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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).

This study demonstrates a novel type of biphasic calcium phosphate (BCP) gyroid scaffolds featuring of gyroid macroporous structure and micropous BCP walls using poly(methyl methacrylate) (PMMA) microspheres as the porogen for ceramic digital light processing (DLP) technique. To tailor the microporosity of the BCP walls and the overall porosity of the dual-scale porous BCP scaffolds, the PMMA content with regard to the BCP powder was controlled in the range of 40 vol% to 70 vol%. After debinding at 600 °C and sintering at 1200 °C for 3 h, micropores were uniformly created throughout each BCP framework, while preserving 3−dimensional gyroid macroporous structures. As the PMMA content increased from 40 vol% to 70 vol%, the microporosity remarkably increased from 31.9 (±2.5) vol% to 55.2 (±1.4) vol%. This approach allowed the achievement of very high overall porosities (82.2–89.7 vol%) for the dual-scale porous scaffolds. However, all the scaffolds showed reasonable compressive strengths (0.8 MPa −2.1 MPa), which are comparable to those of cancellous bones.

The present study reports the manufacturing of a novel type of porous calcium phosphate scaffolds with elongated gyroid structures using digital light processing (DLP), in order to offer significantly enhanced mechanical properties. In particular, solid camphor was employed as the diluent, in order to offer sufficiently low viscosity at high solid loading for conventional layer-by-layer DLP process. Four types of porous CaP scaffolds with different percent elongation (%EL = 0, 20, 40, and 60) were manufactured, and their porous structures and mechanical properties were characterized. All porous CaP scaffolds showed that CaP walls were elongated along the z-direction, while the degree of pore elongation increased with an increase in the designed %EL. Owing to the use of controlled processing parameters, such as layer thickness and exposure time for layer-by-layer photocuring process, and carefully designed debinding process, the photocured layers could be completely bonded together with high densification after sintering at 1,200 °C for 3 h. Such elongation of a gyroid structure offered significantly enhanced mechanical properties − compressive strengths of 4.33 ± 0.26 MPa and 11.51 ± 1.75 MPa were obtained for the porous CaP scaffold with the %EL of 0 and 60, respectively.

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.

The present study describes the manufacturing of 4 mol% yttria partially stabilized zirconia (4Y-PSZ) prostheses with high mechanical properties and translucency using digital light processing (DLP). To formulate 4Y-PSZ suspensions with high solid loading and appropriate viscosity, as-received granules were calcined at 900 °C for 3 h and then crushed into fine particles. In addition, a mixture of low-viscosity hexanediol diacrylate (HDDA) monomer and decalin as the diluent was employed as the photopolymerizable medium. To achieve strong bonding between layers and high accuracy, the photocuring time during DLP process was optimized. 4Y-PSZ prostheses were almost fully densified after sintering at 1,500 °C for 2 h, which had a relative density of 99.4%. Also, no visible interfaces between the layers were noticed. The sintered 4Y-PSZ samples showed high flexural strength of 831 (±74) MPa and high optical transmittance of 30 (±1.2) %.

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.

This paper proposes a photocurable ceramic slurry containing a freezing vehicle as a novel feedstock for digital light processing (DLP) technique, which can produce hierarchical porous ceramic structures. A thin layer, comprised of a 3-dimensionally interconnected ceramic/monomer network surrounded by a frozen camphene-camphor alloy network, can be effectively photopolymerized by the DLP process, and thus micropores can be created after the removal of the camphene-camphor network via freeze-drying. Several processing parameters for the DLP process, including the temperature of the building vat, layer thickness, and UV exposure time, were optimized to produce hierarchical porous ceramic structures. The effect of freezing vehicle content on the microporous structures (e.g., porosity and pore size) and mechanical properties of ceramic frameworks was examined. In addition, hierarchical macro/micro-porous ceramic scaffolds comprised of microporous ceramic frameworks separated by microporous CaP frameworks were produced, and their porous structures and mechanical properties were characterized.

