Novel hydroxyapatite/tantalum surface coating for metallic dental implant

The aim of this study was to design and produce a novel surface composite coating on metallic substrate in order to improve the biocompatibility of metallic dental implant and the bone osteointegration simultaneously.Stainless steel 316L (SS) was used as a metallic substrate and a novel double-layer hydroxyapatite/tantalum (HA/Ta) coating was prepared on it. Tantalum coating was made using physical vapor deposition process and HA coating was produced using plasma-spraying technique on it. X-ray diffraction (XRD) and scanning electron microscopy (SEM) techniques were utilized to investigate the coating characterization. Electrochemical polarization tests were performed in two types of physiological solutions at 37 ± 1 °C in order to determine the corrosion behavior of the coated and uncoated specimens as indication of biocompatibility.The results indicated that the decrease in corrosion current density was significant for HA/Ta coated specimens and was much lower than the value obtained for uncoated 316L SS. The novel double-layer HA/Ta composite coating could improve the corrosion resistance and thus the biocompatibility of 316L SS dental implant.     

Reducing Staphylococcus aureus biofilm formation on stainless steel 316L using functionalized self-assembled monolayers

Stainless steel 316L (SS316L) is a common material used in orthopedic implants. Bacterial colonization of the surface and subsequent biofilm development can lead to refractory infection of the implant. Since the greatest risk of infection occurs perioperatively, strategies that reduce bacterial adhesion during this time are important. As a strategy to limit bacterial adhesion and biofilm formation on SS316L, self-assembled monolayers (SAMs) were used to modify the SS316L surface. SAMs with long alkyl chains terminated with hydrophobic (? CH₃) or hydrophilic (oligoethylene glycol) tail groups were used to form coatings and in an orthogonal approach, SAMs were used to immobilize gentamicin or vancomycin on SS316L for the first time to form an “active” antimicrobial coating to inhibit early biofilm development. Modified SS316L surfaces were characterized using surface infrared spectroscopy, contact angles, MALDI-TOF mass spectrometry and atomic force microscopy. The ability of SAM-modified SS316L to retard biofilm development by Staphylococcus aureus was functionally tested using confocal scanning laser microscopy with COMSTAT image analysis, scanning electron microscopy and colony forming unit analysis. Neither hydrophobic nor hydrophilic SAMs reduced biofilm development. However, gentamicin-linked and vancomycin-linked SAMs significantly reduced S. aureus biofilm formation for up to 24 and 48 h, respectively.     

In vitro study of the SBF and osteoblast-like cells on hydroxyapatite/chitosan–silica nanocomposite

Hydroxyapatite/chitosan–silica (HApCSi) nanocomposites were synthesized by co-precipitated method and their potential application as filler materials for bone regeneration were investigated in simulated body fluid (SBF). To study their biocompatibility, they were cultured with rat osteoblast-like UMR-106 cells for 3, 7, 14, and 21 days. Studies of the silica contents in chitosan matrix showed the presence of silinol (Si–OH) groups in CSi hybrid and their decrease after being composited with calcium phosphate (CaP) which is desirable for the formation of the apatite. XRD and TEM studies showed that the HAp formed in the CSi matrix were nanometer (20–40 nm) in size. Nanocomposites of HApCSi20 processed with 20%v/v silica whisker showed a micro hardness of 84.7 ± 3.3 MPa. Mineralization study in SBF showed the formation of apatite crystals on the HApCSi surface after being incubated for 7 days. In vitro biocompatibility, cell morphology, proliferation, and cell adhesion tests confirmed the osteoblast attachment and growth on the HApCSi20 surface. The density of cells and the production of calcium nodules on the substrate were seen to increase with increasing cultured time. The mechanical evaluation and in vitro experiment suggested that the use of HApCSi composite will lead to the formation of new apatite particles and thus be a potential implant material.     

Low temperature synthesis of hydroxyapatite nano-rods by a modified sol–gel technique

Hydroxyapatite (HAp) nano-rods were successfully synthesized by a modified sol–gel method using a solution of CaCl₂·2H₂O in water, along with a solution of H₃PO₄ in triethylamine and NH₄OH as starting materials. The Ca/P molar ratio was maintained at 1.67. The sol obtained was dried in an oven for 2 days at 100 °C after being dialyzed for 12 h. Pellets were made from the crystalline powders and immersed in simulated body fluid (SBF) to check its biocompatibility after 15, 45 and 180 days of immersion. The HAp powders and pellets were characterized by X-Ray Diffraction crystallography (XRD), Fourier transform Infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and Transmission electron microscopy (TEM). The HAp nano-rods had an average diameter of 25 nm and length 110–120 nm. Immersion of the HAp pellets in SBF led to the formation of a highly porous interconnecting HAp layer on the surface. The porosity increased with increase in immersion time.     

