Mechanically Activated Self-Propagating High Temperature Synthesis (MASHS) Applied to the MoSi<sub>2</sub> and FeSi<sub>2</sub> Phase Formation

About the mechanism of the solid-way synthesis of barium metatitanate. Industrial consequences

Abstract Barium metatitanate BaTiO 3 is the main component of the dielectric material of class 2 ceramic capacitors. The solid state reaction between BaCO 3 and TiO 2 is still one of the main industrial ways for the BaTiO 3 preparation. The aim of the paper is to propose a coherent set of interfacial reactions in order to explain all the experimental results previously published about this well known solid state reaction. The paper gives at first a summary of the main experimental results. Then all the interfacial reactions at the various stages of the advancement are proposed. All these reactions involve the same main point defects in BaTiO 3 which are barium and oxygen vacancies. It has b…

Influence of Grain Size, Oxygen Stoichiometry, and Synthesis Conditions on the γ-Fe2O3 Vacancies Ordering and Lattice Parameters

The soft chemistry method has been used to synthesize γ-Fe2O3 nanoparticles: various synthesis temperature were applied to obtain nanometric powders with crystallite size in the 9–14 nm range. Powders were characterized by X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectrophotometry, surface area measurements, and electron microscopy (TEM, SEM). It is clearly shown that these nanometric powders are very well crystallized as indicated by XRD and IR spectra which present substructural bands attributed to vacancies ordering (P4132). Based on these model materials and in the crystallite size range studied here, cell parameter appears to be not linked to crystallite size. It rat…

Anomalous Valence Contrast of Metal Transition in Nanocrystalline Ferrite

ChemInform Abstract: Neutron Diffraction Study of the in situ Oxidation of UO2.

This paper discusses uranium oxide crystal structure modifications that are observed during the low-temperature oxidation which transforms UO2 into U3O8. The symmetries and the structural parameters of UO2, β-U4O9, β-U3O7, and U3O8 were determined by refining neutron diffraction patterns on pure single-phase samples. Neutron diffraction patterns were also collected during the in situ oxidation of powder samples at 483 K. The lattice parameters and relative ratios of the four pure phases were measured during the progression of the isothermal oxidation. The transformation of UO2 into U3O8 involves a complex modification of the oxygen sublattice and the onset of complex superstructures for U4O…

Forming pressure dependence of the ferroelectric domain structure in green barium titanate pellets

Abstract Modifications of the X-ray diffraction line profiles by die pressing of fine grained powders of barium titanate have been studied. Two main parameters have been considered: the forming pressure and the mechanical characteristics of the binder. The higher the forming pressure, the greater the modifications of the line profiles. Furthermore, the phenomena seems to be related to pressing only; no significant effect related to the nature of the binder has been shown. The modifications of the diffraction line profiles are interpreted by considering a reduction of the size of the ferroelectric domains during pressing. In order to confirm this interpretation, the behaviour of the domain s…

Fine grain barium titanate: ferroelectric domains and X-ray diffraction diagram

Through three different studies using various kinds of BaTiO/sub 3/ samples: as a powder while heating over the Curie temperature; as a green ceramic as a function of the forming pressure; as a ceramic while applying a D.C. field. It is shown how X-ray diffraction is able to give information about the evolution of the 90/spl deg/ ferroelectric domain microstructure.

Dielectric properties of barium strontium titanate / non ferroelectric oxide ceramic composites

International audience; Barium strontium titanate ceramics present high dielectric permittivity and tunability. In order to reduce their permettivity and loss tangent while keeping tunability, various composites of barium strontium titanate oxide...