This study presents the utility of solid camphor as a novel type of diluent for the preparation of photocurable ceramic slurries with sufficiently low viscosity at high solid loading (48 vol%), which can be applicable for the conventional digital light processing (DLP) process. The camphor addition remarkably decreased the viscosity of calcium phosphate (CaP) ceramic slurries without affecting their photopolymerization behavior. This approach could effectively mitigate the clogging of pores with residual slurries, and thus the porous structure of porous CaP scaffolds with 3D channels could be tightly controlled. Furthermore, the high densification of CaP frameworks after sintering at 1250 °C for 3 h could be achieved owing to the use of the high solid loading in the CaP slurry. The porous CaP scaffolds produced displayed high compressive strength (˜ 23.8 MPa) and modulus (˜ 276 MPa) at a high porosity of ˜ 50.6 vol%.

We herein propose a novel type of additive manufacturing (AM) technique, denoted as “in situ photocuring-assisted 3D plotting”, which can rapidly solidify extruded green filaments comprised of ceramic powders and photocurable monomers using UV light during 3D plotting. To accomplish this, the rheological properties and photocuring behavior of the ceramic slurry were carefully tailored, particularly by using a mixture of diruethane dimethacrylate (UDMA) and triethylene glycol dimethacrylate (TEGDMA) monomers as the photocurable vehicle. This innovative approach enabled the favorable extrusion of the ceramic slurry through a fine nozzle with high green strength after photocuring, and thus complex-shaped ceramic architectures with high shape retention could be constructed. As an example, a free-standing helical structure with a circular cross-section was successfully produced even without the use of any supporting materials. In addition, a porous ceramic scaffold with a tightly controlled porous structure could be produced.

A hyaluronic acid (HAc)-hydroxyapatite (HAp) nanocomposite (HAc-nanoHAp) hydrogel was fabricated through an in situ precipitation process for mechanical and biological enhancement as a soft tissue augmentation product. In this study, these composite hydrogel fillers were analyzed from three different perspectives and compared with pure HAc hydrogel for soft tissue augmentation application: (1) rheological behaviors, (2) in vivo lateral diffusion under mouse skin, and (3) wrinkle improvement in a photo-aged mouse model. HAc-nanoHAp provided great improvement to wrinkles because of its higher stiffness and gel cohesiveness in comparison with that of pure HAc. HAc-nanoHAp also presented great enhancement in strengthening the dermal matrix by stimulating the synthesis of collagen and elastin. Thus, HAc-nanoHAp filler has great potential as a soft tissue augmentation product, improving the biophysical and biological performance in skin tissue. © 2017 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 105A: 3315-3325, 2017.

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%.

Bare metal stents are commonly used in interventional cardiology; they provide successful treatment because of their excellent mechanical properties, expandability ratios, and flexibility. However, their insufficient vascular affinity can induce the development of neointimal hyperplasia following arterial injury and subsequent smooth muscle cell overgrowth in the lumen of a stented vessel. Nanoengineering of the bare metal stent surface is a valuable strategy for eliciting favorable vascular responses. In this study, we introduce a target-ion-induced plasma sputtering (TIPS) technique to fabricate a platform with a favorable endothelial environment. This technique enables the simple single-step production of a Ta-implanted nanoridged surface on a stent with a complex 3D geometry that shows a clear tendency to become oriented parallel to the direction of blood flow. Moreover, the nanoridges developed show good structural integrity and mechanical stability, resulting in apparently stable morphologies under high strain rates. In vitro cellular responses to the Co-Cr, such as endothelialization, platelet activation, and blood coagulation, are considerably altered after TIPS treatment; endothelium formation is rapid and surface thrombogenicity is low. An in vivo rabbit iliac artery model is used to confirm that the nanoridged surface facilitates rapid re-endothelialization and limits the formation of neointima compared to the bare stent. These results indicate that the Ta ion implanted nanoridge platform fabricated using the TIPS technique has immense potential as a solution for in-stent restenosis and ensuring the long-term patency of bare metal stents.

This study demonstrates a novel, simple way of synthesizing bone morphogenetic protein (BMP)-loaded hydroxyapatite (HA) microspheres for enhanced bone regeneration. To accomplish this, calcium phosphate cement (CPC) microspheres, consisting of α-TCP and TTCP powders, were prepared using water-in-oil (W/O) emulsion, followed by treatment at 37 °C for 3 days to convert the CPC to HA. The BMP-loaded HA microspheres with a well-defined spherical shape had a highly porous structure, which was created by the entanglement of precipitated HA crystals with a needle-like morphology. The unique porous structure with the bone mineral-like HA phase resulted in a considerable improvement in in vitro biocompatibility. In addition, the bone regeneration ability of the HA microspheres was significantly enhanced by BMP loading, which was examined by in vivo animal testing using a rabbit vertical guided bone regeneration model.

