Effect of CO32− Incorporation on the Mechanical Properties of Wet Chemically Synthesized β-Tricalcium Phosphate (TCP) Ceramics

Calcium-deficient hydroxyapatite (CDHA) powders were synthesized by a wet chemical precipitation method using Ca(OH)₂ and H₃PO₄ solutions. Single-phase β-tricalcium phosphate (β-TCP) powder with a molar (Ca+Mg)/P ratio of 1.5 was obtained after calcination of CDHA synthesized under vacuum. During synthesis in air, CO₂ can be adsorbed and HBO₄²⁻ is partly substituted by CO₃²⁻, resulting in a lower phosphorous content and consequently an increase of the molar (Ca+Mg)/P ratio to 1.53. A two-phase β-TCP powder containing 20 wt% hydroxyapatite (HA) was obtained after calcination. Samples prepared from β-TCP powders synthesized under vacuum achieved a compressive strength of 301±23 MPa at 99.6% fractional density, while TCP/HA samples prepared in air achieved a maximum compressive strength of 132±29 MPa at 91.7% fractional density. This decrease in strength can be correlated to the porosity retaining due to CO₂ release during sintering and residual tensile stresses in the TCP matrix caused by the thermal expansion mismatch of β-TCP and HA.     

The Effects of Calcium‐to‐Phosphorus Ratio on the Densification and Mechanical Properties of Hydroxyapatite Ceramic

In this work, hydroxyapatite (HA) powders were synthesized using calcium hydroxide Ca(OH)₂ and orthophosphoric acid H₃PO₄ via wet chemical precipitation method in aqueous medium. Calcium‐to‐phosphorus (Ca/P) ratio was set to 1.57, 1.67, 1.87 that yield calcium‐deficient HA, stoichiometric HA, and calcium‐rich HA, respectively. These synthesized HA powders (having different Ca/P ratio) were characterized in terms of particle size and microstructural examination. Then, the densification and mechanical properties of the calcium‐deficient HA, stoichiometric HA, and calcium‐rich HA were evaluated from 1000 to 1350°C. Experimental results have shown that no decomposition of hydroxyapatite phase was observed for stoichiometric HA (Ca/P = 1.67) and calcium‐deficient HA (Ca/P = 1.57) despite sintered at high temperature of 1300°C. However, calcium oxide (CaO) was detected for calcium‐rich HA (Ca/P = 1.87) when samples sintered at the same temperature. The study revealed that the highest mechanical properties were found in stoichiometric HA samples sintered at 1100–1150°C, having relative density of ~99.8%, Young's modulus of ~120 GPa, Vickers hardness of ~7.23 GPa, and fracture toughness of ~1.22 MPam^1/2.     

Sintering behavior and mechanical properties of hydroxyapatite ceramics prepared from Nile Tilapia (Oreochromis niloticus) bone and commercial powder for biomedical applications

In this work, Nile tilapia (Oreochromis niloticus) bone was calcined at 800 °C for 5 h in an air atmosphere to obtain hydroxyapatite powder (FB powder). The elemental composition, phase structure, and morphology of the FB powder were investigated and compared with commercial hydroxyapatite powder (SM powder). The FB-powder exhibited 1.01 at. % of Mg while the SM-powder showed Mg in ppm-level. Carbonate groups were detected in the two powders. Both HAp and β-tricalcium phosphate (β-TCP) structures were found in the FB powder, but the SM powder exhibit only the HAp phase. Irregular-shaped particles were observed in the FB powder. After the two HAp powders were sintered at 1200 °C and 1250 °C for 2 h (FB-1200, FB-1250, SM-1200, and SM-1250), the β-TCP intensity peaks of the FB-ceramic samples significantly increased with increasing sintering temperature. The highest relative density, well-packed grains, and β-TCP stabilization by Mg at the Ca5 site of the FB-1250 structure were the dominant factors governing the highest mechanical properties. Although high density was observed in the SM-1200 sample, Vickers hardness of the SM-1200 sample is lower than the FB-1250 sample. This may be attributed to the partial decomposition of HAp into β-TCP, α-tricalcium phosphate (α-TCP), and Ca₁₀(PO₄)₆O phases. In addition, the increase of grain size was the main factor that governs the increasing compressive strength and Young's modulus instead of density and phase decomposition of the SM-ceramic samples.     

