Table of contents

Much research has been devoted recently to developing technologies for renewable energy and improving the efficiency of the processes and devices used in industry and everyday life. Efficient solutions have been found using novel materials such as platinum and palladium-based catalysts for car exhaust systems, samarium–cobalt and neodymium–iron–boron permanent magnets for electrical motors, and so on. However, their realization has resulted in an increasing demand for rare elements and in their deficit, the development of new materials based on more abundant elements and new functionalities of traditional materials. Moreover, increasing environmental and health concerns demand substitution of toxic or hazardous substances with nature-friendly alternatives.

In this context, this focus issue on advanced ceramics aims to review current trends in ceramics science and technology. It is related to the International Conference on Science and Technology of Advanced Ceramics (STAC) held annually to discuss the emerging issues in the field of ceramics.

An important direction of ceramic science is the collaboration between experimental and theoretical sciences. Recent developments in density functional theory and computer technology have enabled the prediction of physical and chemical properties of ceramics, thereby assisting the design of new materials. Therefore, this focus issue includes articles devoted to theory and advanced characterization techniques. As mentioned above, the potential shortage of rare elements is becoming critical to the industry and has resulted in a Japanese government initiative called the 'Ubiquitous Element Strategy'. This focus issue also includes articles related to this strategy and to the associated topics of energy conversion, such as phosphors for high-efficiency lighting and photocatalysts for solar-energy harvesting.

We hope that this focus issue will provide a timely overview of current trends and problems in ceramics science and technology and promote new research and development in this field.

Magnesium dititanate (MgTi₂O₅, MT₂) has been synthesized since the early 1930s. It has the pseudobrookite structure (general formula Me₃O₅), corresponding to the Mg-enriched artificial endmember of the Fe₂TiO₅ (pseudobrookite)–FeTi₂O₅ (ferropseudobrookite)–Mg_0.5Fe_0.5Ti₂O₅ (armalcolite) solid solution. Since MgTi₂O₅ has relativity high thermal stability among pseudobrookite-type phases, it is expected to be a well-balanced low-thermal-expansion material. Here we review both the historical and recent studies on MgTi₂O₅, particularly on its crystal structure, cation order–disorder, physical properties and synthesis methods.

Recent first-principles studies of point defects in ZnO are reviewed with a focus on native defects. Key properties of defects, such as formation energies, donor and acceptor levels, optical transition energies, migration energies and atomic and electronic structure, have been evaluated using various approaches including the local density approximation (LDA) and generalized gradient approximation (GGA) to DFT, LDA+U/GGA+U, hybrid Hartree–Fock density functionals, sX and GW approximation. Results significantly depend on the approximation to exchange correlation, the simulation models for defects and the post-processes to correct shortcomings of the approximation and models. The choice of a proper approach is, therefore, crucial for reliable theoretical predictions. First-principles studies have provided an insight into the energetics and atomic and electronic structures of native point defects and impurities and defect-induced properties of ZnO. Native defects that are relevant to the n-type conductivity and the non-stoichiometry toward the O-deficient side in reduced ZnO have been debated. It is suggested that the O vacancy is responsible for the non-stoichiometry because of its low formation energy under O-poor chemical potential conditions. However, the O vacancy is a very deep donor and cannot be a major source of carrier electrons. The Zn interstitial and anti-site are shallow donors, but these defects are unlikely to form at a high concentration in n-type ZnO under thermal equilibrium. Therefore, the n-type conductivity is attributed to other sources such as residual impurities including H impurities with several atomic configurations, a metastable shallow donor state of the O vacancy, and defect complexes involving the Zn interstitial. Among the native acceptor-type defects, the Zn vacancy is dominant. It is a deep acceptor and cannot produce a high concentration of holes. The O interstitial and anti-site are high in formation energy and/or are electrically inactive and, hence, are unlikely to play essential roles in electrical properties. Overall defect energetics suggests a preference for the native donor-type defects over acceptor-type defects in ZnO. The O vacancy, Zn interstitial and Zn anti-site have very low formation energies when the Fermi level is low. Therefore, these defects are expected to be sources of a strong hole compensation in p-type ZnO. For the n-type doping, the compensation of carrier electrons by the native acceptor-type defects can be mostly suppressed when O-poor chemical potential conditions, i.e. low O partial pressure conditions, are chosen during crystal growth and/or doping.

