Homogeneous dispersion of boron nitride nanoplatelets in powder feedstocks for plasma spraying

Hexagonal Boron nitride nanoplatelet (BNNP) with the combination of excellent mechanical properties, high-temperature thermal stability, and self-lubrication is a promising strengthening agent in plasma-sprayed composite coatings. However, it is a significant challenge to produce plasma sprayable feedstocks with homogeneously dispersed BNNPs owing to the intrinsic agglomeration of BNNPs. In this research, three powder preparation processes (electrostatic interaction, ball milling, and shear mixing) were employed to disperse BNNPs in Ni-Cr-Cr₂O₃ (NCCO) powders. The shear mixing process presents a competitive advantage in powder preparation, providing stable shear force and achieving exfoliated BNNPs homogeneous distribution in the composite powders. The spray drying technique was finally utilized to obtain spherical agglomerated BNNP-NCCO feedstocks with characteristics of relatively smooth surface and uniform size distribution. Hence, shear mixing and spray drying processes are expected to produce large-scale spherical composite powders with a homogeneous distribution of 2D layered nanomaterials for industrial application.     

Investigation of High-Velocity Suspension Flame Sprayed (HVSFS) glass coatings

High-Velocity Suspension Flame Spraying (HVSFS) has recently emerged as a potential alternative to conventional HVOF-spraying: employing liquid suspensions instead of dry powder feedstock enables the use of very fine grain-sized particles, resulting in small-sized lamellae. Thin, low-porosity coatings can thus be manufactured. This paper details the first attempt at manufacturing glass coatings using the HVSFS technique: these coatings can have multiple applications (anti-corrosion coatings on metal and ceramic substrates, bio-compatible coatings, etc). A CaO–ZrO₂–SiO₂ glass frit was selected for this attempt. Excellent potentialities emerged (very low porosity), but some problems still existed (big “droplet-like” features on the coating surface), which have recently been largely overcome thanks to process modifications.     

Microstructural evolutions of nickel-aluminide nanocomposites during powder synthesis and thermal spray processes

The synthesis and microstructural evolutions of the NiAl-15 wt% (Al₂O₃–13% TiO₂) nanocomposite powders were studied. These nanocomposite powders are used as feedstock materials for thermal spray applications. These powders were prepared using high and low-energy mechanical milling of the Ni, Al powders and Al₂O₃–13% TiO₂ nanoparticle mixtures. High and low-energy ball-milled nanocomposite powders were also sprayed by means of high-velocity oxy fuel (HVOF) and air plasma spraying (APS) techniques respectively. The results showed that the formation of the NiAl intermetallic phase was noticed after 8 h of high-energy ball milling with nanometric grain sizes but in a low-energy ball mill, the powder particles contained only α-Ni solid solution with no trace of the intermetallic phase after 25 h of milling. The crystallite sizes in HVOF coating were in the nanometric range and the coating and feedstock powders showed the same phases. However, under the APS conditions, the coating was composed of the NiAl intermetallic phase in the α-Ni solid solution matrix. In both of the nanocomposite coatings, reinforcing nanoparticles (Al₂O₃–13% TiO₂) were located at the grain boundaries of the coatings and pinned the boundaries, therefore, the grain growth was prohibited during the thermal spraying processes.     

Glazing of alumina by a fluoroapatite-containing glass-ceramic

Glazing of alumina substrates was performed in order to prepare bioactive glass-ceramic coatings for biomedical applications. The coating material was a fluoroapatite-containing glass-ceramic (SAF) with a good degree of bioactivity. A careful optimisation of the coating conditions was carried out. The obtained coatings were characterized by means of scanning electron microscopy (SEM), compositional analysis (EDS), X-Ray diffraction (XRD), and in vitro tests (soaking into a simulated body fluid). Direct firing of SAF powders on the ceramic substrates gave unsatisfactory results in terms of crack propagation and bioactivity, due to the nucleation of a non-bioactive Al-rich phase (leucite) with high linear expansion coefficient. The use of an intermediate layer based on a SiO₂-CaO glass (SC) was necessary in order to avoid Al ions diffusion through the coating and thus the formation of undesired additional phases. The coatings obtained with the optimised processing parameters resulted to be adherent, defect-free, and characterized by unchanged composition and structure as well as unmodified bioactivity if compared with the bulk SAF glass-ceramic.     

