Effect of multi-ions doping on the properties of carbonated hydroxyapatite bioceramic

The effect of multi-ions (Mg²⁺, SiO₄^4-, Zn²⁺, Cu²⁺) doping on the properties of carbonated hydroxyapatite (CHA) prepared by a wet chemical method has been investigated. Different combinations of ions were doped into the CHA and the as-synthesized compacts were sintered at 900?°C prior to body characterization. It was found that regardless of ions doping, the lattice structure of the CHA was not disrupted. In addition, secondary phases were not detected for all the multi-ions doped samples. The XRD and FTIR results further confirmed the presences of a B-Type CHA in the sintered samples. The XRD analysis revealed that the lattice parameters (c/a ratio) increased with dopant addition and resulted in a smaller crystallite size. The FESEM examination also showed the presences of smaller grain size for the multi-ions doped CHA samples thus indicating that the doping was beneficial in suppressing grain coarsening in carbonated hydroxyapatite.     

Effect of silicon and heat-treatment temperature on the morphology and mechanical properties of silicon - substituted hydroxyapatite

The precipitation method was used to synthesize silicon-substituted hydroxyapatite with different Si contents of 0.4, 0.8 and 1.6 wt.% (0.4, 0.8 and 1.6Si-HA) using silicon acetate [Si(OCOCH₃)₄] as a Si source. As-synthesized hydroxyapatite (HA) and Si-HA powders/bulks were heat-treated at different temperatures of 1150, 1200 and 1250 °C for 1 h. Pure 0.4Si-HA and 1.6Si-HA were obtained after heat-treatment at all temperatures, whilst α-TCP phase was formed in the 0.8Si-HA sample after heat-treatment at 1250 °C. SEM observation clearly showed that the substitution of Si in HA inhibited the grain growth of Si-HA even at high heat-treatment temperatures (1200 or 1250 °C). The highest diametral tensile strength (DTS) of 15.93 MPa was obtained in the 1.6Si-HA sample after heat-treatment at 1250 °C.     

Effect of sintering temperature on mechanical properties of magnesia partially stabilized zirconia refractory

The optimized sintering conditions for a 3.5 wt% magnesia partially stabilized zirconia (Mg-PSZ) refractory were proposed in our recent research. The influence of the sintering temperature on the development of phase composition, microstructure, densification, thermal expansion and mechanical strength was studied in detail by X-ray diffraction (XRD), scanning electron microscope (SEM), He-pycnometer, high temperature dilatometry and three-point bending test. The samples sintered at 1670 °C had the highest bend strength, the maximum densification, the lowest thermal expansion coefficient (CTE), a homogeneous microstructure and a linear change in thermal expansion.     

Effect of sintering temperature on microstructure and mechanical properties of zirconia-toughened alumina machinable dental ceramics

This study investigated the effect of sintering temperature on the microstructure and mechanical properties of dental zirconia-toughened alumina (ZTA) machinable ceramics. Six groups of gelcast ZTA ceramic samples sintered at temperatures between 1100 °C and 1450 °C were prepared. The microstructure was investigated by mercury intrusion porosimetry (MIP), X-ray diffraction (XRD), and scanning electron microscopy (SEM) techniques. The mechanical properties were characterized by flexural strength, fracture toughness, Vickers hardness, and machinability. Overall, with increasing temperature, the relative density, flexural strength, fracture toughness, and Vickers hardness values increased and more tetragonal ZrO₂ transformed into monoclinic ZrO₂; on the other hand, the porosity and pore size decreased. Significantly lower brittleness indexes were observed in groups sintered below 1300 °C, and the lowest values were observed at 1200 °C. The highest flexural strength and fracture toughness of ceramics reached 348.27 MPa and 5.23 MPa m^1/2 when sintered at 1450 °C, respectively. By considering the various properties of gelcast ZTA that varied with the sintering temperature, the optimal temperature for excellent machinability was determined to be approximately 1200–1250 °C, and in this range, a low brittleness index and moderate strength of 0.74–1.19 µm^−1/2 and 46.89–120.15 MPa, respectively, were realized.     

