Porous ceramics with tri-modal pores prepared by foaming and starch consolidation

Porous silica ceramics with tri-modal pores were prepared, based on the generation of foams from silica/starch composite slurry and the subsequent stabilization of the structure by starch consolidation. The rheology of the original slurry and the foamed one were evaluated and compared. After drying, the green bodies were debindered and sintered at 1250 °C for 5 h. The resulting materials consisted of a hierarchical structure with large-sized cells, moderate-sized pores in cell wall and small-sized voids among silica grains. The compressive strength of the sintered samples varied within the range of 4–17 MPa, corresponding to relative densities of 18–30%.     

Effect of forming process on the integrity of pore-gradient Al2O3 ceramic foams by gelcasting

Pore-gradient Al₂O₃ foams were produced by gelcasting using the epispastic polystyrene (EPS) sphere template. This approach allows the design of porous ceramics with degree of pore connectivity and height of gradient layers via appropriate selection of the sizes and numbers of spheres. The fabrication processing of open-cell porous ceramics limited by polymeric sponge template, sharp cracks at the strut edges and closed pores can be resolved by this approach. To achieve the optimal manufacturing conditions of maintaining integrity of the network, the effects of solid loads, height of the slurry and the pre-removal of the polymeric foam template on the struts of the ceramic foams were studied. The results revealed that 55 vol.% Al₂O₃ slurries with 0.5 wt.% ammonium polyacrylate kept good fluidity for casting and avoided the inner inordinate shrinkage. Different shrinkage behavior of the top and bottom of the sample was effectively reduced due to approximately same water vapor diffusion areas on the top and bottom. The integrity of dendritic solidification structure maintained perfectly through template pre-removed in dichloromethane compared with direct heating.     

A new direct coagulation casting process for alumina slurries prepared using poly(acrylate) dispersant

Direct coagulation casting (DCC) of concentrated aqueous alumina slurries prepared using ammonium poly(acrylate) dispersant has been studied using MgO as coagulating agent. Addition of small amounts of MgO increased the viscosity of the concentrated alumina slurries with time and finally transformed it in to a stiff gel. Sufficient working time for degassing and casting could be achieved by cooling the slurries to a temperature of ∼5 °C after proper homogenization after the addition of MgO. The DCC slip with alumina loading in the range of 50–55 vol% showed relatively low viscosity (0.12–0.36 Pa s at shear rate of 93 s⁻¹) and yield stress (1.96–10.56 Pa) values. The wet coagulated bodies prepared from slurries of alumina loading in the range of 50–55 vol% had enough compressive strength (45–211 kPa) for handling during mould removal and further drying. The coagulated bodies prepared from slurries of alumina loading in the range of 50–55 vol% showed linear shrinkage in the range of 4.8–2.3 during drying and 17.1–16.2 during sintering respectively. Near-net-shape alumina components with density >98% TD could be prepared by the DCC process.     

Ultrahigh-strength alumina ceramic foams via gelation of foamed boehmite sol

Ceramic foams with significant porosity and robust mechanical properties have received extensive attentions. However, it is still difficult to achieve excellent compressive strength at high porosity levels. In this work, a gelation of foamed boehmite sol method is proposed to settle this issue. The technological parameters during preparation process are systematically investigated. As-prepared alumina ceramic foams possess unprecedentedly high compressive strength of 34.1-89.1 MPa at high porosity levels of 66.0%-87.2%, which is attributed to the present of hierarchical pore structure, small grain size and pore size. This work demonstrates a facile and novel method for the fabrication of high-performance alumina ceramic foams toward practical applications.     

Silicon carbide particle reinforced mullite composite foams

Silicon carbide particle reinforced mullite composite foams were produced by the polymer replica method using alumina and kaolin to form in situ mullite matrix. Up to 20 wt.% silicon carbide particles (SiCp) were added to aqueous ceramic slurry to explore its effect on the rheological behaviour of ceramic slurries and also properties of as sintered products. By means of solid loading optimisation and sintering enhancement by silicon carbide, mullite based ceramic composite foams of higher strength were obtained. The strength of the as sintered foams was found to depend greatly on the phase composition, relative density of the structures and the amount of SiCp addition. By studying the effect of the additive concentration, on the mechanical properties of the ceramic matrix, it is found that the optimal silicon carbide addition is 20 wt.%.     

