Porous alumina ceramics with highly aligned pores by heat-treating extruded alumina/camphene body at temperature near its solidification point

This study reports a novel way of increasing the pore size of highly aligned porous alumina ceramics by heat-treating an extruded alumina/camphene body at a temperature near its solidification point. The pore size obtained increased remarkably from 51 ± 8 to 125 ± 27 μm with increasing heat-treatment time from 1 to 24 h, due to the continuative overgrowth of the camphene dendrites during heat-treatment, while a highly aligned porous structure was preserved. In addition, interestingly, this heat-treatment enabled alumina walls to be densified quite well, whereas porous walls were observed in the sample produced without heat-treatment, which led to a considerable increase in compressive strength. The sample produced with a heat-treatment time of 12 h showed a high compressive strength of 11.6 ± 1.2 MPa at a porosity of approximately 84 vol%, which was much higher than that (0.28 ± 0.1 MPa) of the sample produced without heat-treatment.     

Assembling unidirectionally frozen alumina/camphene bodies for aligned porous alumina ceramics with larger dimensions

This paper proposes a novel way of producing aligned porous alumina ceramics with larger dimensions by assembling unidirectionally frozen alumina/camphene bodies, particularly those containing polystyrene (PS) polymer as the binder. The compressive strength of the samples sintered at 1450 °C for 3 h increased remarkably from 2 ± 0.1 to 16 ± 2 MPa with increasing PS content from 5 to 20 vol.% due to the prevention of cracks generally caused by drying shrinkage. In addition, frozen samples with a PS content of 20 vol.% could be assembled into larger dimensions without difficulty. The height of the assembled sample produced with a lamination number of 5 could be increased to ∼24 mm without a severe decrease in compressive strength (16 ± 3 MPa at a porosity of ∼79 vol.%) due to the maintenance of an aligned porous structure with good interfacial bonding between the laminations.     

Three‐dimensional Ceramic/Camphene‐based Coextrusion for Unidirectionally Macrochanneled Alumina Ceramics with Controlled Porous Walls

We report the utility of three‐dimensional ceramic/camphene‐based coextrusion, newly developed in this study, for the production of unidirectionally macrochanneled alumina ceramics with three‐dimensionally interconnected porous alumina walls. In this technique, a continuous ceramic/camphene filament with a diameter of 1 mm, comprised of a pure camphene core and a frozen alumina/camphene shell, was produced by the coextrusion process and then deposited in a layer‐by‐layer sequence using a computer‐controlled 3‐axis moving table. Unidirectionally aligned macrochannels (~400 μm in diameter) and three‐dimensionally interconnected pores (several tens of micrometers in size) in the alumina walls were created by removing the camphene core and the camphene dendrites formed in the alumina/camphene region, respectively. The sample showed much higher compressive strength in the macrochannel direction than in the perpendicular direction. In addition, the compressive strength of the sample could increase with an increase in initial alumina content owing to a decrease in the total porosity.     

Injection molding of surface modified powders with high solid loadings: A case for fabrication of translucent alumina ceramics

Solid loading is a critical key to the fabrication of ceramic compacts with high densities via ceramic injection molding. As reported in most previous work, solid loading of ultra-fine alumina feedstock system could be achieved only up to ∼58 vol% with stearic acid (SA) as the surface modification agent. In present work, different from the traditional work in which SA has been introduced just in the powder blending process, we have successfully prepared the feedstock with a much higher solid loading up to ∼64 vol% by a prior ball milling treatment of ceramic powders with a small amount of SA before the traditional blending process. It can be attributed to that SA can be coated homogeneously around the powder surfaces by a chemical reaction induced by ball milling treatment. Highly translucent Al₂O₃ ceramics have been fabricated, which suggests an alternative route for fabrication of translucent ceramics with high quality.     

Freezing Dilute Ceramic/Camphene Slurry for Ultra-High Porosity Ceramics with Completely Interconnected Pore Networks

Highly porous alumina ceramics with completely interconnected pore channels were fabricated by freezing dilute alumina/camphene slurries with solid loadings ranging from 5 to 20 vol%. This method fundamentally made full use of the three-dimensional camphene dendritic network for producing interconnected pore channels and the concentrated alumina powder network for achieving dense alumina walls. Firstly, alumina/camphene slurries were prepared at 60°C using ball milling and then cast into molds at 20°C. After subliming the frozen camphene, the samples were sintered at 1400°C for 5 h. This method enabled us to freeze very dilute ceramic slurries with a low solid loading of ≤20 vol% without the collapse of the sample after sintering. As the initial solid loading decreased from 20 to 5 vol%, the porosity linearly increased from 66% to 90% with an increase in the pore size, while completely interconnected pore networks were obtained in all cases. In addition, the free surfaces of the alumina walls showed full densification after sintering even at a low temperature of 1400°C, while some pores were present in the inner regions of the alumina walls.     

