Application of hydrophilic ionic liquid treatment to the morphological observations of hydrated porous ceramic green bodies

In this study, a simple and convenient method for observing the surface morphology of hydrated porous ceramic green bodies is proposed. The porous hyrdoxyapatite (HAp) green body was prepared by a gelcasting process and was dried in a humid chamber from 90 to 50% relative humidity at 25 °C before subsequent treatment with a hydrophilic ionic liquid (IL). The surface morphology of the IL-treated porous HAp green body was observed using FE-SEM. The results showed that the pore morphology and microstructure of the HAp green body was readily observable without evidence of charging. The as-prepared sample showed pores approximately 300–600 μm in diameter, which gradually contracted to approximately 200–400 μm upon drying in the humid chamber. Following sintering at 1000 °C, the pores had further contracted to approximately 100–300 μm. The IL binds with the surrounding water to prevent the sample from drying in vacuum and acts as a conductive media, allowing the HAp ceramics to be observed in the electron microscope. In comparison to the micro-focused X-ray CT analysis, the fine pore structure (less than 100 μm) could only be observed using FE-SEM when the porous body had also been subjected to the IL treatment.     

Preparation and properties of bimodal porous apatite ceramics through slip casting using different hydroxyapatite powders

A bimodal porous hydroxyapatite (HAp) body with high flexural strength was prepared through slip casting. The effect of different particle sizes on the flexural strength and microstructure of three different types of hydroxyapatite (HAp) powders was studied. The powder characteristic of laboratory-synthesized HAp powder (L-HAp) was obtained through a wet-milling method, drying and heating of a mixture of calcium hydrogen phosphate di-hydrate and calcium carbonate. The median particle size of L-HAp was 0.34 μm, and the specific surface area was 38.01 m²/g. The commercial HAp had median particle sizes for the K-HAp (Kishida chemical Co. Ltd., K-HAp) and T-HAp (Taihei chemical Co. Ltd., T-HAp) of 1.13 and 3.65 μm, and specific surface areas of 11.62 and 6.23 m²/g, respectively. The different powder characteristics affected the slip characteristics, and the flexural strength and microstructure of the sintered porous HAp bodies were also different. The flexural strengths of the porous HAp ceramics prepared by heating at 1200 °C for 3 h in air were 17.59 MPa for L-HAp with a porosity of 60.48%, 3.92 MPa for commercial K-HAp with a porosity of 79.37%, and 4.55 MPa for commercial T-HAp with a porosity of 76.46%.     

Effects of inert filler addition on the structure and properties of porous SiOC ceramics derived from silicone resin

Porous SiOC ceramics were obtained from a new self-blowing precursor silicone resin DC217, by pyrolysis at 1200 °C in argon. Silicon carbide powders were incorporated into the silicone resin as inert fillers. The effects of the mean particle size of SiC fillers on the porosity, compressive strength and microstructure of the porous ceramics were investigated. With the mean particle size of SiC powders increasing from 5 μm to 10 μm, the porosity (total and open) of the porous ceramic increased and the compressive strength decreased. However, the porosity, compressive strength and cell morphology of the porous ceramics showed no evident changes when the mean particle size of fillers increased from 10 μm to 15 μm. Micrographs indicated that, when the mean particle size of fillers exceeded 5 μm, the porous ceramics could have a well-defined and regular pore structure. Furthermore, comparing with the porous ceramics which fabricated under the same condition with the SiOC powders as fillers, the cell morphology was similar. But the compressive strength and the oxidation resistance of the porous ceramics with SiC powders as fillers were much better.     

Preparation of dense β-CaSiO3 ceramic with high mechanical strength and HAp formation ability in simulated body fluid

In present study, dense CaSiO₃ (CS) ceramics have been fabricated through spark plasma sintering (SPS) technique using β-CS powder prepared by chemical precipitation method. The β-CS ceramic sintered at 950 °C has a relative density of about 95% and shows a fine microstructure with an average grain size of 0.6 μm, thus expresses good bending strength of about 294 MPa. The simulated body fluid (SBF) immersion tests show that the dense β-CS ceramic has a high hydroxyapatite (HAp) formation rate on its surface. The HAp layer formed on the CS ceramic surface has a granular structure consisting of silkworm-like HAp grains, and the thickness of HAp and Si-rich layer are 70 and 120 μm, respectively.     

