Fabrication of Porous Ceramics with Unidirectionally Aligned Continuous Pores

Porous alumina ceramics with unidirectionally aligned continuous pores were fabricated via the slurry coating of fugitive fiber. Cotton thread was coated with ceramic slurry by pulling it through the slurry, and specimens were produced by spooling the coated thread. The obtained porous alumina ceramics had an average pore diameter of 165 μm, 35% open porosity, and a bending strength of 160 MPa. It was suggested that the pore size and the porosity could be adjusted using the diameter of the cotton thread and the solids concentration of the slurry, respectively.     

Lost Mold Rapid Infiltration Forming of Mesoscale Ceramics: Part 1, Fabrication

Free-standing mesoscale (340 μm × 30 μm × 20 μm) bend bars with an aspect ratio over 15:1 and an edge resolution as fine as a single grain diameter (∼400 nm) have been fabricated in large numbers on refractory ceramic substrates by combining a novel powder processing approach with photoresist molds and an innovative lost-mold thermal process. The colloid and interfacial chemistry of the nanoscale zirconia particulates has been modeled and used to prepare highly concentrated suspensions. Engineering solutions to challenges in mold fabrication and casting have yielded free-standing, crack-free parts. Molds are fabricated using high-aspect-ratio photoresist on ceramic substrates. Green parts are formed using a rapid infiltration method that exploits the shear thinning behavior of the highly concentrated ceramic suspension in combination with gelcasting. The mold is thermally decomposed and the parts are sintered in place on the ceramic substrate. Chemically aided attrition milling disperses and concentrates the as-received 3Y-TZP powder to produce a dense, fine-grained sintered microstructure. Initial three-point bend strength data are comparable to that of conventional zirconia; however, geometric irregularities (e.g., trapezoidal cross sections) are present in this first generation and are discussed with respect to the distribution of bend strength.     

Preparation of alumina membranes for micro- and ultrafiltration applications

Abstract

A very thin disc type ceramic membrane (0·3-0·8 mm thickness, 25-30 mm diameter) made of pure alumina and suitable for microfiltration applications has been prepared by a tape casting process. A sol coating was applied to the disc to form an ultrafiltration membrane. T he pore size of the membrane could be varied in the range 0·1-0·7 μ m and porosity in the range 25-55% by optimising the ex perimental parameters. The most important factor for determining the pore size of the membrane was found to be the initial particle size distribution of the ceramic powder. Firing temperature and soaking time are other crucial parameters affecting volumetric porosity. Water permeability through the membrane under suction and under positive pressure is comparable with that of ceramic membranes prepared by conventional methods. In addition, a typical membrane shows a very narrow pore size distribution in the range 0·1-0·4 μm, with a median pore size of 0·28 μm. A very sharp drop in the pore size distribution pattern around 0·4 μm indicates that no pores larger than this exist. This implies that all particles with radius > 0·4 μm are trapped in the membrane, providing excellent separation efficiency. Results of microbial separation tests confirmed the possibility of micro-organism separation through these membranes.     

Intrinsic microstructural anisotropy in tape cast ceramics by ice templating

Ice templating concepts based on tape cast processing technology are capable of creating continuous columnar-graded pore structures using a wide variety of ceramic oxides with thicknesses from 100 µm up to 1 cm for applications including fuel cells, compositional grading templates, filtration/separation membranes, and catalyst supports. The merging of the tape casting process allows for the preparation of large area flexible green tapes as well as the long-range alignment of the acicular ice crystals transverse to the cross-section, yielding an additional degree of microstructure control beyond traditional freeze cast processing. Moreover, optimization of the freeze tape casting processing parameters has proven effective in tailoring porosity in aqueous cast ceramics. Magnetic resonance microscopy (MRM) combined with scanning electron microscopy (SEM) has revealed inherent microstructural anisotropy in the morphology of pores related to the direction of the cast tape. Due to the ability of MRM to image noninvasively with volume averaging over a range of slice thicknesses, the MRM images provide complementary information to the higher resolution single plane SEM images. Morphological variance as observed at different orientations through the cross-sections of cast yttria stabilized zirconia is reported.     

Overview of Fine-Scale Piezoelectric Ceramic/Polymer Composite Processing

In the past two decades, piezoelectric ceramic/polymer composites with different connectivities have been developed for transducer applications such as hydrophones, biomedical imaging, nondestructive testing, and air imaging. Recently, much attention has been given to fine-scale piezoelectric ceramic/polymer composites. These composites allow higher operating frequencies, and thus increased resolution, in medical imaging transducers. In this review, methods for processing fine-scale piezoelectric ceramic/polymer composites are discussed. The current capabilities, strengths, and weaknesses of each method are compared. The importance of spatial scale in composite performance is also reviewed. Several of the processing methods have demonstrated composites with fine-scale ceramic phases (<50 μm), and others have potential to form composites with a ceramic scale of under 20 μm.     