Macroporous bioactive glass-ceramic scaffolds for tissue engineering

Highly bioactive scaffolds for tissue engineering were synthesized using a glass belonging to the SiO₂-CaO-K₂O (SCK) system. The glass SCK was prepared by a traditional melting-quenching route and its bioactivity was assessed by in vitro tests in a simulated body fluid (SBF). The glass was ground and sieved to obtain powders of specific size that were subsequently mixed with polyethylene particles of two different dimensions. The powders were then uniaxially pressed to obtain a crack free green compact that was thermally treated to remove the organic component and to sinter the inorganic phase. The obtained biomaterial was characterised by means of X-ray Diffraction, SEM equipped with EDS, mercury intrusion porosimetry, density measurements, image analysis, mechanical tests and in vitro evaluations. A glass-ceramic macroporous scaffold with a homogenously distributed and highly interconnected porosity was obtained. The amount and size of the introduced porosity could be tailored using various amounts of polyethylene powders of different size.     

Thermisches Spritzen neuartiger SiC und TiC Pulver mit oxidischer Binderphase

Processing of newly developed SiC and TiC Powders with Oxide‐Ceramic Matrix by means of Thermal Spraying Intermediate results of an actual project are presented. The investigations concern newly developed SiC and TiC powders, their processing by means of thermal spraying and the characterization of produced coatings. Development and optimization of powders, thermal spray process and spray parameter optimization are carried out on permanent feedback. The powder production line is spray‐drying, sintering and conditioning. The binder matrix phase is aluminum oxide / yttrium oxide. The produced powders SiC – Al₂O₃/Y₂O₃ and TiC – Al₂O₃/Y₂O₃ show different specific chemical compositions and morphologies each. Carbide contents of >65 % are aimed at. Applied thermal spray processes are atmospherical plasma spraying and high velocity oxygen fuel spraying. The results demonstrated characterize feedstock powders as well as produced coatings. The investigations are done by means of light and scanning electron microscopy.     

Preparation and characterization of bioactive monolayer and functionally graded coatings

Hydroxyapatite powders were made by reacting orthophosphoric acid with calcium hydroxide and dense bioactive coatings were subsequently produced by the plasma spray technique. Three types of hydroxyapatite (flame spheroidized) monolayer coatings and three types of functionally graded coatings were manufactured. It was found that average microhardness values of monolayer coatings decreased as the indentation load increased. The relationship between indentation load and indent diagonal length observed Meyer's law. Microhardness and fracture toughness of coatings were affected by characteristics of feedstock powders for plasma spraying. The indentation fracture toughness of coatings could be significantly increased by incorporating a toughening phase. ©1999 Kluwer Academic Publishers     

Surface silver-doping of biocompatible glasses to induce antibacterial properties. Part II: plasma sprayed glass-coatings

A 57% SiO₂, 3% Al₂O₃, 34% CaO and 6% Na₂O glass (SCNA) has been produced in form of powders and deposited by plasma spray on titanium alloy and stainless steel substrates. The obtained coatings have been subjected to a patented ion-exchange treatment to introduce silver ions in the surface inducing an antibacterial behavior. Silver surface-enriched samples have been characterized by means of X-ray diffraction, SEM observation, EDS analysis, in vitro bioactivity tests, leaching tests by GFAAS (graphite furnace atomic adsorption spectroscopy) analyses, cells adhesion and proliferation, and antibacterial tests using Staphylococcus Aureus strain. In vitro tests results showed that the modified samples acquired an antimicrobial action against tested bacteria maintaining unaffected the biocompatibility of the glass. Furthermore the ion-exchange treatment can be successfully applied to glass-coated samples without affecting the properties of the coatings; the simplicity and reproducibility of the method make it suitable for glass or glass-ceramic coatings of different composition in order to produce coated devices for bone healing and/or prostheses, able to reduce bacterial colonization and infections risks.     

