High Velocity Suspension Flame Spraying (HVSFS) of Metal Suspensions.

Thermal spraying of metal materials is one of the key applications of this technology in industry for over a hundred years. The variety of metal-based feedstocks (powders and wires) used for thermal spray is incredibly large and utilization covers abrasion and corrosion protection, as well as tribological and electrical applications. Spraying metals using suspension- or precursor-based thermal spray methods is a relatively new and unusual approach. This publication deals with three metal types, a NiCr 80/20, copper (Cu), and silver (Ag), sprayed as fine-grained powders dispersed in aqueous solvent. Suspensions were sprayed by means of high-velocity suspension spraying (HVSFS) employing a modified TopGun system. The aim was to prepare thin and dense metal coatings (10-70 µm) and to evaluate the process limits regarding the oxygen content of the coatings. In case of Cu and Ag, possible applications demand high purity with low oxidation of the coating to achieve for instance a high electrical conductivity or catalytic activity. For NiCr however, it was found that coatings with a fine dispersion of oxides can be usable for applications where a tunable resistivity is in demand. The paper describes the suspension preparation and presents results of spray experiments performed on metal substrates. Results are evaluated with respect to the phase composition and the achieved coating morphology. It turns out that the oxidation content and spray efficiency is strongly controlled by the oxygen fuel ratio and spray distance.

Additive Manufacturing of ß-Tricalcium Phosphate Components via Fused Deposition of Ceramics (FDC).

Bone defects introduced by accidents or diseases are very painful for the patient and their treatment leads to high expenses for the healthcare systems. When a bone defect reaches a critical size, the body is not able to restore this defect by itself. In this case a bone graft is required, either an autologous one taken from the patient or an artificial one made of a bioceramic material such as calcium phosphate. In this study ß-tricalcium phosphate (ß-TCP) was dispersed in a polymer matrix containing poly(lactic acid) (PLA) and poly(ethylene glycole) (PEG). These compounds were extruded to filaments, which were used for 3D printing of cylindrical scaffolds via Fused Deposition of Ceramics (FDC) technique. After shaping, the printed parts were debindered and sintered. The components combined macro- and micropores with a pore size of 1 mm and 0.01 mm, respectively, which are considered beneficial for bone healing. The compressive strength of sintered cylindrical scaffolds exceeded 72 MPa at an open porosity of 35%. The FDC approach seems promising for manufacturing patient specific bioceramic bone grafts.

Inversely 3D-Printed ß-TCP Scaffolds for Bone Replacement.

The aim of this study was to predefine the pore structure of ß-tricalcium phosphate (ß-TCP) scaffolds with different macro pore sizes (500, 750, and 1000 µm), to characterize ß-TCP scaffolds, and to investigate the growth behavior of cells within these scaffolds. The lead structures for directional bone growth (sacrificial structures) were produced from polylactide (PLA) using the fused deposition modeling techniques. The molds were then filled with ß-TCP slurry and sintered at 1250 °C, whereby the lead structures (voids) were burnt out. The scaffolds were mechanically characterized (native and after incubation in simulated body fluid (SBF) for 28 d). In addition, biocompatibility was investigated by live/dead, cell proliferation and lactate dehydrogenase assays. The scaffolds with a strand spacing of 500 µm showed the highest compressive strength, both untreated (3.4 ± 0.2 MPa) and treated with simulated body fluid (2.8 ± 0.2 MPa). The simulated body fluid reduced the stability of the samples to 82% (500), 62% (750) and 56% (1000). The strand spacing and the powder properties of the samples were decisive factors for stability. The fact that ß-TCP is a biocompatible material is confirmed by the experiments. No lactate dehydrogenase activity of the cells was measured, which means that no cytotoxicity of the material could be detected. In addition, the proliferation rate of all three sizes increased steadily over the test days until saturation. The cells were largely adhered to or within the scaffolds and did not migrate through the scaffolds to the bottom of the cell culture plate. The cells showed increased growth, not only on the outer surface (e.g., 500: 36 ± 33 vital cells/mm² after three days, 180 ± 33 cells/mm² after seven days, and 308 ± 69 cells/mm² after 10 days), but also on the inner surface of the samples (e.g., 750: 49 ± 17 vital cells/mm² after three days, 200 ± 84 cells/mm² after seven days, and 218 ± 99 living cells/mm² after 10 days). This means that the inverse 3D printing method is very suitable for the presetting of the pore structure and for the ingrowth of the cells. The experiments on which this work is based have shown that the fused deposition modeling process with subsequent slip casting and sintering is well suited for the production of scaffolds for bone replacement.

Mechanical behaviour of extremely tough TZP bioceramics.

Tetragonal Zirconia Polycrystals (TZP) is attractive for structural biomedical applications because of their excellent mechanical properties at room-temperature, which include high strength, fracture toughness and wear resistance. In this work, zirconia stabilized with Y or Yb or Yb+Nd, all containing 0.5 vol.% Al2O3, were prepared by hot-pressing (HP) at 50-60 MPa and sintered at 1300-1350 °C for 1 h. Microstructural features, phase composition and mechanical properties were investigated. The strength was measured by 4-point bending (4P-B), piston-on-three-balls (P-3B) and three-balls-on-three-balls (3B-3B) biaxial methods. Toughness was determined by indentation strength in bending (ISB). Vickers hardness (Hv) and the Young modulus (E) were also estimated. Preliminary aging behaviour (LTD) was also here considered. Measured biaxial strength was significantly higher (until 1.83 times) than the uniaxial one because of the tetragonal to monoclinic (t-m) zirconia phase transformation which is strongly influenced by the loading configuration. The variation of the strength with the testing method is attributed to the compressive stresses generated by the phase transformation which is particularly favoured under P-3B tests and also to the calculation of the stresses from elastic theories. LTD preliminary tests showed excellent aging resistance of 3Yb-0.5A ceramics.

