Institut de Recherche sur les Céramiques

<p>Journal of Physics D: Applied Physics published the first Plasma Roadmap in 2012 consisting of the individual perspectives of 16 leading experts in the various sub-fields of low temperature plasma science and technology. The 2017 Plasma Roadmap is the first update of a planned series of periodic updates of the Plasma Roadmap. The continuously growing interdisciplinary nature of the low temperature plasma field and its equally broad range of applications are making it increasingly difficult to identify major challenges that encompass all of the many sub-fields and applications. This intellectual diversity is ultimately a strength of the field. The current state of the art for the 19 sub-fields addressed in this roadmap demonstrates the enviable track record of the low temperature plasma field in the development of plasmas as an enabling technology for a vast range of technologies that underpin our modern society. At the same time, the many important scientific and technological challenges shared in this roadmap show that the path forward is not only scientifically rich but has the potential to make wide and far reaching contributions to many societal challenges.</p>

This article intends to summarize our actual knowledge in plasma spraying with an emphasis on the points where work is still in progress. It presents successively: the plasma torches with the resulting plasma jets and their interactions with the surrounding environment; the powder injection with the heat, momentum and mass transfers between particles and first plasma jets and then plasma plume; the particles flattening and solidification, forming splats which then layer to form the coating; the latest developments related to the production of plasma sprayed finely structured coatings.

Yttrium-oxide-partially-stabilized zirconia (YPSZ) belongs to a new class of ceramics exhibiting an improved toughness when compared to alumina. The toughening mechanism is related to a martensitic-like transformation of tetragonal metastable grains into a monoclinic state occurring at the crack tip. Specific tests showed that YPSZ exhibited a high bending strength (900-1200 MPa), a low Young's modulus (200 GPa), and a high toughness (KIC = 9-10 MN/m3/2). Its average grain size of 0.5 microns allows a surface roughness as low as 0.008 microns. Sterilization or aging in saline solution at room temperature for 100 days did not affect the toughness of this material. Cylindrical YPSZ samples, manufactured by cold isostatic pressing and sintering, were implanted in the paraspinal muscles in the rat up to 12 weeks. The tissue reaction was evaluated with reference to alumina (ISO requirements) by means of quantitative histomorphometry. No significant differences were found between YPSZ and alumina for both the membrane thickness and cell distributions surrounding the implants.

This study shows for the first time that the rhombohedral to tetragonal phase transition in Na0.5Bi0.5TiO3 (NBT) is a two step phase transition. The transformation begins by a first order phase transition involving the reconstructive transformation of the rhombohedral phase into an orthorhombic one, through the formation of an intermediate modulated phase. This phase transition begins slightly over 200 °C by the disappearance of the ferroelectric−ferroelastic domains. The intermediate modulated phase is then formed from 230 to 300 °C, the temperature at which it disappears. The modulated phase corresponds to an intergrowth of rhombohedral perovskite blocks in which Pnma orthorhombic sheets are formed by a microtwinning process of the rhombohedral phase. The intermediate orthorhombic phase is then formed at 300 °C and immediately turns to the tetragonal one. A model is presented explaining the formation of the modulated phase and the origin of the antiferroelectric and relaxor behaviors of NBT.

Inkjet printing is emerging at the forefront of biosensor fabrication technologies. Parallel advances in both ink chemistry and printers have led to a biosensor manufacturing approach that is simple, rapid, flexible, high resolution, low cost, efficient for mass production, and extends the capabilities of devices beyond other manufacturing technologies. Here we review for the first time the factors behind successful inkjet biosensor fabrication, including printers, inks, patterning methods, and matrix types. We discuss technical considerations that are important when moving beyond theoretical knowledge to practical implementation. We also highlight significant advances in biosensor functionality that have been realised through inkjet printing. Finally, we consider future possibilities for biosensors enabled by this novel combination of chemistry and technology.