Research of phase transformation induced biodegradable properties on hydroxyapatite and tricalcium phosphate based bioceramic

Biodegradable calcium phosphate composites consisting of tricalcium phosphate (α-TCP) and hydroxyapatite (HA) were prepared using a two-step sintering method. The ratio of α-TCP/HA was controlled by modulating the sintering temperature. The initial calcination process at 800 °C causes HA dehydroxylation and induces the early transformation of HA into α-TCP in subsequent sintering processes. At the optimum sintering temperature of 1300 °C, the material is comprised of a moderate ratio of α-TCP to HA (3:7) and possesses a hardness of 5.0 GPa. The high temperature phase transformation from HA to α-TCP accompanied by bonded water loss, which results in the formation of nano-pores within the α-TCP matrix, hardly deteriorated the mechanical strength of the composite. This pore-containing structure also provided a convincing evidence for the origin of the high degradability of α-TCP in a biological environment.     

Effects of powder stoichiometry on the sintering of β-tricalcium phosphate

The impact of weak stoichiometry variations on β-TCP sintering behaviour was studied. β-Tricalcium phosphate (β-TCP) powders were synthesised by chemical precipitation through aqueous solution of diammonium phosphate and calcium nitrate. Excess or deficiency of nitrate salt leads to compositions with Ca/P ratios below or over 1.5. These powders, calcined at various temperatures (800–950 °C), were shaped by slip casting process and sintered at 1100 °C. The microstructure, phase composition, specific surface area and density of powders and sintered compacts were analysed by SEM, XRD, FTIR, BET, Archimedes methods and dilatometry.This study shows that the presence of calcium pyrophosphate or the hydroxyapatite phases affects considerably the physical characteristics of the β-TCP powders and in particular specific surface area and consequently their sinterability.A precise determination of the β-TCP chemical composition after synthesis allows to adapt the calcination temperature of the raw powder in order to obtain a maximum densification of the compact. The beneficial role of small quantity of HA phase inside β-TCP powder on their sinterability was also shown in this work.     

Comparative analysis and antibacterial properties of thermally sintered apatites with varied processing conditions

Hydroxyapatite (HA) and biphasic hydroxyapatite/beta-tricalcium phosphate (biphasic HA/β-TCP) were synthesized using thermal sintering. The parameters- sintering temperature (600°C, 900°C, and 1200°C), biological source used (fish bone, egg shells, and fish scales), and soaking time (2, 6, and 10 hours) were permuted to study their effects on the properties of the resultant apatite. Morphological study revealed that the smallest (60 nm) spherical particle and the largest (470 nm) irregular shaped particle were obtained from the fish bone sample sintered at 600°C and at 1200°C respectively. FTIR and XRD results showed that as the sintering temperature is increased, the phase transformation from HA to β-TCP takes place. Only the final products from fishbone sample at 600°C are pure carbonated HA. The crystallinity of synthesized particles ranged from 79% to 98%. Soaking time has no effect on phase composition of the apatite but has significant effect on crystallite size; increase in soaking time increases crystallite size and particle shape becomes more spherical. Interestingly, the fish bone sample sintered at 900°C has higher crystallinity and crystallite size compared to the fish scale sample sintered at the same temperature. EDX confirmed that non-stoichiometric apatite with Ca/P ratio ranging from 1.47 to 1.91 can be obtained by varying the sintering conditions. The antibacterial test revealed that both calcium apatite obtained from fish bones and fish scales have inhibited bacterial growth; apatite from fish bone works faster than fish scales. The in vitro cytotoxicity test ensured that all the calcium apatite except for eggshell are non-cytotoxic. Thus, apatite with excellent microbial activity can be obtained by using fish wastes, and by tuning the sintering parameters, the apatite with desired types and properties can be synthesized for different biomedical applications.     

Sintering properties of hydroxyapatite powders prepared using different methods

In the present work, the sintering behaviour of HA particles prepared via the wet precipitation method (HAp) and wet mechanochemical technique (HAwm) was investigated. The sintering behaviour of a commercial HA powder (HAc) was also studied for comparison purpose. All the three powders were characterised in terms of particle size, Ca/P ratio and crystal size. Green samples were prepared and sintered in air at temperatures ranging from 1000 °C to 1400 °C. The sintered bodies were studied in terms of the phase stability, relative density, Young's modulus, Vickers hardness, fracture toughness and grain size. The results indicated that HAwm samples suffered phase decomposition while the HAp and HAc sintered samples showed no phase disruption throughout the temperature range employed. The HAp samples exhibited the overall best densification and properties when compared to the HAc and HAwm samples. Furthermore, the results showed that mechanical properties of sintered samples were governed by both the bulk density and the grain size.     

