Production of porous calcium phosphate (CaP) ceramics with highly elongated pores using carbon-coated polymeric templates

This study reports a new way of enhancing the compressive strength of porous calcium phosphate (CaP) ceramics by creating highly elongated pores. These elongated pores were produced by casting a CaP/camphene slurry into stretched polymeric sponges with a thick carbon coating layer used as a template. The sample produced after sintering at 1250 °C for 3 h showed a highly elongated porous structure with a porosity of 38 ± 1.2 vol%, where elongated pores with a size of 512 ± 96 μm were formed as a replica of the template. In addition, CaP walls with a thickness of 841 ± 239 μm were fully densified without any noticeable defects due to the high CaP content of 40 vol% in the CaP/camphene slurry. The compressive strength of the sample was as high as 21 ± 4.9 MPa when tested parallel to the direction of pore elongation, which is much higher than that (12 ± 2.4 MPa) of the sample tested normal to the direction of pore elongation. The sample also showed good biocompatibility, as assessed by the in vitro cell test using a pre-osteoblast cell line.     

Modelling the mechanical properties of microporous and macroporous biphasic calcium phosphate bioceramics

Macroporous biphasic calcium phosphate bioceramics, for use as bone substitutes, have been fabricated by cold isostatic pressing and conventional sintering, using naphtalen particles as a porogen to produce macropores. The resulting ceramics, composite materials made of hydroxyapatite and β-tricalcium phosphate (TCP) containing 45% macropores and with various microporosities, have been submitted to compression and three-point bending tests, toughness tests by single-edge-notched-bending (SENB), and spherical indentation tests. By combining two approaches at two different scales, one for closed porosity and one for open porosity, a model is established to describe mechanical properties as a function of the amount and morphology of porosity. The model assumes a quasi-continuous matrix containing macropores, the matrix being itself microporous, and considers that fracture always initiates on a macropore. The preliminary mechanical tests performed on the sintered ceramics tend to validate the modelling approach.     

Preparation and properties of mullite-bonded porous fibrous mullite ceramics by an epoxy resin gel-casting process

Porous fibrous mullite ceramics with a narrow range of pore size distribution have been successfully prepared utilizing a near net-shape epoxy resin gel-casting process by using mullite fibers, Al₂O₃ and SiC as raw materials. The effects of sintering temperatures, different amounts of fibers and Y₂O₃ additive on the phase compositions, linear shrinkage, apparent porosity, bulk density, microstructure, compressive strength and thermal conductivity were investigated. The results indicated that mullite-bonded among fibers were formed in the porous fibrous mullite ceramics with a bird nest pore structure. After determining the sintering temperatures and the amount of fibers, the tailored porous fibrous mullite ceramics had a low linear shrinkage (1.36–3.08%), a high apparent porosity (61.1–71.7%), a relatively high compressive strength (4.4–7.6 MPa), a low thermal conductivity (0.378–0.467 W/m K) and a narrow range of pore size distribution (around 5 µm). The excellent properties will enable the porous ceramics as a promising candidate for the applications of hot gas filters, thermal insulation materials at high temperatures.     

Fabrication,characterization and cellular biocompatibility of porous biphasic calcium phosphate bioceramic scaffolds with different pore sizes

Facile wet-chemical methods are applied to synthesize hydroxyapatite and β-tricalcium phosphate nanoparticles, respectively. Porous biphasic calcium phosphate (BCP) bioceramic scaffolds are then fabricated using as-prepared HA and β-tricalcium phosphate nanoparticle powders. The macro pore diameter of BCP bioceramic scaffolds can be controlled by adjusting the amount of surfactants. The average diameter of the macro pores in BCP bioceramic scaffolds increases from 100 to 600 µm with the decrease amount of sodium dodecyl sulfate from 0.8 to 0.5 g, respectively. The BCP bioceramic scaffolds gradually degrade and the calcium-phosphate compounds fully deposit when soaking in simulated body fluid solution. Moreover, The BCP bioceramic scaffolds have outstanding biocompatibility to promote the cellular growth and proliferation of human dental pulp stem cells (hDPSCs). The hDPSCs also demonstrate favorable cellular adhering capacity on the pore surface of scaffolds, especially on the scaffolds with 100–200 µm pore diameter. The porous BCP bioceramic scaffold with inter-connected pore structure, outstanding in vitro cellular biocompatibility, favorable cell viability and adhesion ability will be a promising biomaterial for bone or dentin tissue regeneration.     

