Plasma-sprayed hydroxyapatite coating: effect of different calcium phosphate ceramics

Three kinds of calcium phosphate ceramic powders, namely commercial hydroxyapatite (CHA), self-made hydroxyapatite (SMHA) and synthesized hydroxyapatite (SHA), are employed as starting materials for plasma-sprayed coating onto a stainless steel (316L) substrate. Results show a mixture of hydroxyapatite (HA), tricalcium phosphate (TCP), and tetracalcium phosphate (TeCP) phases appearing in the CHA and SHA-derived coatings and a primary of a HA with trace contents of tricalcium phosphate phases resulting in the SMHA-derived coating. The HA appears to be the only observable crystalline phase present in the SMHA-derived coating after 7 days of incubation with a simulated body fluid (SBF); however, part of the impurities, i.e. TCP and TeCP, remain in the other coatings. No apparent microcracks can be found on the coated surfaces when SMHA and SHA are used. The poor packing density of SHA reflects its weakness in bonding strength to the substrate surface compared with that obtained using CHA and SMHA powders. The surface morphology of the coatings was found to alter significantly after a sufficient period of incubation.     

Porous low modulus Ti40Nb compacts with electrodeposited hydroxyapatite coating for biomedical applications

Porous ß-type non-toxic Ti40Nb alloy was prepared by compaction of mechanically alloyed powder mixed with NaCl or Mg particles as space-holder material. The compacts with porosity of 36–80% demonstrated a very low Young's modulus of ~ 1.5–3 GPa and compression strength of ~ 10–35 MPa, which is suitable for potential implant material application. Porous samples were electrochemically covered with hydroxyapatite. The influence of the deposition time and of the electrolyte concentrations on the morphology of the hydroxyapatite coating was studied. It is demonstrated that a homogenous coating of hydroxyapatite crystals with different shape and size can be obtained on the surface of the porous samples.     

Synthesis of hydroxyapatite nanotubes for biomedical applications

Single phase, stoichiometrically pure, hollow nanotubes of hydroxyapatite have been synthesized and single-particle analysis has been performed to successfully prove the sole formation of Ca₁₀(PO₄)₆(OH)₂ phase. The facile synthesis involves a sol–gel process under neutral conditions in the presence of a sacrifical anodic alumina template. The structures formed are hollow nanotubes that have been characterized by XRD, SEM, TEM, SAED, EELS, EDS and BET measurements. The diameter of the resulting tubes is in the range of 140–350 nm, length is on the order of a few microns and the wall thickness of the tubes was found to be ca. 30 nm. Moreover these tubes had a large BET surface area of 115 m²/g and were found to be biocompatible. They displayed inertness in the presence of NIH 3T3 mouse fibroblast cells as dictated by an MTT assay.     

Control of phase composition in hydroxyapatite/tetracalcium phosphate biphasic thin coatings for biomedical applications

Biphasic calcium phosphates comprising well-controlled mixtures of nonresorbable hydroxyapatite and other resorbable calcium phosphate phases often exhibit a combination of enhanced bioactivity and mechanical stability that is difficult to achieve in single-phase materials. This makes these biphasic bioceramics promising substrate materials for applications in bone tissue regeneration and repair. In this paper we report the synthesis of highly crystalline, biphasic coatings of hydroxyapatite/tetracalcium phosphate with control over the weight fraction of the constituent phases. The coatings were produced by pulsed laser deposition using ablation targets of pure crystalline hydroxyapatite. The fraction of tetracalcium phosphate phase in the coatings was controlled by varying the substrate temperature and the partial pressure of water vapor in the deposition chamber. A systematic study of phase composition in the hydroxyapatite/tetracalcium phosphate biphasic coatings was performed with X-ray diffraction. Tetracalcium phosphate in the coatings obtained at high substrate temperature is not formed by partial conversion of previously deposited hydroxyapatite. Instead, it is produced by nucleation and growth of tetracalcium phosphate itself from the ablation products of the hydroxyapatite target or by accretion of tetracalcium phosphate grains formed during ablation. This finding was confirmed by formation of calcium oxide, not tetracalcium phosphate, after annealing of pure hydroxyapatite coatings at high temperatures of 700–850∘C.     

