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Interatomic potential models for natural apatite crystals: incorporating strontium and the lanthanides.

A comprehensive set of interatomic potential parameters for modeling natural apatite crystals is presented. These potentials build on those previously used in research on apatites with new potentials fitted empirically to crystal structures and their properties using the GULP program. We demonstrate that the new potentials produce good models for the different compounds used for fitting, as well as for several natural apatites. Also presented are predicted enthalpies of mixing of strontium and calcium apatites and predicted cation site preferences in strontium calcium fluorapatite.

Apatites↗

Development of apatite-type oxide ion conductors.

Research into materials displaying oxide ion conductivity is attracting considerable attention due to their potential technological applications in devices such as Solid Oxide Fuel Cells. In this paper, recent work on apatite-type oxide ion conductors is reviewed, showing that a wide range of cation substitutions are possible, due to the flexibility of the apatite structure in accommodating a range of ion sizes. The conductivity studies on these doped samples show that to achieve high oxide ion conduction, non-stoichiometry in terms of cation vacancies and/or oxygen excess is required, with the latter resulting in the highest conductivities. In contrast to most common oxide ion conductors, e.g. perovskite and fluorite in which oxide ion conduction proceeds via oxygen vacancies, the research on these apatite systems suggests that the conductivity involves interstitial oxide ions. With further optimization of these materials, particularly in terms of the Ge-containing systems, significant improvements in conductivity are likely, leading to the very real possibility of the application of apatite-type electrolytes in fuel cell and other applications.

Apatites↗

F--CO3(2-)-interaction in IR spectra of fluoridated CO3-apatites.

Spectroscopic properties of fluoridated CO3-apatites were studied by means of infrared (IR) absorption analysis. The peak of the IR band caused by CO32-ions at 875 cm-1 shifted to a lower frequency with the degree of fluoridation. This result suggests that there is a significant interaction between F and CO32-ions in the apatite crystals. The interaction of both these ions is discussed with regard to the solubility behavior of fluoridated CO3- apatites in the acetate buffer solution at pH 4.0 and at 37 degrees C. Solubility of these fluoridated CO3-apatites approached that of fluoridated hydroxyapatites at high fluoride content.

Apatites↗

Phosphoprotein modulation of apatite crystallization.

Several phosphoprotein preparations (phosvitin, rat incisor and fetal calf molar dentin phosphoproteins) all inhibit apatite growth/replication from pre-existing crystal seeds in metastable solutions. Two stages of the crystal growth process were inhibited by these phosphoproteins. First an initial lag period was induced, probably associated with seed surface phenomena. This period was prolonged indefinitely when a combination of phosphoprotein precoated seeds was used together with soluble phosphoproteins in the crystal growth reaction. Second, the phosphoproteins prolonged that stage of the reaction where octacalcium phosphate is the predominant mineral phase present prior to its conversion to the final apatite product. Pre-treatment of the phosphoproteins with calcium diminished their inhibitory activity to seeded crystal growth as well as towards de novo apatite formation in synthetic extracellular fluids. The presence of collagen diminished the inhibitory activity of the phosphoproteins towards de novo precipitation but had no effect on phosphoprotein-modulated apatite crystal growth in the seeded systems. These results suggest a potential regulatory role for phosphoproteins in dentin mineralization.

Animals↗

Fluoride analysis of apatite crystals with a central planar OCP inclusion: concerning the role of F- ions on apatite/OCP/apatite structure formation.

To study the roles of F- ions in the formation of apatite crystals embedding octacalcium phosphate (OCP) lamella in the center of apatite (Ap), a range of the Ap/OCP/Ap lamellar-mixed crystals were synthesized under various concentrations of fluoride ion (F-) from 0. 1-1.0 ppm at pH 6.5 and 37 degrees C. The products were analyzed for the F- incorporation, F- distribution, and the amount of OCP and Ap by chemical analysis, X-ray diffraction (XRD), electron probe microanalysis (EPMA), and nuclear magnetic resonance (NMR) techniques. The F- content and the amount of apatite in the crystalline product increased with an increase in the F- concentration in solution, whereas the amount of OCP and the yield of total product decreased. EPMA indicated that F- ions are distributed in the crystals almost homogeneously. The combined analysis suggested that a low-substituted fluoridated hydroxyapatite (FHAp) grew on a small amount of F--containing OCP or on a surface-reaction layer of OCP, which has accumulated a small amount of F-. The roles of F- ions were hypothesized as the reduction of the growth rate and/or the critical thickness in the a*-axis direction of OCP, the enhancement of hydrolysis of OCP, and the activation of the growth of FHAp, resulting in thinner OCP lamella and thicker apatite lamella in the a*-axis direction with an increase in F- concentration.

