Effect of ammonium carbonate on formation of calcium-deficient hydroxyapatite through double-step hydrothermal processing

Double-step hydrothermal processing is a process where powder compacts of calcium phosphates are exposed to vapor of solvent solution, followed by being immersed in the solution. In the present study, we investigated the effects of ammonium carbonate on formation of calcium-deficient hydroxyapatite (CDHA) through double-step hydrothermal processing. The synthesized CDHA has high crystallinity when the solution has relatively low concentration of the ammonium carbonate ranging from 0.01 to 0.25 mol dm⁻³. Carbonate content in the prepared samples were distinctly increased with increasing the concentration of ammonium carbonate to indicate formation of carbonate-containing calcium-deficient hydroxyapatite (CHAp) with low crystallinity. Morphology of the CHAp formed on the compacts varied progressively from rods and rosette-like shape to irregular shape with increase in the initial concentration of the ammonium carbonate in the solution. Application of ammonium carbonate in the double-step hydrothermal processing allows fabrication of irregular-shaped CDHA containing carbonate ions in both phosphate and hydroxide site, with low crystallinity, when the initial concentration of ammonium carbonate was 0.5 mol dm⁻³ and more.     

An electron microscopy study of the formation of hydroxyapatite through sol-gel processing

A study of the stages involved in the formation of hydroxyapatite synthesized by a sol-gel route was performed using scanning and transmission electron microscopic techniques as the primary characterization tools. Scanning electron microscopy enabled examination of the samples of the gel heat treated at various temperatures and for different time periods to determine the morphology and size of grains along with the presence and extent of any porosity in the sample surfaces. Thus, phase development could be studied as a function of heat treatment time and temperature. The gel was prepared using calcium acetate and triethyl phosphate as precursors added in a Ca/P molar ratio of 1.67. Characterization of the samples using transmission electron microscopy allowed a closer examination of the interaction between individual particles and also the detection of features on a much finer scale. Results deduced from these techniques were compared with those obtained from X-ray diffraction and FTIR spectroscopy.     

纳米羟基磷灰石粉体的水热合成

采用Ca(NO3)2·4H2O和(NH4)3PO4·3H2O作为反应前驱物,通过水热合成颗粒尺寸在100nm以下的短棒状或针状HA晶体.X射线衍射(XRD)、透射电镜(TEM)和红外光谱(FTIR)分析讨论水热温度、反应时间、表面活性剂和烧结与物相组成、晶粒尺寸和晶体形貌的关系.实验结果表明升高反应温度和延长反应时间有利于HA的生成;表面活性剂有助于改善粉体的分散性能;烧结能提高晶体的结晶程度,但粉体易团聚,当温度高于800℃时HA发生分解.     

N-Lauroyl sarcosine sodium salt mediated formation of hydroxyapatite microspheres via a hydrothermal route

Dandelion-like hydroxyapatite (HA) microspheres were successfully prepared using Ca(NO₃)₂·4H₂O and (NH₄)₃PO₄·3H₂O as raw materials and N-Lauroyl sarcosine sodium salt (Sar-Na) as template via a hydrothermal route. The chemical composition, structure, morphology and thermal properties of the samples were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscope (FTIR), Scanning electron microscope (SEM) and Thermal gravimetric analysis (TG), respectively. The results demonstrate that, Sar-Na has great impact on the morphology of HA. With increasing the amount of Sar-Na, the morphology of HA varies from nanograins to nanorods, finally grows into dandelion-like microstructure. The obtained dandelion-like HA microspheres about 6 μm in diameter are composed of radially oriented nanorods. Furthermore, the possible formation mechanism of morphology change is also discussed.     

Effect of pH on crystallization of sputtered hydroxyapatite film under hydrothermal conditions at low temperature

Hydroxyapatite (HA) was coated onto titanium substrates using radio frequency sputtering, and the as-sputtered films were placed under hydrothermal conditions in distilled water solutions at pH 5.0, 7.0 and 9.0 and 110°C. The crystallinity, the Ca/P ratio, thickness, and the surface of the films were observed using XRD, EDS, and SEM, respectively.The as-sputtered film was crystallized in distilled water at varying pH after the hydrothermal treatment, and the crystallinity of the film increased with treatment time. The HA crystal size increased with pH. At pH 5.0, β-TCP was produced as well as HA. The Ca/P ratio of the film decreased with increasing treatment, and the ratio at pH 9.0 was 1.74 after 48 h, while in pH 5.0 and 7.0 it was 1.63. After hydrothermal treatment, the film remnant ratio increased with pH, with 75.9, 82.4 and 91.7% of the film remaining after 48 h at pH 5.0, 7.0 and 9.0, respectively.     