Near-Net-Shape Fabrication of Ti3AlC2-Based Composites

A porous ceramic preform was fabricated by printing a powder blend of TiC, TiO₂, and dextrin. The presintered preforms contained a bimodal pore size distribution with intra-agglomerate pores ( d ₅₀≈0.7 μm) and inter-agglomerate pores ( d ₅₀≈30 μm), which were subsequently infiltrated by aluminum melt spontaneously in argon above 1050°C. A redox reaction at 1400°C resulted in the formation of dense Ti–Al–O–C composites mainly composed of Ti₃AlC₂, TiAl₃, Al, and Al₂O₃, which attained a bending strength of 320 MPa, a Young's modulus of 184 GPa, and a Vicker's hardness of 2.5 GPa.     

Conversion of Oak to Cellular Silicon Carbide Ceramic by Gas-Phase Reaction with Silicon Monoxide

Oak has been converted to a porous biocarbon template by annealing in an inert atmosphere above 800°C. Subsequent infiltration with gaseous SiO at 1550–1600°C under flowing argon of atmospheric pressure finally resulted in the formation of a porous, cellular β-SiC ceramic. The conversion retains the biomorphic cellular morphology of oak tissue. While pores in the cell walls with a diameter less than ∼1 μm vanished, two distinct pore channel maxima representing tracheidal cells and large vessels remained in the SiC ceramic. Depending on the cellular morphology of different kinds of wood, e.g., strut thickness and pore size distribution, gas-phase conversion to single-phase β-SiC can be used to manufacture cellular ceramics with a wide range of pore channel diameters.     

Effect of Unfired Tape Porosity on Surface Film Formation by Dip Coating

Thin ceramic layers have been fabricated by dipping green tapes of alumina, formed by the doctor-blade casting method, into aqueous slurries containing mixtures of alumina and either unstabilized zirconia (MZ–ZrO₂) or mullite. It was observed that the formation of a thin layer on the surface of the tape is governed by both liquid entrainment and slip-casting mechanisms, and was accelerated by increasing the withdrawal rate, immersion time, or volume fraction of solids in the slurry used for dip coating. By modifying these parameters, layers as thin as 2 μm and as thick as 108 μm were easily formed. Layer formation was found to be strongly influenced by the structure of the tape surface. Layers formed on the top surface of the tape were found to be as much as 48% thicker than those formed on the bottom surface. This difference appears to be related to the smaller amount of porosity on the bottom surface of the tape. Evidence suggests that the polymer binder, used for doctor-blade casting, concentrated on the bottom of the tape as evaporation occurred from the top surface. The lower porosity on the bottom reduced the casting rate during dip coating and produced significantly thinner layers, relative to the top surface.     

Fabrication of Ceramics with Complex Porous Structures by the Impregnate–Freeze-Casting Process

The ceramics with complex porous structures were fabricated by a combination of impregnating and freeze-casting process. The polyurethane sponge was impregnated in the mold with 20 vol% of aqueous alumina slurry, and then the bottom of the cast body was kept at a constant cooling rate of 6°C/min to induce unidirectional solidification. After drying and sintering of the green part, porous ceramic with obvious lamellar architectures was prepared. The lamellae thickness and interlayer distance were as large as ∼9 and ∼15 μm, respectively. The large pores, which resulted from the burn-up of sponge struts were homogeneously distributed in the sample. The use of the porous template introduced some local interruption of the lamellar structures. However, high compression strength for the porous ceramic can still be obtained.     

Study of Porosity in Corroded Refractories

In this work, computer image analysis was used in order to characterize the complex porosity found in ceramic refractory materials. The porosities of SiC and Al₂O₃ refractory bricks before and after slagging tests have been examined by both mercury porosimetry and image analysis techniques; the results obtained by these two methods were compared and their differences discussed. Mercury porosimetry underestimated the volume fraction of pores larger than 100 μm, which contributed significantly to the total pore volume of analyzed materials. In contrast, image analysis did not reveal finer porosity, the contribution of which was, however, less important, Image analysis appeared to have the advantage of quantification of local heterogeneities of porosity, and the capabilities of this technique to quantify the variations in the volume of pores adjacent to reaction zones are documented and supported by microscopic observations.     