Suivi par diffraction de rayons X “in situ” de l'évolution du paramètre de maille du ferrite nanométrique γ-Fe2O3lors de l'isotherme d'adsorption d'eau

La methode de synthese par chimie douce a ete utilisee pour synthetiser des nanoparticules de maghemite γ-Fe 2 O 3 dans une gamme de taille allant de 9 a 14 nm. Ces poudres, parfaitement cristallisees en phase spinelle, exemptes d'impuretes, avec une stoechiometrie en oxygene parfaitement controlee, ont servi de materiaux modeles pour cette etude. Le parametre de maille de ce materiau (0,8346 nm) s'avere etre non dependant de la taille. Cependant, le suivi en Diffraction de Rayons X in-situ revele des variations de ce parametre avec la modification de la surface en presence de vapeur d'eau. Les phenomenes de chimisorption et de physisorption jouent un role preponderant dans les evolutions o…

Phénomènes de ségrégation dans les ferrites de titane nanométriques : apports complémentaires de différentes techniques expérimentales (DRX, XPS, EXAFS ...)

Grâce a la complementarite de diverses techniques deux phenomenes de segregation ont ete mis en evidence dans les ferrites de titane nanostructures: une segregation cinetique (dite dynamique) et une segregation thermodynamique. Par des techniques d'analyse locales (MET, XPS) et statistiques (DRX...), des heterogeneites au sein des grains de poudre contenant des cations Fe 2+ ont ete mises en evidence lors de leur etude a l'air. Leur origine est cinetique et decoule d'une oxydation incomplete des cations Fe 2+ . Des affinement de Rietveld de diagrammes de diffraction des rayons X et diffraction de neutrons ont permis de montrer quant a eux que le titane ainsi que toutes les lacunes creees lo…

Influence on the phase transitions of barium titanate of the manganese valency, introduced as a substituant in the titanium site

Abstract A small amount of manganese introduced in BaTiO3 modifies strongly the vibrational and electronic properties of the pure compound. Dielectric response and EPR measurements are reported in order to study the influence of the manganese valency on the ferroelectric-paraelectric phase transition.

Synthesis and characterization of nanometric powders of UO2+x, (Th,U)O2+x and (La,U)O2+x

This paper describes a new way of preparing nanometric powders of uranium oxide, to fit the needs of studies on UO{sub 2} oxidation, through the electrochemical reduction of U(VI) into U(IV). These powders can also be doped with radionuclides if necessary. The precipitation of oxides occurs in reducing and anoxic conditions. This original method makes it possible to synthesize nanometric UO{sub 2} powders with a calibrated size, as well as the Th- and La-doped UO{sub 2} powders with a predefined composition. The powder characterization by the X-ray diffraction, X-ray photoelectron spectroscopy and transmission electron Microscopy shows the formation of spherical crystallites of UO{sub 2+x},…

Crystal chemistry and phase transitions in mixed niobates crystallizing with tetragonal tungsten bronze structure

Abstract New compounds crystallizing with tungsten bronze structure are reported. A dielectric study and X-ray analysis at various temperatures have allowed to describe some phase transitions.

Cation Distribution in a Titanium Ferrite Fe2.75Ti0.25O4Measured byin-SituAnomalous Powder Diffraction Using Rietveld Refinement

Many ferrites contain different cations with various valence states and location in the spinel structure. In compounds such as these, only a combination of different techniques such as Mussbauer spectroscopy, IR analysis, and thermogravimetry allows the distribution of cations to be obtained. For very complicated distributions, the mathematical decomposition of derivative thermogravimetric curves (DTG) leading to quantitative distribution is uncertain. In this paper, we present an alternative technique based on resonant diffraction. The anomalous scattering of each cation in the crystalline material is used to determine its amount and position by Rietveld refinement. Since the energy for su…

Dielectric and E.P.R. studies of Mn-doped barium titanate

Manganese introduced in BaTiO3 as a substituant of titanium is able to trap the electrons produced during a sintering under a very low oxygen pressure. However it strongly modifies the vibrational ...