Photo-induced formation of hydroxyapatite on TiO2 synthesized by a chemical–hydrothermal treatment

The formation of hydroxyapatite (HAp) on TiO₂ surfaces under continuous ultraviolet (UV) irradiation was investigated. Pure Ti substrates were chemically treated with H₂O₂/HNO₃ at 353 K for 20 min to form a TiO₂ gel layer. The specimens were then hydrothermally treated with an aqueous NH₃ solution in an autoclave at 453 K for 12 h. An adhesive and sufficiently crystallized anatase-type TiO₂ film could be synthesized on the Ti surface. The specimens were immersed in simulated body fluid in darkness or under UV irradiation with a centered wavelength of λ = 365 nm. Under dark conditions, a thin homogeneous HAp film was formed, with just a few spherical clusters of HAp. The UV illumination promoted the formation of HAp clusters, which may be due to the generation of functional Ti–OH or Ti–O groups on the TiO₂ surface. On the other hand, the UV light produced electron-hole pairs in the TiO₂, and the photogenerated holes that migrated to the surface repelled the Ca²⁺ ions in the solution. As a consequence, the UV irradiation suppressed the formation of a HAp thin film.     

水热法合成羟基磷灰石晶须的工艺研究

纳米羟基磷灰石（HAP）增强聚合物基复合材料是替换硬组织的最理想材料，是植入材料的研究重点之一。为了制备与天然骨结构非常相似的复合材料，必须首先制备出性能优良的的纳米HAP粉体。对水热法制备HAP纳米晶须的工艺进行了研究，研究了反应时间、温度、起始反应物的浓度、钙磷比以及反应体系的pH值对合成HAP纳米晶须形貌的影响。用X射线衍射（XRD）、扫描电镜（SEM）和红外光谱（FT-IR）法，对制备的羟基磷灰石进行了表征和分析。结果表明：生成的HAP晶须的长度及长径比随反应时间的延长而增大。温度〈150℃时，得到HAP晶须；温度〉180℃，则得到细小HAP晶体的聚集产物。当反应物的pH=9时，得到的是缺钙型的HAP；当反应物的pH〈4时，产物中出现新相磷酸氢钙；当pH=2时，得到纯的磷酸氢钙。     

Preparation of anatase nanocrystals deposited on hydroxyapatite by hydrothermal treatment

TiO₂-deposited hydroxyapatite (HAp) crystals have been successfully synthesized by hydrothermal treatment of nearly neutral suspension of HAp powders in 10 vol.% of TAS-FINE™ (Titanium amine complex) solutions at 120 or 180 °C. Resultant products were characterized by XRD, SEM–EDX, Vis-Raman and TEM. SEM and TEM observation showed that small rodlike TiO₂, identified as anatase crystals of 100–150 nm in length, were deposited on HAp plates/crystals. The anatase crystals seem to be formed by heterogeneous nucleation on the surfaces of HAp crystals. A higher temperature and a longer reaction period promoted the cystallization of anatase TiO₂.     

Microwave sintering improves the mechanical properties of biphasic calcium phosphates from hydroxyapatite microspheres produced from hydrothermal processing

Starting from two microspherical agglomerated HAP powders, porous biphasic HAP/TCP bioceramics were obtained by microwave sintering. During the sintering the HAP powders turned into biphasic mixtures, whereby HAP was the dominant crystalline phase in the case of the sample with the higher Ca/P ratio (HAP1) while α-TCP was the dominant crystalline phase in the sample with lower Ca/P ratio (HAP2). The porous microstructures of the obtained bioceramics were characterized by spherical intra-agglomerate pores and shapeless inter-agglomerate pores. The fracture toughness of the HAP1 and HAP2 samples microwave sintered at 1200 °C for 15 min were 1.25 MPa m^1/2. The phase composition of the obtained bioceramics only had a minor effect on the indentation fracture toughness compared to a unique microstructure consisting of spherical intra-agglomerate pores with strong bonds between the spherical agglomerates. Cold isostatic pressing at 400 MPa before microwave sintering led to an increase in the fracture toughness of the biphasic HAP/TCP bioceramics to 1.35 MPa m^1/2.     