Effect of carbonate content on the in vitro bioactivity of carbonated hydroxyapatite

The effect of carbonate content on the apatite-forming ability of carbonated hydroxyapatite (CHA) in simulated body fluid (SBF) has been investigated. Five different nanocrystalline B-type CHA with carbonate content ranged from 2.01 to 5.25 wt% were prepared, sintered, and assessed for their in vitro bioactivity in SBF solution for 7-weeks under static conditions at 36.5 °C. The formation of the apatite layer and the surface morphology of CHA were examined by using a scanning electron microscope (FESEM) at week 1, 3, and 7 of SBF immersion, respectively. The Ca/P molar ratio of the CHA was determined by X-ray fluorescence (XRF). In addition, the sample weight changes and the pH of the SBF solution were measured. The results show that the formation of apatite layer depends on the carbonate content of CHA. Increasing the carbonate content caused significant increases in the surface area of CHA and the rate of apatite formation. Weight loss was observed for all CHA samples during the first week of SBF immersion, and thereafter followed by weight regain weekly until week 7. The changes in the pH of SBF and the Ca/P molar ratio were proportional to the carbonate content of CHA. This study thus highlights the importance of determining carbonate content aspect that govern the bioactivity of CHA.     

Effects of sintering temperature on mechanical properties of 3D mullite fiber (ALF FB3) reinforced mullite composites

A new method to weaken the interfacial bonding and increase the strength of 3D mullite fiber reinforced mullite matrix (Mu_f/Mu) composites is proposed and tested in this paper. Firstly, Mu_f/Mu composites were fabricated through sol–gel process with varied sintering temperature. Then, the effects of sintering temperature on mechanical properties of the composites were tested. As sintering temperature was raised from 1000 °C to 1300 °C, the three-point flexural strength of the composites firstly decreased from 66.17 MPa to 41.83 MPa, and then increased to 63.17 MPa. In order to explain the relationship between composite strength and sintering temperature, morphology and structure of the mullite fibers and mullite matrix after the same heat-treatment as in the fabrication conditions of the composites were also investigated. Finally, it is concluded that this strength variation results from the combined effects of matrix densification, interfacial bonding and fiber degradation under different sintering temperatures.     

Effect of composition and sintering process on mechanical properties of glass ceramics from solid waste

Sintered diopside glass ceramics were successfully prepared from mixtures of blast furnace slag, fly ash and mining tailing. Results showed that sample C2 with relatively low iron oxides and mass ratio of CaO/SiO₂ possessed the highest bending strength value among samples. A low content of iron oxide enhanced densification degree because pores were developed by reduction of ferric oxide into ferrous oxide. Moreover, a low CaO/SiO₂ mass ratio also greatly promoted the densification process by prolonging the sintering time and delaying the crystallisation. In addition, sample C1 developed by one-stage sintering had a worse mechanical performance than that obtained by two-stage sintering although they had the same crystals. For all samples, despite of different compositions and sintering processes, the main crystal phases are augite and diopside ferrian.     

Effect of TiO2 doping on densification and mechanical properties of hydroxyapatite by microwave sintering

Hydroxyapatite (HAP) possesses excellent bioactivity/osteointegration properties. Nevertheless, its inferior flexural strength and fracture toughness limit its use in human weight-bearing parts. We investigated a microwave sintering technology which can be effectively used to develop titanium dioxide-hydroxyapatite (TiO₂-HAP) ceramics with different amounts of TiO₂ (0.8,1.6,2.4,3.2,4.0,4.8,5.6 and 6.4 wt%), which contribute to extremely high flexural strength (90–130 MPa) along with a good combination of elastic modulus and fracture toughness. The results of the Rietveld refinement show that multiphase bioceramics (HAP, β-TCP) can be achieved by doping nano-TiO₂ under microwave sintering. Despite the fact that the main phases of the sintered TiO₂-HAP ceramics are HAP and β-TCP, X-ray diffraction confirms the formation of the CaTiO₃ and CaTi₂O₄(OH)₂ phases. Furthermore, the sintering reactions to form these phases are discussed and the results show that an appropriate amount of nano-TiO₂ can not only effectively inhibit the growth of grain, but also change the fracture mode and increase the relative density. Finally, it is found that doping nano-TiO₂ by microwave heating is an effective technique for producing HAP/β-TCP composite load-bearing implants in clinical applications without coarsening the size of grain.     

