Photocurable ceramic/monomer feedstocks containing terpene crystals as sublimable porogen for UV curing-assisted 3D plotting

This study presents a novel strategy to construct ceramic structures comprised of microporous filaments using photocurable ceramic/monomer feedstocks containing terpene crystals as sublimable porogens for UV curing-assisted 3D plotting technique. The biphasic calcium phosphate (BCP) feedstock, composed of frozen terpene crystals surrounded by BCP/UDMA walls, could be favorably extruded through a fine nozzle and then effectively photopolymerized by UV light. Thus, green filaments with high shape retention could be obtained. In addition, a number of pores could be created in BCP filaments after removing terpene crystals via freeze-drying and the porosity could be tailored by adjusting terpene content in BCP feedstocks. This approach allowed for the construction of dual-scale porous structures comprising microporous filaments in a periodic pattern, with tailored overall porosities and compressive strengths. Several types of self-supporting structures were also successfully constructed using our approach.     

UV curing–assisted 3D plotting of core-shelled feedrod for macroporous hydroxyapatite scaffolds comprised of microporous hollow filaments

The present study demonstrates the manufacturing of macroporous hydroxyapatite (HA) scaffolds, comprised of microporous hollow filaments with high shape retention, by UV curing-assisted 3D plotting using a feedrod comprised of a photocurable HA shell and a carbon black (CB) core. Two types of scaffolds with different filament interspaces (0.5 mm and 1 mm) were produced by depositing core-shelled filaments extruded through a 1.07-mm-diameter nozzle with in situ polymerization process. Both scaffolds exhibited that the hollow HA filaments were produced after the removal of CB core by heat-treatment, while micropores in the HA walls were created as the replica of camphene-camphor crystals. Overall porosity and macroporosity obtained using a camphene-camphor content of 60 vol% increased from 74.3 vol% to 79.3 vol% and from 50.7 vol% and 64.6 vol%, respectively, with an increase in filament interspace sizes from 0.5 mm to 1 mm. Both scaffolds exhibited reasonably high compressive strengths (2.36 ― 3.58 MPa) and modulus (68–86 MPa).     

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%).     

Calcium phosphate ceramics with continuously gradient macrochannels using three-dimensional extrusion of bilayered ceramic-camphene mixture/pure camphene feedrod

We herein demonstrate a novel, versatile approach to produce calcium phosphate (CaP) ceramics with continuously gradient macrochannels using three-dimensional extrusion of a bilayered ceramic-camphene mixture/pure camphene feedrod. In this technique, the pure camphene used as the upper part could be preferentially extruded because of the wall slip phenomenon. This enabled the formation of green filaments comprised of a camphene core surrounded by a ceramic/camphene shell, where the core/shell thickness ratio increased gradually as extrusion proceeded. CaP ceramics with continuously gradient macrochannels could be successfully produced by three-dimensionally depositing the extruded filaments layer-by-layer. With increasing the distance from the dense bottom layer, macrochannels created after the removal of the camphene cores via freeze-drying became larger, while the CaP walls became thinner. The local porosity could increase gradually and continuously from the dense bottom and reach up to ~72 vol%.     

Production of highly aligned porous alumina ceramics by extruding frozen alumina/camphene body

We herein propose a new technique for producing highly aligned porous ceramics by extruding a frozen ceramic/camphene body. To accomplish this, an alumina/camphene slurry with an initial alumina content of 10 vol% was first frozen unidirectionally in a 20 mm × 20 mm mold and extruded through a reduction die with a cross-section of 5 mm × 5 mm at room-temperature. This simple process enabled the formation of porous alumina ceramics with highly aligned pores as a replica of the camphene dendrites with a preferential orientation parallel to the extrusion direction. The sample showed much higher compressive strength of 280 ± 80 kPa with a porosity of 83 vol% when tested parallel to the direction of pore alignment. In addition, these materials could be used as a valuable framework for the production of ceramic/epoxy composites, particularly with a lamellar structure, which would result in a remarkable increase in mechanical properties.     