Effect of coherency of domain walls on X-ray diffraction diagrams: Case a crystal with a low tetragonality

Les diagrammes de diffraction des rayons X d'une poudre ou d'une ceramique de BaTiO 3 tetragonal ont ete etudies. Une correlation entre les caracteristiques des profils des raies de diffraction (intensite, forme, position,...) et la microstructure en domaines ferroelectriques a ete mise en evidence. A partir d'une approche numerique, le calcul des diagrammes de diffraction montre que la modification des profils des raies de diffraction du compose tetragonal est fortement dependante de la microstructure en domaines ferroelectriques. Ce a du prendre en compte l'existence d'un certain degre de coherence dans les murs de domaines entre deux domaines a 90° adjacents. Il a par ailleurs ete mis en…

Microstructure of 90° Domains in Ferroelectric Materials studied by XRD

Influence of Twinning Microstructure of Crystals with Low Tetragonality on a X-Ray Diffraction

The intensity distributions of the X-rays scattered in the tetragonal single crystal, which represent a complex of the twin domains separated by the coherent parallel boundaries, are simulated. The calculations are performed by using the Monte Carlo method within the framework of a kinematical approach. The thickness distributions of the twin domains are defined according to the geometrical, Gaussian and log normal functions. ‘Critical’ effects of the X-ray scattering are found, namely there is transformation of the tetragonal doublet into singlet or multiplet. As demonstrated, each of characteristics of the tetragonal doublet profile depends on a few parameters of the twin microstructure o…

Cation Distribution in Ferrites with Spinel Structure Measured by Anomalous Powder Diffraction

Application of gas separation membranes to detritiation systems

The use of gas separation membranes in tritium removal systems has been studied to develop a new detritiation process. The main advantage of this new process is to reduce the number and/or the size of equipments in comparison to conventional detritiation systems. The objective of this study is to choose the best suited membrane for this application. The hydrogen or its isotopes recovery performance of several commercial hollow fiber organic membranes has been analyzed thanks to three devices. Experiments are performed with small quantities of hydrogen gas or deuterium gas or tritium gas in the range representative of the radioactive contamination level in tritium handling gloveboxes. A math…

Ferroelectric domains in BaTiO3powders and ceramics evidenced by X-ray diffraction

Abstract Through three different studies, using BaTiO3 samples, as a powder while heating over the Curie temperature, and as a ceramic while applying an electric field, it is shown how X-ray diffraction (XRD) is able to give information about the evolution of the ferroelectric domain microstructure. Firstly, the relative intensities of the 002 and 200 lines, as a function of the applied electric field, exhibit the motion of the 90[ddot] domain walls. However, XRD is unable to provide any distinction between two 180[ddot] domains. Secondly, the profile of those two lines and of the other double (hhl), (lhh) lines is particular: the unusual diffracted intensity between such double lines has t…

On the origin of the sigmoid shape in the UO2 oxidation weight gain curves

International audience; Cracking and spalling are known to occur during the oxidation of UO2. However, these phenomena are not considered by the existing kinetic models of the oxidation of UO2 into U3O8. In this study the oxidation of UO2 samples of various sizes from the single crystal to nanopowders, has been followed by isothermal and isobaric thermogravimetry, environmental scanning electron microscopy and in situ X-ray diffraction at temperatures ranging from 250 to 370°C in air. It has been shown that cracking occurs once a critical layer thickness of intermediate oxide has been reached, which corresponds to the beginning of the sigmoid kinetic curve. Cracking contribution to the sigm…

Enhancement of self-sustaining reaction by mechanical activation: case of an FeSi system

Mechanical high energy ball milling of an Fe2Si elemental powders mixture was used to activate a self sustaining combustion reaction or so-called self-propagating high-temperature synthesis (SHS) to form iron disilicide, a reaction for which the thermodynamic criterion is not favorable. A complete characterization of the milled powders before reaction was performed with energy dispersive X-ray spectrometry, specific surface measurements and X-ray diffraction profile analysis. Thermal and structural information describing the combustion front initiated by heating up a sample to 400°C in a Fe‐Si system is communicated. In order to isolate the phases involved in the gasless reaction, a time-re…

Synchrotron diffraction study of the isothermal oxidation of uranium dioxide at 250°C

ABSTRACTThe structural evolution of UO2 during its oxidation to U3O8 at 250°C in air was studied by in-situ synchrotron X-ray diffraction on the D2AM-CRG beamline at ESRF. The aim of this study is to determine the phases that are likely to appear during the long-term storage of spent nuclear fuel. Our results are in disagreement with the literature in which the existence of an intermediate cubic phase is not reported. Instead, an α-U3O7 tetragonal phase (c/a < 1) was mentioned but not definitively observed. These previous interpretations may have been the result of poor instrumental resolution.