Fabrication of magnesium aluminate (MgAl2O4) spinel foams

This paper reports on a novel-processing route for fabricating magnesium aluminate (MgAl₂O₄) spinel (MAS) foams from aqueous suspensions containing 30–35 vol.% solids loading. A stoichiometric MAS powder formed from alumina (71.8%) and magnesia (28.2%) at 1400 °C was surface passivated against hydrolysis in an ethanol solution of H₃PO₄ and Al(H₂PO₄)₃ at 80 °C for 24 h. Stable aqueous suspensions with 30–35 vol.% solids loading were prepared using the surface passivated MAS powder with the help of tetra-methylammonium hydroxide (TMAH) and an ammonium salt of polyacrylic acid (Duramax D-3005) employed as dispersing agents. An aqueous solution of N-cetyl-N,N,N-trimethylammonium bromide (CTMAB) was utilized to create foam in aqueous MAS suspensions by mechanical frothing. Liquid foam was then consolidated in non-porous moulds by introducing a polymerization initiator and a catalyst under ambient conditions. Dried (at >90 °C for 24 h) MAS foams were then sintered for 1 h at 1650 °C. For comparison purposes, dense MAS bodies out of an un-passivated stoichiometric MAS powder, and, dense as well as foams out of alumina were also prepared in this study. The sintered properties of MAS and alumina ceramics were characterized by various means and thus obtained results are presented and discussed in this paper. The sintered MAS foams exhibited a porosity of about 74–76% and a compressive strength of about 4–7.2 MPa inline to values reported for other ceramic foams in the literature.     

Complex ceramic architectures by directed assembly of ‘responsive’ particles

Surface functionalization of alumina powders with a responsive surfactant (BCS) leads to particles that react to a chemical switch. These ‘responsive’ building blocks are capable of assembling into macroscopic and complex ceramic structures. The aggregation follows a bottom up approach and can be easily controlled. The directed assembly of concentrated suspensions leads to highly dense (∼99%) ceramic components with average 4-point bending strength of ∼200 MPa. On the other hand, the emulsification of suspensions with concentrations from 7 to 43 vol% and 50 vol% decane results in emulsions with different properties (stability, droplet size and distribution). The oil droplets provide a soft template confining the alumina particles in the continuous phase and at the oil/water interfaces. Aggregation of these emulsions followed by drying and sintering leads to macroporous (pore sizes ranging from 30 to 4 μm) alumina structures with complex shapes and a wide range of microstructures, from closed cell structures to highly interconnected foams with total porosities up to 83%. Alumina scaffolds with ∼55% porosity can reach crushing strength values above 300 MPa in compression and ∼50 MPa in 4-point bending.     

Effect of carboxymethyl cellulose addition on the properties of Si3N4 ceramic foams

The effect of carboxymethyl cellulose (CMC) addition on the preparation of Si₃N₄ ceramic foam by the direct foaming method was investigated. The addition of CMC in the foam slurry can reduce the surface tension, increase the viscoelasticity of foams, and improve their stability and fluidity. The foam ceramics show low shrinkage during drying owing to the CMC and the gelation of acrylamide monomers. The surface structure of dried foam is uniform, and there are no macropores and cracks on the surface. The sintered Si₃N₄ foam ceramics have very uniform pore distribution with average pore size of about 16 μm; the flexure strength is as high as 3.8–77.2 MPa, and the porosity is about 60.6–82.1%.     