Pressureless sintering and mechanical properties of 3Y-TZP-reinforced LZAS glass-ceramic composites

LZAS glass-ceramic composites toughened by 5, 10, 15 and 20 vol% 3-mol%-Y₂O₃-tetragonal-ZrO₂-polycrystal (3Y-TZP) were prepared via pressureless sintering. Sinterability of composites was investigated in the temperature range of 520–720 °C using soaking time of 30 min. The sintered specimens were characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD) methods. The results revealed that during sintering 3Y-TZP particles agglomerated between the glass powders and were not dissolved by glass-matrix. Mechanical properties of the sintered samples such as bending strength, Vickers micro-hardness and fracture toughness were also investigated. Measurements showed that the relative density of the samples decreased with increasing 3Y-TZP content. The composite containing 15 vol% 3Y-TZP has a best mechanical properties and it would be the optimum composition. It can be confirmed that crack deflection and transformation toughening are the dominant mechanisms for improving mechanical properties of the composites.     

The influence of simultaneous divalent cations (Mg2+, Co2+ and Sr2+) substitution on the physico-chemical properties of carbonated hydroxyapatite

Bone is generally known as calcium-apatite which contains considerable amounts of various trace elements, mainly carbonate. Thus, bone is usually referred as carbonated hydroxyapatite (CHA). The incorporation of dopants into calcium-apatite has been proposed. This approach provides a safer and efficient platform for enhancing bone remodelling. However, reports that emphasize on the influence of multi-dopant substitutions into the CHA structure particularly in the form of as-synthesized powders are limitedly available. The present study investigates the influence of simultaneous substitution of divalent cations, Mg²⁺, Co²⁺ and Sr²⁺ into CHA structure by a nanoemulsion method. Several combinations of ions were doped into the CHA structure. The XRD and FTIR results confirmed that the phase purity and crystallinity were not affected by the simultaneous incorporation of multi-doped ions; all powders remained as amorphous B-type CHA. Despite the small amount of dopants used, all the three cations were successfully substituted into the Ca²⁺ site of CHA structure. The crystallite size of the as-synthesized powder decreased as the amount of incorporated dopants increased. Interestingly, the particle shape showed the transformation from near spherical structures into needle-like structures with increasing amount of dopants. Our finding highlights that the incorporation of these cations into the CHA structure results in crystal imperfections, which cause a substantial dislocation of the crystal lattice, as seen by the alteration of the lattice parameters, crystallite and particle sizes of the as-synthesized powders.     

Hydroxyapatite nanocomposites: Synthesis,sintering and mechanical properties

Two different hydroxyapatite based composites reinforced by oxide ceramic (20 wt%) nano crystals were synthesized by high-energy ball milling and sintered by pressure less technique. Alumina and titania nanoparticles as secondary phases improved densification and mechanical behavior of apatite and postponed its decomposition to the tricalcium phosphate (TCP) phases at elevated temperatures. Increasing the relative density of apatite using nano reinforcements leads to enhance the bending strength by more than 40% and 27% (as compared to the pure HA) and increase the hardness from 2.52 to 5.12 (Al₂O₃ composite) and 4.21 (TiO₂ addition) GPa, respectively. Transmission electron microscopy (TEM), scanning electron microscopy (SEM) and X-ray diffraction spectroscopy were employed to study morphologies, fracture surfaces and phase compositions, respectively. The morphological study and micro structural analysis confirm the X-ray diffraction and relative density diagrams.     

Effect of manganese addition on sintering behavior and mechanical properties of alumina toughened zirconia

The effect of MnO₂ additives on the sintering behavior and mechanical properties of alumina-toughened zirconia (ATZ, with 10 vol% alumina) composites was investigated by incorporating different amounts of MnO₂ (0, 0.5, 1.0, and 1.5 wt%) and sintering at various temperatures ranging from 1300 to 1450 °C. The addition of MnO₂ up to 1.0 wt% improved the sintered density, hardness, flexural strength, and fracture toughness of the composite. However, the addition of 1.5 wt% MnO₂ degraded the relative density, hardness, and flexural strength of the composite due to the transformation of the ZrO₂ phase from tetragonal to monoclinic and grain coarsening. Optimal results were obtained with 1.0 wt% MnO₂ and sintering at 1450 °C, which improved the mechanical properties (hardness: 13.5 GPa, flexural strength: 1.2 GPa, fracture toughness: 8.5 MPa m^1/2) and lowered the sintering temperature compared to the conventional sintering temperature of ATZ composites (1550 °C). Thus, the ATZ composite doped with MnO₂ is a promising material for structural engineering ceramics owing to its improved mechanical properties and lower sintering temperature.     