Microstructure and mechanical properties of ZrB2–SiC porous ceramic by camphene-based freeze casting

Camphene-based freeze casting technique was adopted to fabricate ZrB₂–SiC porous ceramic with 3-dimensional (3D) pore network. ZrB₂–SiC/camphene slurries (initial solid loading: 20 vol%, 25 vol% and 30 vol%) were prepared for freeze casting. Regardless of initial solid loading, the fabricated sample had dense/porous dual microstructure. The thickness of dense layer was about 200–300 μm. The microstructures of ZrB₂–SiC porous ceramics were significantly influenced by the initial solid loading, which determines the pore size, porosity and mechanical properties of the final products.     

Effects of PMMA on porous structure of pollucite

The effects of PMMA as a pore-forming reagent and the powder for Cs-deficient pollucite, Cs₉Al_0.9Si_2.1O₆, calcined at 1073 K, on the microstructure of the porous body of Cs_0.9Al_0.9Si_2.1O₆ were investigated. The Cs_0.9Al_0.9Si_2.1O₆ porous bodies were fabricated by sintering the green compacts of the calcined powder and PMMA adding 35 mass% to the calcined powder. When the green compact was heated at 873 K in air for 20 h, pores <1 μm were observed in the porous body, suggesting that the PMMA previously dissolved in acetone was uniformly distributed in the calcined powder by the ball milling. The pore size of the obtained porous structure increased with increasing the size of the aggregated particles and the pore size distribution was significantly related to the size of Al₂O₃ balls and the time for the ball milling for mixing the calcined powders and PMMA.     

The effect of surface treatment on CaP deposition of Ti6Al4V open cell foams in SBF solution

The effects of alkali and nitric acid surface treatment and acid etching on the CaP deposition of an open cell Ti6Al4V foam (60% porous and 300–500 μm in pore size) developed for biomedical applications were investigated in a simulated body fluid (SBF) solution for 14-day. The surface roughness of the foam specimens ground flat surfaces was measured in nano-metric scale before and after SBF immersion using an atomic force microscope (AFM). A significant increase in the surface roughness of alkali treated foam specimen after SBF immersion indicated a smaller crystal size CaP deposition, which was also confirmed by the AFM micrographs. The microscopic evaluation clearly showed that alkali treatment and nitric acid treatment induced a continuous, uniform CaP deposition on the cell wall surfaces of the foam (interior of cells). While in untreated foam specimen the cells are filled with CaP precipitates and acid etching did not produce a continuous coating layer on particles interior of the cells. The coating layer thickness was ～3 μm in alkali treated foam specimens after 14-day of SBF immersion, while nitric acid treatment induced relatively thinner coating layer, 0.6 μm.     

Synthesis of hierarchical porous silicon oxycarbide ceramics from preceramic polymer and wood biomass composites

Hierarchical porous SiOC ceramics were successfully prepared using a polysiloxane preceramic polymer mixed with wood biomass by annealing at different temperatures under Ar atmosphere. These SiOC ceramics display a trimodal pore size distribution in the micro-, meso- (micropores + mesopores, 1.7–14 nm) and macro-size scale (1–15 μm). The mesopores and micropores mainly originate from the formation of large amounts of SiC crystals and nanowires, graphite-like microcrystallites, and nm-scale pores of ray parenchyma cells and pits of the wood biomass. The SiOC sample prepared at a higher temperature processes the specific surface area up to 180.5 m²/g. The specific surface area, pore volume and average pore width of the samples can be controlled by adjusting the pyrolysis temperature.     

Preparation and hierarchical porous structure of biomorphic woodceramics from sugarcane bagasse

Biomorphic woodceramics with controllable pore structure were prepared from sugarcane bagasse impregnated with epoxy resin followed by sintering at different temperatures. The phase composition, chemical composition, morphology and pore texture of the products were characterized by XRD, FTIR, SEM, mercury porosimetry and N₂ adsorption. The biomorphic woodceramics are typical non-graphitizable carbon and display a hierarchical porous structure from micrometer (0.6–21 μm) to nanometer scale (3.1–9.3 nm). The woodceramics retain the tubular structures of sugarcane bagasse before calcination at 1100 °C. Furthermore, an increase in the sintering temperature results in the decrease of BET surface area, average pore diameter and pore volume in the mesopore scale. This work provides a simple, economical, and environmentally friendly method for the production of hierarchical porous woodceramics. The final products have their potential applications as adsorbents, catalyst supports and filters.     

