Biomimetic synthesis of enamel-like hydroxyapatite on self-assembled monolayers

Hydroxyapatite (HAp) crystals mimicking tooth enamel in chemical composition and morphology were formed on sulfonic-terminated self-assembled monolayer (SAM) in 1.5SBF with F⁻ at 50 °C for 7 days. F⁻ ions showed a marked effect on the composition and morphology of deposited HAp crystals. In the absence of F⁻ ions, HAp containing CO₃²⁻ were formed on SAM, and worm-like crystals of 200–300 nm in length aggregated to form a spherical morphology. When F⁻ was added, HAp crystals containing both CO₃²⁻ and F⁻ were formed on SAM. Needle-shaped crystals of high aspect ratio and 1–2 μm in length grew elongated along the c-axial direction. In addition, these needle-shaped crystals grew in bundles, mimicking HAp crystals in tooth enamel. After the process of ripening, the needles in bundle grew to large size of up to 10 μm in length, and still kept no crystal–crystal fusion like enamel HAp crystals. The formation of enamel-like HAp can be attributed to the substitute of F⁻ for OH⁻ by disturbing the normal progress of HAp formation on SAM. The results suggest potential applications in preparing a novel dental material by a simple method.     

Electrolytic deposition of magnesium-substituted hydroxyapatite crystals on titanium substrate

Electrolytic deposition of magnesium-substituted hydroxyapatite (Mg-HAp) coatings on titanium was investigated and Mg-HAp crystals with up to 2 wt.% Mg²⁺ were deposited in electrolytes with various Mg²⁺ concentration. The incorporation of Mg substantially changed the morphology of the HAp crystals and decreased the crystal size and crystallinity of the HAp. The similarity with natural dentin and bone in composition and the increased specific surface of the Mg-HAp coatings on the Ti substrates were believed to benefit the bioactivity and the drug-carrying properties of the coatings.     

Transmission electron microscopic observation of a metastable phase on the thermal decomposition process of Ca-deficient hydroxyapatite

Calcium-deficient hydroxyapatite (Ca-def HAp) decomposes to stoichiometric hydroxyapatite (HAp) and β-tricalcium phosphate (β-TCP) at high temperature. In a previous study, we reported that a metastable phase with a high Ca/P molar ratio appeared in the temperature range from 700 to 800°C. In the present study, the formation process of a metastable phase and the crystallographic relationship between the Ca-rich metastable phase and HAp matrix were investigated by high-resolution transmission electron microscopy (HRTEM). Ca-def HAp was annealed at 600–850°C for 2 or 6 h in air. TEM observations were performed before and after annealing Ca-def HAp. Based on analysis of image of Ca-def HAp before annealing, several HAp crystals with different aspect ratios agglomerated. The metastable phases grew thicker by long-term annealing. HRTEM image suggested that the Ca-rich metastable phase was formed by migration to the interface and continuous accumulation of calcium ions from HAp crystals with a small aspect ratio. From HRTEM images and results of the analysis of selected area electron diffraction patterns along the [010], [110] and [001] zone axes, lattice constants of the metastable phases were determined to be a = 2.86 nm, b = 0.94 nm, and c = 0.69 nm with orthorhombic crystals system.     

Enhancement in CO gas sensing properties of hydroxyapatite thick films: Effect of swift heavy ion irradiation

This paper investigates the effect of swift heavy ion (SHI) irradiation on surface morphology of Hydroxyapatite (HAp) thick films and modification in gas sensing characteristics. The HAp nanopowder is synthesized by wet chemical process and the thick films are prepared by screen printing technique. These films are irradiated with Ag⁷⁺ ions with energy of 100 MeV at different fluences ranging from 3 × 10¹⁰ to 3 × 10¹³ ions/cm². X-ray diffraction and atomic force microscopy tools are employed to examine the phase and surface modification in HAp thick films due to swift heavy ion irradiation. The ion irradiation study shows that crystallinity decreases and grain size changes with increase in ion fluence. A precise study on gas sensing is carried out to confirm operating temperature of HAp thick film sensor to detect CO gas. Saturation region of the film with increasing gas concentration and other parameters such as response and recovery time are also investigated from the point of view of using HAp films as a sensor device. SHI irradiated HAp thick film shows enhancement in the gas response and saturation limit for CO gas. Furthermore, the irradiated HAp film shows fast response and recovery time for CO gas. The study concludes that nanoceramic HAp thick film is an excellent CO gas sensor at an operating temperature of 195 °C.     