Effect of collagen fibril formation on bioresorbability of hydroxyapatite/collagen composites

Porous hydroxyapatite/collagen (HAp/Col) composite is a promising biomaterial and a scaffold for bone tissue engineering. The effect of fibril formation of Col in the porous composite on bioresorbability and mechanical strength was investigated. The fibril formation, in mixing a self-organized HAp/Col nanocomposite and sodium phosphate buffer at a neutral condition, occurred during incubation at 37 °C, resulting in gelation of the mixture. The porous composites with and without the incubation were obtained by freeze-drying technique, in which macroscopic open pores were formed. The compressive strength of the porous composite with the incubation (34.1 ± 1.6 kPa) was significantly higher than that without the incubation (28.0 ± 3.3 kPa) due to the fibril formation of Col. The implantations of the porous composites treated with a dehydrothermal treatment in bone holes revealed that bioresorption was clearly depended on the fibril formation. The bioresorbability in vivo was almost matched to the in vitro test using enzymatic reaction of collagenase.     

Preparation of amino-acid-regulated hydroxyapatite particles by hydrothermal method

The hydroxyapatite nanorods (about 80 nm in length and 15 nm in width) with uniform size were achieved by hydrothermal method at 100 °C and pH 10 in the presence of alanine and glutamic acid. A special instillment order was used and the prepared powders were characterized for phase composition by X-ray diffraction and Fourier Transform infrared spectroscopy. The size and morphology of HAP nanoparticles were studied by Transmission electron microscopy. The characterization showed that the amino acid could induce the synthesis of hydroxyapatite nanoparticle and control HAP crystal growth when HAP crystal was formed. An instable monetite phase (CaPO₃OH) was found in the progress of ACP transforming to HAP.     

Tuning optical properties of poly(3-hexylthiophene) nanoparticles through hydrothermal processing

Abstract

Poly(3-hexylthiophene) (P3HT) nanoparticles (NPs) were prepared by a reprecipitation method. Hydrothermal processing applied external pressure to the pristine P3HT NPs at temperatures ranging from 60 to 150 °C. Optical absorption and photoluminescence (PL) spectra for the hydrothermally treated P3HT NPs varied markedly with the processing temperature. With increasing treatment temperature, the absorption peak broadened and the peak position shifted from 510 to 623 nm; moreover, the intensity ratio of the 0–1 to 0–0 emission varied. These changes were caused by interactions between the P3HT main chains and alkyl side groups and conformational modifications induced by the high pressure during the hydrothermal process. The evolution of the optical absorption spectra of the P3HT NPs during the hydrothermal processing was strongly correlated with the variation of PL excitation spectra and with the PL emission spectra of a single NP.     

Tuning optical properties of poly(3-hexylthiophene) nanoparticles through hydrothermal processing

Poly(3-hexylthiophene) (P3HT) nanoparticles (NPs) were prepared by a reprecipitation method. Hydrothermal processing applied external pressure to the pristine P3HT NPs at temperatures ranging from 60 to 150 °C. Optical absorption and photoluminescence (PL) spectra for the hydrothermally treated P3HT NPs varied markedly with the processing temperature. With increasing treatment temperature, the absorption peak broadened and the peak position shifted from 510 to 623 nm; moreover, the intensity ratio of the 0–1 to 0–0 emission varied. These changes were caused by interactions between the P3HT main chains and alkyl side groups and conformational modifications induced by the high pressure during the hydrothermal process. The evolution of the optical absorption spectra of the P3HT NPs during the hydrothermal processing was strongly correlated with the variation of PL excitation spectra and with the PL emission spectra of a single NP.     

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.     