Aerosol deposition of silicon-substituted hydroxyapatite coatings for biomedical applications

Silicon-substituted hydroxyapatite (Si-HA) coatings on commercially pure titanium (Ti) were prepared by aerosol deposition using Si-HA powders. Si-HA powders with the chemical formula Ca₁₀(PO₄)_6 − x(SiO₄)_x(OH)_2 − x, having silicon contents up to x = 0.5 (1.4 wt.%), were synthesized by solid-state reaction of Ca₂P₂O₇, CaCO₃, and SiO₂. The Si-HA powders were characterized by X-ray diffraction (XRD), X-ray fluorescence spectrometry, and Fourier transform infrared spectroscopy. The corresponding coatings were also analyzed by XRD, scanning electron microscopy, and electron probe microanalyzer. The results revealed that a single-phase Si-HA was obtained without any secondary phases such as α- or β-tricalcium phosphate for both the powders and the coatings. The Si-HA coating was about 5 µm thick, had a dense microstructure with no cracks or pores, and showed a high adhesion strength ranging from 28.4 to 32.1 MPa. In addition, the proliferation and alkaline phosphatase activity of MC3T3-E1 preosteoblast cells grown on the Si-HA coatings were significantly higher than those on the bare Ti and pure HA coating. These results revealed the stimulatory effects induced by silicon substitution on the cellular response to the HA coating.     

A novel crosslinkable polymer as drug-loaded coating for biomedical device

A novel copolymer has been synthesized by the radical polymerization of poly (ethylene oxide) methacrylate, stearyl methacrylate, hydroxypropyl methacrylate and trimethoxysilylpropyl methacrylate. The polymer was characterized by Fourier transform infrared spectroscopy, proton nuclear magnetic resonance (1H-NMR) spectroscopy and gel permeation chromatography. The crosslinkable coating was prepared by dip-coating 5mg/ml solution in tetrahydrofuran onto glass substrate. A stable crosslinked coating was obtained after curing the coating at 70 degrees C for 9 h. Contact angle results indicated the possible reorganization of the surface amphiphilic molecule which interpreted the excellent biocompatibility revealed by the results of the platelet adhesion and plasma recalcification time. Rhodamine S and Cibacron Blue were used as model drugs to prepare drug-containing coating at the same conditions. Drug-releasing curves indicated that the mechanism of the release is approximately Fickian release.     

A construction of novel iron-foam-based calcium phosphate/chitosan coating biodegradable scaffold material

Slow corrosion rate and poor bioactivity restrict iron-based implants in biomedical application. In this study, we design a new iron-foam-based calcium phosphate/chitosan coating biodegradable composites offering a priority mechanical and bioactive property for bone tissue engineering through electrophoretic deposition (EPD) followed by a conversion process into a phosphate buffer solution (PBS). Tensile test results showed that the mechanical property of iron foam could be regulated through altering the construction of polyurethane foam. The priority coatings were deposited from 40% nano hydroxyapatite (nHA)/ethanol suspension mixed with 60% nHA/chitosan-acetic acid aqueous solution. In vitro immersion test showed that oxidation-iron foam as the matrix decreased the amount of iron implanted and had not influence on the bioactivity of this implant, obviously. So, this method could also be a promising method for the preparation of a new calcium phosphate/chitosan coating on foam construction.     

Synthesis and sintering of biomimetic hydroxyapatite nanoparticles for biomedical applications

Synthesis of monodisperse nanoparticles with uniform morphology and narrow size distribution as achieved by nature is a challenge to materials scientists. Mimicking the process of biomineralization has led to the development of biomolecules mediated synthesis of nanoparticles that overcomes many of the problems associated with nanoparticle synthesis. Termed as biomimetics this paradigm shift in the philosophy of synthesis of materials is very advantageous for the design-based synthesis of nanoparticles. The effect of concentration of a protein named bovine serum albumin on particle size, morphology and degree of crystallinity of biomimetically synthesized hydroxyapatite particles, has been studied. Results establish 0.5% protein as the required concentration to produce 30–40 nm sized hydroxyapatite particles with an optimum degree of crystallinity as required for biomedical applications. These particles synthesized under certain stringent conditions are found to have stoichiometric calcium:phosphorus ratio of 1.67 and exhibit restricted grain growth during sintering.     

