sprayed TiO₂, the high flame temperatures facilitated the conversion of the anatase phase to the rutile phase, which limited the photocatalytic destruction of the bacterial cells. However, TiO₂-copper composite coatings showed a large bactericidal effect, killing approximately 75% of PAK bacterial cells after 3 h. Under the same conditions, the TiO₂-copper composite coatings had the same bactericidal capabilities as pure copper surfaces, with the composite coatings showing improved bactericidal performance when exposed to light. It was proposed that increased concentrations of reactive oxide species produced due to TiO₂ photocatalysis improved the performance of the irradiated TiO₂-copper composite coatings.     

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.     

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.     

Milestones in Functional Titanium Dioxide Thermal Spray Coatings: A Review

Titanium dioxide has been the most investigated metal oxide due to its outstanding performance in a wide range of applications, chemical stability and low cost. Coating processes that can produce surfaces based on this material have been deeply studied. Nevertheless, the necessity of coating large areas by means of rapid manufacturing processes renders laboratory-scale techniques unsuitable, leading to a noteworthy interest from the thermal spray (TS) community in the development of significant intellectual property and a large number of scientific publications. This review unravels the relationship between titanium dioxide and TS technologies with the aim of providing detailed information related to the most significant achievements, lack of knowhow, and performance of TS TiO₂ functional coatings in photocatalytic, biomedical, and other applications. The influence of thermally activated techniques such as atmospheric plasma spray and high-velocity oxygen fuel spray on TiO₂ feedstock based on powders and suspensions is revised; the influence of spraying parameters on the microstructural and compositional changes and the final active behavior of the coating have been analyzed. Recent findings on titanium dioxide coatings deposited by cold gas spray and the capacity of this technology to prevent loss of the nanostructured anatase metastable phase are also reviewed.     

Microstructure and photocatalytic activity of suspension plasma sprayed TiO2 coatings on steel and glass substrates

In this study, TiO₂ coatings were deposited by suspension plasma spraying (SPS) from a commercial TiO₂ nanoparticle suspension on two different substrates: a standard stainless steel and a Pyrex glass. Coatings were sprayed on both substrates with an F4-MB monocathode torch; a Triplex Pro tricathode torch was also used to spray coatings just on the stainless steel substrates. Spraying distance and cooling were varied.The anatase content in the coatings, determined by XRD, ranged from 32 to 72 wt.%. A significant amount of anatase to rutile transformation was found to occur during cooling. Examination of the microstructure revealed that the coating microstructure was bimodal, involving a non-molten region consisting mainly of anatase nanoparticle agglomerates and a molten region. The glass substrate coatings displayed a segregated phase distribution, particularly when the surface to be coated was cooled. Photocatalytic activity was determined by a methylene blue test.The experimental data fitted well to a first-order kinetic. All the coatings exhibited high photocatalytic activity in comparison with that of a commercial sol–gel coating. However, unlike much of the previous research, photocatalytic activity did not correlate with the anatase content determined by XRD.     

Comparative study on the photocatalytic behaviour of titanium oxide thermal sprayed coatings from powders and suspensions

This work presents a study of the microstructures and photocatalytic behaviour of titanium oxide coatings obtained by thermal spraying of agglomerated nanopowders and suspensions. Fine TiO₂ Degussa P25 nanopowder, generally considered as the reference material in photocatalytic applications, was used as the material feedstock. HVOF process and suspension thermal spraying were used to prepare photocatalytic titania coatings. The coatings were mainly characterised by means of SEM and X-ray diffraction. The photocatalytic performance was evaluated based on decolouration of the pink dye Rhodamine B and degradation of gaseous acetaldehyde. A lower degree of pollutant degradation was found for deposits prepared by HVOF spraying of granules due principally to the low content of the photocatalytically active phase, i.e. anatase. Complete photocatalytic degradation of the organic compounds was recorded for the suspension-sprayed coatings. Based on the current results, suspension thermal spraying appears to be the better choice for preparing photocatalytically active titanium oxide surfaces for the removal of organic pollutants.     

Properties of High Velocity Suspension Flame Sprayed (HVSFS) TiO2 coatings

TiO₂ coatings were manufactured by the High Velocity Suspension Flame Spraying (HVSFS) technique using a nanopowder suspension. Their microstructure, nanohardness, tribological properties and photocatalytic activity were studied and compared to conventional atmospheric plasma sprayed (APS) and HVOF-sprayed TiO₂ coatings manufactured using commercially available feedstock. The HVSFS process leaves a fairly large freedom to adjust coating properties (thickness, porosity, anatase content, hardness, etc…) according to the desired objective. Layers with higher anatase content and higher porosity can be produced to achieve higher photocatalytic efficiency, better than conventional APS and HVOF TiO₂. Alternatively, dense protective layers can be deposited, possessing lower porosity and pore interconnectivity and better wear resistance than as-deposited APS and HVOF layers. In all cases, HVSFS-deposited layers are thinner (20 µm-60 µm) than those which can be obtained by conventional spraying processes.     