Apatites↗

MicroRaman spectral study of the PO4 and CO3 vibrational modes in synthetic and biological apatites.

The carbonate and phosphate vibrational modes of different synthetic and biological carbonated apatites were investigated by Raman microspectroscopy, and compared with those of hydroxyapatite. The nu1 phosphate band at 960 cm-1 shifts slightly due to carbonate substitution in both A and B sites. The spectrum of type A carbonated apatite exhibits two nu1 PO43- bands at 947 and 957 cm-1. No significant change was observed in the nu2 and nu4 phosphate mode regions in any carbonated samples. The nu3 PO43- region seems to be more affected by carbonation: two main bands were observed, as in the hydroxyapatite spectrum, but at lower wave numbers. The phosphate spectra of all biominerals apatite were consistent with type AB carbonated apatite. In the enamel spectrum, bands were observed at 3513 and at 3573 cm-1 presumably due to two different hydroxyl environments. Two different bands due to the carbonate nu1 mode were identified depending on the carbonate substitution site A or B, at 1107 and 1070 cm-1, respectively. Our results, compared with the infrared data already reported, suggest that even low levels of carbonate substitution induce modifications of the hydroxyapatite spectrum. Increasing substitution ratios, however, do not bring about any further alteration. The spectra of dentine and bone showed a strong similarity at a micrometric level. This study demonstrates the existence of acidic phosphate, observable by Raman microspectrometry, in mature biominerals. The HPO42- and CO32- contents increase from enamel to dentine and bone, however, these two phenomena do not seem to be correlated.

Apatites↗

Ion exchanges in apatites for biomedical application.

The modification of the composition of apatite materials can be made by several processes corresponding to ion exchange reactions which can conveniently be adapted to current coatings and ceramics and are an alternative to setting up of new synthesis methods. In addition to high temperature thermal treatments, which can partly or almost totally replace the monovalent OH- anion of stoichiometric hydroxyapatite by any halogen ion or carbonate, aqueous processes corresponding to dissolution-reprecipitation reactions have also been proposed and used. However, the most interesting possibilities are provided by aqueous ion exchange reactions involving nanocrystalline apatites. These apatites are characterised by the existence on the crystal surface of a hydrated layer of loosely bound mineral ions which can be easily exchanged in solution. This layer offers a possibility to trap mineral ions and possibly active molecules which can modify the apatite properties. Such processes are involved in mineralised tissues and could be used in biomaterials for the release of active mineral species.

Apatites↗

Biological evaluation of an apatite-mullite glass-ceramic produced via selective laser sintering.

The biological performance of a porous apatite-mullite glass-ceramic, manufactured via a selective laser sintering (SLS) method, was evaluated to determine its potential as a bone replacement material. Direct contact and extract assays were used to assess the cytotoxicity of the material. A pilot animal study, implanting the material into rabbit tibiae for 4 weeks, was also carried out to assess in vivo bioactivity. The material produced by SLS did not show any acute cytotoxic effects by either contact or extract methods. There was no evidence of an apatite layer forming on the surface of the material when soaked in SBF for 30 days, suggesting that the material was unlikely to exhibit bioactive behaviour in vivo. It is hypothesized that the material was unable to form an apatite layer in SBF due to the fact that this glass-ceramic was highly crystalline and the fluorapatite crystal phase was relatively stable in SBF, as were the two aluminosilicate crystal phases. There was thus no release of calcium and phosphorus and no formation of silanol groups to trigger apatite deposition from solution within the test time period. Following implantation in rabbit tibiae for 4 weeks, bone was seen to have grown into the porous structure of the laser-sintered parts, and appeared to be very close to, or directly contacting, the material surface. This result may reflect the local environment in vivo compared to that artificially found with the in vitro SBF test and, furthermore, confirms previous in vivo data on these glass-ceramics.

