Thermal decomposition of synthesised carbonate hydroxyapatite

Heat treatments are used when sintering hydroxyapatite to make porous blocks and granules and during plasma spraying of coatings. Calcium : phosphorus ratio is known to affect the thermal decomposition behavior of hydroxyapatite. Hydroxyapatite with carbonate ions substituted for phosphate ions is more similar in composition to bone mineral. While it has been shown that carbonate apatite may be sintered, relatively little is known about its high temperature stability. Various atmospheres have been used in investigations into the thermal stability of hydroxyapatites and carbonate hydroxyapatites, including nitrogen, wet carbon dioxide air, water vapor and wet oxygen, but few of these studies were directly comparable. Previous work has shown that loss of carbonate from CHA at high temperature is time dependent, which suggests that rapid high temperature treatment may prevent carbonate loss during processing. This study investigated the effect of dry carbon dioxide, carbon dioxide containing 3% water, nitrogen and nitrogen containing 3% water on the phase composition of hydroxyapatite containing between 1.0 and 11.5 wt % carbonate rapidly heated to temperatures of between 700 and 1400 °C. Carbonate ion substitution was observed to decrease the temperature at which crystallisation occurred to a minimum of 700 °C for 11.8 wt % carbonate apatite heated in wet atmospheres. Atmosphere was found to appreciably affect the crystallization temperature and phase transformations of carbonate apatite containing 7.8 wt % carbonate. In wet and dry carbon dioxide atmospheres, crystallisation began in this material at 1100 and 900 °C, TCP was formed at 1500 and 1300 °C respectively. The high temperature decomposition of carbonate hydroxyapatite would appear to depend on the composition of the apatite and the atmosphere in which it is heated.     

Effect of sintering parameters on the density and microstructure of carbonate hydroxyapatite

This work documents an investigation into the effect of water on the density and microstructure of carbonate hydroxyapatite in carbon dioxide sintering atmospheres. Carbonate apatites with carbonate contents of between 3.2 and 7.8 wt % were precipitated and the precipitates were formed into dry gels. Isothermal and isochronal sintering experiments were performed under dry carbon dioxide and wet carbon dioxide (containing 3 wt % water) atmospheres. The effect of carbonate content was studied by using two gels both with a green density of 37% and with carbonate contents of 5.8 and 7.8 wt %. Both isothermal and isochronal experiments demonstrated that bloating of the apatite occurred and this behavior was associated with the loss of carbonate from the apatite. It was found that only in wet carbon dioxide atmospheres fully dense translucent carbonate apatite could be formed. 93% dense carbonate apatite was formed after 4 h sintering at temperatures as low as 700 °C. © 2000 Kluwer Academic Publishers     

溶胶–凝胶法制备不同形态的半透明羟基磷灰石陶瓷

为探索制备不同形态半透明羟基磷灰石(T-HA)陶瓷的方法, 采用微米级HA粉体为原料, 甲壳素为粘结剂, 用溶胶–凝胶法制备出球状和纤维状的陶瓷初坯, 然后进行常压烧结得到纯HA陶瓷, 最后经过热等静压烧结得到T-HA陶瓷。溶胶–凝胶法赋形简单, 制备出的球状T-HA陶瓷的球形度良好, 纤维状T-HA陶瓷的纵横比高, 其致密度为99.1%, 平均晶粒尺寸为2.2 μm。其中球状半透明HA陶瓷的抗压强度为10.2 MPa, 高于常规烧结得到的球状致密和多孔HA陶瓷(分别为8.9和4.7 MPa)。仿生矿化和细胞培养的结果显示半透明HA陶瓷具有良好的生物相容性。     

Effect of processing conditions on the characteristics of pores in hot isostatically pressed alumina

Effect of processing conditions on the characteristics of residual pores was studied with an optical microscope in hot isostatically pressed translucent alumina ceramics. Green bodies formed by isostatic pressing were sintered at 1300, 1400 and 1600°C and then hot isostatically pressed at a temperature 50°C below the respective sintering temperature for 1 h at 100 MPa. All specimens were fully dense within experimental accuracy (±0.1%), and the grain size increased with increasing sintering/hot isostatic pressing temperatures. A variety of pores were found in all specimens. The distribution of pores was uniform at various locations within the specimen. The pore population decreased with increasing pore size, but was finite in the size range exceeding 84 m. The pores in this range increased with increasing sintering/hot isostatic pressing temperature. Except for these large pores, the pore population was similar under all processing conditions.     