While most ceramics are composed of ubiquitous elements (the ten most abundant elements within the Earth's crust), many advanced materials are based on rare elements. A 'rare-element crisis' is approaching owing to the imbalance between the limited supply of rare elements and the increasing demand. Therefore, we propose a 'ubiquitous element strategy' for materials research, which aims to apply abundant elements in a variety of innovative applications. Creation of innovative oxide materials and devices based on conventional ceramics is one specific challenge. This review describes the concept of ubiquitous element strategy and gives some highlights of our recent research on the synthesis of electronic, thermionic and structural materials using ubiquitous elements.

Recently, graphitic carbon nitride (g-C₃N₄) has been investigated as a photocatalyst for water splitting and organic dye degradation. In this study, we have developed a simple soft-chemical method of doping Zn into g-C₃N₄ to prepare a metal-containing carbon nitride. The doping was confirmed by x-ray photoelectron spectroscopy, and diffusion reflectance spectra revealed a significant red shift in the absorption edge of Zn/g-C₃N₄. This hybrid material shows high photocatalytic activity and good stability for hydrogen evolution from an aqueous methanol solution under visible light irradiation (λ≥420 nm). The hydrogen evolution rate was more than 10 times higher for a 10%-Zn/g-C₃N₄ sample (59.5 μmol h⁻¹) than for pure g-C₃N₄. The maximum quantum yield was 3.2% at 420 nm.

Cesium dihydrogen phosphate (CsH₂PO₄, CDP) and dodecaphosphotungstic acid (H₃PW₁₂O₄₀·nH₂O, WPA·nH₂O) were mechanochemically milled to synthesize CDP–WPA composites. The ionic conductivities of these composites were measured by an ac impedance method under anhydrous conditions. Despite the synthesis temperatures being much lower than the dehydration and phase-transition temperatures of CDP under anhydrous conditions, the ionic conductivities of the studied composites increased significantly. The highest ionic conductivity of 6.58×10⁻⁴ Scm⁻¹ was achieved for the 95CDP·5WPA composite electrolyte at 170 °C under anhydrous conditions. The ionic conduction was probably induced in the percolated interfacial phase between CDP and WPA. The phenomenon of high ionic conduction differs for the CDP–WPA composite and pure CDP or pure WPA under anhydrous conditions. The newly developed hydrogen interaction between CDP and WPA supports anhydrous proton conduction in the composites.

The ferroelectric domain structure of a PbTiO₃ thin film on (100) SrTiO₃ has been investigated by transmission electron microscopy (TEM). Two types of a-domain were found: one extended through the film to the surface and another comprised small a-domains confined within the film. Dark-field TEM (DFTEM) observation revealed that 180° domains formed near the substrate and stopped their growth 100 nm away from the substrate. The DFTEM observation also revealed that 90° domain boundaries had head-to-tail structures. To confirm the polarization direction obtained by experiments, diffracted intensities under a two-beam condition were simulated using the extended Darwin–Howie–Whelan equations. On the basis of the obtained results, a ferroelectric domain structure model of PbTiO₃ thin films on SrTiO₃ is proposed.

