碳酸羟基磷灰石粉体的热处理研究

以沉淀法制备了碳酸根质量分数为8.5%的碳酸羟基磷灰石(carbonated hydroxyapatite, CHA),研究热处理工艺参数对其热稳定性和碳酸根替代的影响.通过XRD、FTIR和C/S碳硫仪等测试手段表征了CHA粉体的特性.结果表明,随热处理温度的升高,碳酸根的含量减少,而碳酸根的A型替代与B型替代之比则呈现先降后升的趋势.与湿N2气氛相比,湿CO2气氛能减少碳酸根的损失,提高热稳定性.与干CO2气氛相比,湿CO2气氛有利于生成以B型替代为主的CHA.热处理过程中CO2分压越高,碳酸根的损失量越少,热稳定性越好.     

Hydrothermal synthesis and nanostructure of carbonated calcium hydroxyapatite

The influence of precursor concentration, pressure, temperature and time of hydrothermal synthesis on the development of calcium hydroxyapatite structure has been analyzed. The obtained results show that it is possible to adjust the conditions of hydrothermal synthesis from solutions of relatively high concentrations to obtain calcium hydroxyapatite nanopowders of well-defined structure. The relationship between the synthesis and the lattice parameters, as well as the crystallite size and the microstructure of synthesized hydroxyapatite has been established. The synthesized powders are preferentially carbonated hydroxyapatite of the B type in the form of agglomerates that accommodate two-modal size pores of 1.5–10 and 50–200 nm. The structure of calcium hydroxyapatite particles consists of crystallites 8–22 nm in size, bound within prime particles, which size is between 10 and 63 nm, that in turn form bigger agglomerates 200 nm in size, which further cluster building up agglomerates 5–20 μm in size.     

Thermal stability of porous A-type carbonated hydroxyapatite spheres

Porous A-type carbonated hydroxyapatite (CHAp) spheres were synthesized in the high-pressure hydrothermal system by the template-directed method. The thermal stability of porous A-type CHAp spheres was first studied via calcining in the wide temperature range from 393 K up to 1173 K, analyzed by FT-IR, XRD and SEM. The results showed that the decomposition of porous A-type CHAp spheres went through two stages, owing to the release of the carbonate from the OH⁻ channel and the collapse of apatite-type structure above 973 K, consecutively. The nanoparticles in situ replaced the flakelets of porous CHAp spheres and packed closely into new regular porous Ca₃(PO₄)₂ spheres.     

Fabrication of mesoporous carbonated hydroxyapatite microspheres by hydrothermal method

Mesoporous carbonated hydroxyapatite microspheres (MCHMs) have been converted from calcium carbonate microspheres (CCMs) by hydrothermal method. After soaking the CCMs in disodium hydrogen phosphate solutions, carbonated hydroxyapatite nanoparticles are formed via a dissolution-precipitation reaction. X-ray diffraction (XRD) and Fourier-transform infrared spectroscopy (FTIR) reveal that the as-obtained samples are calcium deficient hydroxyapatite with B-type CO₃²⁻ substitution. The transmission electron microscopy (TEM) indicates that the MCHMs are composed of many nanoparticles within the whole microspheres. These nanoparticles aggregate to form mesopores with a pore size of 4.5-14.0 nm among them. The formation mechanism of MHAMs has been discussed.     

Template-directed one-step synthesis of flowerlike porous carbonated hydroxyapatite spheres

Flowerlike porous carbonated hydroxyapatite (CHAp) spheres were first synthesized by the template-directed self-assembly method in a high-pressure system. The product was characterized via Fourier transform infrared (FT-IR), X-ray diffraction (XRD) and scanning electron microscopy (SEM). The results showed that flowerlike porous CHAp spheres were obtained, that the average granularity of porous CHAp spheres is about 20 μm, that the average aperture is about 1 μm, and that the average thickness of flakes is about 50 nm. Great amounts of OH channels, high special surface area and regular spherical shape imply potential applications.     