Aluminum Silicates↗

Bone-like apatite-forming ability and mechanical properties of poly(epsilon-caprolactone)/silica hybrid as a function of poly(epsilon-caprolactone) content.

Effect of poly(epsilon-caprolactone) (PCL) content on the bioactivity and mechanical properties of PCL/silica hybrid was investigated. The PCL/silica hybrids with different PCL contents were prepared through co-condensation reaction with triethoxysilane end capped PCL and tetraethyl orthosilicate. The higher the PCL content in the hybrid, the lower the apatite-forming rate and showed polymer-like ductile-tough fracture behavior. On the contrary, the lower the PCL content in the hybrid, the higher the apatite-forming rate and showed ceramic-like hard-brittle fracture behavior. At the intermediate PCL content, the apatite-forming rate and its mechanical properties showed also intermediate behaviors. The highest tensile strength and Young's modulus could be obtained at intermediate PCL content and they were around 20 and 600 MPa, respectively, while the strain at failure was around 50%. This new kind of hybrid material is likely to have the potential to be used as a bone repairing material because of its apatite-forming ability and the mechanical properties comparable to human cancellous bone.

Apatites↗

Biomimetic apatite formation on chemically treated titanium.

Titanium treated in NaOH can form hydroxycarbonated apatite (HCA) after exposition in simulated body fluid (SBF). Generally, titanium is covered with a passive oxide layer. In NaOH this passive film dissolves and an amorphous layer containing alkali ions is formed on the surface. When exposed to SBF, the alkali ions are released from the amorphous layer and hydronium ions enter into the surface layer, resulting in the formation of Ti-OH groups in the surface. The released Na(+) ions increase the degree of supersaturation of the soaking solution with respect to apatite by increasing pH, and Ti-OH groups induce apatite nucleation on the titanium surface. The acid etching of titanium in HCl under inert atmosphere was examined as a pretreatment to obtain a uniform initial titanium surface before alkali treatment. Acid etching in HCl leads to the formation of a micro-roughened surface, which remains after alkali treatment in NaOH. It was shown by SEM, gravimetric and solution analysis that the apatite nucleation was uniform and the thickness of precipitated HCA layer increased continuously with time. The treatment of titanium by acid etching in HCl and subsequently in NaOH is a suitable method for providing the metal implant with bone-bonding ability.

Apatites↗

Biomimetic apatite coatings on micro-arc oxidized titania.

Biomimetic apatite coatings on micro-arc oxidized titania films were investigated and their apatite-inducing ability was evaluated in a simulated body fluid (1.0 SBF) as well as in a 1.5 times concentrated SBF (1.5 SBF). Titania-based films on titanium were prepared by micro-arc oxidation at various applied voltages (250-500 V) in an electrolytic solution containing beta-glycerophosphate disodium salt pentahydrate (beta-GP) and calcium acetate monohydrate (CA). Macro-porous, Ca- and P-containing titania-based films were formed on the titanium substrates. The phase, Ca and P content, morphology, and thickness of the films were strongly dependent on the applied voltage. In particular, Ca- and P-containing compounds such as CaTiO3, beta-Ca2P2O7 and alpha-Ca3(PO4)2 were produced at higher voltages (>450 V). When immersed in 1.0 SBF, a carbonated hydroxyapatite was induced on the surfaces of the films oxidized at higher voltages (>450 V) after 28 days, which is closely related to the Ca- and P-containing phases. The use of 1.5 SBF shortened the apatite induction time and apatite formation was confirmed even on the surface of the films oxidized at 350 V, which suggests that the incorporated Ca and P in the titania films play a similar role to the Ca- and P-containing compounds in the SBF.

Animals↗

Bone-like apatite layer formation on hydroxyapatite prepared by spark plasma sintering (SPS).

Hydroxyapatite (HA) compacts with high density and superior mechanical properties were fabricated by spark plasma sintering (SPS) using spray-dried HA powders as feedstock. The formation of bone-like apatite layer on SPS consolidated HA compacts were investigated by soaking the HA compacts in simulated body fluid (SBF) for various periods (maximum of 28 days). The structural changes in HA post-SBF were analyzed with scanning electron microscopy, grazing incidence X-ray diffraction and X-ray photoelectron spectroscopy. It was found that a layer consisting microcrystalline carbonate-containing hydroxyapatite was formed on the surface of HA compacts after soaking for 24h. The formation mechanism of apatite on the surface of HA compacts after soaking in SBF was attributed to the ion exchange between HA compacts and the SBF solution. The increase in ionic concentration of calcium and phosphorus as well as the increase in pH after SBF immersion resulted in an increase in ionic activity product of apatite in the solution, and provided a specific surface with a low interface energy that is conducive to the nucleation of apatite on the surface of HA compacts.