Novel Three‐Dimensional Extrusion of Multilayered Ceramic/Camphene Mixture for Gradient Porous Ceramics

This study proposes an innovative way of creating porous ceramics with a unique gradient porous structure using three‐dimensional extrusion of a multilayered ceramic/camphene feed rod, denoted as “3D‐Ex_m”. This 3D‐Ex_m technique utilizes the wall slip phenomenon during the extrusion process, which can create a gradient core/shell structure with a gradual change in the core/shell thickness ratio. In addition, the microstructure of ceramic filaments can be tuned through the use of the camphene as a pore‐forming agent. Porous alumina ceramics produced using a bilayered feed rod comprised of the alumina/camphene mixtures with the relatively high (?_H = 40 vol%) and low ceramic contents (?_L = 10 vol%) showed a gradual change in porosity in the intermediate region between the relatively dense (porosity = ~3 vol%) and highly porous regions (porosity = ~85 vol%).     

Improved wear behaviour of alumina-aluminium titanate laminates with low residual stresses and large grained interfaces

The wear behaviour of a monolithic alumina and an alumina-aluminium titanate laminated structure was studied. The laminate, containing surface fine grained alumina layers and internal composite layers with 10 vol.% of aluminium titanate, showed relatively low (≅20 MPa) compressive residual stresses at the surface. Interfaces between layers were constituted by large alumina grains (up to ≅50 μm) that promoted toughening due to crack deflection and branching. Wear tests were performed on square specimens (30 mm × 30 mm × 6 mm) using the pin-on-disc method. The laminates showed higher wear resistance than the monolithic alumina. The analysis of the results together with SEM-EDX observations was performed to identify possible wear mechanisms. The wear resistance improvements are discussed in terms of the residual stresses in the laminate and the properties provided by the special microstructure of the interfaces.     

Highly Aligned Porous Silicon Carbide Ceramics by Freezing Polycarbosilane/Camphene Solution

We fabricated highly aligned porous silicon carbide (SiC) ceramics with well-defined pore structures by freezing a polycarbosilane (PCS)/camphene solution. In this method, the solution prepared at 60°C was cast into a mold at temperatures ranging from 20° to −196°C, which resulted in a bicontinuous structure, in which each phase (camphene or PCS) was interconnected in a regular pattern. After the removal of the frozen camphene network, the samples showed highly porous structures, in which long straight and short elongated pore channels were formed parallel and normal to the direction of freezing, respectively. Thereafter, porous SiC ceramics were produced by the pyrolysis of the porous PCS objects at 1400°C for 1 h in a flowing Ar atmosphere, while preserving their mother pore structures having aligned pore channels.     

Functionally graded porous ceramics with dense surface layer produced by freeze-casting

Graded and porous Al₂O₃ ceramics with dense surface layer were fabricated by camphene-based freeze-casting process. The Al₂O₃/camphene/dispersant slurries were prepared by ball-milling at 60 °C for 24 h, before pouring into silicone rubber die. The warm slurry was cast into a mold at 25 °C, where the top surface of the cast body was exposed to air to allow for the controlled evaporation of molten camphene, and the bottom was attached to a copper plate before being placed on the top of a metal plate immersed in a water bath which can be cooled by ice-water (°C) and liquid nitrogen (−196 °C). This processing method can produce a graded porosity and pore structure distribution. A typical four pore structure, that is surface dense layer, transition layer, aligned pore distribution region and inner porous region is formed between the top surface and bottom surface. This technique is considered potentially useful in fabricating novel porous ceramics with special structure.     

Processing of alumina-coated tetragonal zirconia materials and their response to sliding wear

Alumina-coated tetragonal zirconia stabilised with 3 mol% of Y₂O₃ (YTZP) specimens (30 mm × 30 mm × 6 mm) have been obtained by dipping of pre-sintered YTZP compacts in alumina suspensions and subsequent sintering. The coated specimens present hardness values and a wear resistance similar to those of reference dense alumina specimens and significantly higher than those of the YTZP substrates.     

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.     

