Self-supported ceramic substrates with directional porosity by mold freeze casting

Manufacture of thin-film ceramic substrates with high permeability and robustness is of high technological interest. In this work thin (green state thickness ∼500 μm) porous yttria-stabilized zirconia self-supported substrates were fabricated by pouring stable colloidal aqueous suspensions in a mold and applying directional freeze casting. Use of optimized suspension, cryoprotector additive and mold proved to deliver defect free ceramic films with high dimensional control. Microstructure analysis demonstrated the formation of desirable aligned porosity at macro-structural scale and resulted to be highly dependent on colloidal behaviour and freeze casting conditions. Manufactured green films were joined by lamination at room temperature and sintered to obtain symmetrical cells consisting of two porous self-supported substrate electrodes (∼420 μm) and dense yttria stabilized zirconia electrolyte (∼10 μm).     

Dendritic porous alumina with high porosity by directional freeze casting using a binary solution for bacterial removal

High-porosity dendritic porous alumina was fabricated by using tertiary butanol (TBA) hydrate crystals combined with directional freeze casting. The porosity of this porous alumina approximated 80 %, and its high porosity resulted in high water flux. Dendritic pores improved the physical interception capability of porous ceramics due to the intrinsic moving paths and intercepts from the pore structure. Changes in the TBA content (from 70 vol.% to 85 vol.%) caused a change in pore size from 36.58 μm to 11.54 μm and pore structure (change order: snowflake, dendritic, rod-like, and needle-like), which are important factors affecting water flux and interception capability. The interception and removal of Escherichia coli by 7 mm-height porous ceramics with dendritic structure and an average pore size of 27.90 μm reached 100 % at pH 7.2. This study provides a simple and low-cost method for the effective removal of bacteria.     

Ice-mould freeze casting of porous ceramic components

Porous, hollow ceramic components were produced by freeze casting technique. For this purpose aqueous slurries with high solid contents were prepared which were stable against freezing down to at least −5 °C. Ice cores were made by coating steel components with freezing water which were subsequently dip-coated with the ceramic suspensions. After freeze drying which removes both, the ice core and the frozen suspension liquid, and sintering, ceramic components with a high amount of open porosity including steel parts could be achieved. As an example hydroxyapatite was used for showing the opportunities of the freeze casting technology among others for applications in the field of bone replacement. The influence of the solid content of the hydroxyapatite slurries on the ice crystal growth has been investigated by means of compact hydroxyapatite bodies which were prepared by freeze casting using ice moulds with cylindrical cavities.     

Effect of additives on porosity of alumina materials obtained by freeze casting

The influence of two different additives, glycerol and polyvinyl alcohol (PVA), on the rheological behaviour and freeze casting performance of 35?vol.-% aqueous alumina suspensions is studied. Suspensions with PVA were prepared by either mixing all the components together or adding the PVA in a second step on the dispersed slurry. Although the slight increase in viscosity suggests that competitive adsorption occurs, the microstructure seems not to change depending on the order of addition of additives. Considering its lower molecular weight, glycerol provides lower viscosity, and as a consequence of its cryoprotective character, sintering leads to smaller pore size, being the porosity 35% for an added content of 10?wt-% with respect to solids. In the case of PVA, contents of 2?wt-% are enough to obtain solid firm bodies with a porosity of 48%. The porosity and the size of the pores decrease with increasing concentration of PVA.     

Fabrication of porous silica with controllable and tunable porosity via freeze casting

Porous ceramics offer unique properties that can bring advances to many application areas. The freeze-casting process has a strong potential for fabricating porous ceramics; however, the effects of process parameters on part porosity must be well understood for scalable manufacturing via freeze casting. This paper presents an experimental analysis of the freeze-casting process that correlates the freeze-casting parameters with pore characteristics. A full-factorial design of experiments is conducted on a unidirectional freeze-casting testbed using silica as the ceramic material and camphene as the solvent. The effects of solid loading, particle size, cooling temperature, and the distance from the cooling surface on porosity characteristics are evaluated. The fabricated samples are cross-sectioned vertically and horizontally and imaged using scanning electron microscopy. Image processing is used to obtain the porosity characteristics of areal porosity, pore size, pore shape, and pore orientation. The capability to steer the pore orientation is also demonstrated through bidirectional freezing experiments supported by a finite-element model. As a result, a quantitative understanding of the effects of freeze-casting process parameters on porosity characteristics is gained for the silica–camphene system. These results and the presented approach can be used for reproducible manufacture of porous ceramics with controlled porosity.     