Highly loaded hydroxyapatite microsphere/ PLA porous scaffolds obtained by fused deposition modelling

The goal of the work was the manufacturing of hydroxyapatite microsphere/polylactic acid (PLA) scaffolds by means of fused deposition modelling (FDM). Micrometer-sized hydroxyapatite spheres synthesized by spray drying (sdHA), were dispersed in PLA by extrusion compounding. Composite filaments were obtained from extrusion which were used in FDM 3D printing for the production of macroporous scaffolds. The sdHA microspheres were used in the composite in order to improve the biomimicry and the bioactivity of the 3D printed scaffold to increase the bone regeneration capacity. Morphological, thermal, physical and mechanical characterizations were performed on the 3D printed composites. Pure PLA scaffolds were 3D printed and used as a reference.Thermal analyses, TGA and DSC evidenced that the glass transition temperature and the degree of crystallinity of PLA were not influenced by the presence of sdHA. Morphological analysis showed a smooth surface of the printed samples when pure PLA was used. A rough surface was found on the PLA/sdHA composites, confirming, the homogeneous dispersion of the ceramic phase in the polymeric matrix. The higher porosity of the composite samples compared to PLA ones, most likely caused a decrease of the mechanical performances of the PLA/sdHA scaffolds. Composite scaffolds displayed stiffness values compatible with that of bone tissue.     

Preparation and properties of dense and porous calcium phosphate

A dense tricalcium phosphate possesses E- and shear-modulus of 115 and 86 GPa, respectively. By polyurethane foam and C-fibres a high porous structure with integral porosity of 55–70% was created. The porous tricalcium phosphate possesses a E-modulus of 2–5 GPa, bending strength of 6–11 MPa and compressive strength of 11–22 MPa. Regarding mechanical properties this system could be ranged between cortical and cancellous bone. ©     

叔丁醇基凝胶注模成型制备氧化铝多孔陶瓷

以微米级Al2O3粉料为原料,叔丁醇为溶剂,采用凝胶注模成型工艺制备了氧化铝多孔陶瓷,并研究了Al2O3浆料的固相体积分数(分别为8%、10%、13%和15%)对1 500℃保温2 h烧后氧化铝多孔陶瓷的气孔率、气孔孔径分布、耐压强度、热导率和显微结构的影响.结果表明:当Al2O3浆料的固相体积分数从8%增加到15%时,氧化铝多孔陶瓷烧结体的总气孔率从71.2%逐渐降低至61.2%,气孔平均孔径从1.0 μm逐渐减小至0.78 μm,耐压强度从16.0 MPa逐渐增大至45.6 MPa,而热导率从1.03 W·(m·K)-1逐渐增大至1.83W·(m·K)-1.     

Preparation of calcium hexaluminate porous ceramics by gel-casting method with polymethyl methacrylate as pore-forming agent

Calcium hexaluminate (CA₆) porous ceramics were prepared by gel-casting method, with α-Al₂O₃ and CaCO₃ as raw materials and polymethyl methacrylate (PMMA) microspheres as pore-forming agent. The effects of the amount of pore-forming agent PMMA microspheres on the phase composition, bulk density, apparent porosity, flexural strength, microstructure, thermal shock stability and thermal conductivity of CA₆ porous ceramics were systematically studied. The pores of CA₆ porous ceramics are mainly formed by the burning loss of PMMA microspheres and the decomposition of organic matter. Adding an appropriate amount of PMMA microspheres as pore-forming agent has a positive effect on the thermal shock stability of CA₆ porous ceramics. When the amount of pore-forming agent is 15 wt%, the volume density of CA₆ porous ceramics is 1.33 g/cm³, the porosity is 63%, the flexural strength is 13.9 MPa, the thermal shock times can reach 9 times, and the thermal conductivity is 0.293 W/(m·K), which can meet the application in refractory, ceramics or high temperature cement industries.     