The study of the Na0.5Bi0.5TiO3–K0.5Bio0.5TiO3 (NBT-KBT) system was carried out using X-ray diffraction and dielectric measurements. The limits of rhombohedral and orthorhombic solid solutions were determined, as well as the evolution of their lattice parameters as a function of composition and temperature. Dielectric permittivity measurements in a wide frequency range between 20 and 800°C showed that all materials are ferroelectric at room temperature and exhibit a diffuse, probably second-order phase transition from the ferroelectric to the paraelectric state. Several peculiar compositions showed the best piezoelectric characteristics for this type of ceramic materials. L'étude du système Na0.5Bi0.5TiO3–K0.5Bi0.5TiO3 (NBT-KBT) a été réalisée par diffraction X et mesures diélectriques. Les limites des solutions solides de symétrie rhomboédrique et orthorhombique ainsi que les évolutions des paramètres de maille en fonction de la composition et de la température ont été déterminées. Les mesures de permittivité diélectrique effectuées dans une large gamme de fréquence entre 20 et 800°C ont montré que tous ces matériaux sont ferroélectriques à la température ambiante. Ils présentent une transition de phase diffuse, probablement du deuxième ordre de l'état ferroélectrique vers l'état paraélectrique. Quelques compositions particulières présentent des caractéristiques piézoélectriques dignes d'intérět.

To determine the role of physicochemical characteristics of the surface of dense ceramics on osteoconduction, we studied the proliferation and differentiation of human trabecular (HT) osteoblastic cells, extracellular collagenous matrix production, and biologic apatite formation on stoichiometric hydroxyapatite (HA) and type A carbonate apatite (CA). The surface physicochemical characteristics (composition, roughness) of HA and CA carefully were determined by Fourier-transformed infrared, X-ray photoelectron, and Raman spectroscopies, and by FTIR microscopy, before and after cell culture. On both HA and CA substrates, HT cells attached, proliferated, and differentiated. Cell proliferation did not differ on HA and CA. However, the initial cell attachment and spreading of HT cells were much lower on CA compared to HA. Physicochemical and biologic analyses showed that collagenous synthesis by HT cells after 6 weeks of culture also was lower on CA than on HA. Quantitative histologic analysis confirmed that the collagenous matrix production was lower on CA than on HA. Measurement of wettability showed that the polar interaction energy with water was significantly lower on CA than on HA. The lower cell attachment and collagen production on CA compared to HA clearly were related to the low affinity of HT cells for the CA surface. This study shows that the surface energy of the biomaterial greatly influences the initial cell attachment and spreading of human osteoblastic cells at the surface and affects collagenous matrix deposition on the biomaterial. This suggests that the enhancement of polar components of the surface of dense biomaterials may improve osteoblastic cell attachment and, thereby, osteoconduction.

From the pioneering works of McPherson in 1973 who identified nanometre-sized features in thermal spray conventional alumina coatings (using sprayed particles in the tens of micrometres size range) to the most recent and most advanced work aimed at manufacturing nanostructured coatings from nanometre-sized feedstock particles, the thermal spray community has been involved with nanometre-sized features and feedstock for more than 30 years. Both the development of feedstock (especially through cryo-milling, and processes able to manufacture coatings structured at the sub-micrometre or nanometre sizes, such as micrometre-sized agglomerates made of nanometre-sized particles for feedstock) and the emergence of thermal spray processes such as suspension and liquid precursor thermal spray techniques have been driven by the need to manufacture coatings with enhanced properties. These techniques result in two different types of coatings: on the one hand, those with a so-called bimodal structure having nanometre-sized zones embedded within micrometre ones, for which the spray process is similar to that of conventional coatings and on the other hand, sub-micrometre or nanostructured coatings achieved by suspension or solution spraying. Compared with suspension spraying, solution precursor spraying uses molecularly mixed precursors as liquids, avoiding a separate processing route for the preparation of powders and enabling the synthesis of a wide range of oxide powders and coatings. Such coatings are intended for use in various applications ranging from improved thermal barrier layers and wear-resistant surfaces to thin solid electrolytes for solid oxide fuel cell systems, among other numerous applications. Meanwhile these processes are more complex to operate since they are more sensitive to parameter variations compared with conventional thermal spray processes. Progress in this area has resulted from the unique combination of modelling activities, the evolution of diagnostic tools and strategies, and experimental advances that have enabled the development of a wide range of coating structures exhibiting in numerous cases unique properties. Several examples are detailed. In this paper the following aspects are presented successively (i) the two spray techniques used for manufacturing such coatings: thermal plasma and HVOF, (ii) sensors developed for in-flight diagnostics of micrometre-sized particles and the interaction of a liquid and hot gas flow, (iii) three spray processes: conventional spraying using micrometre-sized agglomerates of nanometre-sized particles, suspension spraying and solution spraying and (iv) the emerging issues resulting from the specific structures of these materials, particularly the characterization of these coatings and (v) the potential industrial applications. Further advances require the scientific and industrial communities to undertake new research and development activities to address, understand and control the complex mechanisms occurring, in particular, thermal flow—liquid drops or stream interactions when considering suspension and liquid precursor thermal spray techniques. Work is still needed to develop new measurement devices to diagnose in-flight droplets or particles below 2 µm average diameter and to validate that the assumptions made for liquid–hot gas interactions. Efforts are also required to further develop some of the characterization protocols suitable to address the specificities of such nanostructured coatings, as some existing ‘conventional’ protocols usually implemented on thermal spray coatings are not suitable anymore, in particular to address the void network architectures from which numerous coatings properties are derived.