Enhancement in CO gas sensing properties of hydroxyapatite thick films: Effect of swift heavy ion irradiation

This paper investigates the effect of swift heavy ion (SHI) irradiation on surface morphology of Hydroxyapatite (HAp) thick films and modification in gas sensing characteristics. The HAp nanopowder is synthesized by wet chemical process and the thick films are prepared by screen printing technique. These films are irradiated with Ag⁷⁺ ions with energy of 100 MeV at different fluences ranging from 3 × 10¹⁰ to 3 × 10¹³ ions/cm². X-ray diffraction and atomic force microscopy tools are employed to examine the phase and surface modification in HAp thick films due to swift heavy ion irradiation. The ion irradiation study shows that crystallinity decreases and grain size changes with increase in ion fluence. A precise study on gas sensing is carried out to confirm operating temperature of HAp thick film sensor to detect CO gas. Saturation region of the film with increasing gas concentration and other parameters such as response and recovery time are also investigated from the point of view of using HAp films as a sensor device. SHI irradiated HAp thick film shows enhancement in the gas response and saturation limit for CO gas. Furthermore, the irradiated HAp film shows fast response and recovery time for CO gas. The study concludes that nanoceramic HAp thick film is an excellent CO gas sensor at an operating temperature of 195 °C.     

Characterisation, corrosion resistance and in vitro bioactivity of manganese-doped hydroxyapatite films electrodeposited on titanium

This work elucidated the corrosion resistance and in vitro bioactivity of electroplated manganese-doped hydroxyapatite (MnHAp) film on NaOH-treated titanium (Ti). The NaOH treatment process was performed on Ti surface to enhance the adhesion of the MnHAp coating on Ti. Scanning electron microscopy images showed that the MnHAp coating had needle-like apatite crystals, and the approximately 10 μm thick layer was denser than HAp. Energy-dispersive X-ray spectroscopy analysis revealed that the MnHAp crystals were Ca-deficient and the Mn/P molar ratio was 0.048. X-ray diffraction confirmed the presence of single-phase MnHAp, which was aligned vertically to the substrate. Fourier transform infrared spectroscopy indicated the presence of phosphate bands ranging from 500 to 650 and 900 to 1,100 cm^?1, and a hydroxyl band at 3,571 cm^?1, which was characteristic of HAp. Bond strength test revealed that adhesion for the MnHAp coating was more enhanced than that of the HAp coating. Potentiodynamic polarisation test showed that the MnHAp-coated surface exhibited superior corrosion resistance over the HAp single-coated surface. Bioactivity test conducted by immersing the coatings in simulated body fluid showed that MnHAp coating can rapidly induce bone-like apatite nucleation and growth. Osteoblast cellular tests revealed that the MnHAp coating was better at improving the in vitro biocompatibility of Ti than the HAp coating.     

Synthesis and in-depth analysis of highly ordered yttrium doped hydroxyapatite nanorods prepared by hydrothermal method and its mechanical analysis

In this study, undoped and yttrium (Y) doped nanocrystalline hydroxyapatite crystals were synthesized by the hydrothermal method at 180 °C for 24 h. Highly ordered and oriented hydroxyapatite (HAp) nanorods were prepared by yttrium doping and their nanostructure and physical properties were compared with those of undoped HAp rods. FESEM images showed that the doping with Y ions reduced the diameter (from 25 nm to 15 nm) and increased the length (from 95 nm to 115 nm) of the synthesized rods. The aspect ratio of the undoped and Y-doped nanorods were calculated to be 4.303 (SD = 0.0959) and 7.61 (SD = 0.0355), respectively. Specific surface area (SSA) analysis showed that SSA also increased from 66.74 m²/g to 68.57 m²/g with the addition of yttrium. Y-doped HAp nanorod reinforced HMWPE composites displayed the better mechanical performance than those reinforced with pure HAp nanorods. The possible strengthening of nanorods and the increase of SSA due to the reduction in the size of nanorods in the presence of yttrium may have contributed to the strengthening of Y-doped HAp/HMWPE composites.     

Ribbon-like and rod-like hydroxyapatite crystals deposited on titanium surface with electrochemical method

Homogeneous coatings were attained by electrochemical method in electrolytes containing Ca²⁺ and PO₄³⁻ ions with Ca/P ratio being 1.67. SEM observation showed that the hydroxyapatite (HAp,Ca₁₀(PO₄)₆(OH)₂) crystals prepared with higher concentration electrolyte (4 × 10^− 2 M Ca²⁺) are ribbon-like with thickness of nanometer size, a morphology seldom reported previously. In an electrolyte of lower concentration (6 × 10^− 4 M Ca²⁺), the HAp crystals formed are rod-like with a hexagonal cross section and diameter of about 70–80 nm. XRD patterns and IR spectra confirmed that the coatings consist of HAp crystals. TEM micrographs and SAD indicated that the longitude direction for both ribbon-like and rod-like crystal is [002], and the flat surface of the ribbon is (110). HRTEM showed that the ribbon-like crystal is a mixture of HAp and octacalcium phosphate (OCP, Ca₈H₂(PO₄)₆.5H₂O).     