Effect of sintering temperature on compressive strength of porous yttria-stabilized zirconia ceramics

Porous yttria-stabilized zirconia (YSZ) ceramics were fabricated by tert-butyl alcohol (TBA)-based gel-casting method for potential applications in heat-insulation materials. The effect of sintering temperature on compressive strength of porous YSZ ceramics was investigated on the basis of measurements linear shrinkage, porosity and pore size. As the sintering temperature increased from 1350 to 1550 °C, a decrease of porosity from 77 to 65%, a decrease of average pore size from and an increase of linear shrinkage from 15.4 to 31.8% were observed. The compressive strength increased remarkably from 3 to 27 MPa with increasing sintering temperature from 1350 to 1550 °C, which was related to the corresponding change of linear shrinkage, porosity, pore size and microstructure. A remarkable decrease of compressive strength with increasing porosity was observed. The compressive strength decreased also with increasing pore size.     

Fabrication and properties of dense silicon carbide ceramic via gel-casting and gas silicon infiltration

The dense Silicon Carbide (SiC) ceramics are fabricated by means of gel-casting and gas silicon infiltration (GSI) using carbon black and α-SiC as raw materials. We have successfully introduced a new initiator AIBA which is very suitable to aqueous gel-casting system containing carbon black, overcoming the problems posed by the conventionally used initiator. We have investigated the influences of the monomer acrylamide (AM) content, the ratio of the monomer to crosslinking agent AM/MBAM content, the particle size distribution and the solid content on the mechanical and structural properties of samples. The result show that, the linear shrinkage of the green body can be reduced to 1.0% and its bending strength can reach 59.2 MPa at the optimized gel-casting process that has an AM content of 25 wt%, an AM to MBAM ratio of 12, a SiC particle distribution of 3/2 and a solid content of 60 vol%. After the GSI process, the bending strength and elastic modulus of the final products from such green bodies can reach 245 MPa and 220 GPa respectively. The study highlights that the combined application of the gel-casting and the GSI processes can produce high-quality silicon carbide ceramics that are suitable in the space optical applications.     

Fabrication of CaSiO3 bioceramics with open and unidirectional macro-channels using an ice/fiber-templated method

Porous CaSiO₃ bioceramics with open and unidirectional macro-channels of pore size more than 200 μm are of particular interest for biomedical applications. An ice/fiber-templated method was employed for the fabrication of CaSiO₃ bioceramics with interconnected lamellar pores and macro-channels of pore size more than 200 μm. The pores formed by ice crystals transformed from cellular to lamellar, while the pores formed by fibers were aligned macro-channels, which were also in alignment with the lamellar pores. Keeping the initial slurry concentration constant and increasing the packing density of fibers, the volume fraction of macro-channels and open porosity increased, and the compressive strength decreased. Maintaining the packing density of fibers and increasing the initial slurry concentration, the pore sizes of lamellar pores and open porosity decreased, and the compressive strength increased. The results indicated that it was possible to manufacture porous CaSiO₃ bioceramics with the macro-channels of 250–350 μm, lamellae spacing of 50–100 μm, open porosity of 71.12–83.94% and compressive strength of 0.87–3.59 MPa, indicating the suitability for tissue engineering.     

Enhanced mechanical properties and biological responses of SLA 3D printed biphasic calcium phosphate bioceramics by doping bioactive metal elements

Favorable mechanical properties and outstanding bioactivity are necessary for bioceramics used for bone defect repair. The doping of Mg²⁺ and Fe³⁺ can improve the mechanical properties and bone regeneration capacity of calcium phosphate ceramics. In this study, magnesia oxide (MgO), ferric oxide (Fe₂O₃), and iron (Fe) powders are chosen as dopants to enhance biphasic calcium phosphate (BCP) bioceramics, and the MgO-BCP, Fe₂O₃-BCP, Fe-BCP bioceramics are prepared by stereolithography (SLA) for the first time. The effects of these dopants on the curing behavior of bioceramic slurries, mechanical properties, biodegradation, and cytocompatibility of BCP bioceramics are studied. The addition of 1 wt% Fe well enhances the flexural strength of BCP from 91.61 MPa to 122.60 MPa sintered at 1250 °C. The addition of 1 wt% MgO effectively promotes the biodegradation of BCP in simulated body solution (SBF), and enhances the proliferation of mouse pre-osteoblast (MC3T3-E1) cells in vitro. In addition, Fe powder is more suitable as a dopant for SLA 3D printed BCP than Fe₂O₃ powder, and all the performances of Fe-BCP are better than those of Fe₂O₃-BCP. The less microstructure defects and slower Fe³⁺ release rate make Fe-BCP have higher flexural strength and less cytotoxic compared with Fe₂O₃-BCP. This novel way exhibits beneficial effects of bioactive metal elements on mechanical properties and bioactivity, and indicates SLA 3D printed BCP bioceramic doped with MgO, Fe can be promising candidates for bone defect repair.     