NBT presents an orthorhombic to tetragonal second order phase transition that occurs near 320 °C. It corresponds to the so-called antiferroelectric−paraelectric phase transition. A model is presented in which the diffuse phase transition is achieved by the progressive canceling of the antiphase octahedra tilting prevailing within a−b+a− orthorhombic structure, whereas the in-phase tilting is maintained. This transformation gives finally rise to the a0a0c+ octahedra tilting system of the tetragonal phase. Electron diffraction experiments show that a long-range ordering occurs within the tetragonal phase. It probably develops as P42/mnm ordered nanoregions disseminated within a P4/mbm disordered matrix. The order is still visible in the temperature domain of the cubic phase.

Ferroelectric materials exhibit spontaneous and stable polarization, which can usually be reoriented by an applied external electric field. The electrically switchable nature of this polarization is at the core of various ferroelectric devices. The motion of the associated domain walls provides the basis for ferroelectric memory, in which the storage of data bits is achieved by driving domain walls that separate regions with different polarization directions. Here we show the surprising ability to move ferroelectric domain walls of a BaTiO₃ single crystal by varying the polarization angle of a coherent light source. This unexpected coupling between polarized light and ferroelectric polarization modifies the stress induced in the BaTiO₃ at the domain wall, which is observed using in situ confocal Raman spectroscopy. This effect potentially leads to the non-contact remote control of ferroelectric domain walls by light.

Long term stability of ceramics at high temperatures is one of the great challenges of the contemporary technology developments. Multi‐component ceramics such as Si–B–C–N systems gain a lot of interest for high temperature applications due to the stability of their amorphous inorganic network arising from strong covalent bonding. The polymer derived ceramics (PDC) route enables the synthesis of such materials from preceramic polymers as well as their manufacturing as specific ceramic geometries, which are difficult to obtain otherwise. This review proposes an overview of the works related to the development of Si–B–C–N ceramics through the PDC route in the last 30 years. A particular focus is made on the relation between the chemical structure of the precursors and the properties of the resulting ceramics. The main topics reviewed are related to the synthesis of tailor‐made polymeric precursors, to their processing to ceramic components, and to the characterization of the material properties and functionalities. The various strategies adopted for the development of shaped Si–B–C–N ceramics as functional materials are presented and the trend of nowadays research for future evolution of Si–B–C–N materials is discussed.

An interpretation of the Raman spectra of monoclinic ZrO 2 and monoclinic HfO 2 is made by analyzing the results of the zirconia–hafnia substitution jointly with a lattice dynamical treatment of both structures. The Raman spectra of tetragonal ZrO 2 and tetragonal HfO 2 are also interpreted. Emphasis is put on their relations to the spectrum of the parent cubic structure and on the position of the soft mode. The band assignment proposed earlier by other researchers is critically reconsidered.