Effect of Polystyrene Addition on Freeze Casting of Ceramic/Camphene Slurry for Ultra-High Porosity Ceramics with Aligned Pore Channels

We investigated the effect of polystyrene (PS) addition on the freezing behavior of a very dilute alumina/camphene slurry with an initial solid loading of 5 vol% for the fabrication of ultra-high porosity ceramics with aligned pore channels. To accomplish this, slurries with various PS contents (10, 20, and 30 vol% in relation to the alumina powders) were prepared by ball milling at 60°C and then cast into molds at a constant temperature of 20°C. After removing the frozen camphene, the samples were heat treated to burn out the organic phases and sinter the alumina walls. The addition of the PS binder remarkably enhanced the green strength of the sample, making it possible to handle it without difficulty. All of the sintered samples showed ultra-high porosities of >88% without the collapse of the porous structure, wherein the pore channels were completely interconnected. Three distinctive zones having different pore structures were observed, viz. the outer shell with elongated pores, the inner zone with long aligned pore channels, and the center with equiaxed pores. The content of the PS polymer significantly affected the pore morphologies in the three distinctive zones. In addition, it was found that the addition of the PS polymer was highly beneficial to the alignment of the pore channels.     

Reaction sintering of colloidal processed mixtures of sub-micrometric alumina and nano-titania

The fabrication of composites formed by alumina grains (95 vol%) in the micrometer size range and aluminium titanate nanoparticles (5 vol%) by reaction sintering of alumina (Al₂O₃) and titania (TiO₂) is investigated. The green bodies were constituted by mixtures of sub-micrometric alumina and nano-titania obtained from freeze-drying homogeneous water based suspensions, and pressing the powders. The optimization of the colloidal processing variables was performed using the viscosity of the suspensions as control parameter. Different one step and two step sintering schedules using as maximum dwell temperatures 1300 and 1400 °C were established from dynamic sintering experiments. Specimens cooled at 5 °C/min as well as quenched specimens were prepared and characterized in terms of crystalline phases, by X-ray diffraction, and microstructure by scanning electron microscopy of fracture surfaces.Even though homogeneous final materials were obtained in all cases, full reaction was obtained only in materials treated at 1400 °C. The microstructure of the composites obtained by quenching was formed by an alumina matrix with bimodal grain size distribution and submicrometric aluminium titanate grains located inside the largest alumina grains and at triple points. However a cooling rate of 5 °C/min led to significant decomposition of aluminium titanate. This fact is attributed to the small size of the particles and the effect of the alumina surrounding matrix.     

Preparation of porous alumina ceramic with ultra-high porosity and long straight pores by freeze casting

Porous alumina ceramic was prepared by freeze casting method using tert-butyl alcohol as the solvent. The as?Cprepared porous alumina ceramic possessed long straight porous structure. The non-dendrite pore feature was quite distinguished from that prepared based on common solvents such as water and camphene. The porosity of the ceramic could be regulated through the solid loading. When the solid loading in the slurry was 20?vol%, the porosity of the alumina ceramic was 65%. With decreasing the solid loading, the porosity of the alumina ceramic increased linearly. The relationship between the total porosity (P) and initial solid loading (X) can be expressed as P?=?98.8?1.7X. The ultra-high porosity of 82% could be achieved when the solid loading was 10?vol%. Moreover, the density of the porous alumina ceramic with the porosity of 82% was even lower than water??s. The compressive strength of the porous alumina ceramic with the porosity of 63 and 82% was determined to be 37.0 and 2.6?MPa, respectively.     

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.     

Effect of the addition of polyvinylpyrrolidone as a pore-former on microstructure and mechanical strength of porous alumina ceramics

The effect of the solvent on the properties of porous alumina ceramics was studied when polyvinylpyrrolidone (PVP) was used as an organic pore-former. In particular, porous alumina ceramics were produced by dry-pressing of mixed PVP–alumina powder; the mixing of PVP and alumina powder was achieved via ball milling using water or acetone as solvent, or dry ball milling. Due to the different solubility of PVP in water and acetone, porous alumina ceramics with different pore structures and mechanical properties were obtained. Because of its cylindrical pores being aligned to some extent, the sample prepared using acetone as solvent exhibited the highest bending strength (140.2 MPa) and Young's modulus (57.4 GPa), which were 1.6 times and 3.4 times higher compared to that prepared without PVP. Moreover, the addition of PVP via wet ball milling led to more uniform dispersion of PVP in alumina, hence limiting the grain growth during sintering process and increasing the grain bonding.     