Effect of porosity and density on the mechanical and microstructural properties of sintered 316L stainless steel implant materials

In this study, the microstructure and mechanical properties of sintered AISI 316L stainless steel implant materials produced by powder metallurgy (P/M) method were investigated as a function of porosity amount. AISI 316L stainless steel powders were cold-pressed with 800 MPa pressure and sintered at 1200 °C, 1250 °C and 1300 °C for 30 min in a nitrogen atmosphere. The mechanical properties of the 316L implant samples were determined by tensile, fatigue and microhardness tests. Metallographic studies such as pore formation, and fractured surface analyses were performed by Scanning Electron Microscopy (SEM) and Light Optical Microscopy (LOM). The results of this study indicate that, irregular pore formation tendencies increase with an increase in porosity (%). Furthermore, an increase in porosity was shown to decrease the mechanical properties of sintered AISI 316L stainless steel. Sintering temperature is important parameter in decreasing the porosity of P/M materials.     

Oxidation characterization of FeAl coated 316 stainless steel interconnects by high-energy micro-arc alloying technique for SOFC

Fe-based alloys have been extensively evaluated and considered as outstanding metallic interconnect materials for fuel cell. High-energy micro-arc alloying technique has been determined to be a feasible method of producing a consistent and dense FeAl intermetallic coating on 316 stainless steel substrate. The coating had an average thickness of about 50 μm and grain size was significantly refined. When exposed at 800 °C, 900 °C and 1000 °C in air after 100 h, FeAl coating on 316 SS substrate exhibited better high temperature oxidation resistance than electrode materials due to the conversion of non-protective Fe-rich scale into protective Al-rich one. FeAl intermetallic coating deposited by HEMAA will be available as interconnects for SOFC at very low costs.     

Characterization of nanostructured hydroxyapatite prepared by Nd:YAG laser deposition

Pulsed laser deposition, under dry and water vapor conditions, was employed to synthesize nanostructured hydroxyapatite films by pulsed laser deposition (PLD) of chlorapatite target for the purpose of coating metallic bone implants by this material. A pulsed Nd:YAG laser operating at a wavelength of 1064 nm and emitting 9 ns pulses was used for deposition. AFM microscopy, FTIR spectroscopy, optical microscopy, adhesion and microhardness measurements were conducted to characterize the films. The in vitro test for the synthesized hydroxyapatite was performed using simulated body fluid (SBF). The results showed a successful transformation of the chlorapatite to hydroxyapatite films characterized by all the HAp peaks with 60 nm root mean square roughness, (80–327) nm grain size, and a microhardness of 512 HV.     

Preparation of high strength macroporous hydroxyapatite scaffold

Hydroxyapatite (HAp) powder was prepared from CaNO₃·4H₂O and (NH₄)₂HPO₄ by wet-chemical method and has phase stable up to 1250 °C. High strength macroporous HAp–naphthalene (HN) and HAp–naphthalene–benzene (HNB) scaffolds were fabricated by adapting sintering method. The resulting HAp scaffolds have porosity about 60 vol.% with compressive strength of ~ 11 MPa and average pore diameter in the range of ~ 125 μm. The incorporation of benzene in HN scaffold reduces the strength whereas enhanced both the porosity and pore size distribution. XRD, FTIR, SEM and mercury porosimeter techniques were used to study the phase purity, morphology, pore size and pore size distribution of scaffold. The study compared the effect of concentration of naphthalene on strength, porosity and pore size distribution on both HN and HNB scaffold. In-vitro bioactivity studies on HN and HNB scaffolds show the nucleation of spherical carbonated apatite particles on the surface in SBF solution.     

