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Glass-ceramics containing pyroelectric Sr2TiSi2O8 (STS) crystals are produced from parent glasses of compositions STS + 0.8 SiO2 + (0.2 − x) Na2O + x CaO, with x = 0; 0.05; 0.10; and 0.15. The aim of this work is to investigate the effect of the additions to the stoichiometric STS composition on the crystallization mechanisms and on the piezoelectric properties of the glass-ceramic. The DSC analyses evidence that the glass transition temperatures Tg, the onset temperature of the crystallization peak To and the temperature Tc of the maximum of this peak increase with the CaO/Na2O ratio. On the basis of the DSC data, the crystallization of the parent glass samples was operated by thermal treatment. The observation of the cross-sections of the heat-treated samples highlights that the competition between the surface and volume crystallization mechanisms is influenced by the CaO/Na2O ratio and the temperature. For all the samples, the XRD analyses performed on the surfaces as obtained after the crystallization treatment evidenced a preferential orientation of the STS crystals with the plans (00l) parallel to the surface. The XRD analyses performed after grinding the surface show that only the surface crystallized layers are preferentially oriented. Moreover, changes in preferential orientation to plans (202) or (201) are observed over the depth, depending on the composition and the temperature of the thermal treatment. These changes influence the polarization of the surface crystallized layer and, consequently, its piezoelectric charge coefficient d33. The highest values of d33 were measured on the glass-ceramic samples exhibiting mainly a (202) preferential orientation over their thickness.

Understanding the colloidal stability and aggregation behavior of TiO

Because of their characteristics, including a d33 of 10–15 pC/N and high stability up to temperatures over 1000 °C, polar glass–ceramics containing fresnoite crystals can be regarded as highly effective materials for applications requiring piezoelectricity at high temperatures. In the present paper we investigate barium substitutions in an Sr-fresnoite (STS) glass–ceramic. Two aspects are studied: first, the effect of the substitution on the preferential orientation of the crystallization, and second, the ability of the glass–ceramics to generate and propagate surface acoustic waves (SAW) at high temperatures. XRD analyses show that a 10 at.% substitution of Ba allows us to keep a strong preferential orientation of the (00l) planes of the fresnoite crystals down to more than 1 mm below the surfaces. Higher substitution levels (25 and 50 at.%), induce a non-oriented volume crystallization mechanism that competes with the surface mechanism. SAW devices were fabricated from glass–ceramic substrates with 0, 10 and 25 at.% Ba substitutions. Temperature testing reveals the high stability of the frequency and delay for all of these devices. The glass–ceramic with a 10 at.% Ba substitution gives the strongest amplitude of the SAW signal. This is attributed to the high (00l) preferential orientation and the absence of disoriented volume crystallization.

The dissimilarities of the composition, crystal structure, and corrosion resistance of ZnAl hydrotalcite (ZnAl-HT) conversion films grown “in situ” on electrogalvanized (EG) steel substrate were investigated for different Al3+/Zn2+ ratios at pH 12. The corrosion behavior of all conversion films in 0.1 M NaCl was compared through electrochemical techniques. The composition, morphology, structure, and thickness of conversion films with different Al3+/Zn2+ ratios were characterized by Fourier-transform infrared spectroscopy (FT-IR), scanning electronic microscopy (SEM), and electron microscopy/energy dispersive X-ray spectroscopy (SEM/EDS), and X-ray diffraction (XRD). The polarization curves indicated that the ZnAl-HT films provided anodic inhibition for EG steel and the inhibition efficiency of the ZnAl-HT conversion films increases sharply with decreasing the Al3+/Zn2+ ratios from 5/1 to 5/3, while, for the 5/4 and 5/5 ratios, the corrosion resistance of ZnAl-HT conversion films showed a downward trend after two immersion hours. However, the corrosion behavior of HT conversion films with the Al3+/Zn2+ ratios from 5/3 to 5/5 remained stable for a longer immersion time. The protection performance of the ZnAl-HT films can be attributed to the barrier effects, ion-exchange competitive adsorption of chloride ions, and protective deposition of ZnO on the EG steel surface.