Biomimetic synthesis of hydroxyapatite/bacterial cellulose nanocomposites for biomedical applications

Hydroxyapatite (HAp) and bacterial cellulose (BC) are both excellent materials for use in biomaterial areas. The former has outstanding osteoconductivity and bioactivity and the latter is a high-strength nano-fibrous and extensively used biomaterial. In this work, the HAp/BC nanocomposites with a 3-dimensional (3-D) network were synthesized via a biological route by soaking both phosphorylated and unphosphorylated BCs in 1.5 simulated body fluid (SBF). Scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transformed infrared spectroscopy (FTIR), and transmission electron microscopy (TEM) were employed to characterize the HAp/BC nanocomposites. SEM observations demonstrated that HAp crystals were uniformly formed on the phosphorylated BC fibers after soaking in 1.5 SBF whereas little HAp was observed on individual unphosphorylated BC fibers. Our experimental results suggested that the unphosphorylated BC did not induce HAp growth and that phosphorylation effectively triggered HAp formation on BC. Mechanisms were proposed for the explanation of the experimental observations. XRD and FTIR results revealed that the HAp crystals formed on the phosphorylated BC fibers were carbonate-containing with nano-sized crystallites and crystallinities less than 1%. These structural features were close to those of biological apatites.     

Cement from nanocrystalline hydroxyapatite: Effect of calcium phosphate ratio

Nanocrystalline hydroxyapatite (nHA) can be mixed with phosphoric acid to form a brushite cement; a degradable inorganic bone filling material. nHA was precipitated from reactants of calcium to phosphate (Ca/P) ratio 0.8 to 2.0 and mixed with phosphoric acid, which resulted in the formation of a brushite cement. Cement was also formed by mixing microcrystalline calcium phosphates, β-tricalcium phosphate, hydroxyapatite and tetracalcium phosphate with phosphoric acid solution. Cement produced with nHA was stronger in compression than that formed with crystalline calcium phosphate phases. Setting time, strength and composition of cement produced with nHA was dependant on both the Ca/P ratio of nHA and the concentration of phosphoric acid in cement slurry. Increasing phosphoric acid concentration increased compressive strength whilst reducing the initial setting time of cement. Reducing the Ca/P ratio of nHA precipitation reactants retarded the setting and increased the extent of reaction of cements. This finding was unexpected and suggests that Ca/P ratio may strongly affect dissolution behaviour and this parameter is more important than stoichiometry in determining extent of reaction in this system. This study demonstrated that the wide variation in stoichiometry that may be attained in nanocrystalline apatite may be utilised to change cement performance and setting behaviour.     

Porous calcium phosphate ceramics prepared by coating polyurethane foams with calcium phosphate cements

Porous calcium phosphates have important biomedical applications such as bone defect fillers, tissue engineering scaffolds and drug delivery systems. While a number of methods to produce the porous calcium phosphate ceramics have been reported, this study aimed to develop a new fabrication method. The new method involved the use of polyurethane foams to produce highly porous calcium phosphate cements (CPCs). By firing the porous CPCs at 1200 °C, the polyurethane foams were burnt off and the CPCs prepared at room temperature were converted into sintered porous hydroxyapatite (HA)-based calcium phosphate ceramics. The sintered porous calcium phosphate ceramics could then be coated with a layer of the CPC at room temperature, resulting in high porosity, high pore interconnectivity and controlled pore size.     

Characterization of Tb-doped hydroxyapatite for biomedical applications: optical properties and energy band gap determination

In the present work, the synthesis, by means of the sol–gel method, of calcium-deficient hydroxyapatite and Tb-doped calcium-deficient hydroxyapatite with dopant content of 10 and 12 wt% is reported. The synthesized samples exhibit diffraction patterns and structural characteristics consistent with those reported in the literature for synthetic hydroxyapatite. The results of the chemical characterization show that the synthesized samples are suitable for biomedical applications, and the incorporation of Tb³⁺ in the host structure occurs both substitutional and by dopant insertion in calcium vacancy sites. In addition, using spectroscopic techniques, the values of the valence band, optical band gap energies, and luminescent response were determined for all samples, concluding that the increase in dopant has the consequence of decreasing the value of the optical band gap, as it was expected; However, it is also observed that the maximum luminescent emission is obtained for the sample synthesized with 10 wt% of terbium.     