Fabrication of a Continuously Oriented Porous Al2O3 Body and Its In Vitro Study

Continuously oriented porous Al₂O₃ bodies were fabricated by a multi-pass extrusion process using C powders and ethylene vinyl acetate as an agent for pore forming and as a binder, respectively. The main pore size can be easily controlled by increasing the number of extrusion passes. The edges of the pore frame showed a rough surface having many fine pores about 0.2–1 μm in size. In the continuously porous Al₂O₃ bodies having 150 μm pore size, the values of the relative density and bending strength were about 63% and 90 MPa, respectively. These values were higher than those of an Al₂O₃ porous body made by a common process. From the in vitro study using human osteoblast-like MG-63 cells, it was confirmed that the cells grew well and adhered to the top surface and inside pores, as well as the outside wall of the continuously porous Al₂O₃ body. Without the directionality, the cells showed some spindle-shaped, three-dimensional, and network-type structures.     

Characterisation of porous titania yttrium oxide compounds by mercury intrusion porosimetry and X-ray refractometry

Aiming at ceramic materials of low thermal radiation emittance titania yttrium oxide ceramics have been prepared by sintering in air at 1,100 and 1,400 °C, respectively, and characterised. Due to its high infrared refractive index, average pore sizes up to 1 μm for optimal Mie scattering cross sections and over 35% porosity the material is a promising candidate for elevated temperature insulations. The essentially in large pore growth is achieved by graphitic nano and micro particle additives. The microstructure parameters of porosity, specific surface area, median and average pore sizes are determined by mercury intrusion porosimetry. Beyond this classical technique supplementary measurements by X-ray absorption and X-ray refractometry reveal considerably larger average pore sizes due to closed pores not accessible for mercury. An additional advantage of the X-ray techniques is their non-destructive application, which allows other treatments afterwards. The combined application of both methods provides additional information and reliability in case of complex ceramic microstructures and may serve for improved developments of porous ceramics with optimised thermal scattering for energy savings in high temperature applications.     

Fabrication of HAp-Coated Micro-Channelled t-ZrO2 Bodies by the Multi-Pass Extrusion Process

HAp-coated micro-channelled t -ZrO₂ bodies were fabricated using a multi-pass extrusion process in which carbon powders were used to facilitate the formation of pores and ethylene vinyl acetate was used as a binder. The unidirectional pores and HAp coating layers can be obtained easily, using the extrusion process. The micro-channelled bodies were 180 μm in diameter, and the HAp layer was uniformly coated on the pore walls. However, after being sintered above 1200°C, the HAp decomposed and was transformed into β-TCP, in which a large number of pores were observed. The maximum values of bending strength of HAp-coated and uncoated porous t -ZrO₂ bodies sintered at 1500°C were about 116 and 173 MPa, respectively, and their relative densities were about 57% and 63%, respectively.     

Preparation and characterisation of HA/TCP biphasic porous ceramic scaffolds with pore-oriented structure

Porous hydroxyapatite/tricalcium phosphate (HA/TCP) ceramic scaffolds with a uniform unidirectional pore structure were successfully fabricated by an ice-templating method by using Ca-deficient HA whiskers and phosphate bioglass. HA whiskers showed good dispersibility in the slurry and favoured the formation of interconnected pores in the scaffolds. Addition of bioglass powders enhanced the material sintering process and the phase transformation of Ca-deficient HA to β-TCP. Calcium-phosphate-based scaffolds with a composition from HA to an HA/β-TCP complex could be obtained by controlling the freezing moulding system and slurry composition. The fabricated scaffolds had a porosity of 75–85%, compressive strength of 0.5–1.0 MPa, and a pore size range of 130–200 µm.     

Permeability of diatomite layers processed by different colloidal techniques

Recently, efforts have been directed towards the development of ceramic filters for water treatment systems in which the microstructure is tailored to the application, is well characterised and is reproducible. This work reports on the use of slip and tape casting techniques, as well as a new “direct consolidation technique”, to obtain porous diatomite layers for filtration purposes. Diatomite has been chosen because of its low price, abundance, and intrinsic properties such as high porosity and small grain size. Layers prepared by tape casting and lamination, with a bending strength of 57 MPa, were almost 3 times stronger but less permeable than those produced by slip casting, due to the presence of binders and to the lamination step that promoted particle rearrangement. However, both forming techniques gave relatively low permeable layers due to fine (0.25–0.6 μm) and monomodal pore size distributions. The use of starch granules (30–50 wt%) as pore former and consolidator agents enabled to increase the permeability of sintered bodies for almost one order of magnitude as a result of the increasing amount and average size of pores. As expected, porosity and average pore size values show a direct dependence on the starch content.     