Microstructure and in vitro behaviour of 45S5 bioglass coatings deposited by high velocity suspension flame spraying (HVSFS)

The high-velocity suspension flame spraying technique (HVSFS) was employed in order to deposit 45S5 bioactive glass coatings onto titanium substrates, using a suspension of micron-sized glass powders dispersed in a water + isopropanol mixture as feedstock. By modifying the process parameters, five coatings with different thickness and porosity were obtained. The coatings were entirely glassy but exhibited a through-thickness microstructural gradient, as the deposition mechanisms of the glass droplets changed at every torch cycle because of the increase in the system temperature during spraying. After soaking in simulated body fluid, all of the coatings were soon covered by a layer of hydroxyapatite; furthermore, the coatings exhibited no cytotoxicity and human osteosarcoma cells could adhere and proliferate well onto their surfaces. HVSFS-deposited 45S5 bioglass coatings are therefore highly bioactive and have potentials as replacement of conventional hydroxyapatite in order to favour osseointegration of dental and prosthetic implants.     

Low-temperature sintering characteristics of nano-sized BaNd2Ti5O14 and Bi2O3–B2O3–ZnO–SiO2 glass powders prepared by gas-phase reactions

Nano-sized BaNd₂Ti₅O₁₄ (BNT) powders were prepared by spray pyrolysis from solutions containing ethylenediaminetetraacetic acid and citric acid. Treatment at temperatures ≥900 °C and subsequent milling resulted in nanoparticle powders with orthorhombic crystal structures. The mean particle size of the powder post-treated at 1000 °C was 160 nm. Nano-sized Bi₂O₃–B₂O₃–ZnO–SiO₂ glass powder with 33 nm average particle size was prepared by flame spray pyrolysis and used as a sintering agent for the BNT. BNT pellets sintered at 1100 °C without the glass had porous structures and fine grain sizes. Those similarly sintered with the glass had denser structures and larger grains.     

Preparing of nanostructured Al2O3–TiO2–ZrO2 composite powders and plasma spraying nanostructured composite coating

Nanostructured Al₂O₃–TiO₂–ZrO₂ composite powders for plasma spraying were prepared by spray drying granulation technology. The effects of processing parameters on the microstructure and properties of composite powders were investigated. The results show that with increasing the slurry solid content, the particle size of powders increases, and the bulk density of powders increases, and the flowability of powders increases firstly and then decreases. With increasing the binder content, the particle size of powders increases, and the bulk density of powders increases, and the flowability of powders increases firstly and then decreases. With increasing the spray drying temperature, the particle size of powders increases, and the bulk density and flowability of powders increases firstly and then decreases. The most appropriate spray drying parameters are the slurry solid content of 40 wt.%, the binder content of 2.0 wt.% and the spray drying temperature of 250 °C. The nanostructured composite coating was successfully prepared by using the as-prepared nanostructured Al₂O₃–TiO₂–ZrO₂ composite powders as feedstocks. The nanostructured coating possessed higher hardness and toughness compared with the conventional microstructured one, which was attributed to the use of the nanostructured composite powders feedstocks.     

Biofunctionalization of porous titanium coatings through sol–gel impregnation with a bioactive glass–ceramic

In implant technology, open porous Ti coatings are applied as functional surface layers on prosthetic devices to improve osseointegration. Since a successful clinical performance strongly depends on the (initial) quality of bone ingrowth in the porous structure, surface functionalization of the porous Ti to incorporate an additional osteoconductive capacity is recommended. In this paper, a bioactive glass–ceramic coating is applied into the open porous network of Ti coatings with a pore throat size of 1–20 μm through a sol–gel process. Using an all-alkoxide precursor route, homogeneous amorphous powders of three- (SiO₂–CaO–P₂O₅) and four-component (SiO₂–CaO–Na₂O–P₂O₅) bioactive glass compositions are prepared. By sol impregnation followed by a heat treatment, it is possible to deposit a micrometer thin bioactive glass–ceramic layer on the walls of the internal pore surface, while the original porosity and the open pore structure of the Ti coatings are maintained. The tensile adhesion strength of the Ti/bioactive glass–ceramic composite coatings is 22 to 29 MPa, suggesting a good mechanical adhesion.     