Preparation and cellular response of porous A-type carbonated hydroxyapatite nanoceramics

Microwave sintering using the activated carbon as embedding material was applied in preparation of porous A-type carbonated hydroxyapatite ceramics with nano(nCHA) and submicron (mCHA) structure. By examining the linear shrinkages and the compressive strengths of samples at different temperatures, a suitable microwave sintering temperature was achieved. The microwave sintering method was successfully used to prepare A-type CHA with nano or submicron structure, and the mechanism of the formation of A-type carbonate groups was discussed also. Compared with the samples prepared by the conventional sintering method (mHA), the nCHA bioceramics synthesized by the microwave sintering approach had smaller grain size and more uniform microstructure, and showed a compressive strength similar to the conventional samples. In vitro dissolution test proved that nCHA exhibits better degradation property in comparison to pure HA. Rat osteoblasts were cultured with nCHA, mCHA and mHA to evaluate their biocompatibility, and nCHA showed significant enhancement of cells in attachment, proliferation and differentiation. In conclusion, carbonate groups can be easily introduced to HA crystal structure using the activated carbon as embedding material, and microwave sintering is an effective and simple method in preparing A-type CHA with a nanostructure. Results from this in vitro biological study suggest that porous A-type carbonated hydroxyapatite nanoceramics may be a much better candidate for clinical use in terms of bioactivity.     

Bactericidal property and biocompatibility of gentamicin-loaded mesoporous carbonated hydroxyapatite microspheres

Implant-associated infection is a serious problem in orthopaedic surgery. One of the most effective ways is to introduce a controlled antibiotics delivery system into the bone filling materials, achieving sustained release of antibiotics in the local sites of bone defects. In the present work, mesoporous carbonated hydroxyapatite microspheres (MCHMs) loaded with gentamicin have been fabricated according to the following stages: (i) the preparation of the MCHMs by hydrothermal method using calcium carbonate microspheres as sacrificial templates, and (ii) loading gentamicin into the MCHMs. The MCHMs exhibit the 3D hierarchical nanostructures constructed by nanoplates as building blocks with mesopores and macropores, which make them have the higher drug loading efficiency of 70–75% than the conventional hydroxyapatite particles (HAPs) of 20–25%. The gentamicin-loaded MCHMs display the sustained drug release property, and the controlled release of gentamicin can minimize significantly bacterial adhesion and prevent biofilm formation against S. epidermidis. The biocompatibility tests by using human bone marrow stromal cells (hBMSCs) as cell models indicate that the gentamicin-loaded MCHMs have as excellent biocompatibility as the HAPs, and the dose of the released gentamicin from the MCHMs has no toxic effects on the hBMSCs. Hence, the gentamicin-loaded MCHMs can be served as a simple, non-toxic and controlled drug delivery system to treat bone infections.     

Carbonate release from carbonated hydroxyapatite in the wide temperature rage

Synthetic carbonated apatite ceramics are considered as promising alternative to auto- and allograft materials for bone substitute. The aim of this study was to investigate the thermal stability of an AB-type carbonated apatite in the wide temperature range. The data on the thermal stability have to allow the conditions of the sintering of the ceramics to be controlled. Initial carbonated apatite powders were prepared by interaction between calcium oxide and ammonium hydrogen phosphate with addition of ammonium carbonate. Decomposition process was monitored by infra red spectroscopy, weight loss and X-ray diffraction of solid, and by infra red analysis of condensed gas phase resulted from the thermal decomposition of the sample in equilibrium conditions. Features of carbon monoxide and carbon dioxide release were revealed. The synthesized AB-type carbonated apatite is started to decompose at about 400°C releasing mainly carbon dioxide, but retained some carbonate groups and apatite structure at the temperature 1100°C useful to prepare porous carbonate-apatite ceramics intended for bone tissue engineering scaffolds.     

Thermal impurity reactions and structural changes in slightly carbonated hydroxyapatite