Dense fine-grained biphasic calcium phosphate (BCP) bioceramics designed by two-step sintering

In this study, dense, fine-grained biphasic calcium phosphate bioceramics were designed via the two-step sintering method. The starting powder was nanosized calcium-deficient hydroxyapatite, whose phase composition, average particle size and morphology were characterized by XRD, FTIR, Raman spectroscopy, laser diffraction and FE-SEM. The phase transformations of the initial powder during heating up to 1200 °C were examined using TG/DSC. At first, conventional sintering was performed and the recorded shrinkage/densification data were used to find out the appropriate experimental conditions for two-step sintering. The obtained results show that two-step sintering yields BCP ceramics, consisting of hydroxyapatite and β-TCP, with full dense, homogeneous structure with average grain size of 375 nm. Furthermore, BCP ceramics obtained by the two-step sintering method exhibit improved mechanical properties, compared to conventionally sintered BCP.     

Evolution of the microstructural and mechanical properties of hydroxyapatite bioceramics with varying sintering temperature

This study highlights the effects of sintering temperature on the microstructures, densification, grain sizes/boundaries, calcium/phosphorus (Ca/P) ion ratios, mechanical and bioactive properties of biocompatible hydroxyapatite (HA) ceramics prepared via cold isostatic pressing. X-ray diffraction refinement analysis revealed that the phase ratios of hexagonal HA and secondary phases were sensitive to the sintering temperature. Grain sizes, densities, and shrinkages of the as-sintered HA ceramics increased with increasing sintering temperature. The Ca/P ratios of the as-sintered HA specimens ranged from 1.63 to 1.71 for sintering temperatures of 900–1300 °C. The maximum mechanical hardness was achieved in the specimen sintered at 1200 °C due to the dense matrix formed with a smaller grain size and fewer flawed grain boundaries, as determined by high-resolution transmission electron microscopy. Ion release analysis (in a simulated body fluid solution) indicated that phosphorus ions were absorbed and rapid deposition of calcium ions occurred after immersion periods of above 4 days.     

Processing and properties of biphasic calcium phosphates bioceramics obtained by pressureless sintering and hot isostatic pressing

Calcium phosphate powders were obtained from coprecipitation method using diammonium phosphate and calcium nitrate solutions. The adjustment of experimental parameters and Ca/P initial ratio allowed synthesizing stoichiometric HA and β-TCP powders and four biphasic calcium phosphates (BCP) with compositions equal to 20/80, 40/60, 60/40, 80/20, of HA and TCP respective in mass. Two sintering techniques, pressureless sintering and hot isostatic pressing (HIP) were performed to compare the sinterability of the stoichiometric and biphasic compounds. By pressureless sintering, densities higher than 98% were obtained. Results illustrate the negative impact of hydroxyapatite on the densification of BCP but its benefit effect on grain growth inhibition. After HIP treatment, transparent ceramics were obtained. The mechanical behavior of these fully densified compounds was examined in order to determine the role of the chemical composition on mechanical properties.     

Phase transformation on hydroxyapatite decomposition

The collapse of sintered hydroxyapatite (HA) has been attributed to HA decomposition; however, the detailed variations in microstructure are still unclear. Two phase transformation routes of HA decomposition during sintering were identified by transmission electron microscopy in this study. In the first route, HA is transformed to tetracalcium phosphate and needle-like β-tricalcium phosphate which is subsequently converted to α-tricalcium phosphate (α-TCP) above 1100 °C. In the second route, HA is transformed directly to α-TCP and calcium oxide at 1400 °C, accompanied by nanopore formation. In the second route, the α-TCP grew with a preferred orientation to form stripe-like grains. Further holding at 1400 °C for 4 h resulted in recrystallization; i.e., equi-axial grains formed within a stripe-like grain. Nanopore defects dispersed in the α-TCP grains are the main factor for the low density and decreased mechanical strength of the sintered bulk.     

Fabrication of dense and porous biphasic calcium phosphates: Effect of dispersion on sinterability and microstructural development

The particle size distribution of a commercial Mg-doped hydroxyapatite powder was tailored through two different milling procedures, carried out under wet or dry conditions. Wet milling gave rise to finer particles, with a narrower size distribution. Tailoring the particles size was the key to produce homogeneous gelcast green bodies, as well as fully dense and fine microstructures. In fact, wet-milled samples achieved full densification and compressive strength of about 300 MPa, five times higher than the values achieved by the dry milled samples. During the calcination treatments, HA progressively decomposed into β- and α-TCP phases, promoted by the progressive Mg²⁺ substitution inside the HA and β-TCP lattices. As a result, a biphasic (HA/β-TCP) calcium phosphate ceramic was successfully obtained. Gelcast macroporous materials were prepared by direct foaming, starting from both milled powders. Highly porous samples (73%-77% porosity) with a high degree of interconnectivity within pores were successfully produced. However, dry milled-foamed materials were characterized by a significant residual porosity within the struts, whereas in wet-milled foams struts and pore windows were highly compact, the key to provide sufficient mechanical strength to such highly porous open-cell foams, thus suggesting a possible use as implantable scaffolds.     