We have synthesized Yb²⁺-activated Si_6−zAl_zO_zN_8−z (0.05⩽z⩽2.3, 0.03 mol% ⩽Yb²⁺⩽0.7 mol%) green phosphors by solid-state reaction at 1900 °C for 2 h under a nitrogen pressure of 1.0 MPa. Phase purity, photoluminescence and its thermal quenching were investigated. A single phase was obtained for all values of z and Yb²⁺ concentration. A distinct emission band was observed at 540 nm originating from the 5d–4f electronic transition in Yb²⁺ under 480 nm excitation. The photoluminescence properties mainly depended on the Yb²⁺ concentration and chemical composition of the matrix. The resultant phosphor showed high thermal stability, that is, the emission intensity at 150 °C was about 82% of that measured at room temperature. The experimental results indicate that β-SiAlON:Yb²⁺ is a potential green phosphor for white light-emitting diodes (LEDs), which use blue LEDs as the primary light source.

Overexpression of Cbfa1 (a transcription factor indispensable for osteoblastic differentiation) is expected to induce the formation of bone directly and indirectly in vivo by accelerating osteoblastic differentiation. Adenoviral vectors carrying the cDNA of Cbfa1/til-1(Adv-Cbf1) were allowed to be adsorbed onto porous blocks of β-tricalcium phosphate (β-TCP), a biodegradable ceramic, which were then implanted subcutaneously and orthotopically into bone defects. The adenoviral vectors were released sustainingly by biodegradation, providing long-term expression of the genes. Results of the subcutaneous implantation of Adv-Cbfa1-adsorbed β-TCP/osteoprogenitor cells suggest that a larger amount of bone formed in the pores of the implant than in the control material. Regarding orthotopic implantation into bone defects, the released Adv-Cbfa1 accelerated regeneration in the cortical bone, whereas it induced bone resorption in the marrow cavity. A safer gene transfer using a smaller amount of the vector was achieved using biodegradable porous β-TCP as a carrier.

TiO₂ thin films with a periodical two-dimensional close-packed hemispherical structure were prepared on Si substrates using pulsed laser deposition and close-packed monolayer polystyrene colloidal crystals as a template. Compared with conventional methods, which use a top-down approach, this route supports low-cost production of a periodic structure. Additionally, it is applicable to various ceramics for use in applications related to photonic crystals, surface self-cleaning materials, data storage media, bioassays, and so on.

We have prepared silica glass by the sol–gel method and studied its ability to disperse the Ca-α-SiAlON:Eu²⁺ phosphor for application in white light emitting diodes (LEDs). The emission color generated by irradiating doped glass with a blue LED at 450 nm depended on the concentration of SiAlON and the glass thickness, resulting in nearly white light. The luminescence efficiency of 1-mm-thick glass depended on the SiAlON concentration, and was highest at 4 wt% SiAlON.

Thin films composed of MgAl₂O₄ and (Ni_0.5Zn_0.5)Fe₂O₄ ([MA(100-x)-NZFx] films) were grown on fused SiO₂ substrates by pulsed laser deposition. X-ray diffraction measurements revealed that the films were polycrystalline, and that their lattice constant varied linearly with composition, indicating the formation of a solid solution. The film with x=60 was paramagnetic and those with x ≥ 70 were ferromagnetic. The films had a transparency above 75% in the visible range, but the transparency decreased with the x value. The optical band gaps were 2.95, 2.55, 2.30 and 1.89 eV for x=20, 40, 60, 80 and 100, respectively. The Faraday rotation angle increased with x in the visible range, and the film with x=70 exhibited a value of 2000 degrees cm^-1 at 570 nm, which is comparable to the rotation angle of Y₃Fe₅O₁₂. Owing to their high transparency, which extends into the visible range, the [MA(100-x)-NZFx] films can be used in novel magneto-optical devices.

Femtosecond time-resolved pump–probe experiments were carried out to study ultrafast lattice dynamics of ferroelectric lithium tantalate. Both the fully symmetric (A₁ mode) and doubly degenerate (E mode) coherent phonons at the center of the Brillouin zone were excited via impulsive stimulated Raman scattering, as confirmed by the excitation intensity dependence.

