Hydrothermal preparation of tailored hydroxyapatite

Hydrothermal vapor treatment method was applied for preparation of ceramic biomaterials. Hydroxyapatite (Ca₁₀(PO₄)₆(OH)₂; HA) ceramics prepared by sintering with random crystal surface have already been used as bone-repairing materials which can directly bond to natural bones. If materials of HA could have the tailored specific crystal surface, they should have the advantage of adsorptive activity and osteoconductivity in comparison with the sintered HA. In the present study, porous HA sheets of about 50 μm to 1 mm in thickness and porous HA granules of about 50 μm to 1 mm in size with tailored crystal surface were prepared by the hydrothermal vapor exposure method at temperatures below 200°C. Porous sheets and porous granules of HA with controlled crystal surface should be suitable for scaffold of cultured bone, for bone graft material and for drug delivery system (DDS).     

Abnormal polymorph conversion of calcium carbonate from calcite to vaterite

Inspired by mineralization in biological organisms, the production of higher ordered CaCO₃ crystals modified by surfactants has received much attention. Normal micelles formed by anionic surfactant, sodium bis-2-ethylhexyl-sulfosuccinate (aerosol OT, AOT), was used as a template to direct the growth of CaCO₃ crystals in the present work. When the concentration of the AOT increased from 0.5 to 5.0 mM, the polymorph of CaCO₃ crystals changed from almost pure aragonite to almost pure vaterite at 150 °C. In the meantime, various morphologies of vaterite were obtained, such as astral and hexagonal structures. Based on the time-resolved experiments, we suggested that AOT micelles induced the formation of these structures. And the micelles were wrapped in the hexagonal structures, and dissolved in the aqueous solution with increase of the experimental time. Thus, hollow shells were produced. Abnormal polymorph transformation of CaCO₃ crystals from the calcite to the vaterite was found. These effects of AOT on polymorph and morphology of CaCO₃ crystals have not been reported as far as we know.     

Hydrothermal growth of calcite from alkali carbonate solutions

Optically clear rhombohedral crystals of calcite can be grown from 5m solutions of K₂CO₃ and Rb₂CO₃ in the range of 400–600°C and pressures of 1–2 kbar. Phase equilibria for both systems were determined. Growth from K₂CO₃ must be carried out above the decomposition pressure of the double salt K₂CO₃ · CaCO₃ of approximately 1 kbar. Growth from Rb₂CO₃ does not have this limitation.     

Hydrothermal synthesis of hydroxyapatite from natural source

Dicalcium phosphate dihydrate (DCPD) and anhydrous dicalcium phosphate (DCPA) extracted from a by-product in a manufacture of gelatin from bovine bone are used as starting materials for the hydrothermal synthesis of hydroxyapatite (HA) at temperatures of 160 and 200 °C under vapor pressures of 1 and 2 MPa, respectively. The suspension of DCPA with water gives a mixture of DCPA and HA as product but after adjusting the Ca/P molar ratio to 1.50 and 1.67 by addition of Ca(OH)₂, a single phase of HA with needle-like crystals is obtained. DCPA whiskers are produced in the suspension of DCPD with water but, on addition of Ca(OH)₂, the product obtained is again, a mixture of DCPA and HA. The coexistence of DCPA and HA is observed not only in the acidic region at pH 4.6 which is close to the known quasi-invariant point but also in the basic region at pH 12.3. Without addition of Ca(OH)₂ to the system, the complete conversion of DCPA or DCPD to HA is not possible.     

纳米羟基磷灰石的水热合成

采用CaCO3 和CaHPO4·2H2 O的混合物为前驱物 ,在蒸压釜内经不同温度和时间的水热处理获得了晶粒完整、粒度在 10 0nm以下的HA粉体。借助X射线衍射 (XRD)、扫描电镜(SEM )及红外光谱 (FTIR)对HA的晶相组成、粒度、形貌及化学组成进行分析。研究结果表明 :随水热温度的提高及时间的延长 ,晶体发育越完整 ,粒度越大 ;当温度为 2 0 0℃ ,反应时间为8h时 ,HA为端面尺寸约 60nm的柱状或针状晶体 ,有少量CO3 2 -进入磷灰石结构。这种纳米羟基磷灰石晶体在形态、结构和组成上与人骨相似 ,更有利于作为生物医用材料应用     

Hydrothermal synthesis and biocompatibility of hydroxyapatite nanorods

A facile micelle precursor having cyclohexane/ethanol/cetyl trimethyl ammonium bromide/aqueous phase was treated hydrothermally to form nanohydroxyapatite. The synthesized products were characterized by means of X-ray diffraction, thermogravimetric analysis, transmission electron microscopy and energy-dispersive X-ray spectroscopy. The results showed that the synthesized products display the crystalline structure and vibration modes of hydroxyapatite. Transmission electron micrograph revealed that nanohydroxyapatite exhibits elongated rod morphology with large aspect ratios. Nanohydroxyapatite prepared from a surfactant of 1.25 millimole showed good thermal stability at 1000 degrees C on the basis of thermogravimetric analysis. Simulated body fluid immersion test indicated that an apatite layer can be readily deposited on the nanohydroxyapatite surface demonstrating its good bio-resorbability.     