Bioactivity of degradable polymer sutures coated with bioactive glass

Novel bioactive materials have been prepared by coating violet resorbable Vicryl sutures with a bioactive glass powder derived from a co-precipitation method. Two techniques have been chosen for the composite preparation: pressing the sutures in a bed of glass powder and slurry-dipping of sutures in liquid suspensions of bioactive glass powders. The uniformity and thickness of the coatings obtained by the two methods were compared. The bioactivity of the sutures with and without bioactive glass coating was tested by soaking in an inorganic acellular simulated body fluid (SBF). The composite sutures were characterised by XRD, SEM and FTIR analyses before and after soaking in SBF solution to assess the formation of hydroxyapatite on their surfaces, which is a qualitative measure of their bioactivity. The possible use of bioactive sutures to produce tissue engineering scaffolds and as reinforcement of resorbable calcium phosphates is discussed.     

Plasma spray synthesis of TiB2-Fe coatings

A limiting feature of the plasma spray process is the need for the powder to melt during its passage through the plasma flame. It is quite impossible to obtain coatings with materials that are difficult to melt. However, metal borides, particularly titanium boride, are attractive. Because of their high melting point, satisfactory coatings based on these materials have not been achieved.To overcome this problem, a process for making TiB₂-Fe coatings was studied. The TiB₂-based coatings were produced by the reaction of ferrotitanium with boron. The TiB₂ formation was first studied by thermal differential analysis and X-ray diffraction. It was observed that TiB₂ is formed at low temperature by an exothermic reaction. The characteristics of the reaction products obtained at different reaction temperatures are described.Agglomeration techniques were used to prepare the reagents: fine powders of ferrotitanium alloy and boron. TiB₂-Fe coatings were produced by plasma spraying the agglomerated powders. The influence of the plasma spray process parameters and the powder preparation techniques on the coating microstructure is discussed.Thick hard coatings comprising compounds of the reagent materials are produced during spraying by this synergetic process. Such coatings may be suitable for wear resistance applications.     

Oxide powders for plasma spraying-the relationship between powder characteristics and coating properties

In order to obtain predictable and reproducible properties from plasma-sprayed oxide coatings, it is required to control the spray parameters. In addition, powders should be chemically uniform so that reproducible particle melting can be achieved. Such melting behavior is obtainable from fused oxides. It is shown here for Al₂O₃-TiO₂ mixed oxides that fused powders can yield coatings with superior microstructures and improved industrially relevant properties.     

Synthesis and characterization of nanocrystalline CoCr coatings by plasma spraying

The present paper describes the synthesis and characterization of nanocrystalline CoCr (ASTM F75) coating produced by plasma spraying for possible surgical implant applications. The feedstock powders were synthesized by mechanical milling to produce irregular agglomerates with an average grain size of less than 100 nm. The powders were then introduced into an argon plasma spray to successfully produce a nanocrystalline coating. Scanning electron microscopy and transmission electron microscopy were used to study the morphology of the nanometric particles and the resultant sprayed coatings. Microhardness and porosity measurements were performed on the conventional and the nanocrystalline coatings to characterize and compare the physical and mechanical properties.     

High strength bioactive glass-ceramic scaffolds for bone regeneration

This research work is focused on the preparation of macroporous glass-ceramic scaffolds with high mechanical strength, equivalent with cancellous bone. The scaffolds were prepared using an open-cells polyurethane sponge as a template and glass powders belonging to the system SiO₂–P₂O₅–CaO–MgO–Na₂O–K₂O. The glass, named as CEL2, was synthesized by a conventional melting-quenching route, ground and sieved to obtain powders of specific size. A slurry of CEL2 powders, polyvinyl alcohol (PVA) as a binder and water was prepared in order to coat, by a process of impregnation, the polymeric template. A thermal treatment was then used to remove the sponge and to sinter the glass powders, in order to obtain a replica of the template structure. The scaffolds were characterized by means of X-ray diffraction analysis, morphological observations, density measurements, volumetric shrinkage, image analysis, capillarity tests, mechanical tests and in vitro bioactivity evaluation.     