We present a detailed analysis of the Galaxy Stellar Mass Function of galaxies up to z=2.5 as obtained from the VVDS. We estimate the stellar mass from broad-band photometry using 2 different assumptions on the galaxy star formation history and show that the addition of secondary bursts to a continuous star formation history produces systematically higher (up to 40%) stellar masses. At low redshift (z=0.2) we find a substantial population of low-mass galaxies (<10^9 Msun) composed by faint blue galaxies (M_I-M_K=0.3). In general the stellar mass function evolves slowly up to z=0.9 and more significantly above this redshift. Conversely, a massive tail is present up to z=2.5 and have extremely red colours (M_I-M_K=0.7-0.8). We find a decline with redshift of the overall number density of galaxies for all masses (59+-5% for M>10^8 Msun at z=1), and a mild mass-dependent average evolution (`mass-downsizing'). In particular our data are consistent with mild/negligible (<30%) evolution up to z=0.7 for massive galaxies (>6x10^10 Msun). For less massive systems the no-evolution scenario is excluded. A large fraction (>=50%) of massive galaxies have been already assembled and converted most of their gas into stars at z=1, ruling out the `dry mergers' as the major mechanism of their assembly history below z=1. This fraction decreases to 33% at z=2. Low-mass systems have decreased continuously in number and mass density (by a factor up to 4) from the present age to z=2, consistently with a prolonged mass assembly also at z<1.

The properties of calcium phosphates of biological interest depend strongly on their calcium/phosphorus atomic ratios (Ca/P). Therefore, the precision for the determination of this ratio is crucial. We have investigated the accuracy of quantitative X‐ray diffractometry (QXRD) analysis for the determination of Ca/P in compounds with Ca/P ranging from 1.5 to 2. For 1.5 < Ca/P < 1.667, a high accuracy is obtained with relative uncertainties on Ca/P values between 0.1% and 0.4%. In this domain of composition, QXRD is more accurate than classical wet methods. For 1.667 < Ca/P < 2, the precision is lower and wet chemical methods appear to be superior.

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Among transition metal nitrides, molybdenum nitrides have been much less studied even though their mechanical properties as well as their electrical and catalytic properties make them very attractive for many applications. The δ-MoN phase of hexagonal structure is a potential candidate for an ultra-incompressible and hard material and can be compared with c-BN and diamond. The predicted superconducting temperature of the metastable MoN phase of NaCl-B1-type cubic structure is the highest of all refractory carbides and nitrides. The composition of molybdenum nitride films as well as the structures and properties depend on the parameters of the process used to deposit the films. They are also strongly correlated to the electronic structure and chemical bonding. An unusual mixture of metallic, covalent and ionic bonding is found in the stoichiometric compounds.

We report the fabrication of VO2-based two terminal devices with ∼125-nm gaps between the two electrodes, using a simple, cost-effective method employing optical lithography and shadow evaporation. Current-voltage characteristics of the obtained devices show a main abrupt metal-insulator transition (MIT) in the VO2 film with voltage threshold values of several volts, followed by secondary MIT steps due to the nanostructured morphology of the layer. By applying to the two-terminal device a pulsed voltage over the MIT threshold, the measured switching time was as low as 4.5 ns and its value does not significantly change with device temperature, supporting the evidence of an electronically driven MIT.

