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Directionally solidified Al2O3/Y3Al5O12 (YAG), Al2O3/YAG/ZrO2, Al2O3/GdAlO3 (GAP), Al2O3/GAP/ZrO2 and Al2O3/ZrO2 eutectic/non eutectic ceramics were prepared with laser zone melting. Their microstructure, phase component and shape were investigated. The results indicated that the molar ratio of Zr4+ to rare earth ions (Y3+, Gd3+) in the ZrO2 phase of the ternary eutectic was closed to 2:1. The free energy of chemical reaction was the key to determine the precipitation order of phase. The growth of the firstly-precipitated phase could be divided into the formation of ordered Bravais lattice composed by the oxygen ions, the diffusion of metal cations in this lattice and the change of phase morphology. The unfilled cation gap might be a fast channel for the ion transport. On the same growth plane, the nucleation of the later-precipitated phase began only after the firstly-precipitated phase was fully formed. The triangular was the main ion arrangement way for the stable nucleation and growth of phases. The effects of the precipitation temperature, the phase size, the eutectic type and the growth rate on the microstructure were discussed. This improved theory provided a more reasonable explanation for the formation of rod-shaped, layered, triangular, Chinese script (CS) and cellular microstructures, which might be of significance to regulate the morphology of microstructures.

Directionally solidified oxide eutectic ceramic (DSOEC) has been one of the focuses of ceramic materials because of its excellent mechanical properties and oxidation resistance at ultra-high temperature (above 1600 ℃). Al2O3/GdAlO3/ZrO2 ternary DSOEC was prepared with induction heating zone melting method, of which microstructure and mechanical properties’ involution with the growth rate was revealed. As the growth rate increased, the microstructure of Al2O3/GdAlO3/ZrO2 DSOEC became into a complex regular structure from an irregular network structure, and the eutectic spacing decreased continuously. Its fracture toughness increased first from 4.75 to 6.55 MPa m1/2 and then decreased to 5.48 MPa m1/2, while its hardness increased continuously from 12.20 to 15.56 GPa. The third component ZrO2 made GdAlO3 phase microstructure in the binary eutectic Al2O3/GdAlO3 from a complex regular structure transformed into an irregular network one in the ternary Al2O3/GdAlO3/ZrO2 for the low growth rate, while from the regular layered microstructure to the regular triangular one in the ternary eutectic for the high growth rate, ZrO2 phase also increased the eutectic spacing, improved the fracture toughness. The fracture toughness at room temperature (4.75–6.55 MPa m1/2) of Al2O3/GdAlO3/ZrO2 ternary DSOEC was much higher than that of Al2O3/GdAlO3 binary DSOEC (1.47–3.24 MPa m1/2).

Al2O3/Er3Al5O12(EAG)/ZrO2 directionally solidified eutectic ceramics (DSECs) were prepared with high frequency induction heating zone melting (IHZM), and heat treated at high temperature. Their phase components, microstructures, flexural and tensile strengths were investigated. The results indicated that the microstructures were composed of the mutually interpenetrated Al2O3, EAG and ZrO2 (stabilized by Er3+ ion) phases. As the growth rate increased from 2 mm/h to 20 mm/h, the phase size decreased and the irregular microstructure became regular. When the heat treatment temperature was up to 1400 °C, the ionic diffusion was triggered and the phase began to grow. Under the action of surface energy and special microstructure, the growth of phase stopped after it reached a certain threshold. The sample with smaller phase size exhibited higher strength at room temperature, which was dependent on the crack propagation resistance. However, the speed of strength reduction was faster. The formation of surface groove, microcrack and malignant growth phase was responsible for this rapidly decreasing of strength. The flexural and tensile strengths of eutectic ceramic with larger phase size remained at 671.6 MPa and 359.45 MPa after long-term heat treatment at 1500 °C, respectively. The smaller difference between the original phase size and the maximum coarsened phase size was beneficial to avoid the occurrence of the above mentioned harmful factors and was the source of strength stability.