Apatites↗

Biomimetic growth of apatite on hydrogen-implanted silicon.

Hydrogen in silicon has been widely applied in semiconductor fields. In this paper, the application of hydrogen-implanted silicon wafer in biomedical fields was explored by investigating its bioactivity. Hydrogen implanted silicon wafers were prepared using plasma immersion ion implantation. The surface structures of the 1.4 x 10(17) cm(-2) hydrogen-implanted silicon wafers were investigated using atomic force microscopy and transmission electron microscopy (TEM). The hydrogen depth profiles were acquired by SIMS and the crystal quality of the as-implanted silicon was studied by channeling Rutherford backscattering spectrometry (RBS). The bioactivity of the implanted silicon was evaluated using the biomimetic growth of apatite on its surface after it was soaked in simulated body fluid for a period of time. The TEM, SIMS and RBS results indicate the formation of an amorphous hydrogenated silicon (a-Si:Hx) layer has been formed on the surface of the hydrogen-implanted silicon wafer. After immersion in SBF for 14 days, bone-like apatite is observed to nucleate and grow on the surface. With longer soaking time, more apatite appeared on the surface of the hydrogen implanted silicon but our control experiments did not reveal any apatite formation on the surface of the un-implanted silicon wafer, hydrogenated crystalline silicon wafer (with hydrogen, but no amorphous surface), or argon-implanted silicon wafer (amorphous surface but without hydrogen). Our results indicated that the bioactivity of silicon wafer can be improved after hydrogen implantation and the formation of the amorphous hydrogenated silicon (a-Si:Hx) surface also plays a synergistic role to improve the bioactivity.

Alpha Particles↗

Structure and immersion behavior of plasma-sprayed apatite-matrix coatings.

The microstructure and properties of a series of plasma-sprayed coatings from sinter-granulated powders fabricated from SiO2, CaO, P2O5 and Na2O-containing HA composite powders on Ti-6Al-4V substrate were reported. The immersion behavior of these coatings in a simulated body fluid (SBF) was also investigated. The results showed that sinter-granulated apatite-matrix powders were irregularly shaped and appeared quite similar. XRD patterns showed that during fabrication of the powders, P2O5 and SiO2 enhanced the decomposition of HA structure, while CaO and Na2O did not. Reasonably high bond strengths (45-50 MPa) were obtained from all coatings. The plasma spray process itself enhanced the decomposition of apatite and chemical reactions among different phases. When immersed in SBF, the intensities of such phases as alpha- and beta-TCP in all coatings decreased with immersion time and an apatite precipitation took place on all coating surfaces. The immersed SiO2- and CaO-containing HA (HSC) coating had the highest rate of apatite precipitation among all coatings. The variations in calcium ion concentration in simulated body fluid indicated that the HSC-immersed solution reached its maximal Ca concentration the earliest, while the HSCP (HA, SiO2, CaO and P2O5)-immersed solution reached its maximum the latest.

Apatites↗

Apatite-forming ability and mechanical properties of PTMO-modified CaO-SiO2 hybrids prepared by sol-gel processing: effect of CaO and PTMO contents.

Transparent monolithics of triethoxysilane end-capped poly(tetramethylene oxide) (Si-PTMO)-modified CaO-SiO2 hybrids were successfully synthesized by hydrolysis and polycondensation of Si-PTMO, tetraethoxysilane (TEOS) and calcium nitrate. As for the samples with varying (Ca(NO3)2)/(TEOS) molar ratios under constant ratio of (Si-PTMO)/(TEOS) of 2/3 in weight. the apatite-forming ability in a simulated body fluid (SBF) which is indicative of bioactivity. remarkably increased with increasing CaO content, although the tensile strength and Young's modulus decreased. The hybrid with (Ca(NO3)2)/(TEOS) = 0.15 in mol formed an apatite on its surface within only 1 day. For this series of samples, the strain at failure which is a measure of capability for deformation of material, was found to be about 30% and almost independent of CaO content. As for the samples with varying (Si-PTMO)/(TEOS) weight ratios under constant ratio of (Ca(NO3)2)/(TEOS) of 0.15 in mol, the strain at failure increased with increasing Si-PTMO content, but the apatite-forming ability, tensile strength and Young's modulus decreased. Thus, the synthesis of the hybrids exhibiting both high apatite-forming ability and high extensibility can be achieved by selecting suitable CaO and Si-PTMO contents. These new kind of hybrid materials may be useful as bioactive bone-repairing materials.