Coatings have historically been developed to provide protection against corrosion and erosion that is to protect the material from chemical and physical interaction with its environment.Corrosion and wear problems are still of great relevance in a wide range of industrial applications and products as they result in the degradation and eventual failure of components and systems both in the processing and manufacturing industries and in the service life of many components.Various technologies can be used to deposit the appropriate surface protection that can resist under specific conditions.They are usually distinguished by coating thickness: deposition of thin films (below 10 to 20 µm according to authors) and deposition of thick films.The latter, mostly produced at atmospheric pressure have a thickness over 30 µm, up to several millimeters and are used when the functional performance and life of component depend on the protective layer thickness.Both coating technology can also be divided into two distinct categories: "wet" and " dry " coating methods, the crucial difference being the medium in which the deposited material is processed.The former group mainly involves electroplating, electroless plating and hot-dip galvanizing while the second includes, among others methods, vapor deposition, thermal spray techniques, brazing, or weld overlays.This chapter deals with coatings deposited by thermal spraying.It is defined by Hermanek (2001) as follows , "Thermal spraying comprises a group of coating processes in which finely divided metallic or non-metallic materials are deposited in a molten or semi-molten condition to form a coating".The processes comprise: direct current (d.c.) arcs or radio frequency (r.f.) discharges-generated plasmas, plasma transferred arcs (PTA), wire arcs, flames, high velocity oxy-fuel flames (HVOF), high velocity air-fuel flames (HVAF), detonation guns (D-gun).Another spray technology has emerged recently ; it is called cold gas-dynamic spray technology, or Cold Spray (CS).It is not really a thermal spray technology as the high energy gas flow is produced by a compressed relatively cold gas (T < 800°C) expanding in a nozzle and will not be included in this presentation.Most processes are used at atmospheric pressure in air, except r.f.plasma spraying, necessarily operated in soft vacuum.Also, d.c.plasma spraying can be carried out in inert atmosphere or vacuum and Cold Spray is generally performed at atmospheric pressure but in a controlled atmosphere chamber to collect and recycle the spray gas (nitrogen or helium) because of the huge gas flow rates used (up to 5 m 3 .min - ).In the following only processes www.intechopen.comwww.intechopen.comThermal Sprayed Coatings Used Against Corrosion and Corrosive Wear 5 -Coatings used against high-temperature corrosion: carburization, nitriding, sulfidation, molten salt, and molten glass.-Coatings used against high-temperature oxidation.-Coatings used against corrosive wear at different temperatures -Examples of industrial applications to illustrate the interest of thermal sprayed coatings.

Among the different rapid prototyping technologies, solid freeform fabrication (SFF) is the most suitable for ceramics. Here a stereolithographic technique is presented that allows the usage of pastes composed of ceramic particles dispersed in a photocurable resin for the fabrication of alumina pieces. They exhibit a similar flexural strength than alumina parts made by classical techniques like pressing.

Microstructure of calcium phosphate ceramics has been shown to influence long-term in vitro cellular events like proliferation and differentiation, and to favor bone integration in vivo. As long-term cellular events are known to be dependent of early cell adhesion events, we decided to study the in vitro influence of the microstructure of a microporous hydroxyapatite (mHA) and a nonmicroporous hydroxyapatite (pHA) ceramic on serum protein adsorption and SaOs-2 human bone cells attachment after 30 min, 1, 4, and 24 h and cell growth after 96 h. Plastic coverslips were used as controls. Hydroxyapatite composition of mHA and pHA was confirmed by X-ray diffraction and Fourier transform infra-red spectroscopy. The surface energies of ceramics were calculated from contact-angle measurements in di-iodomethane, water or complete culture medium. The total surface energy was 44.8 mJ/m(2) for pHA and 48.7 mJ/m(2) for plastic. The contact-angle measurement was impossible on mHA likely because they displayed 12% of open microporosity, pHA ceramic exhibiting only closed pores (2.5%). Moreover, the roughness amplitude was largely higher on mHA (Sa = 4.35 microm) than on pHA (Sa = 0.065 microm) and plastic (Sa = 0.042 microm). Three different techniques were used to evaluate protein adsorption on the ceramics. SDS-PAGE of desorbed proteins demonstrated that more proteins desorbed from mHA (66.02 microg/m(2)) than from pHA (17.2 microg/m(2)) or plastic (0.08 microg/m(2)). A new method was used to evaluate in situ the quantity of adsorbed total proteins: the temperature-programmed desorption (TPD) analysis coupled with mass spectrometry. The TPD analysis confirmed that 10-fold more proteins adsorbed on mHA compared with those on pHA. A direct immunolabeling on ceramics revealed than more fibronectin and serum albumin adsorbed on microporous ceramic than on dense ceramic. The morphology of SaOs-2 cells was the same on all the substrates after 30 min. At later time points, cell morphology on mHA was radically different than on other surfaces, with the particularity of the cytoplasmic edge that appeared undistinguishable from the surface. Only the extremity of the cells and lamellipodia were visible. Cells seemed like "adsorbed" by the mHA surface, whereas on plastic and pHA surfaces the cells displayed classical aspects of polygonal spreading. The cells displayed on mHA the highest initial attachment potential after 30 min, 1, 4, 24 h but the lower proliferation potential after four days. This study confirms that a microporous ceramic surface can modulate the adsorption of proteins and further the adhesion and proliferation of human bone cells.