Effect of particle size on the in vitro bioactivity,hydrophilicity and mechanical properties of bioactive glass-reinforced polycaprolactone composites

Polycaprolactone (PCL) composite films containing 5 wt.% bioactive glass (BG) particles of different sizes (6 μm, 250 nm, < 100 nm) were prepared by solvent casting methods. The ultra-fine BG particles were prepared by high-energy mechanical milling of commercial 45S5 Bioglass® particles. The characteristics of bioactive glass particles were studied by field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), dynamic light scattering (DLS), and X-ray diffraction (XRD) methods. In vitro bioactivity of the PCL/BG composite films was evaluated through immersion in the simulated body fluid (SBF). The films were analyzed by FE-SEM, energy dispersive spectrometry (EDS), XRD, and atomic force microscopy (AFM). The mechanical properties of highly-porous PCL/BG composites were examined on cylindrical specimens under quasi-static compression load. It was found that partial crystallization of amorphous BG particles during a prolonged mechanical milling occurred and calcium silicate (CaSiO₃) and sodium calcium silicate (Na₂CaSiO₄) phases were formed. The introduction of submicron BG particles (250 nm) was shown to improve the bioactivity of PCL films. In contrast to BG microparticles, the submicron BG particles were distributed on the film surfaces, providing a high surface exposure to SBF with an improved nanotopography. A notable increase in the stiffness and elastic modulus of the composite was also obtained. As compared to submicron BG particles, lower bioactivity and elastic modulus were acquired for PCL/BG nanoparticles. It was also shown that in spite of high specific surface area of the nanoparticles, partial crystallization during mechanical milling and agglomeration of the nanoparticles during processing decrease the bioactivity, hydrophilicity and mechanical response of the BG-reinforced PCL composites.     

Fabrication and characterization of heat and plasma treated SiC/Al2O3-YSZ feedstocks used for plasma spraying

The SiC/Al₂O₃-YSZ (ZrO₂ + 8 wt.% Y₂O₃) powders with different SiC particle sizes were fabricated and treated from spray drying, heat treatment, and plasma spraying. The morphology, phase composition, flowability and density of powders were analyzed. The sphericity and flowability of powders treated by plasma flame are increased greatly, and the particle surface is very smooth. The flowability and density of powder with nano SiC were evident better than those of powder with submicron SiC. The optimum flowability and compactness of powder with submicron SiC is obtained when the critical plasma spray parameter is 341 and 325, respectively. For nano size SiC, the optimum flowability and the maximum compactness of powders are obtained with critical plasma spray parameter of 341. The grain size of powders is increased after heat treatment and plasma spraying. The SiC is oxidized to SiO₂ in the powders after heat treatment and plasma spraying. The Y₂O₃ dissolved from 8YSZ solid solution at higher critical plasma spray parameter. Besides, there is no phase transformation of ZrO₂ for powders. The metastable phase of Al₂O₃ appeared in feedstocks with submicron SiC, but no metastable phase was formed in feedstocks with nano SiC particles, which nano SiC can hinder the formation of Al₂O₃ metastable phase. The densification process and mechanism of reconstituted particles used for plasma spraying were analyzed from surface morphology, cross section and simulation.     

Preparation and properties of antioxidative BaO–B<Subscript>2</Subscript>O<Subscript>3</Subscript>–SiO<Subscript>2</Subscript> glass-coated Cu powder for copper conductive film on LTCC substrate

In this study, uniform BaO–B₂O₃–SiO₂ glass coatings on micro Cu powders with different glass/Cu ratio were prepared by sol–gel method. The pastes prepared with the glass-coated Cu powders were screen printed on low temperature co-fired ceramic (LTCC) substrate. Then the dry films on substrate were binder-burned-out at 400 °C in air and co-fired at 910 °C in N₂ atmosphere. During the binder-burning-out process, the oxidization of the films with 9 and 11 wt% glass was slight because of the improvement of oxidization resistance of the glass-coated Cu powders. Moreover, the sintered film with 9 wt% glass coating showed no crystal phase of copper oxide and had small sheet resistance of 1.3 mΩ/□, which can be used as good conductive thick film on LTCC substrate for microelectronic packaging.