12CaO·7Al₂O₃ electride, a sub-nanoporous compound having a work function of 2.4 eV, was examined as a candidate cathode material in fluorescent lamps. The electron emission yield was higher and the discharge voltage was lower for 12CaO·7Al₂O₃ than for existing cathode materials such as Ni, Mo or W; therefore, the energy consumption of the fluorescent lamps can be improved using 12CaO·7Al₂O₃ cathodes. Prototype glow-discharge lamps using 12CaO·7Al₂O₃ were constructed and exhibited reasonable durability.

Competitive adsorption of two-component solutions containing fibronectin (Fn) and albumin (Ab) on hydroxyapatite (HAp) nanocrystals was analyzed in situ using the quartz crystal microbalance with dissipation (QCM-D) technique. Adsorption of the one-component protein (Fn or Ab) and the two-component proteins adjusted to different molar ratios of Fn to Ab at a fixed Fn concentration was investigated. The frequency shift (Δf; Hz) and the dissipation energy shift (ΔD) were measured with the QCM-D technique, and the viscoelastic changes of adlayers were evaluated by the saturated ΔD/Δf value and the Voigt-based viscoelastic model. For the adsorption of the one-component protein, the Fn adlayer showed a larger mass and higher viscoelasticity than the Ab adlayer, indicating the higher affinity of Fn on HAp. For the adsorption of the two-component proteins, the viscoelastic properties of the adlayers became elastic with increase in Ab concentration, whereas the adsorption mass was similar to that of Fn in the one-component solution regardless of the Ab concentration. The specific binding mass of the Ab antibody to the adlayers increased with increase in Ab concentration, whereas that of the Fn antibody decreased. Therefore, Fn preferentially adsorbs on HAp and Ab subsequently interacts with the adlayers, indicating that the interfacial viscoelasticity of the adlayers was dominated by the interaction between Fn and Ab.

The invention of electrospinning has solved the problem of producing micro- and nanoscaled metal oxide fibres in bulk quantities. However, until now no methods have been available for preparing a single nanofibre of a metal oxide. In this work, the direct drawing method was successfully applied to produce metal oxide (SnO₂, TiO₂, ZrO₂, HfO₂ and CeO₂) fibres with a high aspect ratio (up to 10 000) and a diameter as small as 200 nm. The sol–gel processing includes consumption of precursors obtained from alkoxides by aqueous or non-aqueous polymerization. Shear thinning of the precursors enables pulling a material into a fibre. This rheological behaviour can be explained by sliding of particles owing to external forces. Transmission (propagation) of light along microscaled fibres and their excellent surface morphology suggest that metal oxide nanofibres can be directly drawn from sol precursors for use in integrated photonic systems.

We have studied the strain field around the 90° domains and misfit dislocations in PbTiO₃/SrTiO₃ (001) epitaxial thin films, at the nanoscale, using the geometric phase analysis (GPA) combined with high-resolution transmission electron microscopy (HRTEM) and high-angle annular dark field––scanning transmission electron microscopy (HAADF-STEM). The films typically contain a combination of a/c-mixed domains and misfit dislocations. The PbTiO₃ layer was composed from the two types of the a-domain (90° domain): a typical a/c-mixed domain configuration where a-domains are 20–30 nm wide and nano sized domains with a width of about 3 nm. In the latter case, the nano sized a-domain does not contact the film/substrate interface; it remains far from the interface and stems from the misfit dislocation. Strain maps obtained from the GPA of HRTEM images show the elastic interaction between the a-domain and the dislocations. The normal strain field and lattice rotation match each other between them. Strain maps reveal that the a-domain nucleation takes place at the misfit dislocation. The lattice rotation around the misfit dislocation triggers the nucleation of the a-domain; the normal strains around the misfit dislocation relax the residual strain in a-domain; then, the a-domain growth takes place, accompanying the introduction of the additional dislocation perpendicular to the misfit dislocation and the dissociation of the dislocations into two pairs of partial dislocations with an APB, which is the bottom boundary of the a-domain. The novel mechanism of the nucleation and growth of 90° domain in PbTiO₃/SrTiO₃ epitaxial system has been proposed based on above the results.