Formation of porous alumina with oriented pores

Adopting the theories describing the bubble forming in the metal–hydrogen solidification process, porous alumina with oriented pores was prepared by combining a foaming method with sol-gel technology. The bubble forming process in the sol-gel is different from that in the metal–hydrogen system. Samples were calcined at temperature from 800 to 1200C. The volume-shrinkage and compressive-strength increased with increasing calcination temperature. The porous alumina exhibited a bimodal pore structure when prepared below 1200°C.     

Pore structure and thermal oxidation curing behavior of porous polymer derived ceramics with superhigh porosity fabricated by freeze casting

Porous ceramics with porosity up to 92.5 % have been successfully fabricated by freeze casting of polycarbosilane (PCS) solution. The effect of PCS concentration and thermal oxidation curing on the pore structure and compressive properties was investigated. Curing mechanism and thermodynamics were illuminated through analyzing the molecular structure, curing activation energy, and curing degree. Porous ceramics, mainly composed of SiC and a small amount of SiO₂, have dendritic pore structure which well replicates the solidification morphology of camphene solvent. Results of FT-IR and Gaussian computation of PCS electron density show that Si–H and Si–CH₃ bonds play a dominant role in thermal oxidation curing reaction. Both curing degree and ceramic yield increase with the increase in curing temperature and time. The curing degree of Si–H bond is close to 52 % and the corresponding ceramic yield is about 83 % when the porous PCS was cured at 200 °C for 90 min. Both polymer concentration and curing time have influences on the compressive strength of porous ceramics.     

Preparation of porous TiO2 by a novel freeze casting

Highly porous and open interconnected pore structural TiO₂ were prepared by a novel freeze casting method. In the experiment, the well-dispersed aqueous slurries were first frozen, and then dried at a reduced vacuum. Since the sublimation of ice crystals developed in the freezing process, the green bodies with highly porous were obtained. The phase composition and the microstructure of the sintered samples were characterized by XRD, SEM, porosity and the pore size distribution was measured by mercury porosimetry. The results demonstrated that the PVA concentration in the slurries remarkably affect the microstructure of TiO₂ ceramics. The pore morphology of TiO₂ ceramics with 3 wt.% polyvinyl alcohol (PVA) addition was dendritic, and however, the pore morphology of TiO₂ ceramics with 6 wt.% PVA addition changed into columnar. The reason for the variation of the pore morphology was ascribed to the effect of the PVA gelation on the growth behavior of the ice crystals.     

Preparation of high strength lamellar porous calcium silicate ceramics by directional freeze casting

In this study, porous calcium silicate (CS) ceramics with oriented arrangement of lamellar macropore structure were prepared by directional freeze casting method. The lamellar macropores were connected by the micropores on the pore wall, which had good pore interconnectivity. The effects of solid loading of the slurry, freezing temperature, sintering additive content, and sintering temperature on the microstructures and compressive strength of the synthesized porous materials were investigated systematically. The results showed that with the increase of solid loading (≤20 vol%) and sintering additive content, the sizes of lamellar pores and pore walls increased gradually, the open porosity decreased and the compressive strength increased. The sintering temperature had little effect on the pore size of the ceramics, but increasing the sintering temperature (≤1050 °C) promoted the densification of the pore wall, reduced the porosity, and improved the strength. The decrease of freezing temperature had little effect on porosity, but it reduced the size of lamellar pore and pore wall, so as to improve the strength. Finally, porous CS ceramics with lamellar macropores of about 300–600 μm and 2–10 μm micropores on the pore wall were obtained. The porous CS ceramics had high pore interconnectivity, an open porosity of 66.25% and a compressive strength of 5.47 MPa, which was expected to be used in bone tissue engineering.     

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.     