Porous SiC/SiCN composite ceramics fabricated by foaming and reaction sintering

Porous SiC/SiCN composite ceramics with heterogeneous pore structure and rod-like SiCN grains were fabricated by foaming and reaction sintering. The mixture slurry containing SiC and silicon as raw materials, cornstarch as binder, Y₂O₃ as sintering additive and an electrosteric dispersant was stirred with foams derived from pre-foaming using foaming agent. The casted green body was sintered at 1650 °C under nitrogen atmosphere. The results demonstrated that the porous SiC/SiCN ceramics exhibited hierarchical vias ranging from 1 μm to 1 mm and the rod-like crystalline SiCN grains generated in the SiC matrix.     

Fabrication and thermal conductivity of highly porous alumina body from platelets with yeast fungi as a pore forming agent

A highly porous alumina body was fabricated by heating a green clinker body consisting of platelets and yeast fungi as a pore forming agent. Four kinds of alumina platelets were used. When green clinker bodies of platelet aggregates (A11) with 10 and 30 mass% of yeast fungi were heated at 1500 °C for 2 h, their porosities reached 72% and 78%, respectively. In contrast, when the green clinker bodies composed of platelets with an average size of 10 µm and an aspect ratio of 25–30 (SERATH①), and 20 mass% of yeast fungi were heated at 1400 °C for 2 h, the porosity of the resultant porous alumina body was also approximately 72%. However, the room temperature thermal conductivities of the porous alumina bodies with 72% porosity derived from A11 and SERATH① were 0.86 and 0.50 W m⁻¹ K⁻¹, respectively. The decrease in the thermal conductivity of the porous alumina body produced from SERATH① is caused by the long path route for heat transfer.     

Preparation and properties of porous alumina ceramics with oriented cylindrical pores produced by an extrusion method

Porous alumina ceramics with unidirectionally-oriented pores were prepared by extrusion. Carbon fibers of 14 μm diameter and 600 μm length to be used as the pore-forming agent were kneaded with alumina, binder and dispersing agent. The resulting paste was extruded, dried at 110 °C, degreased at 1000 °C and fired at 1600 °C for 2 h. SEM showed a microstructure of dispersed highly oriented pores in a dense alumina matrix. The pore area in the cross section was 25.3% with about 1700 pores/mm². The pore size distribution of the fired body measured by Hg porosimetry showed a sharp peak corresponding to the diameter of the burnt-out carbon fibers. The resulting porous alumina ceramics with 38% total porosity showed a fracture strength of 171 MPa and a Young's modulus of 132 GPa. This strength is significantly higher than the reported value for other porous alumina ceramics even though the present pore size is much larger.     

Porous β-Ca2SiO4 ceramic scaffolds for bone tissue engineering: In vitro and in vivo characterization

The biodegradable ceramic scaffolds with desirable pore size, porosity and mechanical properties play a crucial role in bone tissue engineering and bone transplantation. A novel porous β-dicalcium silicate (β-Ca₂SiO₄) ceramic scaffold was prepared by sintering the green body consisting of CaCO₃ and SiO₂ at 1300 °C, which generated interconnected pore network with proper pore size of about 300 μm and high compressive strength (28.13±5.37–10.36±0.83 MPa) following the porosity from 53.54±5.37% to 71.44±0.83%. Porous β-Ca₂SiO₄ ceramic scaffolds displayed a good biocompatibility, since human osteoblast-like MG-63 cells and goat bone mesenchymal stem cells (BMSCs) proliferated continuously on the scaffolds after 7 d culture. The porous β-Ca₂SiO₄ ceramic scaffolds revealed well apatite-forming ability when incubated in the simulated body fluid (SBF). According to the histological test, the degradation of porous β-Ca₂SiO₄ ceramic scaffolds and the new bone tissue generation in vivo were observed following 9 weeks implantation in nude mice. These results suggested that the porous β-Ca₂SiO₄ ceramic scaffolds could be potentially applied in bone tissue engineering.     