Lattice and surface impurity reactions and structural changes induced by them in slightly carbonated hydroxyapatite (SCHA) treated at 25–1100oC were comprehensively studied. The SCHA was processed by a conventional wet synthesis at a high possible temperature (96oC) using ammonium containing parent reagents. IR-spectroscopy, XRD, TG-DTA technique and mass spectrometric thermal analysis (MSTA) were employed for characterization of the samples. with in cationic- and (A- and B-positions) with in anionic sites, and H₂O, () , N _x H _y on the surface of particles were found and considered as impurity groups. Complicated changes in lattice constants of the SCHA stepwise annealed in air (for 2 h) were revealed; the changes were associated with reactions of the impurity groups. Filling the hexed sites with hydroxyl ions above 500oC was shown to happen partly due to lattice reactions but was mainly owing to hydrolysis of the SCHA by water molecules in air. Decomposition of groups proceeded through both thermal destruction and reactions with some of the impurity ions. The decarbonation in A-sites occurred at much lower temperatures (450–600oC) than in B-sites (700–950oC) and was first revealed to happen in two stages: due to an impurity reaction around 500oC, and then through thermal destruction at 570oC. A redistribution of ions, decreasing in amount on the whole, was observed upon annealing above 500oC. To avoid possible erroneous conclusions from TG-data, a sensitive method was shown to be required for monitoring gaseous decomposition products (such as the MSTA in this study), in case several impurity groups were present in a SCHA.     

Faster synthesis of A-type carbonated hydroxyapatite powders prepared by high-temperature reaction

Synthesis of A-type carbonated hydroxyapatite (CHA) materials has typically involved heating of a hydroxyapatite composition for 24 h or greater. In this study, a hydroxyapatite powder was heated at 800, 900 or 1000 °C for 1, 8 or 16 h in dry CO₂. Samples heated for 8 and 16 h at 900/1000 °C were fully-carbonated A-type CHAs. After only one hour at 1000 °C, the carbonate content approached 95% of the theoretical maximum. Preparing compositions with more than 95% of the theoretical maximum with reduced thermal energy (1000 °C for 1 h, or 900 °C for 8 h) results in powders with higher surface areas and a reduced level of sintering, compared to powders prepared with typical thermal treatments reported for A-type CHAs, such as 1000 °C for 16 h. As far as the authors are aware, these are the shortest heating times reported for the preparation of fully-carbonated A-type CHAs which is significant for future applications of such powders, particularly in applications beyond medical devices such as chromatography, remediation and carbon capture.     

Characterization of hydroxyapatite and carbonated apatite by photo acoustic FTIR spectroscopy

An understanding of the interfacial relationship between a bioceramic implant and the adjacent bonet issue is facilitated by precise characterization of the associated structures. The structure of different commercial synthetic hydroxyapatite powders and a novel carbonated apatite have been studied with photo-acoustic (PAS) Fourier transform infrared (FTIR) spectroscopy. The PAS technique is an ideal method for analysing biomaterials, as materials can be analysed without the need to reduce the particle size or to dilute with KBr. Spectra from carbonated apatite appear to be different from those of commercial hydroxyapatite powders, with the main difference lying in the carbonate and phosphate ratio. Commercial hydroxyapatite powders from different sources have also been analysed and compared.     

Synthesis of polyaniline/Ag composite nanospheres through UV rays irradiation method

In this paper, a novel morphology of polyaniline (PANI)/Ag composite nanospheres was obtained through UV rays irradiation method. The structure and morphology of the product were characterized by Fourier transform infrared (FT-IR) spectrum, X-ray diffraction (XRD) pattern, Scanning electron micrograph (SEM) and Transmission electron microscopy (TEM) images, energy-dispersive X-ray (EDAX) analysis, and electron diffraction (ED), respectively. The results showed that the diameters of the PANI nanospheres and the Ag nanofilaments were 10–60 nm and 2–5 nm, respectively. UV rays played an important role for forming PANI nanospheres underpinned by Ag nanofilaments. A potential formation mechanism of PANI nanospheres underpinned by Ag nanofilaments was investigated.     

Preparation and structure of carbonated calcium hydroxyapatite substituted with heavy rare earth ions

Calcium hydroxyapatite (CaHap) particles substituted five types of heavy rare earth ions (Ln: Y³⁺, Gd³⁺, Dy³⁺, Er³⁺ and Yb³⁺) were synthesized using a precipitation method and characterized using various means. These Ln ions strongly affected the crystal phases and the structures of the products. With increasing Ln/(Ln + Ca) in the starting solution ([X_Ln]), the length and the crystallinity of the particles first increased and then decreased. The rare earth metal-calcium hydroxyapatite (LnCaHap) solid solution particles were obtained at [X_Y] ≤ 0.10 for substituting Y system and at [X_Ln] ≤ 0.01–0.03 for substituting the other Ln systems. LnPO₄ was mixed with LnCaHap at higher [X_Ln] for all Ln systems. A series of yttrium-calcium hydroxyapatite (YCaHap) solid solutions with [X_Y] = 0–0.10 were investigated using XRD, TEM, ICP-AES, IR and TG–DTA in detail.     