The resonant cross relaxation processes between Yb3+ and Er3+ ions in calcium alumino-silicate glasses have been quantified under selective Er3+ excitation. The infrared emission spectra, measured under steady state conditions (CW excitation to the 4I9/2 erbium level), have allowed to obtain an experimental relationship linking the transfer (Yb3+ → Er3+) and back transfer (Er3+ → Yb3+) parameters. These measurements combined with the dynamics of the main emitting levels, measured under pulsed excitation to the 2H11/2 erbium level, have allowed the fully quantification of the energy transfer parameters. The obtained values, C25 = 5.5 × 10− 18 cm3s− 1 (Yb3+ → Er3+), C52 = 1.5 × 10− 18 cm3s− 1 (Er3+ → Yb3+) and C27 = 7.6 × 10− 18 cm3s− 1 (up-conversion mechanism, estimated from the Judd-Ofelt analysis previously reported), can be used to predict the temporal evolution of the main luminescent emission bands.

In this work, we have developed and characterized a ceramic composite based on a core of directionally solidified calcium zirconate-calcium stabilized zirconia (CZO-CSZ) eutectic composite coated with a bioactive glass-ceramic. The aim is to research new orthopedic implants as an alternative to conventional 3Y-TZP bioinert ceramics. The CZO-CSZ eutectic rods were grown from the melt of rods of CaO-ZrO2 in the eutectic composition using the laser floating zone technique (LFZ). The mechanical results indicated that directional eutectics prepared with this technique exhibited good mechanical strength and significant hardness and toughness. The LFZ technique was also used to melt the bioactive coating previously placed by dip coating on the CZO-CSZ rod surface. Depending on the thickness of the coating and the applied laser power, an alloying or coating process was achieved. In the first case, the coating was diluted with the surface of the eutectic cylinder, leading to the segregation of the calcium zirconate and zirconia phases and the formation of a bioactive phase embedding zirconia particles. In the second case, a layer of ceramic glass was formed, well attached to the eutectic cylinder. These layers were both studied from the microstructural and bioactivity points of view.

Praseodymium oxides present redox properties analogous to those of Ce-based systems and have been proposed for catalytic applications in combination with CeO2, ZrO2, or both. However, uncertainties remain concerning the nature and redox behavior of Pr-rich mixtures, especially with ZrO2. Here we study the eutectic composites of the ZrO2–PrOx system, focusing on the sensitivity of their microstructure, phase symmetry, and composition to variations of the processing atmosphere from oxidizing to reducing. Mixed oxides have been produced by a laser-assisted directional solidification technique in O2, air, N2, or 5%H2(Ar) environment, and the resulting materials have been analyzed by scanning electron microscopy/energy-dispersive X-ray spectroscopy, X-ray diffraction, Raman spectroscopy, and magnetic susceptibility. In air, N2, or 5%H2(Ar) atmosphere, a lamellar, eutectic-like microstructure forms, the major phase being the one with less Pr content. Both the Pr concentration in each phase as the PrOx molar percentage of the eutectic composites decrease as the atmosphere becomes more reducing. Both eutectic phases are fluorite-like when processing in air, whereas in N2 or 5%H2(Ar), the phase with high Pr content is of the A-R2O3 type, and the phase with low Pr content can be described as a fluorite phase containing C-R2O3-like short-range-ordered regions. The results obtained for samples processed in O2 suggest that for high enough pO2 no eutectic forms, in analogy with the ZrO2–CeO2 system. The evolution of the phase composition and symmetry is discussed in terms of the limited stability of the phases found in the ZrO2–Pr2O3 system, namely, A- or C-R2O3-like, beyond a certain Pr oxidation degree and oxygen content.

Cobalt-doped MgO-MgAl2O4 eutectic composites were explored for their use as selective emitters for thermophotovoltaic devices. Eutectic ceramic rods with different cobalt content were directionally solidified by using the laser floating zone technique at two processing rates to obtain microstructures with different domain sizes. Thermal emission between 1000 °C and 1500 °C and optical properties (reflectance and transmittance) at room temperature were measured in the Co-doped composites and the effect on microstructure and cobalt content was investigated. Thermal emission consisted of an intense broad band at about 1.67 µm matching with the bandgap of the InGaAs cell. The emission was ascribed to the de-excitation from the 4T1(F) multiplet to the 4A2(F) ground state of the thermally excited Co ions located in the tetrahedral sites of the MgAl2O4 phase. The selectivity of the thermal emission showed a decrease with the cobalt content due to the enhancement of other electronic transitions, which leads to keeping the cobalt content in these composites at low levels (<0.15% at Co) for their use as selective emitters.