Capillary rise properties of porous mullite ceramics prepared by an extrusion method using organic fibers as the pore former

Porous mullite ceramics with unidirectionally oriented pores were prepared by an extrusion method to investigate their capillary rise properties. Rayon fibers 16.5 μm in diameter and 800 μm long were used as the pore formers by kneading with alumina powder, kaolin clay, China earthen clay and binder with varying Fe₂O₃ contents of 0, 5 and 7 mass%. The resulting pastes were extruded into cylindrical tubes (outer diameter (OD) 30–50 mm and inner diameter (ID) 20–30 mm), dried at room temperature and fired at 1500 °C for 4 h. The bulk densities of the resulting porous ceramics ranged from 1.31 to 1.67 g/cm³, with apparent porosities of 43.2–59.3%. The pore size distributions measured by Hg porosimetry showed a sharp peak at 10.0 μm in the sample without Fe₂O₃ and at 15.6 μm in the samples containing Fe₂O₃; these pores, which arose from the burnt-out rayon fibers, corresponded to total pore volumes ranging from 0.24 to 0.34 ml/g. SEM showed a microstructure consisting of unidirectionally oriented pores in a porous mullite matrix. Prismatic mullite crystals were well developed on the surfaces of the pore walls owing to the liquid phase formed by the Fe₂O₃ component added to color the samples. The bending strengths of the tubular samples ranged from 15.6 to 26.3 MPa. The height of capillary rise, measured under controlled relative humidities (RH) of 50, 65 and 85%, was greater in the ceramics containing Fe₂O₃ than in those without Fe₂O₃, especially in the thinner samples. The maximum capillary rise reached about 1300 mm, much higher than previously reported. This excellent capillary rise ability is thought to be due to the controlled pore size, pore distribution and pore orientation in these porous mullite ceramics.     

Preparation and characterization of porous mullite ceramics via foam-gelcasting

Porous mullite ceramics were prepared via foam-gelcasting using industrial grade mullite powder as the main raw materials, Isobam-104 as the dispersing and gelling agent, sodium carboxymethyl cellulose as the foam stabilizing agent, and triethanolamine lauryl sulfate as the foaming agent. The effects of processing parameters such as type and amount of additive, solid loading level and gelling temperature on rheological properties and gelling behaviors of the slurries were investigated. The green samples after drying at 100 °C for 24 h were fired at 1600 °C for 2 h, and the microstructures and properties of the resultant porous ceramic samples were characterized. Based on the results, the effects of foaming agent on the porosity level, pore structure and size and mechanical properties of the as-prepared porous mullite ceramics were examined. Porosity levels and pore sizes of the as-prepared samples increased with increasing the foaming agent content up to 1.0%, above which both porosity levels and pore sizes did not change. The compressive strength and flexural strength of the as-prepared sample with porosity of 76% and average pore size of 313 μm remained as high as 15.3±0.3 MPa and 3.7±0.2 MPa, respectively, and permeability increased exponentially with increasing the porosity.     

Effects of solid content on the phase assemblages,mechanical and dielectric properties of porous α-SiAlON ceramics fabricated by freeze casting

Porous Y-α-SiAlON ceramics were prepared by freezing camphene-based suspensions at 0 °C and subsequently sintering at 1900 °C for 1 h. The effects of solid loading content in the suspensions on porosities and formation of α-SiAlON as well as mechanical and dielectric properties of the porous ceramics were investigated. An XRD analysis performed on sintered samples indicated that the α-SiAlON did not fully form in the sample with initial solid loading content of 10 vol%, due to the high porosity of 90 vol% and interconnected pore of the green body. With the increase of initial solid loading content from 10 vol% to 30 vol%, the porosity decreased from 62.3% to 23.1% and the average pore size decreased from 19 μm to 8 μm. As a result, the flexural strength increased significantly from 72.4 MPa to 190.2 MPa, fracture toughness increased from 1.20 MPa m^1/2 to 3.48 MPa m^1/2, as well as the dielectric constant increased from 3.3 to 6.3. The dielectric loss (tan δ) of obtained material varied between 1.4×10^?2 and 2.8×10^?2, which did not depend on the porosity of samples.     