An improvement in processing of hydroxyapatite ceramics

Hydroxyapatite ceramics have been fabricated via two different processing routes, a conventional processing route and an emulsion-refined route. The conventional precipitation processing of powder precursors for hydroxyapatite ceramics results in the formation of hard particle agglomerates, which degrade both the compaction and densification behaviour of the resultant powder compacts. An emulsion-refinement step has been shown to be effective in softening particle agglomerates present in the conventionally processed powder precursor. As a result, the emulsion-refined powder compact exhibits both a higher green density and a higher sintered density than the un-refined powder compact, on sintering at temperatures above 800 °C. The effect of powder agglomeration on densification during both the initial and later stage of sintering is discussed. The attainable sintered density of the conventionally processed material was found to be limited by the presence of hard powder agglomerates, which were not effectively eliminated by the application of a pressing pressure of 200 MPa. These hard powder agglomerates, which form highly densified regions in the sintered ceramic body, commenced densification at around 400 °C which is more than 100 °C lower than the densification onset temperature for the emulsion-refined powder compact, when heated at a rate of 5 °C min^–1. The inter-agglomerate voids, manifested by the differential sintering, resulted in the formation of large, crack-like pores, which act as the strength-limiting microstructural defects in the conventionally processed hydroxyapatite. A fracture strength of 170±12.3 MPa was measured for the emulsion-refined material compared to 70±15.4 MPa for the conventionally processed material, when both were sintered at 1100 °C for 2 h.     

Effect of cerium addition on phase transformation and microstructure of cordierite ceramics prepared by sol-gel method

Low-temperature sintering of cordierite ceramic depends on the phase transformation into cordierite and the properties depend on its microstructure. In the present work, the effect of cerium on the phase transformation and microstructure of cordierite ceramics prepared by sol-gel method is studied by X-ray diffraction (XRD), differential thermal analysis (DTA) and scanning electron microscopy (SEM) in order to lower the sintering temperature and improve the properties of cordierite ceramic with the addition of cerium. It is observed that the cerium addition obviously lowers the crystallization temperature of -cordierite while slightly raises that of -cordierite. The lowest temperature for cordierite transformation, which approaches the crystallization temperature of -cordierite, is achieved in the sample containing 4 wt% of cerium, implying a possibility to lower the sintering temperature of cordierite ceramics. The Ce-contained ceramics show a biphasic microstructure that is dependent on sintering temperature. Sintered below 1300°C, a cordierite-CeO₂ microstructure is present; while sintered at the temperature above 1300°C, appears a cordierite-glass microstructure, of which the amount of glass phase is limited to a small extent. Since the addition of 4 wt% cerium to this MgO-Al₂O₃-SiO₂ system substantially enhances the densification of cordierite ceramics and lowers the sintering temperature to the level of around 1000°C, it makes the ceramics suitable for such applications, where the low-temperature sintering is required, as the substrates for electronic circuit and the catalytic supports (with oxygen storage capacity) for cleaning of automotive exhaust emissions.     