New consolidation process inspired from making steamed bread to prepare Si3N4 foams by protein foaming method

A new consolidation process had been developed for preparing Si₃N₄ ceramic foams by using protein foaming method, which was inspired from the preparation of steamed bread. The main advantage of this consolidation process was no crack development during foamed slurry consolidation process. By using this new consolidation, Si₃N₄ ceramic foams with open porosities of 79.6–87.3% and compressive strength of 2.5–22 MPa were prepared. Protein addition and solid content on mechanical properties and pore structures of the as-prepared ceramic foams were investigated. Results indicated that the open porosity decreases with protein addition and solid content while compressive strength increased with solid content. With the increase of solid content, pores of the ceramic foams became regular in shape and uniform in size while both size and number of windows on the walls decreased.     

Influence of Slurry Characteristics on Porosity and Mechanical Properties of Alumina Foams

Alumina foams with porosity ranging between 50% and 92% were fabricated by foaming followed by coagulation of ovalbumin based aqueous slurries. Different combinations of ovalbumin–water mix and alumina loading provided a means to vary slurry viscosity over a wide range. Slurry viscosity influenced the foaming behavior leading to variation in microstructure and mechanical properties of alumina foams. Controlling the slurry viscosity resulted in controlled the total porosity, microstructures and mechanical properties. Mechanical properties were correlated with different micro-mechanical models. Both microstructure and mechanical properties agreed well as closed cell alumina foam due to presence of low percent area of interconnections.     

Rheology of foamed cement

Foams are being used in a number of petroleum industry applications that exploit their high viscosity and low density. Foamed cement slurries can have superior displacement properties relative to non-foamed cement slurries. This article presents results of an experimental study of foamed cement rheology. Viscosity curves of foamed cements were obtained using a flow-through rotational viscometer. Foamed cements with different foam qualities were generated under different pressures using a foam generator/viscometer apparatus. The foam qualities during the tests ranged from 0% to 30%, and the shear rate varied between 5 s^− 1 and 600 s^− 1. Experimental results indicate that: i) unlike conventional aqueous foams, low-quality cement foams have a lower viscosity than the base fluid; ii) as the cement foam quality (gas volumetric fraction) increases from 10% to 30%, the viscosity also increases; and iii) the viscosity of low-quality cement foam slightly increases after depressurization or expansion.     

Effect of freeze-drying treatment on the optical properties of SPS-sintered alumina

This study looks at the influence of alumina powder processing on the preparation of transparent alumina by Spark Plasma Sintering (SPS). Zeta potential measurements were carried out on alumina suspensions in order to determine the best dispersion conditions. Stable slurries were submitted to a spray freeze drying process and their sintering behavior was compared with the corresponding non spray freeze dried powders. Transparent alumina samples were successfully prepared from alumina powders by Spark Plasma Sintering. An optical model considering pore and grain size distributions has been developed to obtain information about porosity in dense materials. It was found that the final density and, accordingly, the optical properties were improved when spray freeze dried starting powder was used.     

A Simple Direct Casting Route to Ceramic Foams

A simple direct foaming and casting process using ovalbumin-based aqueous slurries for fabricating ceramic and metal foams is demonstrated. Foaming of aqueous ceramic slurries and the foam microstructure were seen to be a strong function of slurry rheology. Setting of foams with ceramic solids loading above 20 vol% was achieved by addition of acid, which also prevented binder migration. Acid addition resulted in excessive shrinkage, causing cracking of foams with ceramic loading below 20 vol%. Addition of sucrose to the slurries suppressed shrinkage leading to defect-free foams with porosity exceeding 95%. Overall porosity and foam microstructure could be controlled through ceramic solids loading, ovalbumin–water ratio, foaming time and sucrose amount, and sintering temperature. The ceramic foams fabricated by the process were strong enough to be green machined to different shapes.     