Annealed thin-film zirconia coating adhered on 316L stainless steel as a bio-inert indwelling needle

A 316L stainless steel plate was covered with a ZrO₂ coating using the sol–gel dip coating technique, and preliminary in vitro and in vivo studies were conducted. The morphology and crystal structure of the coatings were examined using scanning electron microscope and X-ray diffraction, and their surface chemical structures were characterised using X-ray photoelectron spectroscopy. The quality and adhesion of the coatings on the substrate were measured using a nano-indenter with lateral force and scratch modes. ZrO₂ was formed on a 316L plate at various temperatures, resulting in different crystalline structures, surface morphologies, and integration with the 316L surface. The optimal conditions to produce ZrO₂–316L are an annealing temperature of 500 °C and duration of 1 h (ZrO₂/316L_500), yielding an adhesive force of 595 μN. 3T3 cell morphology, adhesion, and viability using the live/dead cell staining protocol were assessed. Cell affinity was significantly enhanced on the surface of ZrO₂/316L_500, compared to the as prepared sample. Furthermore, after mice were injected with 316L and ZrO₂/316L_500 needles for durations of up to 72 h, wound contraction, inflammation, and proliferation were compared. The results indicate that the ZrO₂/316L_500 needle exhibits high potential as a bio-inert coating and that it can be applied to scalpels and indwelling needles.     

Characterisation of the bioactive behaviour of sol–gel hydroxyapatite–CaO and hydroxyapatite–CaO–bioactive glass composites

The fabrication and characterization of sol–gel derived hydroxyapatite–calcium oxide (HAp–CaO) material is investigated focusing on the effect of the addition of a bioactive glass on the material bioactive behaviour through the fabrication of a novel HAp–CaO (70 wt.%)–bioactive glass (30 wt.%) composite material. The bioactive behaviour of the materials was assessed by immersion studies in Simulated Body Fluid (SBF) and the alterations of the materials surfaces after soaking periods in SBF were characterized by Scanning Electron Microscopy (SEM) and Fourier Transform Infrared Spectroscopy (FTIR). A brittle and weakly crystalline carbonate hydroxyapatite (HCAp) layer was found to develop on the surface of all samples, few hours after immersion in SBF, confirming the high bioactivity of the material. Alterations of the morphology of the developed HCAp layer, which led to a more compact structure, were observed on the surface of composite samples after 7 days of immersion in SBF. The presence of the CaO phase seems to accelerate the formation of HCAp, while the bioactive glass affects both the morphology and cohesion of the developed layer.     

Electrophoretic bilayer deposition of zirconia and reinforced bioglass system on Ti6Al4V for implant applications: An in vitro investigation

The physical, chemical and biological properties of the bioglass reinforced yttria-stabilized composite layer on Ti6Al4V titanium substrates were investigated. The Ti6Al4V substrate was deposited with yttria stabilized zirconia — YSZ as the base layer of thickness ≈ 4–5 μm, to inhibit metal ion leach out from the substrate and bioglass zirconia reinforced composite as the second layer of thickness ≈ 15 μm, which would react with surrounding bone tissue to enhance bone formation and implant fixation. The deposition of these two layers on the substrate was carried out using the most viable electrophoretic deposition (EPD) technique. Biocompatible yttria-stabilized zirconia (YSZ) in the form of nano-particles and sol gel derived bioglass in the form of micro-particles were chosen as precursors for coating. The coatings were vacuum sintered at 900 °C for 3 h. The biocompatibility and corrosion resistance property were studied in osteoblast cell culture and in simulated body fluid (SBF) respectively. Analysis showed that the zirconia reinforced bioglass bilayer system promoted significant bioactivity, and it exhibited a better corrosion resistance property and elevated mechanical strength under load bearing conditions in comparison with the monolayer YSZ coating on Ti6Al4V implant surface.     

Biocomposite of hydroxyapatite-titania rods (HApTiR): Physical properties and in vitro study

The aim in this research is to study the physical and biocompatible properties of hydroxyapatite (HAp) composites (HApTiR) having different amounts of titania rod (TiR) in them (10–90 wt.%). The HAp and TiR were produced using hydrothermal and co-precipitation under reflux methods, respectively. The physical properties and the in vitro biocompatibility of the composites to simulated body fluid (SBF) were investigated. They were also cultured with rat osteoblast-like UMR-106 cells. The synthesized powder showed a core-shell structure with the titania rod as the core and the apatite as the shell. The hardness of the composites of HApTiR's whisker increased from 74.8 to 92.9 MPa as the TiR content was increased from 10 to 90 wt.%. Mineralization study in SBF showed the formation of apatite crystals on the HApTiR's surface after 7 days of incubation. In vitro cell adhesion tests confirmed the osteoblast attachment and growth on the HApTiR's surface. The density of cells, spread and the production of calcium nodules on the substrate were seen to increase with increasing TiR contents except for HApTiR90 (TiR = 90 wt.%) which exhibited lesser growth. MTT tests on HApTiR70 indicated that UMR-106 cells were viable and the density of cells on the substrate was seen to increase with increasing culturing time.     