Apatites↗

Characterization of the bone-like apatite precipitated on high velocity oxy-fuel (HVOF) sprayed calcium phosphate deposits.

Bone-like apatite was precipitated on the surface of thermal sprayed calcium phosphate coatings following in vitro incubation in a simulated body fluid. The coatings were initially deposited on titanium alloy substrates by the high velocity oxy-fuel (HVOF) spray technique. Structural characterization and mechanical evaluation of the precipitated apatite layer were conducted. Results showed that the precipitation rate was directly influenced by the local Ca(2+) concentration in the vicinity of the coating's surface and that preferential dissolution of certain phases was found to accelerate the precipitation of the bone-like apatite. The dense precipitates exhibited a competitive Young's modulus value of approximately 120GPa, which was obtained through nanoindentation. This compared favorably to the calcium phosphate matrix. Differences in microstructure at various locations within the layer resulted in altered Young's modulus and microhardness values. Precipitation mechanism investigation was carried out through a comparative experiment. Chemical analysis showed that the precipitation of bone-like apatite on the calcium phosphate coating was quite conceivably a partial diffusion-controlled process.

Apatites↗

Synthesis of functionally graded CO3 apatite as surface biodegradable crystals.

Apatite, which will have a degradable surface and a relatively stable core, was synthesized at 80+/-1 degrees C and pH 7.4+/-0.2 using a specially generated gradient carbonate supply system. X-ray diffraction analysis showed that the (300) reflection peak shifted to the higher angle direction due to the substitution of CO3(2-) ions into the PO4(3-) positions and was broader than that of homogeneous hydroxyapatite. Scanning electron microscopy indicated that the apatite was composed of small coagulated ellipsoidal crystals differing from needle-like crystals with hexagonal section of hydroxyapatite. Electron spectroscopy for chemical analysis showed a negative gradient of carbonate concentration with depth in the crystals. The apparent solubility in 0.5 moll(-1) acetate buffer solution (37 degrees C, pH 4.0) was much higher than that of homogeneous hydroxyapatite. The residual sample showed slim needle-like crystals. These results suggested that graded carbonate-containing apatite, namely CO3 apatite with solubility gradient in its crystal structure, was formed by this process and may be useful from the view point of surface biodegradable materials as bone representatives.

Apatites↗

Fluoridated apatite synthesized using a multi-step fluoride supply system.

Fluoridated apatite was synthesized at 80 +/- 1 degrees C, pH 7.4 +/- 0.2, using a 5-step fluoride supply system. During the synthesis experiment, 0, 5, 10, 15 and 20 mmol/l of fluoride were each supplied for one-fifth of the experimental period with calcium and phosphate. X-ray diffraction analysis showed a typically apatitic pattern, although the (3 0 0) reflection was broader than that of homogeneous fluorapatite. Scanning electron micrographic observation indicated that the apatite was composed of needle-like crystals similar to hydroxyapatite and fluorapatite. High-resolution transmission electron microscopy showed a slender hexagonal shape similar to homogeneous hydroxyapatite in cross-sections perpendicular to the c-axis and the structural damage in the core of the crystal, although no boundary of step-like layers was observed. The apparent solubility in 0.5 mol/l acetate buffer solution (37 degrees C and pH 4.0) was 12.1 +/- 0.2 mmol/l, much less than that of homogeneous hydroxyapatite 32.3 +/- 1.9 mmol/l, and similar to that of heterogeneous two-layer fluoridated apatite with an outer fluoride-rich layer 12.5 +/- 0.6 mmol/l, which was synthesized previously by supplying fluoride during the latter half of the experimental period.

Apatites↗