Hydrotalcites intercalated with sebacate (HT-SB) were prepared by a coprecipitation method. The synthesized powder was characterized using infrared spectroscopy (FT-IR), X-ray diffraction (XRD), transmission electron microscopy (TEM) and zeta potential measurements. The inhibitor release from HT-SB in a chloride solution has been determined by total organic content (TOC) analysis. The inhibitive action of HT-SB on carbon steel was investigated and compared with hydrotalcites intercalated by benzoate (HT-BZ) and 2-benzothiazolythio-succinic acid (HT-BTSA) using electrochemical measurements and SEM/EDX analysis. The results showed that the zeta potential of modified hydrotalcites and the release of corrosion inhibitors from modified hydrotalcites depend on the chemical structure of inhibitors. The anodic polarization curves showed that the three modified hydrotalcites behave as anodic corrosion inhibitors with an efficiency, at a concentration of 3 g/L, of 94% for HT-SB, 81% for HT-BZ and 92% for HT-BTSA. These efficiencies are higher than those measured for the organic inhibitors in chloride solutions highlighting a synergistic effect due to the combination of the hydrotalcite structure and carboxylate inhibitors. The inhibition effect of modified hydrotalcite depends not only on the intercalated organic inhibitors but also on the capability of adsorption of the hydrotalcite structure on a steel surface. HT-SB was easily dispersed in an epoxy coating improving the barrier properties at concentrations lower than 5 wt.%. The best protection was obtained with 1.5 wt.% HT-SB.

This paper aims at studying the influence of the reinforcement particle size and morphology on the wear resistance properties of NiCrBSi-based composites. Numerous papers have already been written on this subject but almost all of them studied the “conventional” particle size for laser cladding (i.e. between 20 and 200 μm). The objective of this study is to see the influence of coarser reinforcement particles, up to 1.2 mm, and the influence of the morphology (spherical and random shaped) on the coatings erosive and sliding wear resistance. Laser clad coatings were deposited on low carbon steel substrate S235JR with various amounts of WC/W 2 C particles up to 50 vol.%. The coatings were processed by using a 3.8 kW High Power Diode Laser (HPDL). Spherical tungsten carbide particles from 40 μm up to 1200 μm were used in this study as well as random shaped particles from 40 μm to 400 μm. To assess the influence of the reinforcement particle properties on wear properties, wheel tests and pin-on-disk tests were performed on each composition. From this study, it can be concluded that there is an obvious advantage in using larger particles (750–1200 μm) in harsh conditions while smaller particles (40–160 μm) improve the resistance in sliding conditions. The effect of morphology has not been proved significant.

Alternatives to lead crystal glass were initially selected from CD-ROM ‘interglad’ data, and then elaborated. These samples have properties closer to those of conventional lead crystal, are completely lead free. In this study, vitrifiable mixtures based on silicon, barium, strontium and zinc oxides were melted at 1450 °C, annealed at 580 °C, and characterized by x-ray diffraction, infrared spectroscopy, Raman spectroscopy and Calorimetric Thermal Analysis (DSC). X-ray diffraction confirms the amorphous character of all investigated glasses. The vibration bands are identified by infrared and Raman spectroscopy. These results highlight the influence of glass composition on structural properties. The glass transition temperatures (Tg) were determined by differential scanning calorimetric analysis (DSC). The obtained results vary from 546.8 °C to 632.6 °C, confirming the effect of the composition on the thermal properties.

The context of the present work is a large research project aiming at manufacturing functionalised surfaces by selected laser treatment with a focused beam [1]. More specifically, this paper aims at showing the possibility of obtaining a dense glass ceramic layer, with controlled microstructure, from a glass powder coating. In the present state of the research, laser scans are performed on glass powder compacts in order to investigate the operating conditions (power, speed and vectorisation) required to achieve the objective. The selected glass belongs to the Sr–Ti–Si–Al–K–O system, its crystalisation leads to a glass–ceramics containing piezoelectric Sr–fresnoite crystals (Sr2TiSi2O8) Maury et al. (2011). The selective laser treatment is carried out by mean of a focused Nd–YVO4 laser beam. Characterisation of the thermal state of the surface during the treatment is performed thank to an IR camera. The surface microstructure is evaluated by X-ray diffraction and scanning electron microscopy. The results presented shows that Sr–fresnoite glass ceramics layers can be processed by applying a two stage process: first the melting of a glass powder to form a dense amorphous layer; then the crystallisation of this layer. However, the microstructures resulting of a crystallisation step performed by mean of a one-scan laser treatment are heterogeneous. IR camera analysis highlights that this heterogeneity is due to thermal profile strongly depending on the position on the scanned surface. Moreover, the high energy scanning conditions required to promote crystallisation make that this later takes place on cooling after surface has been re-melted. Processing by a multi-scan mode (numerous successive rapid scans) seem more suitable. In that case, IR camera analysis shows a homogeneous thermal state of the surface. Additional investigations have to be performed in order to be able to master the relation between the thermal profile and the laser scan parameters.