Zinc phosphate as versatile material for potential biomedical applications Part II

Surface chemical reactivity of two modifications of synthetic zinc phosphate tetrahydrate (α - and β -form of Hopeite, α -,β -ZPT) has been studied by selective chemical and e-beam etching in presence of diluted phosphoric acid and ammonia by Scanning Electron Microscopy (SEM) and microelectrophoresis (zeta potential measurements) in correlation with the corresponding bulk properties and crystal size distributions. The subtitle crystallographic differences between α -and β -ZPT originating from a unique hydrogen bonding pattern, induce drastic variations of both surface potential and surface charge. Biogenic Hydroxyapatite (HAP) and one of its metastable precursors, a calcium dihydrogen phosphate dihydrate (DCPD) or Brushite were used to underline this resulting variation of chemical reactivity in zinc phosphates. In-situ monitoring of the transformation of Brushite in Hydroxyapatite is also reported.     

Zinc phosphate as versatile material for potential biomedical applications Part 1

Synthetic α - and β -Hopeite, two polymorphs of zinc phosphate tetrahydrates (ZPT) have been synthesized by hydrothermal crystallization from aqueous solution at 20 ^∘C and 90 ^∘C respectively. Aside from their subtitle crystallographic differences originating from a unique hydrogen bonding pattern, their thermodynamic interrelation has been thoroughfully investigated by means of X-Ray diffraction (XRD) and differential scanning calorimetry (DSC), combined with thermogravimetry (TGA-MS). Using a new heterogeneous step-reaction approach, the kinetics of dehydration of the two forms of ZPT was studied and their corresponding transition temperature determined. Low temperature DRIFT, FT-Raman and ¹H, ³¹P MAS-NMR reveal an oriented distortion of the zinc phosphate tetrahedra, due to a characteristic hydrogen bonding pattern and in accordance with the molecular tetrahedral linkage scheme of the phosphate groups. Biogenic Hydroxyapatite (HAP) and one of its metastable precursors, a calcium dihydrogen phosphate dihydrate (DCPD) or Brushite were also obtained and used to underline the resulting variations of chemical reactivity in zinc phosphates.     

Fabrication of novel TiZr alloy foams for biomedical applications

Bone injuries and failures often require the inception of implant biomaterial. Research in this area has received increasing attention recently. In particular, porous metals are attractive due to its unique physical, mechanical, and new bone tissue ingrowth properties. In the present study, TiZr alloy powders were prepared using mechanical alloying. Novel TiZr alloy foams with relative densities of approximately 0.3 were fabricated by a powder metallurgical process. The TiZr alloy foams displayed an interconnected porous structure resembling bone and the pore size ranged from 200 to 500 μm. The compressive plateau stress and the Young’s modulus of the TiZr foam were 78.4 MPa and 15.3 GPa, respectively. Both the porous structure and the mechanical properties of the TiZr foam were very close to those of natural bone.     

Formation of hydroxyapatite coating using novel chemo-biomimetic method

A novel chemo-biomimetic method was developed to deposit hydroxyapatite (HA), simulating the porous nano-scale structure and chemical composition of natural bone. Electrochemical activation in NaOH solution, a prerequisite process to heterogeneously nucleate hydroxyapatite in this investigation, creates nano-scale porous structure on the surface of Ti6Al4V alloy. XPS analysis confirmed that the surface of activated Ti6Al4V substrate converted to TiO(2) during activation, existing in the form of hydrated TiO(2). Benefiting from the biocompatible top-layer of hydrated TiO(2) and the favorable alkaline surface chemistry created through the electrochemical activation, the HA coating nucleates heterogeneously and grows continuously on the activated substrate resembling the nano-scale porous bone-like structure. The coating was characterized using XRD, SEM/FESEM/EDX, TEM and FTIR, and was confirmed as pure hydroxyapatite. A coating thickness of 50 mum was achieved, which is preferable and acceptable for medical implant application to promote bone ingrowth, thus enhancing fixation and biocompatibility of implant surface.     