Carbon-Fibre-Reinforced SiC Composite (C/SiSiC) as an Alternative Material for Endoprosthesis: Fabrication, Mechanical and In-Vitro Biological Properties.

Particle-induced periprosthetic osteolysis and subsequent aseptic implant loosening are a major cause of compromising the long-term results of total joint replacements. To date, no implant has been able to mirror radically the tribological factors (friction/lubrication/wear) of in vivo tribological pairings. Carbon-Fibre Reinforced SiC-Composites (C/SiSiC), a material primarily developed for brake technology, has the opportunity to fulfil this requirement. Until now, the material itself has not been used in medicine. The aim of this investigation was to test the suitability of C/SiSiC ceramics as a new material for bearing couples in endoprosthetics. After the preparation of the composites flexural strength was determined as well as the Young's-modulus and the coefficient of friction. To investigate in vitro biological properties, MG 63 and primary human osteoblasts were cultured on C/SiSiC composites. To review the proliferation, the cytotoxicity standardized tests were used. The cell morphology was observed by light microscopy, ESEM, confocal and 3D-laserscanning microscopy. C/SiSiC possesses a high resistance to wear. Cells exhibited no significant alterations in morphology. Vitality was not impaired by contact with the ceramic composite. There was no higher cytotoxicity to observe. Regarding these results, C/SiSiC ceramics seem to be biologically and mechanically appropriate for orthopaedic applications.

3D Powder Printed Bioglass and ß-Tricalcium Phosphate Bone Scaffolds.

The use of both bioglass (BG) and ß tricalcium phosphate (ß-TCP) for bone replacement applications has been studied extensively due to the materials' high biocompatibility and ability to resorb when implanted in the body. 3D printing has been explored as a fast and versatile technique for the fabrication of porous bone scaffolds. This project investigates the effects of using different combinations of a composite BG and ß-TCP powder for 3D printing of porous bone scaffolds. Porous 3D powder printed bone scaffolds of BG, ß-TCP, 50/50 BG/ß-TCP and 70/30 BG/ß-TCP compositions were subject to a variety of characterization and biocompatibility tests. The porosity characteristics, surface roughness, mechanical strength, viability for cell proliferation, material cytotoxicity and in vitro bioactivity were assessed. The results show that the scaffolds can support osteoblast-like MG-63 cells growth both on the surface of and within the scaffold material and do not show alarming cytotoxicity; the porosity and surface characteristics of the scaffolds are appropriate. Of the two tested composite materials, the 70/30 BG/ß-TCP scaffold proved to be superior in terms of biocompatibility and mechanical strength. The mechanical strength of the scaffolds makes them unsuitable for load bearing applications. However, they can be useful for other applications such as bone fillers.

Issues in nanocomposite ceramic engineering: focus on processing and properties of alumina-based composites.

Ceramic nanocomposites, containing at least one phase in the nanometric dimension, have received special interest in recent years. They have, in fact, demonstrated increased performance, reliability and lifetime with respect to monolithic ceramics. However, a successful approach to the production of tailored composite nanostructures requires the development of innovative concepts at each step of manufacturing, from the synthesis of composite nanopowders, to their processing and sintering.This review aims to deepen understanding of some of the critical issues associated with the manufacturing of nanocomposite ceramics, focusing on alumina-based composite systems. Two case studies are presented and briefly discussed. The former illustrates the benefits, in terms of sintered microstructure and related mechanical properties, resulting from the application of an engineering approach to a laboratory-scale protocol for the elaboration of nanocomposites in the system alumina-ZrO2-YAG (yttrium aluminium garnet). The latter illustrates the manufacturing of alumina-based composites for large-scale applications such as cutting tools, carried out by an injection molding process. The need for an engineering approach to be applied in all processing steps is demonstrated also in this second case study, where a tailored manufacturing process is required to obtain the desired results.

Suspension thermal spraying of hydroxyapatite: microstructure and in vitro behaviour.

In cementless fixation of metallic prostheses, bony ingrowth onto the implant surface is often promoted by osteoconductive plasma-sprayed hydroxyapatite coatings. The present work explores the use of the innovative High Velocity Suspension Flame Spraying (HVSFS) process to coat Ti substrates with thin homogeneous hydroxyapatite coatings. The HVSFS hydroxyapatite coatings studied were dense, 27-37µm thick, with some transverse microcracks. Lamellae were sintered together and nearly unidentifiable, unlike conventional plasma-sprayed hydroxyapatite. Crystallinities of 10%-70% were obtained, depending on the deposition parameters and the use of a TiO2 bond coat. The average hardness of layers with low (<24%) and high (70%) crystallinity was ≈3.5GPa and ≈4.5GPa respectively. The distributions of hardness values, all characterised by Weibull modulus in the 5-7 range, were narrower than that of conventional plasma-sprayed hydroxyapatite, with a Weibull modulus of ≈3.3. During soaking in simulated body fluid, glassy coatings were progressively resorbed and replaced by a new, precipitated hydroxyapatite layer, whereas coatings with 70% crystallinity were stable up to 14days of immersion. The interpretation of the precipitation behaviour was also assisted by surface charge assessments, performed through Z-potential measurements. During in vitro tests, HA coatings showed no cytotoxicity towards the SAOS-2 osteoblast cell line, and surface cell proliferation was comparable with proliferation on reference polystyrene culture plates.