NiCrBSi/WC composite coatings containing various amounts of WC/W2C particles were laser cladded on low carbon steel substrate S235JR. Coatings were processed using two different laser systems, a 1 kW Nd:YAG and a 3.8 kW high power diode laser (HPDL). Coatings obtained with the Nd:YAG source demonstrate significant changes in the matrix microstructure with WC/W 2 C particle addition. Specific analysis shows the formation of new carbides (W,Cr) x C y and boride phases (W,Cr) x B y resulting from a partial dissolution of the WC/W 2 C particles within the metal matrix. The Brinell macrohardness of the coatings reveals surprisingly low values for coatings containing 10 vol.% and 20 vol.% WC/W 2 C. Through nanoindentation measurements, it is suggested that the low hardness of these new carbide and boride phases most likely counteracts the WC/W 2 C addition and may explain this unexpected behavior. On the contrary, the same coatings deposited using the HPDL source exhibits no change in the microstructure of the NiCrBSi matrix and display an expected monotonic increase of composite hardness with WC/W 2 C amount. It is suggested that the microstructural appearance of new carbide and boride phases may not be related to the type of laser used but to the specific laser energy during the coating process. Contrarily to hardness, measurements show that the erosive wear is marginally affected by the microstructural differences of the coatings. These results demonstrate that evaluating the quality of laser cladded coatings by simply assessing their density and the absence of a crack (as usually done) is insufficient as it does not automatically guarantee reaching optimal mechanical performance.

International audience; In this work, foams were obtained by direct foaming of aqueous alumina suspensions containing butyric acid. Butyric acid is incorporated in the suspensions in order to hydrophobize alumina particles, leading to their adsorption at the air/water interface. After setting and drying, wet foams were sintered at 1585 °C for 2 h. The resulting porous samples were characterized in terms of microstructure, mechanical properties and thermal conductivity. Microstructures of sintered alumina foams reveal closed pores surrounded by a thin alumina layer. The microstructure of these macroporous ceramics is related to (i) the composition of the initial suspension (alumina and butyric acid contents) and (ii) the stirring velocity during the foaming process. Macroporous ceramics with pore sizes (d50) ranging from 20 µm to 140 µm and porosities between 25% and 89% were obtained. Three-point bending tests were performed on foams with porosities between 65% and 89%. The results of mechanical tests were analyzed with Weibull statistic. The bending strength values are between 5 MPa and 42 MPa. The Young’s modulus, obtained from 3-point bending tests, decreases with the porosity level according to Gibson–Ashby model. Thermal diffusivity measurements were made with the laser flash technique in order to determine the effective thermal conductivity. Experimental values are significantly higher than the predictions with Landauer’s relation and almost close to Maxwell/Hashin–Shtrikman upper bound.

This paper presents a new method for manufacturing macroporous ceramics by partial sintering of controlled ceramic powder agglomerates packing. Using this route, the final ceramic material is characterized by a hierarchical porous network that can contain up to three levels of interconnected pores: (i) the voids existing between the agglomerates (typically ≥10 µm in size), (ii) the porosity remaining inside the agglomerates after partial sintering (typically ≈100–1000 nm in size), (iii) the pores that may exist within the initial ceramic particles (typically

Spark Plasma Sintering presents many advantages in comparison with more conventional sintering techniques. Nevertheless, one of its main drawbacks is the heterogeneity of temperature field during the dwell of the temperature cycle, giving heterogeneous final microstructure. In this article, we propose to optimize the temperature field in the compact in order to obtain an almost homogeneous temperature only by modifying the tools dimensions. This optimization is based on the use of a coupled thermoelectric finite element model of the process. Finally, we present the sintering conditions influencing the optimization parameter.

The research work reported in this paper is an investigation of the behavior of barium titanate powders under selective laser irradiation. Our goal is to determine suitable conditions to sinter the powders and form dense layers usable in some electronic components. On that purpose, compacts of micro/nano BaTiO 3 powder mixes are used for a parametric investigation of the laser scans parameters (power, speed, etc.) with a Nd-YVO 4 laser (23 W). The microstructures obtained after laser treatments are evaluated by XRD, SEM and EDS and compared to a reference specimen manufactured in a conventional way. From this work it can be concluded that a high laser beam power is required to obtain a consolidation of the powder grains and the use of a high scan speed avoids the melting. The scanning speed also influences the final crystallographic state of BaTiO 3 . Optimal parameters were founded in order to form a dense and homogeneous tetragonal BaTiO 3 surface.

This paper shows that glass-ceramics containing highly surface and bulk preferentially oriented fresnoite Sr2TiSi2O8 crystals can be synthesised by a simple isothermal heat treatment of suitable glass compositions in the Sr–Ti–Si–K–B–O system. For all tested compositions, crystallisation starts from the free surfaces of the specimens and propagates to bulk with time. If most of these compositions lead to (00l) preferential orientation at the specimens' surfaces, bulk crystal texture is very composition dependent. The effects of variation in K2O and B2O3 contents on the crystallisation have been studied. It is shown that low K2O and high B2O3 contents are required to keep the (00l) orientation from the surface into the bulk. This result seems to be explained by the viscosities of the initial and residual glasses at the temperature of crystallisation: a low viscosity leads to a fine and homogeneous microstructure with small and strongly (00l) bulk oriented crystals.