A novel snail-inspired bionic design of titanium with strontium-substituted hydroxyapatite coating for promoting osseointegration

As the population ages,more and more people are suffering from osteoarthritis (OA),resulting in an increasing requirement for joint implants.Surface modification to improve the topology and compo-sition of the implants has been proved to be an effective way to improve the primary stability and long-term success rate of joint implants.In this work,a bionic micro/nano-structure accompanied with a strontium-substituted hydroxyapatite (SrHA) coating was fabricated on titanium (Ti) surface via elec-trochemical corrosion,ultrasonic treatment,and hydrothermal deposition methods.The in vitro study demonstrated that the bionic structure and the bioactive apatite could synergistically increase the expres-sions of integrin-related gene (ITG α5β1) and osteoblastic genes (Col-I and OCN),and thus promote osteoblast growth.In addition,owing to the anti-bone resorption property of Sr2+,the coating could effectively inhibit osteoclast differentiation and proliferation.In a word,the prepared samples not only promoted osteogenesis but also inhibited osteoclastogenesis.The in vivo experiment via a rabbit model found that the bionic structured surface provided the pore for new bone ingrowth,which was beneficial to the mechanical interlocking between the implant and bone.Moreover,the bionic structure and bioactive SrHA coating had a synergistic effect on promoting bone formation,osseointegration,and bone-implant bonding strength.This study therefore presented a new strategy to fabricate bio-functionalized Ti-based implants for potential application in orthopedics field.     

Electrohydrodynamic deposition of nanotitanium doped hydroxyapatite coating for medical and dental applications

Nano-sized titanium containing hydroxyaptite has been prepared, the particle size of nanoTiHA was shown to be 12–20 nm in width and 30–40 nm in length, smaller than that of nanoHA. X-ray diffraction analysis revealed the phase purity of nanoTiHA produced. Antimicrobical assays demonstrated that nanoTiHA has excellent growth inhibitory properties, and is able to inhibit the growth of all bacterial strains tested, both Gram-negative and Gram-positive species, including multi-antibiotic resistant EMRSA 15 and EMRSA 16 ‘superbugs’. Biocidal activity against all four Staphylococcus spp was also shown at the concentration tested. Nanostuctured TiHA coating was successfully deposited onto Ti surfaces using EHDA spraying under optimized processing conditions with the thickness of the coating being further controlled by the spraying time. All of the nanoTiHA coated Ti surfaces were able to support human osteoblast (HOB) cell attachment and growth. The coating thickness did not significantly influence the proliferation of HOB cells on nanoTiHA coatings, while the ability of nanoTiHA coating to support HOB cell differentiation was demonstrated from the alkaline phosphatase activity. Our study showed that nanoTiHA has excellent anti-bacterial properties and the thin nanoTiHA coating was also able to support the attachment, growth and differentiation of HOB cells. Therefore, nanoTiHA coating could pave the way for the development of the next generation of dental and orthopedic implants by offering anti-infection potential in addition to osteoconductivity.     

Microwave assisted preparation of magnesium phosphate cement (MPC) for orthopedic applications: A novel solution to the exothermicity problem

There are two interesting features of this paper. First, we report herein a novel microwave assisted technique to prepare phosphate based orthopedic cements, which do not generate any exothermicity during setting. The exothermic reactions during the setting of phosphate cements can cause tissue damage during the administration of injectable compositions and hence a solution to the problem is sought via microwave processing. This solution through microwave exposure is based on a phenomenon that microwave irradiation can remove all water molecules from the alkaline earth phosphate cement paste to temporarily stop the setting reaction while preserving the active precursor phase in the formulation. The setting reaction can be initiated a second time by adding aqueous medium, but without any exothermicity. Second, a special emphasis is placed on using this technique to synthesize magnesium phosphate cements for orthopedic applications with their enhanced mechanical properties and possible uses as drug and protein delivery vehicles.The as-synthesized cements were evaluated for the occurrences of exothermic reactions, setting times, presence of Mg-phosphate phases, compressive strength levels, microstructural features before and after soaking in (simulated body fluid) SBF, and in vitro cytocompatibility responses. The major results show that exposure to microwaves solves the exothermicity problem, while simultaneously improving the mechanical performance of hardened cements and reducing the setting times. As expected, the cements are also found to be cytocompatible. Finally, it is observed that this process can be applied to calcium phosphate cements system (CPCs) as well. Based on the results, this microwave exposure provides a novel technique for the processing of injectable phosphate bone cement compositions.