Cytocompatibility and mechanical properties of novel porous 316 L stainless steel

Novel 316 L stainless steel (SS) foam with 85% porosity and an open pore diameter of 70–440 μm was developed for hard tissue application. The foam sheet with a 200-μm diameter had superior cell proliferation and penetration as identified through in vitro experiments. Calcification of human osteosarcoma cells in the SS foam was observed. Multi-layered foam preparation is a potential alternative technique that satisfies multi-functional requirements such as cell penetration and binding strength to the solid metal. In tensile tests, Young's modulus and the strength of the SS foam were 4.0 GPa and 11.2 MPa respectively, which is comparable with human cancellous bone.     

Polydopamine as an intermediate layer for silver and hydroxyapatite immobilisation on metallic biomaterials surface

Hydroxyapatite (HA) coated implant is more susceptible to bacterial infection as the micro-structure surface which is beneficial for osseointegration, could also become a reservoir for bacterial colonisation. The aim of this study was to introduce the antibacterial effect of silver (Ag) to the biomineralised HA by utilising a polydopamine film as an intermediate layer for Ag and HA immobilisation. Sufficient catechol groups in polydopamine were required to bind chemically stainless steel 316 L, Ag and HA elements. Different amounts of Ag nanoparticles were metallised on the polydopamine grafted stainless steel by varying the immersion time in silver nitrate solution from 12 to 24 h. Another polydopamine layer was then formed on the metallised film, followed by surface biomineralisation in 1.5 Simulated Body Fluid (SBF) solution for 3 days. Several characterisation techniques including X-Ray Photoelectron Spectroscopy, Atomic Force Microscopy, Scanning Electron Microscopy and Contact Angle showed that Ag nanoparticles and HA agglomerations were successfully immobilised on the polydopamine film through an element reduction process. The Ag metallisation at 24 h has killed the viable bacteria with 97.88% of bactericidal ratio. The Ag was ionised up to 7 days which is crucial to prevent bacterial infection during the first stage of implant restoration. The aged functionalised films were considered stable due to less alteration of its chemical composition, surface roughness and wettability properties. The ability of the functionalised film to coat complex and micro scale metal make it suitable for dental and orthopaedic implants application.     

Engineering of bone fixation metal implants biointerface—Application of parylene C as versatile protective coating

The tribological and protective properties of parylene C coatings (2–20 μm) on stainless steel 316L implant materials were investigated by means of electrochemical measurements and wear tests. The thickness and morphology of the CVD prepared coatings were characterized by scanning electron and laser confocal microscopy. The stability of the coatings was examined in contact with Hanks' solution and H₂O₂ (simulating the inflammatory response). It was concluded that silane–parylene C coating with the optimum thickness of 8 μm exhibits excellent wear resistance properties and limits the wear formation. The engineered versatile coating demonstrates sufficient elastomer properties, essential to sustain the implantation surgery strains and micromotions during long-term usage in the body.     

Development and evaluation of a magnesium–zinc–strontium alloy for biomedical applications — Alloy processing,microstructure, mechanical properties,and biodegradation

A new biodegradable magnesium–zinc–strontium (Mg–Zn–Sr) alloy was developed and studied for medical implant applications. This first study investigated the alloy processing (casting, rolling, and heat treatment), microstructures, mechanical properties, and degradation properties in simulated body fluid (SBF). Aging treatment of the ZSr41 alloy at 175 °C for 8 h improved the mechanical properties when compared to those of the as-cast alloy. Specifically, the aged ZSr41 alloy had an ultimate tensile strength of 270 MPa, Vickers hardness of 71.5 HV, and elongation at failure of 12.8%. The mechanical properties of the ZSr41 alloy were superior as compared with those of pure magnesium and met the requirements for load-bearing medical implants. Furthermore, the immersion of the ZSr41 alloy in SBF showed a degradation mode that progressed cyclically, alternating between pitting and localized corrosion. The steady-state average degradation rate of the aged ZSr41 alloy in SBF was 0.96 g/(m²·hr), while the pH of SBF immersion solution increased. The corrosion current density of the ZSr41 alloy in SBF solution was 0.41 mA/mm², which was much lower than 1.67 mA/mm² for pure Mg under the same conditions. In summary, compared to pure Mg, the mechanical properties of the new ZSr41 alloy improved while the degradation rate decreased due to the addition of Zn and Sr alloying elements and specific processing conditions. The superior mechanical properties and corrosion resistance of the new ZSr41 alloy make it a promising alloy for next-generation implant applications.     