Fabrication of mesoporous carbonated hydroxyapatite/carbon nanotube composite coatings by microwave irradiation method

Carbonated hydroxyapatite/carbon nanotube composite coatings (MHCs) with mesoporous structures were fabricated by electrophoretic deposition of nacre powders and carbon nanotubes on Ti6Al4V substrates followed by treatment with a phosphate buffer solution (PBS) by microwave irradiation method. The carbon nanotubes are dispersed uniformly on the whole MHCs. The conversion mechanism of the crack-free nacre/carbonate nanotube composite coatings (NCCs) to MHCs is a dissolution-precipitation reaction. After soaking in PBS, calcium ions are released from the nacre powders and react with phosphate ions to form carbonated hydroxyapatite nanoparticles. These nanoparticles aggregate to form mesopores with the pore sizes of ~ 3.9 nm among them. Simulated body fluid (SBF) immersion tests reveal that MHCs have a good in vitro bioactivity.     

Synthesis of sealed sponge ZnO nanospheres through a novel NH(3)-evaporation method

Sealed sponge ZnO nanospheres are prepared through a novel NH(3)-evaporation method. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM) and N(2) physisorption analysis show that the samples obtained are ZnO nanospheres with hexagonal wurtzite structure. The particle size is in the range 80-130?nm and the pores inside are estimated to be in the range 2-35?nm. During the preparation process, the carboxyls derived from the polyacrylamide hydrolyzation tend to attach to the particle surface and bring about the interaction between particles by hydrogen bonding. Results show that the polyacrylamide and alcohol are crucial to the formation of the sealed sponge ZnO, by forming a diffusion layer around the particle. The formation mechanism is considered to be controlled by the diffusion of Zn(2+) through the diffusion layer, and the mass transmission between the initial particles.     

Synthesis of nano-sized hydroxyapatite powders through solution combustion route under different reaction conditions

Calcium hydroxyapatite, Ca₁₀(PO₄)₆(OH)₂ (HAp) was synthesized by combustion in the aqueous system containing calcium nitrate-diammonium hydrogen orthophosphate with urea and glycine as fuels. These ceramics are important materials for biomedical applications. Thermo-gravimetric and differential thermal analysis were employed to understand the nature of synthesis process during combustion. Effects of different process parameters namely, nature of fuel (urea and glycine), fuel to oxidizer ratio (0.6-4.0) and initial furnace temperature (300-700 °C) on the combustion behavior as well as physical properties of as-formed powders were investigated. A series of combustion reactions were carried out to optimize the reaction parameters for synthesis of nano-sized HAp powders. The combustion temperature (T_f) for the oxidant and fuels were calculated to be 896 °C and 1035 °C for the stoichiometric system of urea and glycine respectively. The stoichiometric glycine-calcium nitrate produced higher flame temperature (both calculated and measured) and powder with lower specific surface area (8.75 m²/g) compared to the stoichiometric urea-calcium nitrate system (10.50 m²/g). Fuel excess combustion in both glycine and urea produced powders with higher surface area. Nanocrystalline HAp powder could be synthesized in situ with a large span of fuel to oxidizer ratio (φ) in case of urea system (0.8 < φ < 4) and (0.6 < φ < 1.5) for the glycine system. Calcium hydroxyapatite particles having diameters ranging between 20 nm and 120 nm could be successfully synthesized through optimized process variable.     

Hollow carbonated hydroxyapatite microspheres with mesoporous structure: Hydrothermal fabrication and drug delivery property

Hollow carbonated hydroxyapatite microspheres with mesoporous structure (HCHAs) have been fabricated by using calcium carbonated microspheres as sacrificial templates according to the following routes: (i) the in situ deposit of carbonated hydroxyapatite on the surfaces of CaCO₃ microspheres by hydrothermal method and (ii) the removal of CaCO₃ by chemical etching. The HCHAs consist of a hollow core and a mesoporous shell. Interestingly, the shell of the microspheres is constructed by carbonated hydroxyapatite nanoplates as building blocks. Moreover, these nanoplates are composed of many smaller nanoparticles with different crystal orientations, and the mesopores exist among these nanoparticles. The HCHAs exhibit the high drug-loading capacity and sustained drug release property, suggesting that the hierarchically porous microspheres have great potentials for bone-implantable drug-delivery applications.     