Nanostructured Photocatalytic TiO<Subscript>2</Subscript> Coating Deposited by Suspension Plasma Spraying with Different Injection Positions

High plasma power is beneficial for the deposition efficiency and adhesive strength of suspension-sprayed photocatalytic TiO₂ coatings, but it confronts two challenges: one is the reduced activity due to the critical phase transformation of anatase into rutile, and the other is fragmented droplets which cannot be easily injected into the plasma core. Here, TiO₂ coatings were deposited at high plasma power and the position of suspension injection was varied with the guidance of numerical simulation. The simulation was based on a realistic three-dimensional time-dependent numerical model that included the inside and outside of torch regions. Scanning electron microscopy was performed to study the microstructure of the TiO₂ coatings, whereas x-ray diffraction was adopted to analyze phase composition. Meanwhile, photocatalytic activities of the manufactured TiO₂ coatings were evaluated by the degradation of an aqueous solution of methylene blue dye. Fragmented droplets were uniformly injected into the plasma jet, and the solidification pathway of melting particles was modified by varying the position of suspension injection. A nanostructured TiO₂ coating with 93.9% anatase content was obtained at high plasma power (48.1 kW), and the adhesive coating bonding to stainless steel exhibited the desired photocatalytic activity.     

Effect of Spray Distance on Microstructure and Tribological Performance of Suspension Plasma-Sprayed Hydroxyapatite–Titania Composite Coatings

Hydroxyapatite (HA)–titania (TiO₂) composite coatings prepared on Ti6Al4V alloy surface can combine the excellent mechanical property of the alloy substrate and the good biocompatibility of the coating material. In this paper, HA–TiO₂ composite coatings were deposited on Ti6Al4V substrates using suspension plasma spray (SPS). X-ray diffraction, scanning electron microscopy, Fourier infrared absorption spectrometry and friction tests were used to analyze the microstructure and tribological properties of the obtained coatings. The results showed that the spray distance had an important influence on coating microstructure and tribological performance. The amount of decomposition phases decreased as the spray distance increased. The increase in spray distance from 80 to 110 mm improved the crystalline HA content and decreased the wear performance of the SPS coatings. In addition, the spray distance had a big effect on the coating morphology due to different substrate temperature resulting from different spray distance. Furthermore, a significant presence of OH^? and CO₃ ^2? was observed, which was favorable for the biomedical applications.     

Photocatalytic Activity of Nanostructured Anatase Coatings Obtained by Cold Gas Spray

This article describes a photocatalytic nanostructured anatase coating deposited by cold gas spray (CGS) supported on titanium sub-oxide (TiO_2?x ) coatings obtained by atmospheric plasma spray (APS) onto stainless steel cylinders. The photocatalytic coating was homogeneous and preserved the composition and nanostructure of the starting powder. The inner titanium sub-oxide coating favored the deposition of anatase particles in the solid state. Agglomerated nano-TiO₂ particles fragmented when impacting onto the hard surface of the APS TiO_2?x bond coat. The rough surface provided by APS provided an ideal scenario for entrapping the nanostructured particles, which may be adhered onto the bond coat due to chemical bonding; a possible bonding mechanism is described. Photocatalytic experiments showed that CGS nano-TiO₂ coating was active for photodegrading phenol and formic acid under aqueous conditions. The results were similar to the performance obtained by competitor technologies and materials such as dip-coating P25^® photocatalysts. Disparity in the final performance of the photoactive materials may have been caused by differences in grain size and the crystalline composition of titanium dioxide.     

Electrodeposition of composite Fe–TiO<Subscript>2</Subscript> coatings from methanesulfonate electrolyte

The process of electrodeposition of an iron–titania composite electrochemical coating from methanesulfonate electrolyte is studied. TiO₂ Degussa P 25 nanopowder (a mixture of crystalline modifications of rutile and anatase, with the latter prevailing) is used for preparation of suspension electrolyte. The dispersed phase content in the composition coating increases at a decrease in current density and increase in TiO₂ in the suspension. It is shown that kinetics of codeposition is adequately described by the improved Guglielmi model. It is shown that inclusion of TiO₂ particles into an iron matrix results in an increase in microhardness of the coating due to dispersion strengthening. Fe–TiO₂ (anatase+rutile) coatings manifest photocatalytic activity with respect to the reaction of destruction of the methyl orange dye in aqueous solutions under exposure to UV radiation, and this activity is higher than in the case of similar coatings containing TiO₂–rutile particles.     