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-Exm”. This 3D-Exm 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 (ϕH = 40 vol%) and low ceramic contents (ϕL = 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%).

This study proposes a novel type of macroporous ceramic scaffolds, which are comprised of hollow tubular filaments with a highly microporous structure, using 3-dimensional ceramic/camphene-based co-extrusion (3D-CoEx). The use of an initial feedrod, comprised of a camphene core and an alumina/camphene shell, enabled the construction of hollow tubular frameworks and micropores through the removal of the camphene phase. The produced scaffolds showed 3-dimensionally interconnected macropores with dimensions of ∼250–300 μm × 400–550 μm, which were surrounded by hollow alumina filaments (∼500 μm in diameter) featuring a number of micropores (several tens of microns in size). This unique macro/micro-porous structure could achieve a combination of both the reasonably high compressive strength of ∼5.4 MPa and very high porosity of 86 vol%. In addition, the final mechanical properties and overall porosity of the porous alumina scaffolds could be fine-tuned by adjusting initial alumina content in the alumina/camphene.

This study demonstrates the versatility of 3-dimensional ceramic/camphene-based extrusion (3D-Ex) using a frozen alumina/camphene body as a feedstock for the production of porous alumina scaffolds with a biomimetic macro/micro-porous structure. Three-dimensionally interconnected macropores were constructed through the deposition of frozen alumina/camphene filaments at a stacking sequence of 0°/90°, while aligned micropores were created in alumina frameworks as the replica of camphene dendrites that had been extensively elongated by the extrusion of a frozen alumina/camphene body. The macro/micro-porous structure and compressive strength of porous alumina scaffolds could be tailored by adjusting initial alumina content in alumina/camphene slurries.

We herein propose a novel way of creating porous biphasic calcium phosphate (BCP) scaffolds with tightly controlled 3-D macrochannels using rapid direct deposition of ceramic paste (RDD-C). This newly developed RDD-C technique can rapidly solidify deposited green BCP filaments through the precipitation of a methylcellulose (MC) polymer used as the binder in aqueous BCP paste via solvent extraction mechanism. This allowed porous scaffolds produced with various initial distances between green filaments (0.5 mm, 1 mm, and 1.5 mm) to have tightly controlled 3-D macrochannels with good shape tolerance. As the initial distance between green filaments increased from 0.5 mm to 1.5 mm, overall porosity increased from 44.3±4.9 vol% to 63.5±2.5 vol%, while compressive strength decreased from 30.1±7.6 MPa to 11.6±3.8 MPa. The porous scaffold showed good biocompatibility assessed by in vitro cell tests.

Changes in the internal structure of nonwoven mats during tensile testing were investigated in situ with micro X-ray computer tomography (CT). Fiber orientation and volume fraction, as well as fiber–fiber contact, were quantitatively characterized at several strain levels. These parameters are apt to change under tensile loading and are important in determining the mechanical properties of nonwoven mats. The reorientation of fibers along the tensile direction was restricted at large deformations due to interlocked structures, which formed as a result of inherent entanglements in the nonwoven mats. In addition, contact efficiency, which describes the relative degree of fiber–fiber contact and was shown to be a suitable geometrical parameter for characterizing the microstructure of nonwoven mats, decreased at low strain and then increased with increasing strain until failure.

We produced highly porous triphasic calcium phosphate (CaP) scaffolds, comprising of hydroxyapatite (HA), β-tricalcium phosphate (β-TCP), and α-TCP phases, using vacuum-assisted foaming of a ceramic suspension (VFC) technique. In particular, vigorously foamed CaP green bodies with a composition of ∼60 wt% HA and 40 wt% β-TCP were sintered at relatively high temperatures (1200, 1250, 1300, and 1350 °C) to control the amount of three constituent phases. All the produced samples showed a highly porous structure (porosity ∼ 83.5–84.5 vol%, pore size ∼ 312–338 μm, and interconnection size ∼ 61–74 μm) with a number of microchannels in the CaP walls. However, sintering at relatively high temperatures≥1250 °C induced considerable phase transformation of the β-TCP to α-TCP phases. The presence of the more soluble α-TCP phase in the triphasic CaP scaffolds significantly enhanced the in vitro bioactivity of the porous CaP scaffolds, which was assessed in terms of their apatite-forming ability in simulated body fluid (SBF).