Sintering condition and PTCR characteristics of porous (Ba,Sr)(Ti,Sb)O3

We fabricated porous (Ba,Sr)(Ti,Sb)O₃ ceramics by adding potato-starch (1–20 wt %) and investigated the effects of sintering temperature (1300–1450 °C) and time (0.5–10 h) on the positive temperature coefficient of resistivity characteristics of the porous ceramics. The room-temperature electrical resistivity of the (Ba,Sr)(Ti,Sb)O₃ ceramics decreased with increasing sintering temperature, while that of the ceramics increased with increasing sintering time. For example, the room-temperature electrical resistivity of the (Ba,Sr)(Ti,Sb)O₃ ceramics for the samples sintered at 1300 °C and 1450 °C for 1 h is 6.8×10³ and 5.7×10² cm, respectively, while that of the ceramics is 6.5×10² and 1.3×10⁷ cm, respectively, for the samples sintered at 1350 °C for 0.5 h and 10 h. In order to investigate the reason for the decrease and increase of room-temperature electrical resistivity of the samples with increasing sintering temperature and time, the average grain size, porosity, donor concentration of grains (N _d), and electrical barrier height of grain boundaries () of the samples are discussed.     

Solid state reaction, sintering and Pb removal activity of hydroxyapatite/zirconia layered composite

In order to form a layered hydroxyapatite/zirconia ceramic, the solid state reaction and sintering were examined by the three processes of powder mixture, dry-pressing compaction and tape cast. The solid state reaction between hydroxyapatite and zirconia occurred in the thin width of 10–50 m at interface in a layered composite body. In both sintered layer composites from dry compaction and tape cast, the significant deformation of composite bodies was observed, depending on sintering temperatures. By selecting a sintering temperature of 1200°C, we fabricated a layer ceramic composite of hydroxyapatite/zirconia exhibiting the flat film shape. The tape cast process was useful to form a porous sintered composite of hydroxyapatite and zirconia. The porous composite showed the removal performance of aqueous lead from wastewater.     

Solid solution formation at the sintering of hydroxyapatite–fluorapatite ceramics

Fluorhydroxyapatite ceramics are increasingly studied for the use as biomaterials due to their good integration ability in the bone tissue and higher resorption resistance compared to the common hydroxyapatite (HA) ceramics. This study is aimed at the X-ray diffraction investigation of the interaction between HA and fluorapatite (FA) particulates in the sintering temperature range up to 1300 °C. The lattice parameters were calculated in dependence of both the FA content in the powder mixtures and the sintering temperature. From those data, the solid solution formation is concluded, at least in the temperature range from 1200 to 1300 °C. Energy-dispersive X-ray microanalysis confirmed the fluorine distribution to be almost uniform in the sintered at 1300 °C ceramics.     

Solid solution formation at the sintering of hydroxyapatite–fluorapatite ceramics

Fluorhydroxyapatite ceramics are increasingly studied for the use as biomaterials due to their good integration ability in the bone tissue and higher resorption resistance compared to the common hydroxyapatite (HA) ceramics. This study is aimed at the X-ray diffraction investigation of the interaction between HA and fluorapatite (FA) particulates in the sintering temperature range up to 1300 °C. The lattice parameters were calculated in dependence of both the FA content in the powder mixtures and the sintering temperature. From those data, the solid solution formation is concluded, at least in the temperature range from 1200 to 1300 °C. Energy-dispersive X-ray microanalysis confirmed the fluorine distribution to be almost uniform in the sintered at 1300 °C ceramics.     

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.     

Preparation and characterization of magnesium/carbonate co-substituted hydroxyapatites

A new synthesis/processing method has been devised to produce magnesium/carbonate co-substituted hydroxyapatite ceramics that do not decompose to tricalcium phosphate (TCP) on sintering. Using this method, a series of magnesium/carbonate co-substituted hydroxyapatite (Mg/CO₃–HA) compositions, containing between 0 and 0.35 wt % Mg and approximately 0.9 wt % CO₃ were prepared. Sintering the Mg/CO₃–HA compositions in a CO₂/H₂O atmosphere yields a single crystalline phase that appears to be identical to stoichiometric HA. In contrast, when the compositions were prepared in the absence of carbonate and were sintered in air, the phase composition was a biphasic mixture of HA and TCP e.g. for 0.25 wt % Mg substitution the phase composition was approximately 60%HA/40% TCP. Clearly, both the synthesis route and the processing (i.e. sintering) route are of importance in the production of a single-phase Mg/CO₃–HA ceramic. Fourier transform infrared (FTIR) spectroscopy has indicated that the Mg/CO₃–HA ceramics still contained carbonate groups after sintering at 1200 °C. Chemical analysis by X-ray fluorescence spectroscopy (XRF) and C–H–N analysis has shown that the cation/anion molar ratio (i.e. [Ca+Mg]/[P+C/2]) of the different compositions were 1.68(±0.01), which is equivalent to the Ca/P molar ratio of stoichiometric HA. Although the magnesium/carbonate co-substitution had a positive effect in preventing phase decomposition during sintering, it appeared to have a negative effect on the densification of the MgCO₃–HA ceramics, compared to stoichiometric HA.     