Towards engineering isotropic behaviour of mechanical properties in thermally sprayed ceramic coatings

It is widely recognized by the scientific community that thermal spray coatings exhibit anisotropic behaviour of mechanical properties, e.g., the elastic modulus values of the coating in-plane (i.e., parallel to the substrate surface) or through-thickness (i.e., perpendicular to the substrate surface) will tend to be significantly different due to their anisotropic microstructures. This work shows that thermally sprayed ceramic coatings may exhibit isotropic mechanical behaviour similar to that of bulk materials even when exhibiting the typical anisotropic coating microstructure. Elastic modulus values on the in-plane and through-thickness directions were measured via Knoop indention and laser-ultrasonic techniques on a coating produced via flame spray (FS) using a nanostructured titania (TiO₂) powder. No significant differences were found between the coating directions. In addition, four major cracks with similar lengths were observed originating near or at the corners of Vickers indentation impressions on the coating cross-section (i.e., a typical characteristic of bulk ceramics), instead of two major cracks propagating parallel to the substrate surface, which is normally the case for these types of coatings. It was observed by scanning electron microscopy (SEM) that coatings tended to exhibit an isotropic behaviour when the average length of microcracks within the coating structure oriented perpendicular to the substrate surface was about twice that of the microcracks aligned parallel to the substrate surface. Modelling, based on scalar crack densities of horizontal and vertical cracks, was also used to estimate when thermal spray coatings tend to exhibit isotropic behaviour.     

Characterization of Thermal-Sprayed HAP and HAP/TiO<Subscript>2</Subscript> Coatings for Biomedical Applications

In the present study, hydroxyapatite (HAP) coating along with HAP/TiO₂ coating has been deposited by high-velocity flame spray (HVFS) technique onto 316LSS. Titania was used as a bond coat and HAP as top coat in HAP/TiO₂ coating. The main aim of the study is to investigate the corrosion behavior of thermal spray coating of HAP and HAP/TiO₂ on steel. Electrochemical corrosion testing was carried out using potentiodynamic polarization test. The corrosion behavior of bare and as-sprayed specimens was analyzed in simulated body fluid known as Hank’s solution. As-sprayed specimens along with corroded specimens were further characterized by XRD, SEM/EDS, and x-ray mapping analysis. It was observed that the HAP/TiO₂ coating possessed higher microhardness (280 Hv) as compared to HAP coating (254 Hv). Surface roughness also got enhanced in case of HAP/TiO₂ coating (9.35 μm) as compared to pure HAP coating (7.37 μm). The porosity of the HAP coating was found to be higher than the bond coating. It was observed that the Ca/P ratio almost resembled that of the natural bone composition. The corrosion resistance of steel increased after the deposition of HAP and HAP/TiO₂ coatings. The maximum corrosion resistance was exhibited by HAP/TiO₂ coating.     

Grindability Evaluation and Fatigue and Wear Behavior of Conventional and Nanostructured Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-13 Wt.% TiO<Subscript>2</Subscript> Air Plasma Sprayed Coatings

In this paper, air plasma spray Al₂O₃-13% TiO₂ coatings were produced by two type of feedstock powders (agglomerated nanostructured and conventional). Mechanical properties of coatings including hardness, toughness, fatigue, and wear behavior as well as grindability of coatings were evaluated and compared. We report that due to the presence of nanostructure zone in microstructure of air plasma sprayed Al₂O₃-13% TiO₂ nanostructure coatings, a significant gain is observed in toughness, grindability, and fatigue lifetime in nanostructure coating over its counterpart conventional coating.     

Nanoindentation study of the mechanical and damage behaviour of suspension plasma sprayed TiO2 coatings

TiO₂ coatings can be used as self-cleaning surfaces owing to their photocatalytic and hydrophilic properties. Suspension plasma spray (SPS) has proven to be a feasible and cheap technique for producing self-cleaning surfaces with acceptable photo-activity. This paper presents a nanoindentation study of the mechanical properties (hardness, Young's modulus and scratch resistance) of photoactive layers of suspension plasma sprayed TiO₂ coatings applied on to glass substrates. Microstructure observation showed that the rutile grains were surrounded by fine anatase crystals. Under the same spraying conditions, the resulting anatase/rutile concentrations varied depending on the cooling rate (the substrate being either cooled with water or in air). The results showed that higher concentrations of anatase, which is softer than rutile, reduced the scratch damage and increased the friction coefficient.     