A New Possibility for Powder Diffraction: The Characterization of the Domain Microstructure in a Ferroelectric Material

Mechanically Activated SHS Reaction in the Fe-Al System: In Situ Time Resolved Diffraction Using Synchrotron Radiation

The Mechanical Activation Self propagating High temperature Synthesis (M.A.S.H.S.) processing is a new way to produce nanocrystalline iron aluminide intermetallic compounds. This process is maily the combination of two steps ; in the one hand, a mechanical activation where the Fe - Al powder mixture was milled during a short time at given energy and frequency of shocks and in the other hand, a Self propagating High temperature Synthesis (S.H.S.) reaction, for which the exothermicity of the Fe + Al reaction is used. This fast propagated MASHS reaction has been in -situ investigated using the Time Resolved X - Ray Diffraction (TRXRD) using a X - ray synchrotron beam and an infrared thermograp…

Ferroelectric Domain Walls in BaTiO3: Fingerprints in XRPD Diagrams and Quantitative HRTEM Image Analysis

The structure of ferroelectric domain walls in BaTiO3 has been investigated through two complementary approaches, a global one by the fine analysis of X-ray diffraction patterns, the other essentially local via a quantitative image analysis method developed and applied to High Resolution Transmission Electron Microscopy images. These two original approaches converge towards a clear description of 90○ walls which are shown to be a 4–6 nm wide region where the crystallographic discontinuity is accommodated by irregular atomic displacements. The results given here demonstrate that the usual structural theoretical description of walls commonly accepted for energy calculations are far too simpli…

Contribution of Ferroelectric Domains on Diffraction Line Profiles of BaTiO<sub>3</sub>

Desummation of Mixed Powder Diffraction Lines

Contribution of the synchrotron diffraction study of the oxidation of uranium dioxide at 250○C

The structural evolution of UO 2 during its oxidation into U 3 O 8 at 250°C in air was studied by in-situ synchrotron X-ray diffraction on the D2AM-CRG beamline at ESRF. The aim of this study is to determine the phases which are likely to appear during a long term storage of used nuclear fuel. Our results are in disagreement with the literature where the existence of the secondary cubic phase is not reported, and an α-U 3 O 7 tetragonal phase (c/a < 1) is also mentioned but definitely not observed. These previous interpretations are possibly due to a poor instrumental resolution, inducing a sensible broadening of the diffraction peaks. Particularly, the fact that the instrumental resolution…

Diffraction anomale et composition cationique d'une titanomagnétite nanométrique

Les ferrites substitues au titane constituent des materiaux interessants pour aller vers la comprehension des reactions d'oxydo-reduction qui ont lieu dans ces composes de structure spinelle. Ces composes synthetises par chimie douce on ete etudies in-situ par diffraction anomale dans diverses conditions. Dans le cas particulier du compose Fe 2.5 Ti 0.5 O 4 , les premiers resultats montrent que cette methode de synthese ne permet pas d'elaborer directement le ferrite avec la composition esperee. En effet l'analyse structurale met en evidence un taux de titane bien inferieur a 0.5 alors que d'autres techniques,(analyse ICP, methode de Poix), confirment ce taux de substitution.

Crystal chemical and dielectric properties of Pb0.5(5-x)LaxNb5-xFexO15system with “tetragonal tungsten bronze” structural type

The lanthanum-lead and iron-niobium coupled substitution in PbNb 2 O 6 have allowed to isolate new materials of a general formula Pb 0.5(5-x) La x Nb 5-x Fe x O 15 crystallising with the tetragonal tungsten bronze structural type. The resulting influence on the lattice parameters, the ferroelectric Curie temperature and Cole - Cole plots are presented. A typical ferroelectric - paraelectric behaviour occurs in the composition range 0 ≤ x ≤ 0.33 while, a relaxor behaviour is observed in the composition range 0.33 < x < 1.