活性污泥对管式多孔α-Al_2O_3陶瓷膜支撑体性能影响的初步研究

以剩余活性污泥作为支撑体的成孔剂,采用滚压成型及熔膜芯法制备管状多孔α-Al2O3陶瓷膜支撑体,研究了粘结剂羧甲基纤维素(CMC)和活性污泥的加入量对氧化铝陶瓷膜支撑体品质的影响。结果表明,随着成孔剂和粘结剂的增多,支撑体孔隙率和渗透通量呈增大趋势,孔隙率最大可达43.07%,纯水通量在0.4~1.0 MPa压力下变化范围为12 786.67~37 617.84 L/(m2·h·MPa)。     

活性污泥对管式多孔α-Al_2O_3陶瓷膜支撑体性能影响的初步研究

以剩余活性污泥作为支撑体的成孔剂,采用滚压成型及熔膜芯法制备管状多孔α-Al2O3陶瓷膜支撑体,研究了粘结剂羧甲基纤维素（CMC）和活性污泥的加入量对氧化铝陶瓷膜支撑体品质的影响。结果表明,随着成孔剂和粘结剂的增多,支撑体孔隙率和渗透通量呈增大趋势,孔隙率最大可达43.07%,纯水通量在0.4~1.0 MPa压力下变化范围为12 786.67~37 617.84 L/（m2·h·MPa）。     

Properties of phyllosilicate-based porous ceramics shaped by conventional tape casting and freeze tape casting

Silicate ceramics were shaped using tape casting (TC) and freeze tape casting (FTC) processes from three clays labeled HCR, KORS, and KCR. These clays exhibited mass content of 77% halloysite–10 Å, 29% kaolinite, and 98% kaolinite minerals, respectively. After casting the slurries, the dried tapes were sintered at 1200°C. The microstructure changes were characterized before and after sintering using scanning electron microscopy. The apparent porosity of TC samples was lower (36–47 vol.%) compared to values obtained with FTC samples (67–79 vol.%). The latter samples exhibited a highly textured porosity, with micron-sized pores aligned perpendicular to the tape surfaces. Upon sintering, the porosity of TC samples tended to decrease conversely to the case of FTC samples. Such behavior seemed related to the simultaneous effect of organic additives and ice templating. Consequently, the FTC samples showed a relatively low mechanical strength of 3–7 MPa and thermal conductivity of .14– .22 W m⁻¹ K⁻¹. After sintering, the mullite crystallization contributed to strengthen the bulk materials, helping to compensate for the detrimental effect of porosity on the stress to rupture and on thermal conductivity values.     

Preparation and characterization of porous alumina ceramics through starch consolidation casting technique

This work aims at studying the influence of thermal treatment on the microstructure, resistivity and technological properties of porous alumina ceramics prepared via starch consolidation casting (SCC) technique. Colloidal suspensions were prepared with three different contents of alumina solid loading (55, 60 and 65 mass%) and corn starch (3, 8 and 13 mass%). The sintered samples at 1400, 1500, 1600 and 1700 °C, show open porosity between 46 and 64%, depending on the starch content in the precursor suspensions and sintering temperature. The pore structures were analyzed by SEM. The effect of corn starch content on the apparent porosity, pore size distribution, linear shrinkage and electrical resistivity as well as cold crushing strength of the sintered porous alumina ceramics was also measured. These porous alumina ceramics are promising porous ceramic materials for using in a wide range of thermal, electrical and bioceramics applications as well as filters/membranes and gas burners, due to their excellent combination properties.     

Porous asymmetric microfiltration membranes shaped by combined alumina freeze and tape casting

An assembled asymmetric alumina microfiltration membrane with high performance was prepared by combining freeze and tape casting techniques followed by two sintering steps. Freeze casting was used for manufacturing of the porous support layer with a highly interconnected pore network. Tape casting was applied on the top layer to form a pre-membrane with smaller pore size and controlled thickness, which was set on the sintered support. Morphology influences were investigated for different solid loadings, additives content and the assembled layer membrane structures. No delamination among the layers was observed. The assembled ceramic membrane had an average pore size between 30 and 50 μm together with a top surface layer around 0.35 μm, which is suitable to the microfiltration separation process. Porosity in the range of 26–50 % and water flux of 11–32 m³ m^?2 h^?1 bar^?1 were reached for samples prepared with two sintering steps at 1600 and 1300 °C for 2 h.     