This study evaluated the utility of the creation of a nanoporous TiO2 surface to enhance the in vitro biocompatibility and in vivo osseoconductivity of polyetheretherketone (PEEK) implants by providing favorable sites for the effective immobilization of bone morphogenetic protein-2 (BMP-2). A uniform nanoporous TiO2 layer with a pore diameter of ∼70 nm was successfully created by anodizing a Ti film, which had been deposited onto a PEEK substrate via electron beam (e-beam) evaporation technique. This nanoporous, hydrophilic TiO2 surface enabled the efficient immobilization of BMP-2, resulting in a remarkable enhancement in in vitro biocompatibility that was assessed in terms of cell attachment, proliferation, and differentiation. The in vivo animal tests also confirmed that the nanoporous TiO2 surface immobilized with BMP-2 could significantly enhance the osseoconductivity of PEEK implants. The BMP-immobilized PEEK implant with the nanoporous TiO2 surface showed much higher bone-to-implant contact (BIC) ratio (60%) than the bare PEEK (30%), PEEK with the nanoporous TiO2 surface (50%) and even BMP-immobilized PEEK without the nanoporous TiO2 surface (32%).

Magnesium and its alloys are candidate materials for biodegradable implants; however, excessively rapid corrosion behavior restricts their practical uses in biological systems. For such applications, surface modification is essential, and the use of anticorrosion coatings is considered as a promising avenue. In this study, we coated Mg with hydroxyapatite (HA) in an aqueous solution containing calcium and phosphate sources to improve its in vitro and in vivo biocorrosion resistance, biocompatibility and bone response. A layer of needle-shaped HA crystals was created uniformly on the Mg substrate even when the Mg sample had a complex shape of a screw. In addition, a dense HA-stratum between this layer and the Mg substrate was formed. This HA-coating layer remarkably reduced the corrosion rate of the Mg tested in a simulated body fluid. Moreover, the biological response, including cell attachment, proliferation and differentiation, of the HA-coated samples was enhanced considerably compared to samples without a coating layer. The preliminary in vivo experiments also showed that the biocorrosion of the Mg implant was significantly retarded by HA coating, which resulted in good mechanical stability. In addition, in the case of the HA-coated implants, biodegradation was mitigated, particularly over the first 6 weeks of implantation. This considerably promoted bone growth at the interface between the implant and bone. These results confirmed that HA-coated Mg is a promising material for biomedical implant applications.

This paper reports a novel way of enhancing the hardness of a zirconia-toughened alumina (ZTA) composite with a zirconia content of 20 vol% by surface treatments with a boehmite sol. More specifically, a ZTA composite was first prepared by heat-treating a mixture of alumina and zirconia powders containing Cr 2 O 3 and SrAl 11 CrO 19 , as a reinforcement at 1400 °C for 1 h, and then infiltrating them with the boehmite sol, followed by heat-treatment at 1650 °C for 1 h to densify them. This treatment led to a significant increase in the surface hardness of the ZTA composite, which was attributed mainly to an increase in the volume fraction of an alumina phase with greater hardness, whereas the flexural strength and fracture toughness decreased slightly. The Vickers hardness, flexural strength and fracture toughness were 17.1 ± 2.5 GPa, 738 ± 88 MPa and 4.2 ± 0.11 MPa m 1/2 , respectively.

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.

We herein propose a novel way of producing highly aligned porous alumina tubes by co-extruding an initial feed rod, which comprised of a pure camphene core and a frozen alumina/camphene shell. This new and simple technique produced alumina tubes (~4.4 ± 0.1 mm in outer diameter) having uniform alumina walls (~1.1 ± 0.12 mm in thickness) with highly aligned pores, which were created by removing the extensively elongated camphene dendrites in the extruded alumina/camphene shell. Furthermore, the heat treatment of the extruded bodies at 33°C, which is close to the freezing point of the alumina/camphene slurry, led to a considerable increase in the size of the aligned pores formed in the alumina walls, from ~