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.     

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.     

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.     

Novel camphene/photopolymer solution as pore-forming agent for photocuring-assisted additive manufacturing of porous ceramics

This study proposes camphene/photopolymer solutions as a novel pore-forming agent for the photocuring-assisted additive manufacturing of porous ceramics. Unlike conventional techniques using molten camphene, solid camphene can be directly dissolved in the photocurable monomer hexanediol diacrylate (HDDA) at room temperature, which can then crystallize with a dendrite-like morphology based on phase separation at lower temperatures. This unique approach allows alumina suspensions to solidify at ―2 °C and then effectively be photopolymerized using a digital light processing engine, resulting in camphene-rich crystals surrounded by photopolymerized alumina/HDDA walls. Sintered samples exhibited a highly porous structure, with the pores created after the removal of the camphene-rich crystals. Two different pore sizes were obtained in the lower and upper regions of a single layer, due to a decrease in the solidification rate along the building direction, although their porosities were similar (～ 52 vol%). The porous samples exhibited a compressive strength of ～ 265 MPa.     

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.     

Silica strengthened alumina ceramic cores prepared by 3D printing

Ceramic cores based on alumina and silica are important in the manufacturing of hollow blades. However, obtaining good properties and precision is still challenging. In this research, alumina-based ceramics cores were obtained by 3D printing technology, and the effects of silica contents on the mechanical properties of the as-obtained alumina ceramic cores were evaluated. The results showed significant improvements in flexural strengths of the ceramics from 13.3 MPa to 46.3 MPa at silica contents from 0 wt% to 30 wt% due to formation of mullite phase (Al₆Si₂O₁₃). By contrast, the flexural strengths declined as silica content further increased due to the generation of massive liquid phase. Also, porous structures and cracks were observed by scanning electron microscopy due to the removal of cured photosensitive resin and the mullitization reaction between alumina and silica, respectively. The manufacturing process of hollow blades required ceramic cores with flexural strengths greater than 20 MPa to resist the strike of metal liquid, as well as open porosity above 20 % to provide space for alkali liquor to dissolve the ceramic cores. As a result, 10 wt% silica was determined as the optimal value to yield ceramics with improved properties in terms of flexural strength (35.6 MPa) and open porosity (47.5 %), thereby satisfy the application requirement for the fabrication of ceramic cores.     

Effect of MgO sintering additive on mullite structures manufactured by fused deposition modeling (FDM) technology

An optimized recipe for 3D printing of Mullite-based structures was used to investigate the effect of MgO sintering additive on the processing stages and final ceramic properties. To achieve dense 3:2 mullite, ceramic filaments were prepared based on an alumina powder, a methyl silicone resin, EVA elastomeric binder and MgO powder. Using 1 wt% MgO and a dwell time of 5 h at 1600 °C, a dense mullite structure could be obtained from filaments with a diameter of 1.75 mm. Ceramic structures with and without sintering additive were printed in vertical and horizontal direction, to investigate the effect of printing direction on mechanical strength after sintering. Using four-point bending test, it was demonstrated that by using MgO, the printing orientation did not affect the mechanical strength significantly anymore. The low Weibull modulus could be explained by the closed porosity that emerge during the degassing of the preceramic polymer due to cross-linking.     

High strength silica-based ceramics material for investment casting applications: Effects of adding nanosized alumina coatings