Tape casting of polysiloxane-derived ceramic with controlled porosity and surface properties

Tape casting has been applied to produce porous hybrid and SiOC ceramic tapes using ceramic precursors and commercially available polysiloxanes as polymeric binders. SiC particles of two different mean sizes (4.5 or 6.5?μm) were used as inert fillers to prevent shrinkage and increase mechanical stability. Macroporosity was adjusted by varying the azodicarbonamide (ADA) content from 0 to 30?wt.%. Decomposition of the polysiloxanes at 600?°C resulted in the generation of micropores with high specific surface area (187–267 m²?g^?1) and a predominant hydrophobic behavior. At 1000?°C mainly meso/macroporosity were observed (SSA: 32–162 m²?g^?1) accompanied by increased hydrophilicity. The influence of ADA content, SiC size, and pyrolysis temperature on open porosity (2.5–37%), average pore size (<0.01–1.76?μm), surface characteristics, and flexural strength (10.5–121?MPa) were investigated. The porous tapes with different surface characteristics and controlled structure are highly promising for applications involving membrane processes, particularly microfiltration systems (0.1–10?μm).     

Microstructure of TiO2 porous ceramics by freeze casting of nanoparticle suspensions

During freeze casting of TiO₂ porous ceramics, the porous architecture is strongly influenced by TiO₂ particle size, solids loading, and cooling temperature. This work investigates the influences of particle size, freezing substrate, and cooling temperature on the TiO₂ green bodies prepared by freeze casting. The results show that the lamellar channel width with 100 nm particles is larger than that of 25 nm particles, yet the ceramic wall thickness is noticeably decreased. The lamellar structure is more ordered when using a copper sheet than glass as its freezing substrate. A finer microstructure results when frozen at − 50 ℃ than − 30 ℃. Such porous materials have application potentials in a wide range of areas such as photocatalysis, solar cells, and pollutant removal and should be further studied.     

TBA-based freeze/gel casting of porous hydroxyapatite scaffolds

Porous ceramic scaffolds with a controlled “designer” pore structure have been prepared by the freeze/gel casting route using a TBA-based hydroxyapatite slurry system with 20–40 wt.% solid content. The products were characterized in terms of sintered microstructure, together with physical and mechanical properties. After sintering at 1050–1250 °C, the advantages of freeze casting and gel casting appeared in the pore structure and compressive strength of the ceramics, i.e., unidirectional aligned macro-pore channels developed by controlling the solidification direction of the TBA solvent used in the freeze casting together with small diameter (micron sized) isolated pores formed in the dense outer walls of the pore channels when processed by gel casting. The sintered porosity and pore size generally resulted in a high solid loading giving low porosity and small pore size, this leading to higher compressive strengths. The scaffolds obtained exhibited an average porosity and compressive strength in the range 41.9–79.3% and 35.1–2.7 MPa, respectively, depending on the processing conditions used.     

Thermal conductivity of ceramic/metal composites from preforms produced by freeze casting

Porous alumina and zirconia preforms, processed by ice templating, have been used to manufacture ceramic/metal composites by aluminium alloy infiltration. The aim of the present work is to study the influence of the ceramic material nature and of the initial porous structure on the thermal conductivity anisotropy of the composite in order to assess potential applications in the field of thermal management. The materials are characterised in terms of pore volume fraction and pore size before and after metal infiltration. The freeze casted preforms exhibit anisotropic lamellar structures with ellipsoidal pores ranging from 35 µm to 40 µm and porosity fractions from 64 to 67%. After metal infiltration, composite parts present the same anisotropic morphology, which correspond to alternating ceramic and metal layers. Thermal conductivities have been determined, with an average of 80 W m⁻¹ K⁻¹ and 13 W m⁻¹ K⁻¹ parallel and perpendicular to the freezing direction respectively, for zirconia/metal composites. Theoretical values of thermal conductivity can be calculated using the Maxwell-Eucken relation, to handle the residual porosity, in combination with series and parallel resistance models to describe the overall anisotropic character. These give good agreement to experiment.