A collagen–silica xerogel hybrid membrane was fabricated by a sol–gel process for guided bone regeneration (GBR). The silica xerogel synthesized by the sol–gel method was distributed uniformly within the collagen matrix in the form of nanoparticles. The hybridization of the silica xerogel with collagen improved the biological properties of the membrane significantly. Preosteoblast cells were observed to adhere well and grow much more actively on the hybrid membrane than on the pure collagen membrane. In particular, the hybrid membrane containing 30% of the silica xerogel showed the highest level of osteoblast differentiation. Moreover, the GBR ability, as assessed by the in vivo animal test, was superior to that of the pure collagen membrane. These findings suggest that the collagen–silica xerogel hybrid can be used as a GBR membrane. © 2012 Wiley Periodicals, Inc. J Biomed Mater Res Part A:, 2012.

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.

This article reports a novel, simple route for synthesis of sol–gel derived porous, bioactive glass (BG) microspheres using chitosan (CTS) as a biomolecular template in the acid-catalyzed sol–gel process. The use of CTS, which is a natural biocompatible polymer with a unique molecular structure, allowed the synthesis of BG microparticles with a spherical shape, 5–10 μm in size. Furthermore, pores with a size of 5–40 nm were created entirely throughout BG microspheres, which were formed by removing the network of CTS present initially in the CTS-BG composite microparticles via heat-treatment at 600°C for 2 h. These porous BG microspheres induced the vigorous precipitation of apatite crystals on their surface when immersed in simulated body fluid for 24 h, thus suggesting their excellent bioactivity .

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.

This paper proposes a novel, simple way to improve the compressive strength of reticulated porous hydroxyapatite (HA) ceramics using carbon-coated polymeric sponges with elongated pores as a novel template. This template allowed samples to have two interconnected pore networks with a preferential orientation, in which an addition pore network was newly formed by removing the carbon-coated polymeric struts, while preserving the pre-existing pore network. The compressive strength of the sample was as high as 2.9 ± 0.3 MPa with a porosity of 76% when tested parallel to the direction of pore elongation. In addition, the in vitro cell test using a pre-osteoblast cell line revealed the samples to have good biocompatibility.

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.

A novel type of porous hydroxyapatite (HA) scaffolds with a functionally graded core/shell structure was fabricated by freeze casting HA/camphene slurries with various HA contents into fugitive molds containing a graphite template with three-dimensionally interconnected pores for the creation of a highly porous core. All the fabricated samples had functionally graded core/shell structures with 3-D periodic pore networks in a core surrounded by a relatively dense shell. The overall porosity of the sample decreased from 60 to 38 vol% with increasing HA content in the HA/camphene slurry from 20 to 36 vol% due to a decrease in porosity in both the core and shell regions. In addition, the compressive strength was improved remarkably from 12 ± 1.1 to 32 ± 3.0 MPa. The in vitro cell test using a pre-osteoblast cell line showed that the samples had good biocompatibility.

Highly porous calcium phosphate (CaP) ceramics were fabricated by freezing foamed aqueous CaP suspensions with various CaP contents (15, 20, and 25 vol %) containing polyvinyl alcohol (PVA) as the binder and emulsifying agent. All the samples fabricated showed uniformly dispersed macropores, which were created by air bubbles introduced in the suspensions. In addition, aligned micropores were formed in the sintered CaP walls as a replica of the preferentially grown ice dendrites during freezing when CaP contents of 15 and 20 vol % were used. The overall porosity decreased from 83 to 73 vol % with increasing initial CaP content from 15 to 25 vol %, whereas the compressive strength and elastic modulus increased significantly from 1.2 ± 0.2 to 4.7 ± 0.9 MPa and from 20 ± 11 to 163 ± 42 MPa, respectively. The samples showed good biocompatibility, as assessed by the in vitro cell test using a pre-osteoblast cell line.

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.

Ceramic fiber separator is the promising material for thermal battery system because it reduces the production cost and offers the potential to a new application compared to a pellet type electrolyte. The electrolyte separator for thermal battery should be easily handled and loaded a large amount of the molten lithium salt. Ceramic fibers were used as an electrolyte separator and the lithium based molten salts were infiltrated into the ceramic filters. Leakage of molten salt (several lithium salts) leads to short-circuit during the thermal battery operation. In this study, a uniform and fine SiOC mat with fibers ranging from 1 to 3 ㎛ was obtained by electrospinning of polycarbosilane and pyrolysis. The optimum spinning conditions for obtaining fine diameters of SiOC fiber were controlled by the solution composition and concentration, applied voltage and spinning rate, release rate by porosity. The pore structures of the ceramic filter and the melting properties of the lithium salts affected to the electrolyte loading and leakage. The importance of the fiber size and porosity and their control was discussed and the mechanical properties were also discussed.