Synthesis and characterization of carbonate hydroxyapatite

Substituted apatite ceramics are of clinical interest as they offer the potential to improve the bioactive properties of implants. Carbonate hydroxyapatite (CHA) has been synthesized by an aqueous precipitation method and precipitates with two different levels of carbonate, processed as powders. Sintering experiments were performed to establish the influence of carbonate in significantly reducing the temperature required to prepare high-density ceramics when compared with stoichiometric hydroxyapatite (HA). High-temperature X-ray diffraction was used to characterize the phase stability of the apatites on sintering. Increasing carbonate content was shown to reduce the temperature at which decomposition occurred, to phases of CaO and -TCP. Mechanical testing, performed using biaxial flexure, showed that the CHA specimens had strengths similar to stoichiometric HA. © 1998 Kluwer Academic Publishers     

A study on the stability of superconducting YBa2Cu3O7−x phase

The thermal stability of the superconducting phase of nominal composition YBa₂Cu₃O_7–x -sintered pellets has been studied with respect to different temperatures (ranging from 300 to 950° C), time (ranging from 1 to 72 h), oxygen partial pressure (from 4 Pa to 1 atm) and carbon dioxide partial pressure (from 10^–4 Pa to 1 atm). Annealed samples were characterized by X-ray diffraction analysis, optical microscopy, and resistive measurements of the superconductive transition temperature. A stability field of the orthorhombic and tetragonal phases was obtained, showing a region of coexistance. The decomposition of the 1 2 3 phase is found to be strongly influenced by the presence of a small amount of CO₂ (1 p.p.m.) in the sintering atmosphere. A sintering process is proposed to avoid the formation of by-products.     

Kinetics of thermal decomposition of hydroxyapatite bioceramics

The mechanism and kinetics of thermal decomposition of injection moulded hydroxyapatite ceramics were studied over the temperature range of 1473–1758 K. At temperatures below 1473 K the sintering and transformation of hydroxyapatite to hydroxyoxyapatite proceeded to a conversion degree of 0.4 to 0.5. At temperatures between 1473 and 1758 K the hydroxyapatite was decomposed to -TCP, H₂O and CaO. The decomposition of HOA started on the surface of the HOA ceramics. The rate of increase in the thickness of the reaction products (-TCP) was described by the parabolic law. The kinetic analysis of the time dependence of HOA conversion to TCP by means of the J-M-A-J-K equation also showed that the thermal decomposition of HOA ceramics was controlled by diffusion of water from the reaction zone to the surface of the ceramic sample. The activation energy of the thermal decomposition of HOA ceramics amounted to 283.5 kJ/mol.     

Nanosized hydroxyapatite powders derived from coprecipitation process

Nanosized hydoxyapatite (Ca₁₀(PO₄)₆(OH)₂ or HA) powders were prepared by a coprecipitation process using calcium nitrate and phosphoric acid as starting materials. The synthesized powders were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and Brunauer-Emmett-Teller (BET) specific area measurment techniques. Single phase HA, with an average grain size of about 60 nm and a BET surface area of 62 m²/g, was obtained. No grain coarsening was observed when the HA powders were heated at 600°C for 4 hours. HA ceramics were obtained by sintering the powders at temperatures from 1000°C to 1200°C. Dense HA ceramics with a theoretical density of 98% and grain size of 6.5 m were achieved after sintering the HA powders at 1200°C for 2 hours. HA phase was observed to decompose into tricalcium phosphate when sintered at 1300°C. The microstructure development of the sintered HA ceramics with sintering temperature was also characterized and discussed.     