A nanosized alumina coating was synthesized on the surface of fused silica particles by electrostatic attraction. The effects of the coated fused silica particles on the cristobalite crystallization behavior, microstructure evolution, and flexural strength of silica-based ceramic cores were investigated. X-ray diffraction (XRD) was used to characterize phase transformations in the specimens, and the results indicated that the formed nanosized alumina coatings could retard cristobalite formation by inducing compressive stress on the fused silica particle surface. A mullite phase was also found due to the reaction of the nanosized alumina coating and the surface of the fused silica when the sintering temperature was increased to 1300 °C. Analysis using scanning electron microscopy equipped with energy dispersive spectrometry (SEM/EDS) suggested that alumina nanoparticles in the coated layer dispersed into a liquid phase and formed a barrier layer to impede the movement of the liquid phase, preventing the pore-filling process and increasing the open porosity of the ceramic specimens. Flexural strengths at room temperature were tested, indicating that increases in the sintering temperature of the specimens without coated fused silica powders had little effect on flexural strength. However, the flexural strength of the specimens with coated fused silica powders increased with increases in sintering temperature. The improvement in flexural strength was related to the reinforcement by sintering necks between particles and the improvement in the strength of the coated fused silica powder.     

Effects of alumina sources on the microstructure and properties of nitrided Al2O3-C refractories

Fused white alumina, tabular alumina with a plate-like morphology, reactive alumina powder with a high specific surface area and industrial alumina composed of 40 to 76% γ-Al₂O₃ and 60 to 24% α-Al₂O₃ were selected as alumina sources and grouped in this work. The effects of alumina sources on the microstructure of nitrided Al₂O₃-C refractories were investigated. A large number of β-Sialon phases and a small number of SiC phases were formed when the alumina source varied, and α-Si₃N₄ phase was only formed when using tabular alumina. The β-Sialon phase was deemed to be the major ceramic bonding phase, which generated the morphologies of column and tabular column. Columned β-Sialon crystals with conical tips were formed by the direct nitriding of liquid silicon following a VLS (vapor-liquid-solid) growth mechanism, the transformation of the VLS growth mechanism into a VS (vapor-solid) growth mechanism was observed when using industrial alumina with smooth tips on the β-Sialon crystals. β-Sialon crystals with a morphology of tabular column were formed through nitriding of SiO _(g) and Si _(g) following the VS growth mechanism. SiC whiskers were formed by the reacting of CO _(g) and SiO _(g) following a CVD (chemical-vapor-deposition) growth mechanism. The physical, mechanical and thermal properties of these groups after the nitriding process were also investigated and compared. When using reactive alumina powder and fused white alumina as the alumina sources, the optimal cold crushing strength (CCS) and cold modulus of rupture (CMOR) were generated due to the dense reticular structure, and also the optimal hot modulus of rupture (HMOR) was achieved due to the formation of large size of O’-Sialon tabular whiskers in the test atmosphere. Improved thermal shock resistance and oxidation resistance were also observed.     

Crushing behavior of alumina inclusions with different porosity during hot compression

Alumina inclusions in commercial as-cast 2.25Cr1Mo0.25V aluminum deoxidized steel exhibited a feature of porous structure. In order to investigate the crushing characteristics of alumina inclusion during hot working, a series of alumina blocks with different porosity whose properties are similar to the alumina inclusions in ingots were prepared using spark plasma sintering. The crushing behavior of alumina blocks during hot compression with quasi-static load was studied. A prediction model of compressive strength of alumina inclusions considering apparent porosity was established on basis of hyperbolic sine Arrhenius equation. A novel crushing mode diagram for alumina inclusions characterized by Z parameter was proposed. The crushing mechanism of alumina inclusions under different deformation parameters was clarified by fracture characteristics. The results showed that the hot compression process of alumina presented a typical brittle fracture, the compressive strength was more sensitive to deformation conditions at lower apparent porosity as compared with the conditions of higher apparent porosity. With the increase of Z, the crushing mode of alumina inclusions gradually changed from intergranular fracture to transgranular fracture.     