Hertzian indentation was used to assess the fracture toughness (KIc) and the surface residual stresses of tempered soda lime glass. Although such measurements are usually performed on chemically strengthened glasses, where the thickness of the layer under compression is limited to several micrometres, our study considers the most useful case of thermally quenched glass, widely used in industry and where the compressed layer is several hundred micrometres thick. Measurements were performed on annealed and thermally quenched samples and residual stresses were calculated using two different models of the literature. Results were compared to stress measurements performed by a conventional photoelasticimetry technique. It is shown that Hertzian indentation gives qualitatively correct results which are comparable for each of the literature models used, provided that interfacial friction between the spherical indenter and substrate is correctly taken into account in the calculations. It is shown that a scratch tester used to perform sliding indentation onto the surface of the samples is a suitable tool for assessing the friction coefficient value.

The target of this work is to investigate the effects of the relative amounts of the main impurities usually encountered in an alumina powder obtained from the Bayer process. On that purpose, the amounts of Na 2 O and SiO 2 present in a commercial powder, have been modified by doping. The sintering behavior and the microstructure of the sintered ceramics have been investigated. The ratio Na 2 O/SiO 2 strongly influences the shrinkage rates during sintering, the final density and the microstructure. From the commercial powder used (P172SB, Aluminium Pechiney Company, Alcan Group, France), it is shown that an increase in Na 2 O content significantly slows down the densification and also the grain growth. The effect of an increase in SiO 2 additions is less obvious even if the dilatometric curves also show decreases in the sintering rates, particularly in the temperature range 1200–1400 °C. Contrary to Na 2 O, the addition of SiO 2 leads to abnormal grain growth and provokes an increase in the aspect ratio of the grains.

The crystal structure of the compound M 2 SiAlO 5 N “B-phase” (with M=Y, Yb, Er) is determined by Rietveld analysis of X-ray powder diffraction patterns. The pseudo α-wollastonite derived structure, often proposed in the literature [D.P. Thompson, The crystal chemistry of nitrogen ceramics, Materials Science Forum 47 (1989) 21–42], is used as a model for simulation of an X-ray diffraction pattern. The simulated pattern obtained with this model exhibits several peaks that are not observed on the experimental pattern. Moreover, when refining this model by Rietveld analysis, the final atom co-ordinates are strongly shifted with respect to their initial values and lead to aberrant bond lengths. A new model of the structure of B-phase is proposed: after refinement, the final reliability factors show that this new model is in very good agreement with experiments. According to this new model, the alternative layers of yttrium cations and (Si,Al)(O,N) 4 tetrahedra proposed in the pseudo α-wollastonite model is confirmed but the tetrahedra do not form rings as was initially suggested, but instead are randomly linked to each other.

A commercial polysilazane is used as a silicon carbonitride matrix precursor for the manufacture of ceramic matrix composites using bi-directional SiC Nicalon fabrics as reinforcing material. The objective is to develop a simple and fast process leading to materials able to compete with SiC/C/SiC composites obtained by the Chemical Vapour Infiltration (CVI) route. Two processes are investigated: (1) a ‘conventional’ process using the densification of a SiC fibre preform by several cycles of impregnation of the preform with the polymer followed by pyrolysis and (2) a ‘modified’ process consisting in a powder filling of the fibre preform prior to the precursor impregnation and pyrolysis. This paper describes the different steps of both processes. The materials obtained are characterised in terms of their porosity, microstructure and mechanical properties. ©

This paper reports the ability to use a commercial polysilazane † as matrix precursor for the manufacture of ceramic matrix composites. By pyrolysis under nitrogen in the temperature range 1000–1400 °C this polysilazane leads to an amorphous silicon carbonitride with a ceramic yield around 65 wt%. The rheological behaviour and the thermal decomposition of the polysilazane have been studied. Parameters for the impregnation and pyrolysis cycles required by the manufacture of composites are also proposed.

A low temperature process for the manufacture of non-oxide monolithic ceramic bodies is presented. This process is based on the pyrolysis at temperatures between 1000 and 1400 °C of the polysilazane precursor. The different steps of the process are precisely described. The physical (porosity, density, crystalline phases) and mechanical properties (flexural strength, Young's modulus, toughness and hardness) of the bodies obtained are studied versus the maximum temperature of the pyrolysis. The high temperature oxidation resistance in air is also presented.

A new process route for ceramic composites, associating CVI of SiC and impregnation and pyrolysis cycles with a polysilazane precursor, has been developed. The interest of this process is, firstly, a shorter time of elaboration than for CVI alone and, secondly higher mechanical properties than those resulting from a conventional use of the precursor. Composites with mechanical properties comparable to those of composites entirely obtained by CVI of SiC have been realised. The flexual strength of these materials is about 400 MPa, whereas that of composites resulting from a conventional use of the same polysilazane does not exceed 200 MPa.