Influence of sintering temperature on conductivity and mechanical behavior of the solid electrolyte LATP

To warrant long-term reliability for application of electrolytes in solid state batteries also mechanical properties have to be considered. Current work concentrates on Li_1+xAl_xTi_2-x(PO₄)₃ (LATP), which based on its conductivity is a very promising material. Effect of sintering temperature (950, 1000, 1050, 1100 °C) on mechanical properties and conductivity was tested. Impedance tests were carried out and as main focus of the work the mechanical behavior of LATP samples was determined. The impedance tests results revealed that LATP sintered at 1100 °C had the highest ion conductivity. The LATP sintered at 1100 °C revealed also the highest elastic modulus and hardness, which appeared to be related mainly to a smaller lattice parameter with additional effects of lower porosity especially when tested at higher loads. The results indicate that enhancement of both mechanical behavior and conductivity requires lowering secondary phase content and densifying the microstructure of the material.     

Sintering behavior and mechanical properties of spark plasma sintering SiO2-MgO ceramics

SiO₂-MgO ceramics containing different weight fractions (0, 0.5, 1, 2, and 4 wt%) of SiO₂ powder were prepared by mixing nano MgO powder, and the powder mixtures were densified by spark plasma sintering (SPS). The effect of SiO₂ addition and SPS method on the sintering behavior, microstructure and mechanical properties were investigated. Results were compared to specimens obtained by conventional hot pressing (HP) under a similar sintering schedule. The highest relative density, flexural strength and hardness of 2 wt% SiO₂-MgO ceramics reached 99.98%, 253.99 ± 7.47 MPa and 7.56 ± 0.21 GPa when sintered at 1400 °C by SPS, respectively. The observed improvement in the sintering behavior and mechanical properties are mainly attributed to grain boundary "strengthening" and intragranular "weakening" of the MgO matrix. Furthermore, the spark plasma sintering temperature could be decreased by more than 100 °C as compared with the HP method, SPS favouring enhanced grain boundary sliding, plastic deformation and diffusion in the sintering process.     

Microstructure and mechanical properties of hot-pressed carbon nanotubes compacted by spark plasma sintering

Bulk carbon nanotube samples were prepared by spark plasma sintering. The as-prepared bulk carbon nanotube material exhibited brittle fracture similar to that of common ceramics. Its fracture toughness was around 4.2 MPa m^1/2 while flexural strength was 50 MPa due to the weak bonding between carbon nanotubes. Obvious carbon nanotube bridging was found during the development of the crack induced by an indenter, which provides a possibility of carbon nanotube tough material.     

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.     

Gelcasting and sintering of hydroxyapatite materials: Effect of particle size and Ca/P ratio on microstructural,mechanical and biological properties

The sintering behaviour and microstructural evolution of two batches of a commercial calcium-deficient hydroxyapatite powder were investigated. First, the sintered density as a function of the starting particle size distribution was studied, and the minimum particle size to get the desired target density was determined. Then, as the two batches were characterized by a slight difference in Ca/P ratio, the role of such ratio on phase and microstructural evolutions during sintering, as well as on mechanical and biological properties was investigated.It was observed that the powder with lower Ca/P ratio underwent significant hydroxyapatite (HA) to β-tricalcium phosphate (β-TCP) decomposition, with a simultaneous formation of tetracalcium phosphate (TTCP). The microstructure of sintered gelcast samples evolved during isothermal sintering at 1300 °C, moving from a starting homogeneous and narrow grain size distribution to a bimodal distribution after 3 h sintering. In fact, over time, large grains decomposed into smaller ones, finally providing a microstructure composed of coarse grains surrounded by plenty of ultra-fine grains. On the contrary, the powder with the higher Ca/P ratio provided a limited HA to β-TCP transformation, and normal grain growth by increasing the sintering time. Such differences lead to different mechanical properties for gelcast samples produced by the two powder batches, as the material with the lower Ca/P ratio affected by lower mechanical strength. Finally, sintered samples from both powders showed in-vitro bioactivity, with a larger surface coverage observed for the lower Ca/P ratio material. The morphology of the apatite layer seemed to be affected by the material composition, too, showing flake-like and needle-like morphologies depending on the Ca/P ratio of the starting powder.     