Preparation and mechanical properties of machinable alumina/mica composites

Using a mica-crystallizing glass powder in which a large amount of mica crystal was precipitated and a larger amount of MgF₂ component was contained as the raw materials of mica, machinable alumina/mica composites were obtained at 1400 °C. In the firing process, magnesia component in the mica crystals reacted with alumina to form spinel at 1150–1200 °C. The reaction made the mica crystals melt. However, the mica crystals were precipitated again during the cooling. Because a larger amount of MgF₂ component was contained in the mica-crystallizing glass powder, the nucleation of the mica crystals was caused during the cooling by the residual magnesium and fluorine in the liquid phase and succeedingly the mica crystals were precipitated. The precipitated mica crystals grew to anisotropicaly larger size than alumina grains, which lowered the bending strength and Vickers hardness and little heightened the fracture toughness.     

Gas permeability and mechanical properties of porous alumina ceramics with unidirectionally aligned pores

Porous alumina ceramics having unidirectionally aligned cylindrical pores were prepared by extrusion method and compared with porous ceramics having randomly distributed pores prepared by conventional method, and their gas permeability and mechanical properties were investigated. SEM micrographs of the porous alumina ceramics prepared by the extrusion method using nylon fibers as the pore former showed excellent orientation of cylindrical pores. The bending strength and Weibull modulus of the extruded porous alumina ceramics with 39% porosity were 156 MPa and 17, respectively. These mechanical properties of extruded samples were higher than those of the conventional porous alumina ceramics. The strength decreased from 156 to 106 MPa with increasing pore size from 8.5 to 38 μm. The gas permeability of the extrusion samples is higher than that of the conventional samples and increased with increasing of porosity and pore size.     

Transient liquid phase sintering of high-purity mullite for high-temperature structural ceramics

High-purity mullite ceramics, promising engineering ceramics for high-temperature applications, were fabricated using transient liquid phase sintering to improve their high-temperature mechanical properties. Small amounts of ultrafine alumina or silica powders were uniformly mixed with the mullite precursor depending on the silica-alumina ratio of the resulting ceramics to allow for the formation of a transient liquid phase during sintering, thus, enhancing densification at the early stage of sintering and mullite formation by the reaction between additional alumina and the residual glassy phase (mullitization) at the final stage of sintering. The addition of alumina powder to the silica-rich mullite precursor resulted in a reaction between the glassy silica and alumina phases during sintering, thereby forming a mullite phase without inhibiting densification. The addition of fine silica powder to the mullite single-phase precursor led to densification with an abnormal grain growth of mullite, whereas some of the added silica remained as a glassy phase after sintering. The resulting mullite ceramics prepared using different powder compositions showed different sintering behaviors, depending on the amount of alumina added. Upon selecting an optimum process and the amount of alumina to be added, the pure mullite ceramics obtained via transient liquid phase sintering exhibited high density (approximately 99%) and excellent high-temperature flexural strength (approximately 320 MPa) at 1500 °C in air. These results clearly demonstrate that pure mullite ceramics fabricated via transient liquid phase sintering with compositions close to those of stoichiometric mullite could be a promising process for the fabrication of high-temperature structural ceramics used in an ambient atmosphere. The transient liquid phase sintering process proposed in this study could be a powerful processing tool that allows for the preparation of superior high-temperature structural ceramics used in the ambient processing atmosphere.     

Sol-gel infiltration of complex cellular indirect 3D printed alumina

Gelled aqueous solutions containing the soluble precursor aluminum chlorohydrate were developed for the infiltration of porous indirect 3D printed alumina. Viscosity and amplitude sweep tests confirmed the gel formation and sheer thinning behavior beneficial for the subsequent coating and infiltration process. High temperature XRD confirmed the formation of corundum at a temperature of 1000?°C. Complex alumina structures with high surface area and isotropic pore channels were achieved by indirect 3D printing. Coating and infiltration of the pre sintered alumina with a subsequent sintering step transformed the precursor to corundum and partially filled the residual porosity and decreased surface defects after 3D printing. With the gel coating a pronounced improvement up to a maximum value of Δσ_compr?=?61.9?MPa was observed and with the gel infiltration a maximum improvement of ΔE?=?136.2?GPa. The results show the possibility to infiltrate even complex alumina structures with aqueous alumina precursors without the need to disperse ceramic particles.     

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.