Lithium salt have been used mainly as electrolyte of thermal battery for electricity storage. Recently, The 3phase lithium salt(LiCl-LiF-LiBr) is tried to use as electrolyte of thermal battery for high electric power. It is reported that LiCl-LiF-LiBr salt have high ion mobility due to its high lithium ion concentration. Solid lithium salt is melt to liquid state at above 500℃. The lithium ion is easily reacted with support materials. Because the melted lithium ion has small ion size and high ion mobility. For the increasing mechanical strength of electrolyte pellet, the research was started to apply ceramic filter to support of electrolyte. In this study, authors used SiOC web and glass fiber filter as ceramic mat for support of electrolyte and impregnated LiCl-LiF-LiBr salt into ceramic mat at above 500℃. The fabricated electrolyte using ceramic mat was washed with distilled water for removing lithium salt on ceramic mat. The washed ceramic mat was observed for lithium ion reaction behavior with XRD, SEM-EDS and so on.

Lead zirconate titanate [PZT(60/40)] films were deposited by RF-magnetron sputtering using single oxide targets with various levels of excess PbO. The excess PbO in the film played an important role in the pyrochlore-to-perovskite transformation, nucleation and growth processes, orientation control, and crack formation. When 5% or 20% excess PbO was added to the target, pyrochlore phases were created and the films were severely cracked. However, the films had a perovskite structure without any pyrochlore phases when 10% or 15% excess PbO was added to the targets. More interestingly, the crystallographic orientation was strongly dependant on the excess PbO content. A film with a (111) preferred orientation was produced when 10% excess PbO was added to the target. On the other hand, a film with a (100) preferred orientation was deposited by the target with 15% excess PbO. The dielectric, ferroelectric and piezoelectric properties of these films with different orientations and microstructures were examined and correlated with the film structure.

Four calcium phosphate ceramic coatings, the less soluble hydroxyapatite (HA) coating, the more soluble β-tricalcium phosphate (β-TCP) coating, and two biphasic calcium phosphate (BCP) coatings with HA/β-TCP ratios of 70/30 and 30/70 were fabricated by spraying each corresponding powder onto a titanium substrate at room temperature (RT) in a vacuum, in order to investigate the effect of the HA/β-TCP ratio on the dissolution behavior and the cellular responses of the coating. No secondary phases, except for HA and β-TCP, were observed for the coatings in the X-ray diffraction results. The coating compositions were almost the same as those of the starting powders because the coating was conducted at RT. Microscopic examination of the coatings revealed crack-free and dense microstructures. The BCP coatings exhibited dissolution rates intermediate between those of the pure HA and β-TCP coatings. The dissolution rate of the coatings was largely dependent on their HA/β-TCP ratio. The cell proliferation and differentiation results indicated that the cellular responses of the coatings were not proportional to their dissolution rates. The 3HA-7TCP (HA/β-TCP ratio of 30/70) coating exhibited an optimal dissolution rate for excellent biological performance.

In order to improve biocompatibility of Ti metal substrates, 1-μm-thick nanostructured hydroxyapatite (HAp) coatings were deposited on the substrates through aerosol deposition, which sprays HAp powder with an average particle size of 3.2 μm at room temperature in vacuum. The original HAp particles were fractured into nanoscale fragments to form highly dense coating during the deposition process. Density of the HAp coating was 98.5% theoretical density (TD). Transmission electron microscopy observation revealed that the as-deposited coating consisted of HAp crystallites with average grain size of 16.2 nm and amorphous phase. Tensile adhesion strength between the coating and the substrate was 30.5±1.2 MPa. Annealing up to 500°C in air increased crystallinity and grain size in the coating without any delamination or crack according to X-ray diffraction analysis and electron microscopy. MTS assay and alkaline phosphatase activity measurements with MC3T3-E1 preosteoblast cell revealed that the biocompatibility was greatly improved by postdeposition heat treatment at 400°C in air due to well-crystallized HAp with average grain size of 29.3 nm. However, further heat treatment at 500°C deteriorated biocompatibility due to rapid growth of HAp grains to average size of 99 nm. Cross section of the coating on a commercially available Ti dental implant revealed full coverage of the surface with HAp.