Effect of composition on phase assemblage,microstructure, mechanical and optical properties of Mg-doped sialon

Mg-doped sialon (Mg_m/2Si_12−m−nAl_m+nO_nN_16−n) ceramics with different compositions of m = 2n = 0.6, 0.84, 1.0, 1.2, 1.6 were hot pressed at 1850 °C for 1 h. Phase assemblage, microstructure, mechanical and optical properties of these samples were investigated. All samples achieved/approached full densification. However, the densification of Mg-doped sialon ceramics with higher MgO/AlN content becomes more difficult. Additionally, the anisotropic growth of β-sialon grains was significantly inhibited. The unique characteristics of Mg-doped sialon ceramics intrinsically derive from the formation of Mg-containing AlN polytypoids, which consumed most of the high-temperature liquid. Furthermore, their high stability at high temperatures accounts for the difficulty in preparing single-phase Mg-α-sialon., The hardness of these samples gradually increases while indentation fracture toughness gradually decreases with increasing m = 2n value. Due to little residual glassy phase, high infrared transparency/translucency was more readily achieved in Mg-doped sialon. The m = 1.2 sample possesses the maximum transmittance of ∼50% at ∼2 μm.     

Effect of YAG content on creep resistance and mechanical properties of Al2O3-YAG composite

Comprehensive study on effect of YAG amount on densification, creep resistance and room-temperature mechanical properties of Al₂O₃-YAG composite pressureless sintered at 1600 °C was conducted. The main goal was to optimize the amount of YAG in order to fabricate a composite with improved creep resistance and sufficiently good room-temperature mechanical properties. The composite was made by mixing a commercially available Al₂O₃ powder with fine YAG powder obtained by glycine-nitrate combustion synthesis starting from aluminum nitrate and yttrium nitrate. Increased driving force for sintering of fine YAG powder allowed fabrication of dense Al₂O₃-YAG composite with up to 30 vol% YAG. The presence of YAG was found to be very effective in improving creep resistance of Al₂O₃-YAG composite. Large Y³⁺ ions blocked diffusion along Al₂O₃ grain boundaries, reduced diffusivity and therefore enhanced creep resistance of Al₂O₃-YAG composite which continuously increased as the YAG amount increased. Тhe presence of YAG was also found to improve mechanical properties such as hardness and elastic modulus. The improvement of these properties was ascribed to increased density of Al₂O₃-YAG composites owing to high sintering activity of YAG powder. While fracture strength of the composite can be as high as that of monolithic Al₂O₃, fracture toughness of composite decreased continuously as the YAG content increased. The decrease was ascribed to transgranular fracture of both YAG and Al₂O₃ grains in samples containing larger amounts of YAG. The proper balance between fracture toughness and creep resistance was found in composite containing 18 vol% YAG which had considerably improved creep resistance accompanied by a relatively small decrease in fracture toughness.     

Improvement of the hydroxyapatite mechanical properties by direct microwave sintering in single mode cavity

The main purpose of this study consists in investigating the direct microwave sintering of hydroxyapatite (HA) in a single mode cavity. Firstly, stoichiometric HA powders were synthesized by a coprecipitation method from diammonium phosphate and calcium nitrate solutions and shaped by slip-casting. Then, using the one-step microwave process, dense pellets with fine microstructures were successfully obtained in short sintering timespan. A parametric study permitted to determine the influence of powder grain size, sintering temperature and dwell time on the sintered samples microstructures. The Young's modulus (E) and hardness (H) were measured by nanoindentation and the values discussed according to the microstructure. Finally, the resulting mechanical properties determined on the microwave sintered samples (E = 148.5 GPa, H = 9.6 GPa, σ_compression = 531.3 MPa and K_IC = 1.12 MPa m^1/2) are significantly higher than those usually reported in the literature, whatever the sintering process, and could allow the use of HA for structural applications.