Surface modification of nanophase hydroxyapatite with chitosan

Nanophase hydroxyapatite (HAp) particles were aged in 0–2.5 wt.% chitosan acetate solutions for 30 days to evaluate the influence of chitosan on HAp surface chemistry. The HAp characterization results from Fourier transform infra-red spectroscopy (FTIR), thermal gravimetric analysis (TGA), Carbon–Hydrogen–Nitrogen (CHN) analysis, and BET N₂ adsorption revealed measurable changes in the HAp surface chemistry after aging in the chitosan acetate solutions. The TGA mass loss exhibited by HAp increased from 3.3–6.5 mass% as the chitosan acetate gel concentration increased from 0–2.5 mass%. The CHN analysis revealed an increase in C and H contents with increasing chitosan acetate concentration while the N concentration remained relatively constant (0.30–0.32 mass%). Chitosan interactions with HAp caused an increase in specific surface area from 85 m²/g up to 160 m²/g for HAp aged in 1.5 mass% chitosan acetate solution (HAp[1.5]). Chitosan exhibits strong adsorption interactions with HAp and enhances colloid stability for processing of chitosan/hydroxyapatite nanocomposites.     

Influence of pentavalent dopant addition to polarization and bioactivity of hydroxyapatite

Influence of pentavalent tantalum doping in bulk hydroxyapatite (HAp) ceramics has been investigated for polarizability and bioactivity. Phase analysis from X-ray diffraction measurement indicates that increasing dopant concentration decreased the amount of HAp phase and increased β-TCP and/or α-TCP phases during sintering at 1250 °C in a muffle furnace. Results from thermally stimulated depolarization current (TSDC) measurements showed that doping hindered charge storage ability in HAp ceramics, and doped samples stored fewer charge compared to pure HAp. However, doping enhanced wettability of HAp samples, which was improved further due to polarization. In vitro human osteoblast cell–material interaction study revealed an increase in bioactivity due to dopant addition and polarization compared to pure HAp. This increase in bioactivity was attributed to the increase in wettability due to surface charge and dopant addition.     

Fibrous growth of strontium substituted hydroxyapatite and its drug release

The effect of strontium on the crystallization of helical ribbon of hydroxyapatite (HAp) was investigated by single diffusion technique in silica gel matrix at 27 °C and physiological pH. Fibers of HAp were obtained on addition of strontium. The length of the HAp fibers, were found to decrease as the strontium substitution increases. The presence of strontium ion increased the crystallinity as well as crystallite size of HAp. The strontium substituted HAp (Sr-HAp) has similar stoichiometry to that of biological apatite. Sr-HAp was found to have increased surface area (35%) compared to control. Further, strontium substitution leads to an enhancement of in vitro bioactivity. The cumulative in-vitro amoxicillin drug release in phosphate buffer solution (PBS, pH 7.2) showed a prolonged release profile for Sr-HAp.     

Effect of urea on formation of hydroxyapatite through double-step hydrothermal processing

The effect of urea on the formation of hydroxyapatite (HAp) was studied by employing the double-step hydrothermal processing of a powder mixture of beta-tricalcium phosphate (β-TCP) and dicalcium phosphate dihydrate (DCPD). Co-existence of urea was found to sustain morphology of HAp crystals in the compacts under an initial concentration of 2 mol dm^-3 and less. Homogenous morphology of needle-like crystals was observed on the compacts carbonated owing to decomposition of urea. Carbonate ions (CO₃^2-) was found to be substituted in both the phosphate and hydroxide sites of HAp lattice. The synthesized HAp was calcium deficient, as it had a Ca/P atomic ratio of 1.62 and the phase was identified as calcium deficient hydroxyapatite (CDHA). The release of CO₃^2- ions from urea during the hydrothermal treatment determined the morphology of the CDHA in the compacts. The usage of urea in the morphological control of carbonate-substituted HAp (CHAp) employing the double-step hydrothermal method is established.     