An adaptation of the laser floating zone technique is used to modify the surface properties of ceramics with interest for biomedical applications. This new method is based upon the surface remelting of ceramic rods by using laser radiation, and its versatility is demonstrated in the surface structuring of two different eutectic composites with potential application as bone substitutes. Firstly, directionally eutectic rods of wollastonite (W)–tricalcium phosphate (TCP) and magnesium oxide (MgO)–magnesium stabilized zirconia (MgSZ) were grown by the laser floating zone technique. In the case of W-TCP eutectics, materials with crystalline, glass–ceramic, or vitreous microstructure could be obtained as the growth rate was increased. In the other case, a material made up of magnesium oxide and magnesium stabilized zirconia phases arranged in fibrillar or lamellar geometry was obtained. At higher solidification rates, the rupture of the growth front gave rise to the organization of the phases in the form of colonies or cells. The laser zone remelting technique was used to remove defects and to refine the microstructure of the directionally solidified eutectic surfaces as well as to cover MgO–MgSZ rods with W–TCP glass in the eutectic composition. The study provides a promising technique that can tailor the surface properties and functionality of bone repair materials. The products’ properties and challenges in preparation procedures are discussed.

The object of this work is to study the relation between composition, microstructure and oxidation state of Pr2±xZr2∓xO7±y materials produced by the laser–floating zone (LFZ) technique. Three compositions are studied, nominally Pr1.7Zr2.3O7+y, Pr2Zr2O7+y and Pr2.24Zr1.76O7±y, all within the pyrochlore field in the ZrO2–PrOx phase diagram. Samples have been processed under four different atmospheres (O2, air, N2 and 5%H2(Ar)), so as to vary the environmental conditions from oxidising to reducing. Sample colouration ranged from dark brown to bright green, owing to varying Pr4+ content. A close correlation is found between the phase homogeneity, the microstructure and the Pr content. Pr–deficient samples present a homogeneous microstructural aspect and composition, whereas Pr–rich compositions always break into 5–25 µm–sized grains with pyrochlore phases at the grain centre and ill–crystallised, Pr–rich oxidised phases at the grain–boundaries. Raman spectroscopy shows that different types of oxygen disorder occur depending on composition and processing atmosphere: in Pr–poor samples oxygen interstitials are created to compensate for Zr4+ excess charge, whereas in Pr–rich samples oxygen disorder occurs around the Pr3+ or Pr4+ ions substituting for Zr4+, because of size–mismatch. Magnetic measurements showed a high Pr4+ content, which has been attributed to several factors: the highly oxidised state of the feedstock material, the segregation of Pr and O–rich grain boundaries in compositions with praseodymium molar rate> 0.5, and the lower oxide–ion conductivity for PZO compositions, compared to either Pr–poor or Pr–rich compositions. Post–processing thermal annealing in a vacuum at 1000 °C enabled total Pr reduction, with the exception of the Pr–rich P2.24 samples, where some Pr4+ ions remained in the oxidised state.