Pulsed cathodoluminescence of calcite crystals of various origins

We have studied the luminescence of calcites from phlogopite-calcite veins, marbles, leucogranites, apatite-calcite ores, and carbonatites in the spectral range 300–800 nm under excitation with nanosecond electron pulses at an electron beam current density of ∼10 A/cm². All of the calcite varieties have a fast emission component, with a broad spectrum in the near-UV and visible spectral regions, whose decay time is comparable to the excitation pulse duration, and a slow emission component, with a peak-emission wavelength of 610–620 nm and decay time of tens of milliseconds. The spectral composition of the emission depends on the nature of the calcite sample. We analyze the evolution of the spectrum after excitation and discuss the luminescence excitation mechanisms and the nature of the emission centers.     

Convenient conversion of calcium carbonate to hydroxyapatite at ambient pressure

The synthesis of hydroxyapatite is described starting from calcium carbonate and monoammoniumphosphate in stoichiometric amounts. The novel aspect concerns the reaction conditions which are simple mixing in water at ambient pressure and 60 °C. The calcium carbonate solid phase slowly evolves CO₂ gas and buffers the solution at a pH value of 8.05 where hydroxyapatite precipitates. The main advantages of this reaction pathway are the absence of nitrate salts, the availability of the starting materials and the purity of the final product.     

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.     

Hydrothermal synthesis of magnetite crystals: From sheet to pseudo-octahedron

In this paper, we developed a hydrothermal method to fabricate sheet-like and pseudo-octahedral magnetite crystals. X-ray diffraction (XRD) confirmed the products were pure spinel-structured magnetite. Scanning electron microscopy (SEM) was used to investigate the morphology of the obtained crystals. By carefully regulating the initial NaOH concentrations, the morphology of the products could be changed from sheet-like crystals to pseudo-octahedral crystals. Transmission electron microscopy (TEM) analysis indicated the sheet-like crystals were the oriented aggregation of nanoparticles. Pseudo-octahedral magnetite crystals were single crystalline, and were obtained by dissolution-recrystallization of the sheet-like crystals. Vibrating sample magnetometer (VSM)) suggested the magnetic properties of the products were strongly related to the morphology. The coercivity of the sheet-like magnetite crystals was 100 Oe, larger than 30 Oe of the pseudo-octahedral crystals, but the saturation magnetization of the sheet-like magnetite crystals was 40 emu/g, smaller than 85 emu/g of the pseudo-octahedral crystals.     

羟基磷灰石纳米棒的水热制备及其晶体生长机理研究EI北大核心CSCD

以无水CaCl 2和(NH 4)2HPO 4为原料,尿素为均相沉淀剂,十六烷基三甲基溴化铵(CTAB)为模板剂,利用水热法制备了羟基磷灰石(HA)纳米棒。采用X射线衍射仪(XRD)、扫描电镜(SEM)和透射电镜(TEM)对产物的物相组成、微观形貌进行了表征。结果表明:通过改变反应温度和时间,可实现HA纳米形貌的可控微调。在120℃水热反应12 h可以制备出单晶密排六方结构HA纳米棒,其长约为0.5~1.0μm,直径约为15~30 nm。并从晶体结构的角度详细研究了CTAB在合成纳米棒结构中所起的作用,并通过实验进行了验证。     

Hydrothermal conversion of biomass into acetic acid

Hydrothermal process is one of the most promising processes for the conversion of biomass waste into resources among the several biomass conversion processes, because water of high temperature and high pressure has remarkable properties as a reaction medium. This paper described advances in our research involving overall reaction pathways for acetic acid production from biomass, mainly including (1) acetic acid production by controlling pathways of hydrothermal reaction, (2) acid-base behavior of water in the subcritical region and (3) effect of lignin on the acetic acid production in WO of lignocellulosic biomass.     

Hydrothermal synthesis of hydroxyapatite whiskers with sharp faceted hexagonal morphology

We report an effective method for the synthesis of hydroxyapatite whiskers with sharp faceted hexagonal shape employing a low temperature (90 °C) hydrothermal route with calcium nitrate tetrahydrate, diammonium phosphate and urea as starting materials. The key parameters of the synthesis process i.e. duration, temperature cycle of the treatment and starting pH value are carefully varied and the end products are investigated using powder X-ray diffraction (XRD), Raman-scattering, infrared spectroscopy (IR), elemental analysis, scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM), electron diffraction (ED), and high-resolution TEM (HRTEM) in order to find the optimal reaction conditions that lead to the desired hexagonal morphology of HA whiskers. The results demonstrate that gradual and greater increase in solution pH during the hydrothermal process favors large quantity of the single-crystalline hydroxyapatite whiskers with well defined hexagonal morphology.     