Studies of drying and sintering characteristics of gelcast BaTiO3-based ceramic parts

Drying green gelcast parts is an essential step in the gelcasting manufacturing process. In this work, the liquid desiccant method was used for drying of BaTiO₃-based semiconducting ceramic gelcast parts. The results show that the loading level of ceramic powders and the liquid desiccant concentration significantly effect the drying process and the sintering characteristics of the ceramic parts. Lowering the loading level of ceramic powders and increasing the concentration of the liquid desiccant, non-uniform and differential drying in various regions due to great solvent gradient, induces structural and residual stresses which cause defects, such as cracking, bending and other malformations, which make the articles useless during the drying process and sintering procedure. However, when the solid loading of green gelcast parts is increased to more than 45 vol.%, the stresses developed during drying can be greatly reduced, and a higher concentration of the liquid desiccant can be used without inducing defects in the drying process and defect free ceramic with a smooth surface can be obtained. Moreover, the effects of loading level of ceramic powders and thickness of parts on the density of ceramic parts were studied. Higher solid content in the gel, and lower thickness of parts, increase the density of ceramics.     

In situ vibration enhanced pressure slip casting of submicrometer alumina powders

This paper presents a novel method for improvement of particle packing in consolidation of submicrometer alumina powders by pressure slip casting. In this method, filtration cell is subjected to a mechanical vibration field with constant frequency of 50 Hz and vibration amplitudes ranging from 0 (no vibration) to 2 mm. Filtration rate, thickness and green density of the fabricated samples were measured to investigate the influence of vibration on filtration characteristics. It was revealed that employment of vibration can significantly increase filtration rate. Furthermore, there is an optimum vibration amplitude which results in the structure with the highest packing density. This value is shifted to higher vibration amplitudes as more concentrated alumina slurries is used. As the available formulation based on Darcy's law could not predict the results of the present investigation, a “Correction Factor” was utilized in order to increase the accuracy of the prediction in the presence of a vibration field.     

泡沫陶瓷的研制

泡沫陶瓷是一种新型的功能陶瓷材料。它具有独特的结构和性能，在工业中有着广泛的应用前景。泡沫陶瓷具有密度小、透气性高、耐高温、抗化学腐蚀等特性。本研究对用颗粒强化的氧化铝骨架合成泡沫陶瓷进行了分析。这种材料比其它多孔陶瓷材料具有更好的热化学性质。这种材料可以用有机海绵浸浆获得，然后烧去海绵，留下多孔陶瓷网。这种方法的优点是它包含了过程参数和陶瓷结构，同时合成物的烧结情况及其它条件的影响在文中也有阐述。     

The effect of wet foam stability on the microstructure and strength of porous ceramics

Wet foam stability is of prime importance in fabricating porous ceramics with the desired microstructure and mechanical properties. In this research, wet foams were fabricated via direct foaming after separately adding an anionic surfactant (TLS) and a cationic surfactant (DTAC) into alumina slurries with a copolymer of isobutylene and maleic anhydride (PIBM) as both the dispersant and the gelling agent. The foam stability was evaluated by a stability analyzer. The bubble size rapidly increased in the wet foam with TLS as the foam stabilizer and many large bubbles appeared within 60 min. The wet foam containing DTAC was very stable. Cationic DTAC increased the hydrophobicity of alumina particles by interacting with the anionic PIBM adsorbed on the particles. The hydrophobically modified particles acted as the foam stabilizer and enhanced the wet foam stability. Furthermore, the fast gelling speed of the slurry containing DTAC also enhanced the wet foam stability. The average cell size of the ceramic with 82.9% porosity from the wet foam with TLS was 188 µm and the compressive strength was 9.7 MPa. The counterparts from the wet foam with DTAC were 54 µm of average cell size and 18.1 MPa of compressive strength. The superior stability of wet foam brought about a smaller cell size and higher strength of the resultant ceramic.     