Resorcinol-formaldehyde cryogels prepared at different dilution ratios have been activated with phosphoric acid at 450 °C and compared with their carbonaceous counterparts obtained by pyrolysis at 900 °C. Whereas the latter were, as expected, highly mesoporous carbons, the former cryogels had very different pore textures. Highly diluted cryogels allowed preparation of microporous materials with high surface areas, but activation of initially dense cryogels led to almost non-porous carbons, with much lower surface areas than those obtained by pyrolysis. The optimal acid concentration for activation, corresponding to stoichiometry between molecules of acid and hydroxyl groups, was 2 M l⁻¹, and the acid–cryogel contact time also had an optimal value. Such optimization allowed us to achieve surface areas and micropore volumes among the highest ever obtained by activation with H₃PO₄, close to 2200 m² g⁻¹ and 0.7 cm³ g⁻¹, respectively. Activation of diluted cryogels with a lower acid concentration of 1.2 M l⁻¹ led to authentic bimodal activated carbons, having a surface area as high as 1780 m² g⁻¹ and 0.6 cm³ g⁻¹ of microporous volume easily accessible through a widely developed macroporosity.

In this study, a novel artificial small bone consisting of ZrO₂-biphasic calcium phosphate/polymethylmethacrylate-polycaprolactone-hydroxyapatite (ZrO₂-BCP/PMMA-PCL-HAp) was fabricated using a combination of sponge replica and electrospinning methods. To mimic the cancellous bone, the ZrO₂/BCP scaffold was composed of three layers, ZrO₂, ZrO₂/BCP and BCP, fabricated by the sponge replica method. The PMMA-PCL fibers loaded with HAp powder were wrapped around the ZrO₂/BCP scaffold using the electrospinning process. To imitate the Haversian canal region of the bone, HAp-loaded PMMA-PCL fibers were wrapped around a steel wire of 0.3 mm diameter. As a result, the bundles of fiber wrapped around the wires imitated the osteon structure of the cortical bone. Finally, the ZrO₂/BCP scaffold was surrounded by HAp-loaded PMMA-PCL composite bundles. After removal of the steel wires, the ZrO₂/BCP scaffold and bundles of HAp-loaded PMMA-PCL formed an interconnected structure resembling the human bone. Its diameter, compressive strength and porosity were approximately 12 mm, 5 MPa and 70%, respectively, and the viability of MG-63 osteoblast-like cells was determined to be over 90% by the MTT (3-(4, 5-dimethylthiazol-2-yl)-2, 5-diphenyltetrazolium bromide) assay. This artificial bone shows excellent cytocompatibility and is a promising bone regeneration material.

In this paper, the possibility of removing impurities during magnesium recycling with pyrometallurgical techniques has been evaluated by using a thermodynamic analysis. For 25 different elements that are likely to be contained in industrial magnesium alloys, the equilibrium distribution ratios between the metal, slag and gas phases in the magnesium remelting process were calculated assuming binary systems of magnesium and an impurity element. It was found that calcium, gadolinium, lithium, ytterbium and yttrium can be removed from the remelted end-of-life (EoL) magnesium products by oxidization. Calcium, cerium, gadolinium, lanthanum, lithium, plutonium, sodium, strontium and yttrium can be removed by chlorination with a salt flux. However, the other elements contained in magnesium alloy scrap are scarcely removed and this may contribute toward future contamination problems. The third technological option for the recycling of EoL magnesium products is magnesium recovery by a distillation process. Based on thermodynamic considerations, it is predicted that high-purity magnesium can be recovered through distillation because of its high vapor pressure, yet there is a limit on recoverability that depends on the equilibrium vapor pressure of the alloying elements and the large energy consumption. Therefore, the sustainable recycling of EoL magnesium products should be an important consideration in the design of advanced magnesium alloys or the development of new refining processes.