Dissolution of calcite crystals in the presence of some metal ions

A constant composition method has been used for the study of the kinetics of calcium carbonate (calcite) dissolution in which the activities of ionic species in relatively undersaturated solutions are maintained constant. Over a range of relative undersaturation (0.032–0.158) the dissolution reaction appears to be controlled by a bulk diffusion process. The suggestion of a predominantly diffusion-controlled process was supported by the observed low activation energy (2.09 kcal mol^–1). The influence of a number of metal ions on the reaction rate has been investigated. The retardation effect of these additives has been attributed to the blocking of active sites by adsorption of metal ions at the crystal surfaces. Inhibition of dissolution by metal ions can be interpreted in terms of a Langmuir isotherm.     

Hydrothermal preparation of PbS crystals and shape evolution

In the current paper, we successfully prepared lead sulfide (PbS) microcrystals with various shapes in a simple aqueous system using the hydrothermal synthesis route. Experimental results indicated that the change of the molar ratio of Pb²⁺/S₂O₃²⁻ could significantly influence the morphology of the product while keeping the other experimental conditions constant: with the decrease of the molar ratio of Pb²⁺/S₂O₃²⁻ from 1:1 to 1:4, the shape of the products varied from tri-prism, cube to magic-square structure. Changing the reaction temperature had big effect on the shape of the product: flower-shaped product was obtained at 80 °C and cube-shaped products were produced at 120 °C. When the reaction time varied, the shapes of the as-obtained PbS crystals also changed. At the same time, SEM observations showed that the counter-anions for Pb²⁺ could influence the shape of the product: Pb(NO₃)₂ being used as lead ion sources, most flower-shaped and few cubic PbS crystals were produced; while PbSO₄ as lead ion source, the PbS cubes were obtained. An evolution process was described based on experimental facts.     

Rational synthesis of a nanocrystalline calcium phosphate cement exhibiting rapid conversion to hydroxyapatite

The rational synthesis, comprehensive characterization, and mechanical and micromechanical properties of a calcium phosphate cement are presented. Hydroxyapatite cement biomaterial was synthesized from reactive sub-micrometer-sized dicalcium phosphate dihydrate and tetracalcium phosphate via a dissolution-precipitation reaction using water as the liquid phase. As a result nanostructured, Ca-deficient and carbonated B-type hydroxyapatite is formed. The cement shows good processibility, sets in 22 ± 2 min and entirely transforms to the end product after 6 h of setting reaction, one of the highest conversion rates among previously reported for calcium phosphate cements based on dicalcium and tetracalcium phosphates. The combination of all elucidated physical-chemical traits leads to an essential bioactivity and biocompatibility of the cement, as revealed by in vitro acellular simulated body fluid and cell culture studies.The compressive strength of the produced cement biomaterial was established to be 25 ± 3 MPa. Furthermore, nanoindentation tests were performed directly on the cement to probe its local elasticity and plasticity at sub-micrometer/micrometer level. The measured elastic modulus and hardness were established to be E_s = 23 ± 3.5 and H = 0.7 ± 0.2 GPa, respectively. These values are in close agreement with those reported in literature for trabecular and cortical bones, reflecting good elastic and plastic coherence between synthesized cement biomaterial and human bones.     

Hydrothermal synthesis of calcium hydroxyapatite nanorods in the presence of PVP

Calcium hydroxyphosphate (Ca₁₀(PO₄)₆(OH)₂, HAP) nanorods have been successfully synthesized by a simple and mild hydrothermal treatment in the presence of polyvinylpyrrolidone (PVP). A complex of calcium nitrate (Ca(NO₃)₂) and Na₂HPO₄ was used to supply the calcium and phosphate ions during the reactions. The synthesis of pure HAP nanorods was under near neutral condition. The morphology and structure of the samples were characterized by transmission electron microscope (TEM), scanning electron microscope (SEM), X-ray diffraction (XRD), and Fourier transform infrared (FT-IR) spectroscopy analysis. The nanorods were uniform with diameter of 20–25 nm and length ranging from several hundreds of nanometers to several micrometers. The influence of different experiment conditions, i.e., the PVP concentration, molar ratio of Ca²⁺ to HPO₄ ²⁻, reaction time, and temperature, on the morphology of the nanorods was investigated. The formation mechanism of rod-like HAP and effects of PVP on the crystal nucleation and growth have also been discussed.     

Monoclinic-hexagonal transition in hydroxyapatite and deuterohydroxyapatite single crystals

Monoclinic hydrothermally grown hydroxyapatite and deuterohydroxyapatite single crystals undergo a reversible transition to hexagonal symmetry at 211.5(5)°C.     

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.