X-Ray diffraction diagram evolution of a BaTiO3ceramic under an electric field

Abstract The X-ray diffraction diagrams of a coarse grained pure BaTiO3 ceramic have been recorded as a function of the applied electric D.C. field. This field was perpendicular to the X-ray incoming surface. The experimental device used allows to record diffraction diagrams while the electric field step by step increases. The intensity ratio of the 002 line over the 200 line increases with the applied electric field. The evolution of the X-ray diffraction line intensities is in correlation with the first polarization curve of the ferroelectric ceramic. These results evidence a contribution of the 90° ferroelectric domains pattern to the X-ray diffraction diagram of BaTiO3.

Neutron Diffraction Study of the in Situ Oxidation of UO2

This paper discusses uranium oxide crystal structure modifications that are observed during the low-temperature oxidation which transforms UO(2) into U(3)O(8). The symmetries and the structural parameters of UO(2), beta-U(4)O(9), beta-U(3)O(7), and U(3)O(8) were determined by refining neutron diffraction patterns on pure single-phase samples. Neutron diffraction patterns were also collected during the in situ oxidation of powder samples at 483 K. The lattice parameters and relative ratios of the four pure phases were measured during the progression of the isothermal oxidation. The transformation of UO(2) into U(3)O(8) involves a complex modification of the oxygen sublattice and the onset of…

Thermodynamic considerations of the grain size dependency of material properties

Phase transitions which depend on grain size induce very interesting properties in materials such as zirconia or barium titanate. A new and rigorous thermodynamic treatment of this type of phase transition is proposed with consideration of the surface phenomena. An interpretation is given of the observed differences when the material—particularly BaTiO3—under consideration is a fine grain powder or is a fine grain ceramic.

Caractérisation de poudres de zircone synthétisées par voie hydrothermale

La synthese hydrothermale permet la realisation de poudres fines cristallisees et desagglomerees Ces qualites sont appropriees a l'elaboration de composites fins oxyde/oxyde par synthese simultanee des deux phases. Nous avons developpe ce protocole pour la realisation de nanocomposites ahrmine/zircone (Q). Nous presentons ici plus particulierement le travail effectue sur la zircone, Les conditions de traitement hydrothermal et d'un traitement thermique modere supplementaire sont analysees en relation avec les caracteristiques des poudres synthetisees. Differentes techniques complementaires sont utilisees pour ces poudres de zircone: diffraction des rayons X (% de la phase quadratique, taill…

Peculiarities of X-Ray Diffraction in Crystals with Diffuse Boundaries of Twin on System {011}, &lt;011&gt;

Développements récents de l'étude en temps réel par diffraction des rayons X couplée à une thermographie infrarouge : application au suivi de la réaction MASHS dans les systèmes FeAl, et MoSi2

La formation au cours d'une reaction de combustion autoentretenue et mecaniquement activee (MASHS) d'intermetalliques nanometrique, tels que les composes FeAl et MoSi 2 , a pu etre observee in-situ et en temps reel en couplant la diffraction des rayons X, produit par rayonnement synchrotron, et une thermographie infrarouge. La mise en oeuvre d'une telle experience est indispensable en raison de la vitesse importante (10 mm/s) de propagation du front de combustion. Des developpements recents realises au niveau des systemes de detections permettent d'obtenir des temps d'acquisition tres courts (quelques dizaines de millisecondes) et de reveler des etapes intermediaires au cours de la transfor…

Nanocrystalline FeAl Synthesis by MASHS with &lt;i&gt;In Situ&lt;/i&gt; and Post Mortem Characterizations

The materials saga: sintering

In ICV no 1010, we inaugurated our materials saga with the classification and shaping of ceramics. This second and short chapter deals with sintering and its different forms: non reactive or reactive sintering, natural or pressure sintering as well as two essential parameters: density and porosity.