Comparison of the photocatalytic behavior of TiO2 coatings elaborated by different thermal spraying processes

This paper proposes a comparative study on the microstructure and photocatalytic performances of titanium dioxide coatings elaborated by various thermal spraying methods (plasma spraying in atmospheric conditions, suspension plasma spraying, and high-velocity oxyfuel spraying). Agglomerated spray dried anatase TiO₂ powder was used as feedstock material for spraying. Morphology and microstructural characteristics of the coatings were studied mainly by scanning electron microscopy and x-ray diffraction. The photocatalytic behavior of the TiO₂-base surfaces was evaluated from the conversion rate of gaseous nitrogen oxides (NOx). It was found that the crystalline structure depended strongly on the technique of thermal spraying deposition. Moreover, a high amount of anatase was suitable for the photocatalytic degradation of the pollutants. Suspension plasma spraying has allowed retention of the original anatase phase and for very reactive TiO₂ surfaces to be obtained for the removal of nitrogen oxides. 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.     

Effect of Cu2+ doping on photocatalytic performance of liquid flame sprayed TiO2 coatings

Cu²⁺ was added to liquid feedstock to deposit ion doping TiO₂ photocatalytic coatings through liquid flame spraying. The coating microstructure was characterized by x-ray diffraction (XRD), transmission electron microscopy, and x-ray photoelectron spectroscopy (XPS). The photocatalytic performance of coatings was examined by photodegradation of acetaldehyde. The XRD analysis shows that the crystalline structure of coatings is not significantly influenced by Cu²⁺ doping. The photocatalytic activity of the TiO₂ coatings is enhanced by Cu²⁺ doping. It is found that a high concentration of Cu²⁺ doping decreases the activity. The XPS analysis shows that the adsorbed oxygen concentration is increased with the increase of Cu²⁺ dopant concentration and decreases with a further increase of dopant concentration. The enhancement of photocatalytic activity can be attributed to the adsorption ability of oxygen and other reactants on the surface of doping TiO₂ coatings. 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.     

Formation of Pore Structure and Its Influence on the Mass Transport Property of Vacuum Cold Sprayed TiO2 Coatings Using Strengthened Nanostructured Powder

The pore structure in nano-porous TiO₂ coatings influences the ion diffusion property and the photovoltaic performance of dye-sensitized solar cells. In this paper, TiO₂ coatings were deposited by vacuum cold spray (VCS) using a strengthened nanostructured powder. The pore structure, ion diffusion, and dye infiltration properties were examined to understand the coating deposition mechanism. Results showed that the pores in the VCS TiO₂ coatings presented a bimodal size distribution with two peaks at ~15 and ~50?nm. Based on the impact behavior of spray powder particles, a deposition model was proposed to explain the formation mechanism of the pores in the VCS coating using strengthened nanostructured powder. It was found that, compared to the conventional unimodal-sized nano-pores in TiO₂ coatings, the bimodal-sized nano-pores contributed to a higher ion diffusion coefficient of the coatings and thereby a higher photovoltage of the solar cells.     

Introduction to High-Velocity Suspension Flame Spraying (HVSFS)

High-velocity suspension flame spraying (HVSFS) has been developed to thermally spray suspensions containing micron, submicron, and nanoparticles with hypersonic speed. For this purpose, the suspension is introduced directly into the combustion chamber of a modified HVOF torch. The aim in mind is to achieve dense coatings with a refined microstructure. Especially from nanostructured coatings superior physical properties are expected for many potential applications. Direct spraying of suspensions offers flexibility in combining and processing different materials. It is a cost-saving process and allows the allocation of entirely new application fields. The paper gives an overview of the HVSFS spray method and will present some actual results that have been achieved by spraying the nanooxide ceramic materials Al₂O₃, TiO₂, 3YSZ, and Cr₂O₃.     

Deposition and characterization of flame-sprayed aluminum on cured glass and basalt fiber-reinforced epoxy tubes

An oxy-acetylene flame spray torch was used to deposit thin layers of aluminum onto cured glass and basalt fiber-reinforced epoxy tubes. The composite specimens were fabricated by filament winding. Surface coatings embedded in composite laminates were produced. The composite substrates were grit blasted to promote adhesion of the molten aluminum particles. It was found that adhesion increased significantly when the composite substrate was lightly grit blasted, with no adhesion on smooth composite surfaces. The number of passes of the flame spray torch was varied to change the coating thickness and uniformity over the substrate. The electrical resistance of the coatings was measured to assess the suitability of a coating as a conductor. It was found that uniform, electrically conductive coatings were produced with a minimum of two torch passes. Optical images were captured to characterize the coating microstructure and thickness. This investigation did not reveal any visible evidence of damage to the composite substrate. To assess possible degradation effects from the grit blasting and flame spraying processes, the tube specimens were subjected to mechanical testing by applying internal pressurization with hydraulic oil. The tests indicated that the grit blasting and flame spraying processes must be carefully executed to mitigate degradation of the strength of the composite material substrate.