[EN] The laser is a powerful tool for materials processing, incorporated already in many industrial processes and laboratory procedures. In this work, we are concerned with laser processing applied to research and development of ceramics for electrochemical cells and other high temperature oxide ceramics for energy applications. Solidification of single crystals or composites of relevant oxides can be performed by the laser assisted floating zone method, providing samples for structural, mechanical or functional fundamental research, as well as knowledge about its manufacture by melt processes. Selective laser melting of these ceramic oxides is a very promising technology, at the research level. Successful examples of surface laser melting of oxide eutectic composites are presented. The technologies of subtractive laser processing of ceramics (cutting, drilling, structuring, cleaning, etc.) are more developed, and the research is directed towards the optimization of mechanisms, increase of resolution and efficiency and the investigation of the effects of the laser treatment on the functional performance. Different laser processes of SOC (solid oxide cell) components are shown to decrease the ohmic, concentration and activation losses. The manuscript describes the state-of-the art of the technologies as applied to oxide and composite materials present in solid oxide electrochemical devices (SOFC, SOEC, and batteries) and selective emitters for thermophotovoltaics, with emphasis on the last achievements by the authors team., [ES] El láser es una potente herramienta para el procesamiento de materiales, incorporada ya en muchos procesos industriales y procedimientos de laboratorio. En este trabajo nos ocupamos del procesamiento láser aplicado a la investigación y desarrollo de cerámicas para celdas electroquímicas y otras cerámicas de óxido de alta temperatura para aplicaciones energéticas. La solidificación de monocristales o composites de óxidos relevantes se puede realizar mediante el método de zona flotante asistida por láser, proporcionando muestras para investigación básica estructural, de propiedades mecánicas o funcionales, así como conocimiento sobre su fabricación mediante procesos de fusión. La fusión selectiva por láser de estos óxidos cerámicos es una tecnología muy prometedora, cuyo desarrollo es todavía incipiente. Se presentan ejemplos exitosos de fusión por láser de superficie de compuestos eutécticos de óxidos. Las tecnologías sustractivas de procesamiento de cerámicas con láser (corte, taladrado, estructuración, limpieza, etc.) están más desarrolladas, y la investigación se dirige hacia la optimización de procedimientos, aumento de resolución y eficiencia y la investigación de los efectos del tratamiento láser sobre el rendimiento funcional. Diferentes procesos láser de los componentes de celda de óxido sólido disminuyen las pérdidas óhmicas, de concentración y de activación. El manuscrito describe el estado actual de las tecnologías aplicadas a óxidos y materiales compuestos presentes en dispositivos electroquímicos de óxidos sólidos (SOFC, SOEC y baterías) y emisores selectivos para aplicaciones termofotovoltaicas, con énfasis en los últimos logros del equipo.

This paper is devoted to the study of the electrical conductivity of tantalum-doped zirconia ceramics prepared by spark plasma sintering. In this study, the temperature dependence of conductivity in as-prepared specimens and in those previously annealed in air is determined and compared. A semi-empirical model, which is based on the oxidation states of the cations, has been developed and successfully assessed. According to this, the conductivity is basically controlled by the diffusion of tetravalent zirconium cations in both cases, although the concentration of these species varies drastically with the amount of induced oxygen vacancies. This is a quite unexpected fact, since conductivity is normally controlled by anionic diffusion in zirconia ceramics. This option is forbidden here due to the presence of substitutional pentavalent cations. Therefore, conductivity values are much lower than those reported in trivalent or divalent substitutional cation doped zirconia ceramics.

In this work we report on the spectroscopic properties and the near-infrared to visible upconversion of Er3+ ions in aluminosilicate glasses manufactured by directionally solidification with the laser floating zone technique. Glasses were manufactured in a controlled oxidizing atmosphere to provide them with high optical transmission in the visible spectral range. Absorption and emission spectra, and lifetimes were assessed in both the visible and the near infrared spectral range. Green upconversion emissions of the 2H11/2→4I15/2 and 4S3/2→4I15/2 transitions at 525 nm and 550 nm attributed to a two-photon process were observed under excitation at 800 nm. Mechanisms responsible for the upconversion luminescence were discussed in terms of excited state absorption and energy transfer upconversion processes. Excitation spectra of the upconverted emission suggest that energy transfer upconversion processes are responsible for the green upconversion luminescence.

In vitro activity is important when considering the choice of a multiphasic bioceramic scaffold as phases can dissolve or transform at different rates. The aim of this study is focused on the synthesis and in vitro analysis of multiphasic ceramics obtained from the melt by directional solidification. Depending on the growth rate of the new composition different bioactive phases coexist in the same sample: akermanite, monticellite, tricalcium phosphate and Nurse's A phase, all of them with potential in the medical area as implant for bone or dental repair. With the knowledge of what and how phases dissolve first, it was possible to design materials to get porous scaffolds or more stable ceramics.