Fibrous growth of tricalcium phosphate ceramics

Structural transformation and sintering processes of tricalcium phosphate (TCP) ceramics prepared from defective hydroxyapatite (Ca9HPO4(PO4)5OH) were studied by X-ray diffraction (XRD) and atomic force microscopy (AFM). Starting powders with Ca/P ratio 1.5 were obtained by adding 0.5 l of 0.3 M H3PO4 solution to an equal volume of 0.45 M Ca(OH)2. In the prepared ceramics, the onset temperature for transformation of defective hydroxyapatite into TCP (witlokite) agrees with the onset temperature for sintering (800 °C). Sintering occurs through the formation of a fibrous structure, which resembles biological hard tissue. In the 1000–1200°C range, these fibres coalesce into grains of up to 0.6 m in size with a fibrous-laminar morphology. At the end of this sintering stage witlokite transforms into TCP. At about 1450°C, partial decomposition of TCP into Ca2P2O7+Ca4P2O9 is observed. AFM observations suggest that Ca2P2O7 is segregated in the liquid state and increases the velocity of grain growth (up to 12 m).     

Wet synthesis and characterization of modified hydroxyapatite powders

Hydroxyapatite powders with reproducibly different Ca/P ratios and powders with varying amounts of co-precipitated magnesium, sodium and potassium were synthesized by a wet method. Solids composition, particle size and morphology, crystalline structure, sintering behaviour and microstructure were investigated in order to understand the effect of composition in the properties of the powders. Under the present conditions of synthesis, it was concluded that magnesium, sodium and potassium will enter the hydroxyapatite lattice in vestigial amounts. Magnesium gives rise to a co-precipitated amorphous phase which crystallizes as -whitlockite on calcining. A relationship was found between the Ca/P ratio in hydroxyapatite and its sinterability. The sintering process of pure and alkali-containing hydroxyapatites is completed at 1300 °C and leads to dense ceramics in the case of pure and sodium-containing hydroxyapatites but not in potassium-containing material.This paper was accepted for publication after the 1995 Conference of the European Society of Biomaterials, Oporto, Portugal, 10–13 September.     

The time-resolved luminescence characteristics of Ce and Ce/Pr doped YAG ceramics obtained by high pressure technique

Transparent Ce and Ce/Pr doped YAG ceramics were prepared under high pressures (up to 8 GPa) and relative low temperature (450 °C). Grain size of the ceramics is less than 50 nm. However unknown defects or disorders strains on grain boundaries caused the additional absorption in these ceramics. The luminescence intensity, spectra and the decay time dependence on pressure applied during ceramic preparation were studied. Concentration of some intrinsic point defect was reduced under the high pressure applied for sintering process.It is shown that formation time of the excited state of Ce luminescence depends on the pressure applied during ceramic sintering.     

Sinterability,strength and oxidation of alpha silicon carbide powders

Pressureless sintering of commercially available -SiC powders was investigated at temperatures between 1900 and 2150° C for times of 10 to 240 min under one atmosphere of argon pressure. Alpha-SiC powder containing boron and carbon sintering aids was sinterable at 2150° C for a period of 30 min to a high final density greater than 96 per cent of theoretical. In contrast, a final density only about 80 per cent of theoretical was achieved in -SiC powder containing aluminium and carbon sintering aids. Room temperature and high temperature (1370° C) flexure strength and oxidation resistance were determined on sintered high density (>96% of theoretical) -SiC (boron, carbon) material. Both the strength and the oxidation resistance were found to be equivalent and comparable to those of Carborundum Company sintered -SiC, which is representative of the current state-of-the-art material.