Synthesis and characterization of high purity hydroxyapatite nanorods by hydrothermal technique

High purity hydroxyapatite (HAp) nanorods were synthesized by hydrothermal technique using Ca(NO3)2 x 4H2O and (NH4)2HPO4 as starting materials in a hydrothermal reactor at 150-200 degrees C for 12-24 h with pH6 and pH9.5, respectively. The prepared HAp nanorods were characterized by XRD, FTIR, and TEM techniques. The XRD results confirmed the formation of pure phase of HAp at pH9.5. With increasing temperature and time, the crystallinity of the HAp was increased, showing the hexagonal structure of HAp with the lattice parameter a in a range of 1.144-1.148 nm and c of 0.723-0.724 nm. The crystalline sizes of the powders were found to be 44-85 nm as evaluated by the XRD line broadening technique. The chemical compositions of the HAp nanorods were characterized by FTIR spectroscopies. The peaks of the phosphate carbonate and hydroxyl vibration modes were observed in the FTIR spectra for all the samples. The morphology of the HAp was nanorods of diameter less than 100 nm, as revealed by TEM. Increasing the temperature and time resulted in the transition from polycrystalline to single crystalline phase of the HAp, as clearly confirmed by the analysis of TEM diffraction patterns.     

Distribution of hydroxyapatite crystallite orientation and ultrasonic wave velocity in ring-shaped cortical bone of bovine femur

At the nanoscopic level, bone consists of calcium phosphate, which forms incomplete hydroxyapatite (HAp) crystals. The preferred orientation of the c-axis of HAp crystallites induces anisotropy and inhomogeneity of elastic properties in bone. In this study, the effect of the preferred orientation of HAp crystallites on the spatial distribution of ultrasonic wave velocity was experimentally investigated, considering bone mineral density (BMD) and microstructure. Three ring-shaped cortical bone samples were made from a 36-month-old bovine femur. Longitudinal wave velocity was measured by a conventional ultrasonic pulse system, using self-made polyvinylidene fluoride transducers. The integrated intensity of the (0002) peak obtained using X-ray diffraction was estimated to evaluate the amount of preferred orientation. The velocity distribution pattern was similar to the distribution of integrated intensity of (0002). The effect of the preferred orientation of HAp crystallites on velocity was clearly observed in the plexiform structure, despite the fact that the BMD value was almost independent of the preferred orientation of HAp crystallites. Velocity measurement of cortical bone can reveal information about HAp crystallite orientation.     

Designed synthesis of hydroxyapatite nanostructures: bullet-like single crystal and whiskered hollow ellipsoid

Hydroxyapatite (HAp) nanostructures of whiskered hollow ellipsoid and bullet-like single crystal were synthesized under mild reaction conditions by using a template-free “one pot” synthetic method. Immersing calcium carbonate precursor into ammonium phosphate solution resulted in the HAp phase. Formed HAp crystals were characterized by X-ray diffraction and transmission electron microscopy techniques. The stability and phase composition of calcium carbonate influenced the morphology and crystallinity of HAp. The transformation of the most stable calcite precursor yielded the bullet-like HAp single crystal of 300–600 nm in length, ~40 nm in tip diameter and ~80 to ~100 nm in bottom diameter. The metastable vaterite precursor showed the formation of the whiskered hollow ellipsoid nanostructures composed of HAp nanorods of ~10 nm in diameter. The driving force for the whole transformation process was the difference in solubility of calcium carbonate and HAp. At the same time, Kirkendall effect and Ostwald ripening played important roles in the formation of the different HAp nanostructures.     

Preparation of hydroxyapatite by the hydrolysis of brushite

The conversion of brushite (CaHPO₂ · 2H₂O; DCPD) into hydroxyapatite (HAp) by hydrolysis has been studied by separating the conversion process into two stages, i.e. the structural change of DCPD into HAp (1) and the subsequent compositional increase in Ca/P ratio of the HAp (II). In Reaction I at 40°C, HAp formed most rapidly at around pH 7.5 to 8.0. The complete conversion was observed within 2.5 h at 40°C, 1 h at 60°C and only 5 min at 80°C. The compositions of HAp thus formed were nonstoichiometric and had a Ca/P ratio below 1.60. It was difficult to increase the Ca/P ratio up to the stoichiometric value 1.67, because the adjustment of pH to higher values and/or the addition of Ca²⁺ ions to accelerate the increase in Ca/P ratio, retarded the proceeding of Reaction I. On the other hand, in Reaction II, such pH adjustment and Ca²⁺ addition were remarkably effective in increasing the Ca/P ratio. Consequently, two-stage processing was reasonable and convenient for the preparation of stoichiometric HAp, because it was possible to manage the controlling factors in both Reactions I and II independently. The resulting HAp powders showed a comparatively low crystallinity similar to precipitated HAp and large weight losses (above 6%) on heating, and were composed of dense aggregates of irregular thin microcrystals.     