Magnesium-based ceramics are involved in orthopedic applications such as bone scaffolds or implant coatings. They provide structural support to cells for bone ingrowth, but highly porous matrices cannot resist severe mechanical stress during implantation. In this study, the laser floating zone (LFZ) technique is used to prepare a dense crystalline material with composition in the CaO–SiO2–MgO–P2O5 system. This material, under physiological conditions, is able to generate a porous scaffold controlled by the dissolution of the MgO phase, meeting the mechanical advantages of a dense material and the biological features of a porous scaffold. FESEM (Field emission scanning electron microscopy), XRD (X-ray Diffraction), EDS (Energy Dispersive X-rays spectroscopy), and ICP ((Inductively Coupled Plasma) analysis were carried out in order to characterize the samples before and after immersion in simulated body fluid (SBF).

Mg2SiO4-MgAl2O4 eutectic ceramics have been fabricated by means of the laser floating zone (LFZ) technique. The microstructure has revealed as an unusual one at lower growth rate, composed of broken lamellae of MgAl2O4 distributed randomly along one matrix, composed of Mg2SiO4. At higher growth rates, a cell structure with intra-cell lamella structure is dominant. Contrary to most eutectic systems, hardness is not dependent upon the inter-spacing, but it does depend on one characteristic length of lamellae: their perimeter. One simple model based upon the dislocation is proposed, which successfully accounts for such extraordinary hardness law. Accordingly, Mg2SiO4-MgAl2O4 eutectic ceramics fabricated at 50 mm/h growth rate with the smallest MgAl2O4 lamella perimeter favorably showed more elevated hardness (13.4 GPa from Vickers indentation and 15.3 GPa from nanoindentation) and strength (∼430 MPa) than those found in the monolithic Mg2SiO4 matrix.

Boron carbide is among the most promising ceramic materials nowadays: their mechanical properties are outstanding, and they open potential critical applications in near future. Since sinterability is the most critical drawback to this goal, innovative and competitive sintering procedures are attractive research topics in the science and technology of this carbide. This work reports the pioneer use of the laser-floating zone technique with this carbide. Crystallographic, microstructural and mechanical characterization of the so-prepared samples is carefully analysed. One unexpected output is the fabrication of a B6C composite when critical conditions of growth rate are adopted. Since this is one of the hardest materials in Nature and it is achievable only under extremely high pressures and temperatures in hot-pressing, the use of this technique offers a promising alternative for the fabrication. Hardness and elastic modulus of this material reached to 52 GPa and 600 GPa respectively, which is close to theoretical predictions reported in literature.

This work is concentrated on getting a reply to the following question: how does the grain size of boron carbide specimens influence on their mechanical and electrical response? It is a common issue that both essential properties are usually affected by the grain boundaries. To this purpose, a set of near fully-dense boron carbide specimens were prepared by spark plasma sintering. In order to reduce residual porosity and grain-size effects, nanoindentation tests at room temperature were conducted. DC conductivity was measured through four-point test technique from room temperature up to 800 °C. The results show that hardness can reach values as high as ∼60 GPa and plasticity onset takes place at around 23 GPa by dislocation nucleation. Regarding the conductivity, it is found that grain boundaries can block the mobility of bipolarons in an effective way. A simple additive law is provided to account for the resistivity of boron carbide polycrystals.

Accurate positioning of luminescent materials at the microscale is essential for the further development of diverse application fields including optoelectronics, energy, biotechnology and anti-counterfeiting. In this respect, inkjet printing has recently attracted great interest due to its ability to precisely deposit with high throughput and no contact, functional materials on different types of substrates. Here, we present a novel photoacid catalysed organic-inorganic hybrid luminescent ink. The formulation, containing monomers bearing epoxy and silane functionalities, a photoacid generator and a small percentage of Rhodamine-B, shows good jetting properties and adequate wetting of the deposited droplets on the receiving substrates. Ultraviolet exposure of the deposited material triggers the cationic ring-opening polymerization reaction of the epoxy groups. Concomitantly, if atmospheric water is available, hydrolysis and condensation takes place, overall leading to a luminescent crosslinked hybrid organic-inorganic polymeric material obtained through a simple one-step curing process, without post baking steps. Advantageously, protection of the ink from actinic light delays the hydrolysis and condensation conferring long-term stability to the ink. Digital patterning leads to patterned emissive surfaces and elements with good adhesion to different substrates, mechanical and optical properties for the fabrication of optical and photonic elements and devices.