Gelcasting of alumina foams using agarose solutions

Aqueous gelcasting of dense or cellular ceramics by using biopolymers as gel-formers, instead of monomers, is a promising technology mainly in terms of environmental aspects. The main difficulty of using biopolymer solutions in processing of cellular ceramics by foaming method is their high viscosity, which prevents the foaming capacity of the ceramic suspension. In this work, the procedure for preparing concentrated agarose solutions (4 wt.%) by dissolving under overpressure conditions was evaluated for the gelcasting of alumina foams, and the rheological behaviour of alumina suspensions containing agarose was studied. The viscosity of the gelling solution obtained under overpressure conditions was lower than that prepared by simply heating at 90 °C, thus providing high foaming capacity of the alumina suspensions and consequently manufacturing of highly porous ceramics (86–90%). The microstructure of alumina foams was typically composed of approximately spherical cells interconnected by circular windows. The use of different agarose concentrations in alumina suspensions effected the rheological conditions, which resulted in changes in the pore and window sizes of the resulting ceramics. Depending on agarose concentration (0.50–1.0 wt.% on a dry solids basis) in the starting (35 vol.%) alumina slurry, the mean pore size ranged from 529 to 375 μm, while the mean window size varied from 113 to 77 μm.     

An in situ study of the deposition of a calcium phosphate mineralized layer on a silicon-substituted hydroxyapatite sensor modulated by bovine serum albumin using QCM-D technology

The deposition of a calcium phosphate (Ca-P) mineralized layer on Si-HA surface (the blank group, Au and the control group, HA) with and without BSA preadsorption was observed in real time using a quartz crystal microbalance with dissipation (QCM-D) technique. The effect of silicon doping on the adsorption of BSA onto a HA sensor was investigated. Approximately 1.5-fold more BSA adsorbed onto HA than Si-HA, indicating the inhibition of BSA adsorption onto the HA sensor by silicon doping. The decreasing ΔD_sat/Δf_sat value in the plots of ΔD–Δf versus adsorption time was predominantly attributed to BSA adsorption, and the decreasing ΔD value with adsorption time during adsorption equilibrium could be explained by the structural rearrangement of BSA on different substrates. Specifically, BSA preadsorption could be a trigger for the formation of nucleation sites for the mineralized layer, promoting nucleation but inhibiting growth. The growth rate was greater on bare substrates than on BSA adsorption substrates. The growth rate of the mineralized layer on the adsorbed BSA layer depended on the substrates in the following manner: Au>Si-HA>HA. The morphology of the mineralized layer depended on the surfaces, and a greater number and a more uniform distribution of smaller nanoparticles were observed on surfaces with preadsorbed BSA. Therefore, BSA could modulate the growth of the mineralized layer at the interface, which is advantageous for fabricating advanced biomaterials.     

Porous wollastonite-hydroxyapatite bioceramics from a preceramic polymer and micro- or nano-sized fillers

Wollastonite-hydroxyapatite ceramics have been successfully prepared by a novel method, corresponding to the thermal treatment in air of a silicone embedding micro- and nano-sized fillers. CaCO₃ nano-sized particles, providing CaO upon decomposition, acted as “active” filler, whereas different commercially available or synthesised hydroxyapatite particles were used as “passive” filler. The homogeneous distribution of CaO, at a quasi-molecular level, favoured the reaction with silica derived from the polymer, at only 900 °C, preventing extensive decomposition of hydroxyapatite. Open-celled porous ceramics suitable for scaffolds for bone-tissue engineering applications were easily prepared from filler-containing silicone resin mixed with sacrificial PMMA microbeads as templates. The pore size (in the range of 80-400 μm) and the open porosity percentage (40-50%) were evaluated by means of micro-computerized tomographic analysis. A preliminary assessment of the biocompatibility and cell activity of the produced ceramics was performed successfully by in vitro tests using human osteoblast cells.     