Multi-walled carbon nanotube (CNT) reinforced hydroxyapatite composite coating with a thickness of 5 μm has been successfully deposited on Ti substrate using aerosol deposition (AD). The coating had a dense microstructure with no cracks or pores, showing good adhesion with the Ti substrate. Microstructural observation using field-emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM) showed that CNTs with original tubular morphology were found in the hydroxyapatite-CNT (HA-CNT) composite coating. Measurements of hardness and elastic modulus for the coating were performed by nanoindentation tests, indicating that the mechanical properties of the coating were remarkably improved by the addition of CNT to HA coating. Therefore, HA-CNT composite coating produced by AD is expected to be potentially applied to the coating for high load bearing implants.

Lead zirconate titanate films with different Zr/Ti ratios were fabricated on a platinized silicon substrate using radio frequency magnetron sputtering. Crack-free films with a rhombohedral, morphotropic phase boundary and tetragonal compositions were deposited using single oxide targets containing various amounts of excess PbO. When the films showed a (111) preferred orientation, there were no cracks, regardless of the phase, and their microstructures were similar to one another. As the Zr/Ti ratio was changed, the amount of excess PbO necessary for the stoichiometry of the films also changed. When they had a stoichiometric composition, the films had a small grain size and similar microstructures. Moreover, their structural stability increased when the grains had an equiaxed morphology. The ferroelectric and piezoelectric properties of the films were characterized and correlated with their phase and microstructure.

The electrolyte separator for thermal battery should be easily handled and loaded a large amount of the molten salt. Ceramic fibers, especially fibrous commercial glass filters were used as an electrolyte separator and the lithium based molten salts were infiltrated into the ceramic filters. The pore structures of the ceramic filter and the melting properties of the lithium salts affected to the electrolyte loading and leakage. During the infiltration, ions of Li? and F? in the molten salts were reacted with the glass fiber and caused to be weaken the fiber strength.

Ceramic Fiber separator is the promising material for thermal battery system because it reduces the production cost and offers the potential to a new application compared to a pellet type electrolyte. The molten salt electrolytes for thermal battery were prepared by the impregnation of the commercial glass filters such as GF-A, C and F (Whatman, USA) with two types of molten-lithium salts, LiCl-KCl and LiK-LiBr-LiF. The wetting properties were evaluated by wetting balance test and wetting angle measurement. The wetting behaviors were strongly affected by the composition of the molten salts and the pore structure of the glass separators. The optimum wetting conditions for maximum loading and effective retention of the molten electrolyte were also studied.

Calcium sulfate hemihydrate (CSH) powders were synthesized for use as bone cement by heat treating calcium sulfate dihydrate (CSD) powders in boiling CaCl2 solutions with various CaCl2 concentrations, ranging from 23.5 to 35.5 wt%, in order to control their morphology. All of the prepared CSH powders showed X-ray diffraction peaks corresponding to the CSH structure without any secondary phases, implying complete conversion from the CSD phase to the CSH phase. It was also observed that the concentration of CaCl2 significantly affected the morphology of the CSH powder that was synthesized. In other words, as the CaCl2 concentration was decreased from 35.5 to 23.5 wt%, the morphology notably changed from long-and-slim hexagonal rods with an aspect ratio of 5.5 to fat-and-short hexagonal columns with an aspect ratio of 1.4. This reduction in the aspect ratio led to a significant improvement in the compressive strength of the CSD cement prepared by mixing the CSH powders with water.

Porous lead zirconate titanate–lead zinc niobate (PZT–PZN) piezoelectric ceramics with a high degree of pore alignment were fabricated using directional freeze casting of a ceramic/camphene slurry. Well-aligned pores were formed as the replica of the camphene dendrites that grew in a preferential orientation, while a high porosity of 90% was achieved by employing a low initial solid loading of 5 vol%. As the orientation angle of the pores to the poling direction was decreased, the hydrostatic piezoelectric properties, such as hydrostatic piezoelectric strain coefficient (dh), the hydrostatic piezoelectric voltage coefficient (gh), and the hydrostatic figure of merit, increased significantly. The sample containing pores aligned parallel to the poling direction showed an extremely high HFOM of 161019 × 10−15 Pa−1, which was ∼1300 times higher than that (124 × 10−15 Pa−1) of the dense sample, owing to the presence of aligned pores.