Fabrication of translucent alumina ceramics from pre-sintered bodies infiltrated with sintering additive precursor solutions

Translucent alumina ceramics were fabricated by infiltrating aqueous solutions containing sintering dopant ions (Mg²⁺/Y³⁺/La³⁺) into pre-sintered alumina compacts and sintering in H₂ atmosphere. The improved microstructural homogeneity, finer grain size and enhanced transmission properties of infiltration processed samples over those processed by conventional ball-milling method were corroborated by experimental results. Triple doping via infiltration appears to be significantly beneficial for achieving enhanced transmission (36.3% at wavelength 800 nm for sample thickness of 0.75 mm). This study indicates that infiltration technique can be used to fabricate translucent alumina ceramics with improved performance.     

Effect of Al2O3 particle size on preparation and properties of ZTA ceramics formed by gelcasting

Zirconia-toughened alumina (ZTA) ceramics were prepared using three different kinds of Al₂O₃ powders (marked PW-A average particle size: 7.53 μm, marked PW-B average particle size: 1.76 μm, marked PW-C average particle size: 0.61 μm) by gelcasting. Effect of Al₂O₃ particle size on zeta potential, dispersant dosage and solid volume fractions of ZTA suspensions as well as the mechanical properties of ZTA green bodies and ceramics were investigated. The optimum dosages of dispersant for ZTA suspensions prepared by PW-A, PW-B and PW-C are 0.4 wt%, 0.5 wt% and 0.7 wt%, respectively. The highest solid volume fractions of ZTA suspensions can reach 62 vol% (SP-A), 60 vol% (SP-B) and 52 vol% (SP-C), respectively. The green bodies show a bending strength as high as 20 MPa, which can meet the requirement of machining. The Al₂O₃ powder with fine particle size is beneficial to the improvement of mechanical properties. The ZTA ceramics prepared by PW-B Al₂O₃ powder show the highest bending strength (680 MPa) and toughness (7.49 MPa m^1/2).     

OH and COOH functionalized single walled carbon nanotubes-reinforced alumina ceramic nanocomposites

Alumina ceramics reinforced with 1 wt.% single-walled carbon nanotube (SWCNT) were fabricated via spark plasma sintering (SPS) of composite powders containing carboxyl (COOH) or hydroxyl (OH) group functionalized single-walled carbon nanotubes. The samples were SPS’ed at 1600 °C under 50 MPa pressure for holding time of 5 min and at a heating rate of 4 °C/s. The effects of CNT addition having different surface functional groups on microstructure, conductivity, density and hardness were reported. It was shown that nanotube addition decreased the grain sizeof alumina from 3.17 μm to 2.11 μm for COOH-SWCNT reinforcement and to 2.28 μm for COOH-SWCNT reinforcement. The hardness values of the composites are similar for all samples but there is 4.5 and 7.5 times increase in electrical conductivity with respect to monolithic alumina for COOH-SWCNT and OH-SWCNT, respectively. It was also shown by TEM and FEG SEM observations that transgranular fracture behaviour of alumina was changed to mostly intergranular fracture mode by the addition of both types of CNTs which may be due to location of CNTs along the grain boundaries. A significant grain size reduction in alumina is considered toresult fromthe suppressing effect of CNTs during sintering.     

Refined measurements of indentation fracture resistance of alumina using powerful optical microscopy

A round-robin of the indentation fracture (IF) method using two alumina ceramics was performed in 12 laboratories to confirm the significantly improved reproducibility of indentation fracture resistance K_IFR, using powerful optical microscopy. Powerful optical microscopy with both an objective lens of 40× or 50× and a traveling stage was employed to reduce the error in reading crack length. Indentations at 98 N for the two samples had moderate between-laboratory standard deviations of 0.3 and 0.2 MPa m^1/2 for K_IFR of 4.3 and 3.6 MPa m^1/2, respectively, which indicates the effectiveness of this measurement technique to improve the reliability of the IF method. The deviations of the grand average K_IFR reported by the laboratories from those re-measured by the authors using the returned samples were only ca. 0.4 MPa m^1/2, which was attributed to the slight misreading of the crack length by the participant laboratories. Thus, the reliability of the IF method seems reasonable by this advanced approach because our recent round-robins, together with this study, have confirmed that the precision for the three major structural ceramics, SiC, Si₃N₄ and alumina, could meet the necessary condition of reproducibility.