Synthesis and microstructural characterization of nano-size calcium phosphates with different stoichiometry

Calcium phosphates with Ca/P molar ratios of 0.5, 0.75, 1.33, 1.5, 1.55, 1.67, 2.0, and 2.5 were synthesized by a wet chemistry precipitation method and sintered at 500 °C, 700 °C, 900 °C, 1100 °C and 1300 °C for 2 h. Presence of phases and microstructures of calcium phosphates were determined by X-ray diffraction and scanning electron microscopy. In all different Ca/P ratios, the precipitated phase was always hydroxyapatite with very small size and/or partial disorderness regardless of the Ca/P ratios in the starting precipitating medium. For samples with 0.5 and 0.75 Ca/P ratios in starting solution, tricalcium phosphate and calcium pyrophosphate phases were observed. In contrast, for samples with 1.0 and 1.33 Ca/P ratios, the only stable phase was tricalcium phosphate. For the samples with Ca/P ratio of 1.5, the tricalcium phosphate phase was dominant. However, small amounts of hydroxyapatite started to appear. For samples with Ca/P ratio of 1.67, the hydroxyapatite phase was dominant. Lastly, for samples with the Ca/P ratios of 2.0 and 2.5, the CaO phase started to appear in addition to the hydroxyapatite phase which was the dominant phase. Moreover, the average grain size, porosity (%) and the average pore size decreased with increasing the Ca/P ratios.     

Preliminary investigation of hydroxyapatite microstructures prepared by flash sintering

Flash sintering is a novel and emerging route for sintering ceramics within a few seconds, even under pressure-less conditions. In the current study, hydroxyapatite (HA) was fully densified by flash sintering at a furnace temperature of 1020°C. Flash sintering with constant electric fields of 750 and 1000?V?cm^?1 reduced the grain growth rate significantly compared to that sintered in the absence of an electric field at 1400°C. The microstructure of HA consolidated by flash sintering was compared with that of the without electric field sintered samples. The flash-sintered samples showed smaller grains (160?～?320?nm) than the without electric field sintered samples (～15?µm). The samples with a higher applied electric field showed slightly better densification than those with the lower field by flash sintering. Overall, the electric flash reduces the sintering temperature effectively and decreases the holding time to densify highly insulating ceramics, such as HA.     

Properties of hydroxyapatite/zirconium oxide nanocomposites

Effects of zirconium oxide (ZrO₂) nanoparticles additive on the microstructure and physical properties of hydroxyapatite (HA) were investigated. The HA powder was derived from natural bovine bone by a sequence of thermal processes. The composites containing nanoparticles of ZrO₂ (0.2–1.0 vol%) were fabricated by a solid-state reaction mixed oxide method. All samples showed traces of HA, beta-tricalcium phosphate (β-TCP) and alpha-tricalcium phosphate (α-TCP) phases while the x≥0.1 samples also showed ZrO₂ phase. Amount of β-TCP and α-TCP phases tend to decrease with ZrO₂. The additive inhibited grain growth as a result of a decrease in grain size. However, the x=0.2 sample exhibited higher hardness value which is consistent with the density data. In addition, bioactivity test suggested that the additive promoted an apatite forming with the values of Ca/P close to the value obtained from HA.     

Microstructures and grain boundaries of cubic boron nitrides

Two types of chemically pristine polycrystalline cubic boron nitrides (c-BN) are sintered at different conditions using the starting cubic and hexagonal BN powders and their microstructures and grain boundaries are investigated systematically by transmission electron microscopy. The two c-BN samples are found to exhibit a number of twins inside their grains and have a similar grain size, despite their huge differences in the grain size of the starting powders and sintering conditions. Twin width for the c-BN sintered from hexagonal BN is significantly smaller than that for the c-BN sintered from c-BN. Grain boundaries in the two samples can be atomically abrupt without any amorphous or secondary layers and oxygen is detected merely at the grain boundaries of the c-BN sintered from the c-BN powders. Such microstructural differences have a direct impact on mechanical behaviors of the c-BN, as the Vickers hardness of the c-BN sintered from hexagonal BN powders is found to be higher than that of the c-BN sintered from the c-BN powders.     