Fabrication of an alternative regenerated silk fibroin nanofiber and carbonated hydroxyapatite multilayered composite via layer-by-layer

A novel multilayered composite consisting of regenerated silk fibroin (RSF) nanofiber and carbonated hydroxyapatite (CHA) was fabricated with the combination of electrospinning of RSF aqueous solution and soaking in CaCl₂ and Na₂HPO₄ solutions alternately. The chemical composition and morphologies of RSF/CHA composite were characterized by FT-IR, XRD, TGA, EDX, and SEM. The results showed that such an organic/inorganic composite had an alternate layered structure, while the CHA mineral partly penetrated into the porous RSF mats, which was similar to the structure of natural nacre. By tuning the CHA deposition procedure and RSF electrospinning condition independently, the thickness of each layer of CHA and RSF, as well as the layer numbers of composite, could be easily regulated. For example, the average thickness of CHA layers with 5 and 10 mineralization cycles were 1.63 and 3.19 μm, while 9.03 and 30.12 μm of porous RSF nanofiber layers could be formed with 7 and 24 h electrospinning process, respectively. Thus, it may provide an efficient and general approach to produce a series of inorganic/organic multilayered biomaterials for biomedical engineering.     

Formation of the carbonated hydroxyapatite film on Ti-30Zr-5Al-3V bio-alloy

The Ti-30Zr-5Al-3V titanium alloy has an ultra-low Young's modulus. So, it promises great application potential as a hard-tissue implanted biomaterial. However, its surface performances need to be improved before clinical applications. In this work, a carbonated hydroxyapatite film is deposited on the surface of Ti-30Zr-5Al-3V bio-alloy using electrochemical methods. Microstructure, film-substrate adhesion, and electrochemical corrosion behavior of carbonated hydroxyapatite deposited specimens in Ringer's solution are investigated. A homogeneous, dense, and fully covered carbonated hydroxyapatite film forms on the surface after depositing at 3 V, 90 °C for 120 minutes. The formation mechanism of the carbonated hydroxyapatite film on the micro-nano structure surface is revealed. The corrosion performance of carbonated hydroxyapatite deposited specimens in Ringer's solution is evaluated by using potentiodynamic polarization curves. The carbonated hydroxyapatite deposition obviously enhanced the corrosion resistance of the Ti-30Zr-5Al-3V bio-alloy.     

Synthesis and characterization of hydroxyapatite, fluoride-substituted hydroxyapatite and fluorapatite

Powders of hydroxyapatite (HA), partially fluoride-substituted hydroxyapatite (fHA), and fluorapatite (FA) were synthesized in house using optimum methods to achieve relatively pure powders. These powders were assessed by the commonly used bulk techniques of X-ray diffraction (XRD), Fourier transform infra-red (FTIR) and FT-Raman spectroscopies, inductively coupled plasma atomic emission spectroscopy (ICP-AES), and F-selective electrode. In addition, the current study has employed transmission electron microscopy (TEM), involving morphological observation, electron diffraction and energy-dispersive X-ray spectrometry (EDX), as an effective analytical technique to evaluate the powders at a microscopic level. The HA and fHA particles were elongated platelets about 20×60 nm in size, while FA particles were over twice this size. Calcination of the HA and fHA powders at 1000 °C for 1 h resulted in increased grain size and crystallinity. The calcined fHA material appeared to possess a crystal structure intermediate between HA and FA, as evidenced by the (3 0 0) peak shift in XRD, as well as by the position of the hydroxyl bands in the FTIR spectra. This result was consistent with electron diffraction of individual particles. Small levels of impurities in some of the powders were identified by EDX and electron diffraction, and the carbonate content was detected by FTIR. The use of TEM in conjunction with the bulk techniques has allowed a more thorough assessment of the apatites, and has enabled the constituents in these closely related apatite powders to be identified.