Gas flow through highly porous graphite matrices

Highly porous graphite matrices with 20-200 kg m⁻³ of bulk densities have been characterized using helium pycnometer, mercury porosimeter, and fluid flow methods, i.e. both gas permeation and diffusion measurements. The gas permeability is ranging from 10⁻¹² to 10⁻¹⁵ m² and decreases as the bulk density of the graphite matrix increases. According to the Carman-Kozeny correlation, the evolution of the gas permeability with respect to the bulk density is very well correlate with, on the one hand, the increase of the tortuosity, and on the other hand, the decrease of the porosity as well as the pore diameter with the bulk density of the graphite matrix.     

Manufacturing porous multi-channel ceramics by laser gelling

This article describes a novel layer manufacturing process for forming a ceramic part with porous multi-channel architecture by laser gelling under low laser energy. The process involves bonding silica powder by gelled silica sol after exposure by a CO₂ laser. Lower laser energy density of 0.8 J/mm² is required to produce ceramic parts by “gelling effect”. Therefore, the geometrical deflection and thermal distortion can be reduced after laser scanning. The inner porous structures were supported by ceramic slurries to prevent sagged deflection and to enhance dimensional accuracy due to optimal slurry suspension. The flexural strength of the green specimen was 4.7 MPa, while that of the gelled specimen was 12.5 MPa after heat-treatment at 1200 °C for 1.5 h. The proposed process has potential for fabricating complex interconnected porous ceramics for tissue engineering applications.     

Flash sintering of tricalcium phosphate (TCP) bioceramics

Tricalcium phosphate (β-TCP) bioceramic was consolidated by flash sintering in the present work.TCP powders were synthesized by solid-state route, starting from calcium carbonate and ammonium phosphate, and shaped into cylindrical pellets of different height by uniaxial pressing. Sintering was performed within an on purpose modified dilatometer working under constant heating rate and monitoring shrinkage and electrical parameters (current and field), simultaneously.The obtained TCP bodies exhibit well densified microstructure, maintaining the β-TCP composition.A power balance model, based on a thermal runaway mechanism and considering the contribution of the contact resistance on the voltage actually applied on TCP material, is shown to successfully predict the flash phenomenon.The achieved results, although preliminary, show the possibility to employ flash sintering to obtained dense β-TCP products at lower furnace temperature and in shorter time with respect to the conventional process, avoiding the undesirable expansion related to the β–α transition.     

The effect of the shape and size of the pores on the mechanical properties of porous HAP-based bioceramics

In this study, the influence of the shape and size of the pores on the mechanical properties of the obtained porous HAP-based bioceramics was investigated. The porous HAP-based bioceramics were obtained starting from spherical calcium hydroxyapatite powder, obtained by hydrothermal syntheses. The number of shapeless inter-agglomerate pores decreased and amount of spherical intra-agglomerate pores increased on increasing the sintering temperature from 1100 °C to 1250 °C. The shape of pores also changed with thermal treatment of specimens; the small pores remained spherical while the larger pores became more spherical in shape, as was proved by image analysis. A three-dimensional, finite element unit cell model was applied to evaluate the influence of pore shape on the mechanical strength of HAP ceramics. By analyzing the effect of the shape of pores to the fracture toughness of sintered porous HAP bioceramics, it was observed that the more spherical the pores were, the tougher became the bioceramics. After sintering at 1250 °C for 2 h, measured toughness was 1.31 MPa m^1/2, which is a relatively high value for this type of bioceramics.     

Porous fibrous ZrO2-mullite ceramics prepared via tert-butyl alcohol-based gel-casting

Mullite fiber was used to fabricate ZrO₂-mullite based porous ceramic via tert-butyl alcohol (TBA)-based gel-casting process using zirconite and bauxite as raw materials. Phase compositions, microstructure, pore size distribution, linear shrinkage, bulk density, apparent porosity, thermal conductivity, and compressive strength were analyzed to investigate influences of mullite fiber content and added Y₂O₃ on prepared porous ceramics. Results show that bird nest-like three-dimensional fibrous reticular skeleton structure was constructed with mullite fibers that evenly enwrapped rod-like mullite and ZrO₂ grains. Prepared porous fibrous ZrO₂-mullite ceramics had narrow pore size distribution that consisted of mullite and m-ZrO₂. With an increase in mullite fiber content, linear shrinkage and bulk density decreased, apparent porosity increased, and relatively good thermal conductivity was obtained. In addition, added Y₂O₃ reacted with Al₂O₃ and SiO₂ to form Y-Al-Si-O glass phase, which promoted sintering and densification of the ceramic, thus improving its compressive strength.