Premature fracture of a stainless steel 316L orthopaedic plate implant by alternative episodes of fatigue and cleavage decoherence

An orthopaedic SS 316L compression plate implant (dimensions 220 × 15 × 6 mm) with suitably prepared holes was mounted by means of 12 screws after a surgical operation to the left femur bone of a 72 years old patient. Six months after the surgical operation the implant failed by fracture at a central point across its length requiring a second surgery for the replacement of the device. Compression plate implants, when improperly installed, may fail by means of a fatigue mechanism if they are subjected to cyclic loading. This occurs within a short period of time and is followed by a catastrophic final step. This mechanism is manifested by striations on the failed surfaces under scanning electron microscopy. In the present study, the fracture topography of the mating surfaces show a mixed fracture morphology created by alternative episodes of fatigue and cleavage decoherence without any evidence of corrosion assistance. This low energy fracture behaviour was largely due to post operational malpractice, which subjected the implant in cyclic loading during the patient’s walking motion just a few days after the surgery.     

Surface hardness improvement of plasma-sprayed AISI 316L stainless steel coating by low-temperature plasma carburizing

Low-temperature carburizing below 773 K of austenite stainless steel can produce expanded austenite, known as S-phase, where surface hardness is improved while corrosion resistance is retained. Plasma-sprayed austenitic AISI 316L stainless steel coatings were carburized at low temperatures to enhance wear resistance. Because the sprayed AISI 316L coatings include oxide layers synthesized in the air during the plasma spraying process, the oxide layers may restrict carbon diffusion. We found that the carbon content of the sprayed AISI 316L coatings by low-temperature carburizing was less than that of the AISI 316L steel plates; however, there was little difference in the thickness of the carburized layers. The Vickers hardness of the carburized AISI 316L spray coating was above 1000 HV and the amount of specific wear by dry sliding wear was improved by two orders of magnitude. We conclude that low-temperature plasma carburizing enabling the sprayed coatings to enhance the wear resistance to the level of carburized AISI 316L stainless steel plates. As for corrosion resistance in a 3.5 mass% NaCl solution, the carburized AISI 316L spray coating was slightly inferior to the as-sprayed AISI 316L coating.     

Self sensing carbon nanotube (CNT) and nanofiber (CNF) cementitious composites for real time damage assessment in smart structures

The self sensing properties of cementitious composites reinforced with well dispersed carbon nanotubes and carbon nanofibers were investigated. The electrical resistance of cementitious nanocomposites with w/c = 0.3 reinforced with well dispersed carbon nanotubes (CNTs) and nanofibers (CNFs) at an amount of 0.1 wt% and 0.3 wt% of cement was experimentally determined and compared with resistivity results of nanocomposites fabricated with “as received” nanoscale fibers at the same loading. Results indicate that conductivity measurements, besides being a valuable tool in evaluating the smart properties of the nanocomposites, may provide a good correlation between the resistivity values measured and the degree of dispersion of the material in the matrix. The addition of CNTs and CNFs at different loadings was proven to induce a decrease in electrical resistance, with the nanocomposites containing 0.1 wt% CNTs yielding better electrical properties. Furthermore, conductivity measurements under cyclic compressive loading provided an insight in the piezoresistive properties of selected nanocomposites. Results confirm that nanocomposites, reinforced with 0.1 wt% CNTs and CNFs, exhibited an increased change in resistivity, which is indicative of the amplified sensitivity of the material in strain sensing.     

Nanodiamond/poly (lactic acid) nanocomposites: Effect of nanodiamond on structure and properties of poly (lactic acid)

Nanodiamond (ND)/poly (lactic acid) (PLA) nanocomposites with potential for biological and biomedical applications were prepared by using melting compound methods. By means of transmission electron microscopy (TEM), Scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), Thermogravimetric analyses (TGA), Dynamic mechanical analyses (DMA), Differential scanning calorimetry (DSC) and Tensile test, the ND/PLA nanocomposites were investigated, and thus the effect of ND on the structural, thermal and mechanical properties of polymer matrix was demonstrated for the first time. Experimental results showed that the mechanical properties and thermal stability of PLA matrix were significantly improved, as ND was incorporated into the PLA matrix. For example, the storage modulus (E′) of 3 wt% ND/PLA nanocomposites was 0.7 GPa at 130 °C which was 75% higher than that of neat PLA, and the initial thermal decomposition was delayed 10.1 °C for 1 wt% ND/PLA nanocomposites compared with the neat PLA. These improvements could be ascribed to the outstanding physical properties of ND, homogeneous dispersion of ND nanoclusters, unique ND bridge morphology and good adhesion between PLA matrix and ND in the ND/PLA nanocomposites.