Microstructure and high temperature 4-point bending creep of sol–gel derived mullite ceramics

Four-point bending creep behavior of mullite ceramics with monomodal and bimodal distribution of grain sizes was studied in the temperature range of 1320–1400 °C under the stresses between 40 and 160 MPa. Mullite ceramic with bimodal grain size distribution was prepared using aluminum nitrate nonahydrate as alumina precursor. When γ-Al₂O₃ or boehmite were used as alumina precursors, mullite grains are equiaxial with mean particle size of 0.6 μm for the former and 1.3 μm for the latter alumina precursor. The highest creep rate exhibited the sample with monomodal morphology and grains in size of 0.6 μm, which is about one order of magnitude greater than that for the monomodal morphology but with grains in size of 1.3 μm. The highest activation energy for creep (Q = 742 ± 33 kJ/mol) exhibits mullite with equiaxial grains of 1.3 μm, whereas for sample with smaller equiaxial grains the activation energy is much smaller and similar to mullite ceramics with bimodal grain morphology. Intergranular fracture is predominant near the tension surface, while transgranular more planar fracture is predominant near the compression surface zone.     

Preparation and properties of porous alumina ceramics with uni-directionally oriented pores by extrusion method using a plastic substance as a pore former

Porous alumina ceramics with uni-directionally aligned pores were prepared by an extrusion method using 0–40 vol.% poly (vinyl acetate) (PVAC) as the pore former. A paste was prepared by mixing 25 mass% distilled water, 4 mass% methylcellulose, 8 mass% oleic acid and 0.8 mass% ammonium poly (carboxylic acid). This paste was molded into a 10 mm Ø body using a ram-type extruder, dried at room temperature for 24 h, calcined at 600 °C for 1 h and sintered at 1500 °C for 2 h in air. The PVAC added to the paste was homogeneously dispersed and formed particles 0.1–150 μm in size which extended in the extrusion direction and were converted to through-hole pores after sintering. The resulting pore size distribution in the samples was bimodal, centered at about 0.4 μm with a broad peak at about 70 μm dia. The resulting porous alumina ceramics showed high gas permeability because of their uni-directionally oriented through-hole pore structure.     

Mechanical strength and damage tolerance of highly porous alumina ceramics produced from sintered particle stabilized foams

Highly porous alumina particle stabilized foams were prepared by combining the concepts of particle stabilized foams and gelcasting, using sulfonate surfactants and poly vinyl alcohol (PVA) as the gelcasting polymer. The ceramic samples sintered at 1500 °C for 2 h had porosities from 65% to 93%, with pore sizes in two categories: “big pore” around 300 μm and “small pore”, around 100–150 μm, depending on the type and amount of surfactant added. The mechanical behaviour of the foams (axial and diametral compression) depended on the overall porosity and pore size. On average, tensile and compressive strengths around 5 and 16 MPa respectively were measured for samples with bigger pore sizes and larger porosities. Samples with smaller pore sizes and lower porosities produced average values of 12 and 57 MPa for tensile and compressive strengths, respectively. The elastic modulus reached a maximum around 3GPa for “small pore” size samples. The effect of increasing amount of PVA in the samples had a strong effect on the green mechanical strength, but it did not significantly affect the mechanical response of the sintered alumina foams. Large and complex shape sintered components produced using this route showed a remarkable damage tolerance, due to crack tip blunting.     

Nanocomposite polyHIPEs with magnetic nanoparticles: Preparation and heating effect

Emulsion templating of high internal phase emulsions (HIPEs) was used to synthesise microcellular poly(styrene-co-divinylbenzene) magnetic nanoparticle composites with open, interconnected, porous structures. The emulsions were stabilised by a combination of a surfactant and maghemite/magnetite (uncoated or coated with oleic acid) nanoparticles and then cured thermally. Up to 23 wt% (with regards to complete composite mass) of magnetic nanoparticles were incorporated into the polymer matrix. Composite polymers exhibited magnetic properties with a saturation magnetisation of 13 emu/g and a substantial heating effect at the AC magnetic field of 3.8 kA/m and a frequency of 104 kHz. A nanocomposite polyHIPE sample with coated nanoparticles exhibited a higher hyperthermia effect. Samples retained typical polyHIPE morphology with cavity diameters of approx. 8 μm and interconnecting pores of around 0.8 μm in diameter. Compared to styrene/divinylbenzene polyHIPEs without nanoparticles, the openness (interconnecting pore size to cavity size ratio) was slightly reduced. Materials were characterised with gas adsorption porosimetry, XRD, TGA/DSC, SEM, TEM.