Bulk pre-reactional transformations preceding the thermal decomposition of calcium hydroxide into oxide

The present paper is an extended abstract which should be considered as an introduction to the papers already published by us on this new topic. An extended synthesis of these papers was given in the lecture. The original information introduced here is the figure. It is a PH2O vs. T diagram which gives the pre-reactional domain between the stability domains of calcium hydroxide and calcium oxide. Chemical reactions are proposed as an interpretation of the observed pre-reactional transformations.

Glovebox atmosphere detritiation process using gas separation membranes.

Abstract The use of gas separation membranes in atmospheric detritiation systems has been studied. The main advantage of this new process is to reduce the number and/or the size of the equipment in comparison to conventional tritium removal systems. Owing to the constraints linked to tritium handling, the separation performances of several commercial hollow fiber organic membranes have been analyzed, under various operating conditions, with hydrogen/nitrogen or deuterium/nitrogen mixtures. The experiments are performed with small quantities of hydrogen or deuterium (5000 ppm). The experimental results allow to evaluate the separation efficiency of these membranes and to determine the approp…

Cell Parameters of Fine-Grain BaTiO&lt;sub&gt;3&lt;/sub&gt; Powders

BST ceramics: Effect of attrition milling on dielectric properties

Abstract The effect of grain size on the dielectric properties of Ba0.6Sr0.4TiO3 (BST) ceramics is investigated. Attrition milling is chosen to obtain nanometre particle size from micrometre particle size powders. Fine grained ceramics are obtained by hot uniaxial pressing (HUP). Additionally, the present study is focused on the effect of the nature of milling balls on loss tangent and permittivity. For that, three kinds of balls are tested: calcia, yttria or ceria stabilised zirconia balls. The properties of these samples are evaluated in the range of MHz. The balls induce an involuntary doping of powders which modifies the dielectric properties, especially the Curie temperature and loss t…

High magnification SEM observations for two types of granularity in a high burnup PWR fuel rim

Abstract Rim microstructure of an UO2 pellet irradiated up to 61 GWd/tU, observed with high magnification scanning electron microscopy, presented two types of subgrains: polyhedral and round subgrains. Round subgrains were also observed on the surface of fabrication pores along the pellet radius. These round-shaped subgrains seem to be associated to free surface rearrangement. This new type of round subgrains was proved to be independent of the rim effect. Observations of the fuel structure in the vicinity of rim area evidenced two types of defects specific to rim effect: planar defects and small intergranular pores. Hypothesis is made that the accumulation of planar defects could generate …

Synthèse de poudres nanométriques de titanate de strontium par émulsion stabilisée mécaniquement: maîtrise et prédiction de la taille des particules

Resume La synthese de poudres nanometriques de titanate de strontium a partir d'une emulsion eau dans alcool stabilisee par agitation mecanique a ete etudiee avec l'objectif de maitriser a la lois la taille et la stœchiometrie des poudres obtenues. La taille des particules a ete ajustee par l'intermediaire de deux parametres du milieu reactionnel: la fraction volumique de la phase aqueuse et la concentration en precurseurs. Une relation entre la taille des gouttelettes de l'emulsion et la taille des particules des poudres de SrTiO3 obtenues apres precipitation a ainsi ete mise en evidence. Elle s'explique a partir d'un modele qui implique, entre autres hypotheses, que la vitesse de germinat…

From the Powder to the Electro and/or Magnetic Ceramic Component: Fine Grain Size and Properties

In situ synchrotron characterization of mechanically activated self-propagating high-temperature synthesis applied in Mo–Si system

Abstract An original experiment was designed to monitor structural and thermal evolutions during the MASHS (Mechanically Activated Self-propagating High-temperature Synthesis) process in the Mo–Si system. Time-Resolved X-Ray Diffraction (TRXRD) coupled with an infrared imaging technique was performed to study, in situ, the formation of the α-MoSi2 phase in the combustion front. Despite a temporal resolution of 50 ms between two consecutive diffractograms, no intermediate phase was observed during the passage of the combustion front. The only reaction responsible for the self-sustentation is Mo+2Si→MoSi2 in the primary zone inside the combustion wave. The mechanical activation was found to i…