Preparation and properties of high-porosity ZrB2-SiC ceramics by water-based freeze casting

The development of novel cermet composites based on porous ceramics with high porosity, interconnected pore structure and good mechanical property has attracted considerable attention in engineering application. In this work, water-based freeze casting process was employed to fabricate ZrB₂-SiC porous ceramic with aligned lamellar-channels structure using PAA-NH₄ as the dispersant. The results revealed that the well-dispersed suspension with best rheological behavior was obtained using 1.0 wt% PAA-NH₄ at pH 9. The crack-free porous ceramic exhibited small volume shrinkage ranging from 2.59 % to 1.87 %. By varying the solid loading, the fabricated samples displayed a tailored porosity ranging from 76.12% to 59.37% and an excellent compressive strength of 7 MPa to 78 MPa. After oxidation, the samples displayed a decreased porosity and an increased compressive strength. The ZrB₂­SiC porous ceramic fabricated in this work will be a promising candidate for the framework of cermet composite.     

Direct Laser Sintering of Al2O3–SiO2 Dental Ceramic Components by Layer-Wise Slurry Deposition

This publication presents a solid freeform fabrication technique for ceramics in the alumina–silica system by layering binder-free, high-loaded ceramic slurries, followed by selective laser sintering. The low melting silica phase and the reaction sintering between silica and alumina favor the rapid prototyping of pure ceramic parts. On the basis of electroacoustic and viscosity measurements, stable slurries from Al₂O₃/SiO₂ powder mixtures and water with a high fluidity have been prepared for the layer deposition with a doctor blade like in tape casting. Layers with a thickness of about 100 μm were processed. It was found in laser parameter studies that ceramic parts can only be obtained using special alumina contents and laser parameters. But the biphasic approach may allow greater flexibility in the processing regime than is afforded by the use of just one material. The microstructure of these parts depends mainly on the temperature gradient induced by the laser absorption and thermal conduction. The wet shaping facilitates laser-sintered parts with a relatively high density, which could be increased by a thermal post-treatment.     

Porous chitin matrices for tissue engineering: Fabrication and in vitro cytotoxic assessment

A series of porous chitin matrices were fabricated by freezing and lyophilization of chitin gels cast from a 5% N,N-dimethylacetamide (DMAc)/lithium chloride (LiCl) solvent system. The porous chitin matrices were found to have uniform pore structure in the micron range. Scanning electron microscopy (SEM) revealed that the pore size of the porous chitin matrices varied according to the freezing method prior to lyophilization. By subjecting the chitin gels to dry-ice/acetone (−38 °C), the final porous chitin matrix gave pore dimensions measuring 200–500 μm with 69% porosity. A smaller pore dimension of 100–200 μm with 61% porosity was produced when the chitin gels were frozen by liquid nitrogen (−196 °C) and 10 μm pores with 54% porosity were produced when the gels were placed in a freezer (−20 °C) for 20 min. In comparison, lower porosity structures of ca. 10% porosity were obtained from both air-dried and critical point dried chitin gels. Furthermore, a low gel concentration (< 0.5%, w/w) also produced porous morphology by vacuum drying without any freezing and lyophilization. The resulting pore properties influenced the water uptake profile of the materials in water. These porous chitin matrices are found to be non-cytotoxic and to hold promise as potential structural scaffolds for cell growth and proliferation in vitro.     

Facile preparation of ultralight polymer-derived SiOCN ceramic aerogels with hierarchical pore structure

SiOCN ceramic aerogels with lightweight, high surface areas, and macro-meso pores have been synthesized by a facile method combining freeze-drying technique and polymer-derived ceramic route. The wet gels are synthesized via the hydrosilylation reaction between polysilazane and divinylbenzene with cyclohexane as solvent. The solvent is then removed by a freeze-drying process to form pre-ceramic aerogels. The SiOCN ceramic aerogels are finally obtained by pyrolyzing the pre-ceramic aerogels at 1000°C in ultrahigh purity N₂. The thermogravimetric and mass spectrometry system (TG/DSC-MS) is used to investigate the polymer-to-ceramic conversion process during pyrolysis. The phase composition, structure, and morphology of the SiOCN ceramic aerogels are investigated by XRD, FT-IR, XPS, and SEM. The results show that SiOCN ceramic aerogels are composed of amorphous matrix phase and “free carbon” phase. The SiOCN aerogels possess three-dimensional (3D) network porous structure with low density (0.19 g/cm³), high specific surface area (134 m²/g), large pore volume (0.49 cm³/g), and hierarchical pore structures of both macro and meso pores. The formation mechanism and evolution process of SiOCN ceramic aerogels are discussed.