Mechanical behaviour and pore morphology of functionally graded alumina preforms and their composites

Functionally-graded ceramic composites were produced using a hot pour-and-set method via freeze casting of alumina slurries with solid loading between 40% and 20%, with gelatine as a binder. The slurry and additives were tailored for controlling the microstructure and mechanical properties, such as pore morphology, preform density and compressive strength. Varying the gelatine concentration between 2.5% and 9%, transformed the pore morphology from lamelllar to honeycomb and into closed cell. At 3% concentration, increasing the solid loading from 10% to 30% yielded higher compressive strength from 48 MPa to 317 MPa. The resultant compressive behaviour closely matched to Gibson-Ashby closed cell predictive model. Alumina/epoxy composite mechanical performance plateau as the solid loading increased; the 20% solid loading composite produced the best performance. The compressive strengths of the alumina/epoxy and alumina/aluminium composites were on average 300% and 1110% higher than their respective preform counterparts, across a solid loading range of 10–20%.     

Alumina/zirconia ceramic membranes fabricated by temperature induced forming technique

It is well known that the fabrication technique of porous ceramic composites has a significant effect on their microstructure and properties. In the present study, alumina/zirconia ceramic composites doped with magnesia were fabricated by temperature induced forming technique using tri-ammonium citrate and polyacrylic acid (PAA) as dispersant and gelling agents, respectively. The zirconia content was up to 20 wt% and added at the expense of alumina while the magnesia content was up to 2 wt% over the total mass. The optimum amount of ammonium citrate tribasic needed for dispersing the ceramic slurry was determined by measuring zeta potential of slurries. The prepared green alumina/zirconia composites were subjected for solid state sintering at 1550 °C for 1 h. The densification parameters, phase composition, average pore diameter, microstructure and cold crushing strength of sintered alumina/zirconia ceramics were investigated by the suitable techniques. The results revealed that the addition of tri-ammonium citrate to ceramic slurries enhanced the zeta potential which reached ?28.3 mV by adding 1 wt.-%. The bulk density was decreased while the apparent porosity was increased with the increase of zirconia content. The apparent porosities of sintered porous composites were in the range of 38.8–48.5%. The average pore diameter for the composite containing 15% zirconia was 1.79 μm and pore volume was 0.11 ml/g. The obtained microstructure exhibited zirconia grains located on the grain boundaries of Al₂O₃ matrix. The existence of zirconia in addition to magnesia hindered the growth and deformation of the matrix. The cold crushing strength of porous composites was decreased from 16.0 to 8.5 to MPa by increasing the zirconia content from 5 to 20 wt.-%.     

Fabrication of doped β-tricalcium phosphate bioceramics by Direct Ink Writing for bone repair applications

β-tricalcium phosphate (β-TCP, β-Ca₃(PO₄)₂) is one of the most attractive biomaterials for bone regeneration and β-TCP macroporous scaffolds are very promising for both cell proliferation and mechanical support. The Additive Manufacturing (AM) process called Direct Ink Writing (DIW), based on the extrusion of a concentrated ceramic slurry, is particularly adapted to resolve the main drawbacks associated with conventional shaping of ceramic scaffolds. In this work, co-doped β-TCP powders were synthetized and used to print macroporous scaffolds by DIW. Doped β-TCP powders have been proved to exhibit higher thermal stability, densification and mechanical properties compared to undoped β-TCP. Two co-doped compositions were produced via the aqueous precipitation technique combining magnesium, strontium, silver and copper cations: Mg-Sr (2.0–2.0 mol%) and Mg-Sr-Ag-Cu (2.0–2.0–0.1–0.1 mol%). DIW slurries were optimized with undoped and co-doped β-TCP with the use of a dispersant and a carboxymethylcellulose and polyethyleneimine mixture to obtain aqueous slurries filled with 42 vol% of powder. Complete rheological characterizations were realized to assess the suitability of the β-TCP slurries for the DIW process (shear-thinning and thixotropic behaviour). The whole processing chain including printing, osmotic drying (PEG 10000) and sintering (1100 °C, 3 h) was optimized to successfully print co-doped β-TCP macroporous scaffolds. Characterizations after sintering showed a reduction of macropores and microcracks using co-doped β-TCP powders as well as improved compressive strengths and densities compared to undoped β-TCP. A significant enhancement of compressive strength values was obtained compared to literature data.