Effect of hydroxyapatite and tricalcium phosphate addition on protein foaming-consolidation porous alumina

Porous alumina-hydroxyapatite (HA) and alumina-tricalcium phosphate (TCP) composites have been fabricated to investigate the effect of HA and ??-TCP addition on protein foaming-consolidation derived porous alumina. HA and ??-TCP loadings along with yolk content, starch content, and sintering temperature were varied to modulate performance of the porous composites. The rheological behavior of slurry shifted from pseudoplastic flow to a Newtonian fluid with increasing yolk concentration. The foaming capacity of slurry increased with yolk addition. The addition of starch into slurry resulted in bigger pore size and avoided the porous bodies from cracks. The shrinkage of sintered bodies increased with increasing HA loading, but decreased with increasing ??-TCP loading. The compressive strength of porous alumina-HA body was found 2.9?MPa at 45.8% porosity and 20.4?MPa at 36.8% porosity. The increasing porosity of porous alumina-TCP body from 56.1 to 61.6% improved the compressive strength from 3.1 to 4.2?MPa. Increasing sintering temperature resulted in large grain size among powder particles, thus improving the compressive strength of porous bodies. Preliminary results of DF-1 cells culture on the surface of porous alumina and alumina-TCP samples are also reported.     

Grain growth in microwave sintered Si3N4 ceramics sintered from different starting powders

Silicon nitride ceramics have been produced by microwave sintering at 28 GHz with Y₂O₃, Al₂O₃ and MgO as sintering additives. The effect of initial β content of the Si₃N₄ starting powder on the microstructural development has been assessed by scanning electron microscopy (SEM) and quantitative image analysis. Phase transformation behaviour was assessed by X-ray diffraction. Mechanical properties of the sintered bodies were determined through assessment of hardness and fracture toughness. It was found that the samples sintered from powders with lower initial β content developed larger grains than those from higher β content powders, due to fewer nucleation sites during the →β transformation. However, attempts to develop a more bimodal microstructure by using a mixture of the two grades of powder, in an effort to increase both fracture toughness and fracture strength, were unsuccessful. In this case the microstructure was similar to that developed in the materials produced from higher β content powders. The mechanical properties of the sintered bodies were very similar, despite differences in microstructure. This was attributed to the strong bonding between the grains and grain boundary phase resulting in crack paths in all the materials that were predominantly transgranular, with little debonding or crack deflection. Under these circumstances the effect of larger grains is eliminated.     

Properties of calcium phosphates ceramic composites derived from natural materials

In this study, ceramics containing mixed phases of hydroxyapatite/beta-tricalcium phosphate (HA/β-TCP) were fabricated by a solid-state reaction technique. The HA powder was synthesized from cockle shells while the β-TCP powder was synthesized from egg shells. Pure HA and β-TCP fine powders were successfully obtained. The HA and β-TCP were mixed and subjected to a thermal treatment up to 1100 °C. To form the mixed phase ceramics, the resulting powders were sintered at 1350 °C. Effects of HA concentration on the properties of the studied ceramic were investigated. X-ray diffraction analysis revealed that all samples presented multiphase of calcium phosphate compounds. Average grain size of the ceramics decreased with the HA additive content. The 75 wt% HA ceramic showed the maximum hardness value (5.5 GPa) which is high when compared with many calcium phosphate ceramics. In vitro bioactivity test indicated that apatite forming increased with the HA additive content. To increase antibacterial activity, selected ceramics were coated with AgNO₃. Antibacterial test suggested that an Ag compound coating on the ceramics could improve the antibacterial ability of the studied ceramics. In addition, the antibacterial ability for the Ag coated ceramics depended on the porosity of the ceramics.     

医用双相磷酸钙陶瓷的制备工艺研究

医用双相磷酸钙（BCP）陶瓷是β-磷酸三钙（β-TCP）和羟基磷灰石（HA）的复合体,其成分与骨矿物组成类似。它具有良好的生物相容性,在生物医学领域具有非常广阔的应用前景。且在生理环境下能发生不同程度的降解,被组织吸收。通过化学沉淀法制备纳米羟基磷灰石,然后通过可溶性钙盐和磷酸盐反应工艺制得β-磷酸三钙,最后将二者进行机械复合而制得双相磷酸钙,将所得样品用X射线衍射仪（XRD）进行了表征。结果显示：所得的双相磷酸钙中掺杂有β-焦磷酸钙,但是它的结晶较好,并且可以改善双相磷酸钙陶瓷的力学性能。