Structural characterization of zinc-substituted hydroxyapatite prepared by hydrothermal method

Zinc-substituted hydroxyapatite (Zn-HA) powders were prepared by hydrothermal method using Ca(NO₃)₂, (NH₄)₃PO₄ and Zn(NO₃)₂ as reagents. X-ray fluorescence spectroscopy (XRF), X-ray diffraction (XRD), fourier transform infrared spectroscopy (FT-IR) and transmission electron microscopy (TEM) were used to characterize the crystalline phase, microstructure, chemical composition, morphology and thermal stability of Zn-HA. The results show that the substitution content of zinc (Zn) in Zn-HA powders prepared in NaOH solution is higher than that prepared in NH₃ solution, and is lower than that of the corresponding amount of starting materials. The substitution of the Zn ion for calcium ion causes a lower crystallinity of Zn-HA and changes the lattice parameters of Zn-HA, since the ionic radius is smaller in Zn²⁺ (0.074 nm) than in Ca²⁺ (0.099 nm). Furthermore, the substitution of the Zn ions restrains the growth of Zn-HA crystal and decreases the thermal stability of Zn-HA. Zn-HA powder prepared in NH₃ solution starts to decompose at 800 °C when the Zn fraction increases to 15 mol%, while that prepared in NaOH solution start to decompose at 5 mol% Zn. The substitution content of Zn significantly influences the thermal stability, microstructure and morphology of Zn-HA.     

Preparation of thermally stable nanocrystalline hydroxyapatite by hydrothermal method

Thermally stable hydroxyapatite (HAp) was synthesized by hydrothermal method in the presence of malic acid. X-ray diffraction (XRD), Fourier transform infra-red spectroscopy (FT-IR), Raman spectroscopy, scanning electron microscopy (SEM), differential thermal analysis (DTA), thermogravimetric analysis (TGA) was done on the synthesized powders. These analyses confirmed the sample to be free from impurities and other phases of calcium phosphates, and were of rhombus morphology along with nanosized particles. IR and Raman analyses indicated the adsorption of malic acid on HAp. Thermal stability of the synthesized HAp was confirmed by DTA and TGA. The synthesized powders were thermally stable upto 1,400 degrees C and showed no phase change. The proposed method might be useful for producing thermally stable HAp which is a necessity for high temperature coating applications.     

Growth and characterization of hydroxyapatite crystals by hydrothermal method

Hydroxyapatite crystals were grown by hydrothermal method using dicalcium phosphate dihydrate crystals as a starting material. The grown crystals were found to be free from carbonate inclusion. Two distinct morphologies were obtained by following two different growth methods. Controlled slow growth process and rapid growth process results in hexagonal and whisker like morphologies.     

Synthesis and properties of bio-waste-based hydroxyapatite via hydrothermal process

In this study, a facile hydrothermal method is applied to produce hydroxyapatite (HA) particles using egg shells as calcium precursors and fruit waste extracts (banana peel) as biomolecular templates at 150 °C for a reaction time period of 12 hours (h) and 24 hours. The sintering of the green samples of hydroxyapatite were conducted at 1250 °C in air for 2 h. The results showed that pectin extracted from banana peel extracts assisted in regulating crystal growth to obtain homogeneous hydroxyapatite powder, with higher purity observed for 24 h hydrothermal reaction time. Fourier-transform infrared spectroscopy (FTIR) spectra revealed the presences of phosphate (PO₄³⁻) and hydroxyl (OH⁻) groups in the powders. A relative density of 89.6 % was achieved for sintered hydroxyapatite compacts produced via hydrothermal method for 24 h. The sintered body was characterized by having high Vickers hardness of 5.35 GPa and good fracture toughness of 1.23 MPa√m, suitable for biomedical application.     

Sol–gel processing of hydroxyapatite

Hydroxyapatite, a calcium phosphate-based compound with numerous applications in the biological field was synthesized using the sol–gel processing route. The formation of hydroxyapatite and other compounds during the heat-treatment cycle were identified and characterized using thermal analyses and X-ray diffraction together with infrared and Raman spectroscopy. The influence of the addition of various organic alcohols (R–OH, R=CH3–, C2H5– and C3H8–) on the reaction results was studied. © 1998 Kluwer Academic Publishers