Investigation of the drawing mechanism of UHMWPE fibers

The influence of draw ratios (DR) of gel-spun ultrahigh molecular weight polyethylene (UHMWPE) fibers on resultant morphologies, tensile, degrees of orientation, and crystal phase transition properties were investigated using wide-angle X-ray diffraction (WAXD), differential scanning calorimetry (DSC), and scanning electron microscopy (SEM). The anisotropic crystalline structure with full concentric circular rings originally shown on the WAXD patterns of the as-prepared and drawn UHMWPE fibers gradually transform into oriented fibers with azimuthal spots on the equator as their DR values increase from 1 to 20, in which their orthorhombic crystals, percentage crystallinity, crystalline orientation, and the birefringence values increase significantly. As evidenced by SEM and WAXD analysis, the chain-folded molecules originally present in kebab crystals of the as-prepared UHMWPE fiber specimens gradually transformed into shish-like crystals with relatively high orientation as their DR values increase from 1 to 20. In contrast, the crystallinity and crystal orientation values of the drawn UHMWPE specimens increase only slightly, as their DR values increase from 20 to 40, wherein both crystallinity values of orthorhombic and monoclinic crystals increase slightly. In fact, barely any oriented kebab but only shish crystals were observed on the surfaces of drawn UHMWPE fiber specimens with DR values higher than 20. The birefringence values increase only slightly with further increasing DR values, while crystallinity and crystal orientation values of the drawn UHMWPE fiber specimens remained relatively unchanged as their DR values increase from 40 to 150. In the meantime, the monoclinic crystals gradually grow at the expense of the orthorhombic form crystals as the DR values of drawn UHMWPE fiber specimens increase from 40 to 150. Possible reasons accounting for these interesting properties found for the drawn UHMWPE fibers with varying draw ratios are proposed in this study.     

Synthesis of oriented hydroxyapatite crystals: Effect of reaction conditions in the presence or absence of silk sericin

The purpose of this study was to investigate the effect of silk sericin (SS) on the morphology and crystallinity of hydroxyapatite (HAp) crystals synthesized at the pH 7.4-12 and 50 °C via a biomimetic method. Using X-ray diffraction (XRD), transmission electron microscope (TEM) and high-resolution transmission electron microscope (HRTEM), it was revealed that a homogeneous assembly could be obtained in the presence of SS, which held a highly ordered microstructure and poor crystallinity. But in the absence of SS, an oriented aggregate could be prepared at 50 °C and pH 10, which held more confused crystal lattice lines. The results proved that the biomimetic structure of HAp could be constructed under the controlled reaction conditions, which may offer a new clue on the understanding of the process of biomineralization.     

Characterization Techniques for Hydroxyapatite Deposited by Plasma Spray on Hip Prosthesis

As part of a characterization research on hydroxyapatite (HAp) plasma deposits for hip prosthesis, crystallinity and residual stresses weredetemiined at the interface Hap'TA6V. A traditional method employed by several laboratories is based on X-ray diffraction by a powder mixture of the investigated HAp sample with a standard of crystallinity Al₂O₃ Four new methods were investigated for determining the crystallinity of HAp sample, two of which are based on x-ray diffraction, one on neutron diffraction and one on the infrared absorption spectrometry. Whereas the three techniques require the use of powders, the neutron technique can be applied also to the intact HAp deposits. All four methods provide reasonable results, not very different one from each other, with a greater accuracy than for the x-ray and IR methods.     

Mechanical and photocatalytic properties of hydroxyapatite/titania nanocomposites prepared by combined high gravity and hydrothermal process

Hydroxyapatite/titania nanocomposites of different ratios have been successfully synthesized by combined high gravity and hydrothermal methods. SEM and TEM observations showed that small spheres of TiO₂, identified as anatase crystals of 10–15 nm, were deposited on HAp rod-like crystals. EDAX analysis confirmed the presence of Ca, P, Ti and O. X-ray diffraction patterns indicated the presence of hydroxyapatite and anatase phase. More number of anatase peaks appeared in the XRD patterns with higher colloidal concentration of TiO₂ in the HAp/TiO₂ compound. Mechanical stability of the HAp/TiO₂ nanocomposites was determined by reinforcing them with high molecular weight polyethylene (HMWPE) and the tensile strength of the samples was analyzed. Photocatalytic activity of the HAp/TiO₂ particles was examined by decomposition of methyl orange (MO). The results showed that photocatalytic properties of HAp/TiO₂ composites are more effective than that of individual HAp and TiO₂ which implied that the HAp improved the photocatalytic activity of well known photocatalyst TiO₂.