The objective of this study was to fabricate porous hydroxyapatite (HA) scaffolds coated with bioactive A/W glass–ceramics and to examine their mechanical and biological properties. Firstly, the HA scaffolds were prepared by the polymeric sponge replication method, and then A/W glasses were coated on the surface of the struts. All of the scaffolds had a highly porous structure with well-interconnected pores. It was observed that the bioactive glass coating markedly increased the strength of the HA scaffolds. This enhancement was attributed to the formation of a dense and strong coating layer on the weak HA struts. The in vitro bioactivities of the scaffolds were markedly improved by the coatings. When the coated scaffolds were soaked in a simulated body fluid (SBF), the bone-like apatite crystals were well mineralized on their surfaces. Osteoblast-like cells (MC3T3) adhered, spread, and grew well on the porous scaffolds. The cells placed on the glass-coated HA scaffold showed a higher proliferation rate and alkaline phosphatase (ALP) activity than those on the pure HA scaffold. These results demonstrate that the bioactive glass coating is effective in improving the strength and bioactivity of the porous HA scaffolds.

Porous lead zirconate titanate–lead zinc niobate (PZT–PZN) piezoelectric ceramics with interconnected pore channels were fabricated using the camphene-based freeze-casting method. In this method, warm PZT–PZN/camphene slurries with various solid loadings (10, 15, 20, and 25 vol%) were prepared by ball milling at 60°C and then cast into molds at 20°C, resulting in the formation of solidified green bodies comprised of three-dimensionally interconnected camphene dendrite networks and concentrated ceramic particle walls. After the removal of the frozen camphene via sublimation, the samples were sintered at 1200°C for 2 h. All of the fabricated samples showed highly porous structures, consisting of fully dense PZT–PZN walls without defects, such as cracks or pores. As the initial solid loading was decreased from 25 to 10 vol%, the porosity was linearly increased from 50% to 82%. This increase in the porosity led to a reduction in the permittivity, a moderate decline in the d33 value, and a rapid decline in the d31 value, which endowed the porous samples with a high hydrostatic figure of merit (HFOM). The highest HFOM value of 35650 × 10−15 Pa−1 was achieved for the sample with a porosity of 82%, as well as ɛ33=284, dh=298 pC/N, and gh=118 × 10−3 V·(m·Pa)−1.

Polyaluminocarbosilane was synthesized by direct reaction of polydimethylsilane with aluminum(Ⅲ)-acetylacetonate in the presence of zeolite catalyst. A fraction of higher molecular weight polycarbosilane was formed due to the binding of aluminium acetylacetonate radicals with the polycarbosilane backbone. Small amount of Si-O-Si bond was observed in the as-prepared polyaluminocarbosilane as the result. Polyaluminocarbosilane fiber was obtained through a melt spinning and was pyrolyzed and sintered into SiC fiber from 1200~2000℃ under a controlled atmosphere. The nucleation and growth of β-SiC grains between 1400 - 1600℃ are accompanied with nano pores formation and residual carbon generation. Above 1800℃, SiC fiber could be sintered to give a fully crystallized β-SiC with some α-SiC.

The present study reports an innovative way to produce large pore channels with a size >100 μm for applications in bone tissue engineering using the camphene-based freeze casting method, and using an unusually high freezing temperature, which is close to the solidification temperature of the slurry, in order to allow the formation of excessively overgrown camphene dendrites due to the extremely low solidification velocity. To accomplish this, hydroxyapatite (HA)/slurries with various solid loadings (10, 15, and 20 vol%) were frozen at 35°C for 20 h. The frozen samples were freeze dried and sintered at 1250°C for 3 h. All of the fabricated samples showed highly porous structures with large pore channels >100 μm in size and dense HA walls without any noticeable defects, such as cracks or pores. As the initial solid loading was increased from 10 to 20 vol%, the porosity of the sample decreased linearly from 76% to 55%, while the pore channels became narrower. However, the compressive strength was remarkably improved from 2.5 to 16.7 MPa.

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.