Reverse precipitation synthesis and characterization of CeO2 nanopowder

In the present work, CeO2 nanopowder was synthesized via a reverse precipitation method using CeCl3 center dot 7H(2)O, NH4OH and sodium dodecyl sulfate as raw materials. The effect of thermal treatment on the crystal growth, surface area and chemical bonds of the powder was discussed. The structural evolutions and morphological characteristics of the nanopowder were investigated using X-ray diffractometery, transmission electron microscopy, scanning electron microscopy, differential thermal analysis and Fourier transform infrared spectroscopy. The results showed that CeO2 with an average particle size of 45 nm is formed. The BET surface area increased to approximate to 41 m(2)/g, with increasing calcination to 300 degrees C; then, it decreased following calcination at higher temperatures. The particles sintered and agglomerateed together after 500 degrees C. The activation energy for CeO2 nanocrystallite growth during calcination was calculated to be about 14.6 kJ/mol. (C) 2009 Elsevier B.V. All rights reserved.

On the relationship between the microstructure and the mechanical properties of an ODS ferritic/martensitic steel

Amuthan Ramar

In the quest of materials for the first wall of the future fusion reactor, it has been shown that oxide dispersion strengthened (ODS) ferritic / martensitic (F/M) steels appear to be promising candidates. The inherent good mechanical properties supported by a good thermal conductivity, swelling resistance and low radiation damage accumulation of the base material, such as EUROFER97, are further enhanced by the presence of a fine dispersion of nanometric oxide particles. They would allow in principle for a higher operating temperature of the fusion reactor, above 550°C, which improves its thermal efficiency. In effect, their strength remains higher than the base material at high temperatures. There are however limitations to their application in the reactor, which relate to the intimate link between the microstructure and the mechanical properties. These limitations, such as an increased ductile to brittle transition temperature above room temperature relative to the base material, come directly from the role played by the oxide particles but also from their indirect impact on the overall microstructure, stemming from the procedure of elaboration of these materials. In addition, there is a lack of knowledge on their response to irradiation, which, even though it appears to be promising with a reduced irradiation induced hardening, is not very well understood. In this work we have developed and evaluated ferritic/martensitic steel, EUROFER97, strengthened by a dispersion of yttria particles. (1) The powder metallurgical process used to obtain it was optimized, (2) the basic mechanisms of hardening were identified and (3) the impact of irradiation on its microstructure and mechanical properties were investigated. In order to understand the behaviour of this class of material other oxide dispersion strengthened (ODS) ferritic/martensitic steels based on EUROFER97 and model alloys were also investigated. For the elaboration of the ODS steel the powders of atomized EUROFER97 and yttria are ball milled in a planetary ball mill and the material is compacted by hot isostatic pressing (HIP). The mechanical properties are evaluated by uniaxial tensile test, Charpy test and micro-indentation while the microstructure is investigated by optical microscopy, scanning electron microscopy and transmission electron microscopy. The focused ion beam (FIB) technique is also used. In the study of the ball milling it appears that the optimal time is 20 hours, as the X-ray peak broadening, crystallite size and hardness of the particles remain unchanged at longer times. Yttria nanoparticles clusters are no more detectable by X-ray after 2 hrs of milling, which is attributed here to their incorporation in the matrix, as opposed to dissolution in the matrix as is often suggested in the open literature. HR-TEM performed on the yttria particles before and after incorporation in the steel by ball milling shows that the yttria maintain its bcc equilibrium structure throughout the process. This could suggest that they are not dissolved during ball milling. We have clarified this point by a cross sectional examination of the EUROFER97 ball milled particles with 0.3wt% of yttria in an FIB. By X-ray EDS analysis it shows nanometric regions reach in yttrium and oxygen, which are the yttria particles embedded in the EUROFER97 particles, proving that they are not dissolved by ball milling. The mechanism at the origin of the alloy compaction during HIP was elaborated. The alloy compaction was done through HIPing at 1150°C for 2.5 hrs at a pressure of 190 MPa. This condition is shown to provide the highest bulk density, to a value close to 99.9%. In the optimization process, it is found that temperature plays a larger role than pressure for alloy compaction. The compaction appears to be mainly due to diffusion. Also, it appears that the ball milled particle size plays a major role in the alloy compaction. It is shown that smaller particles size induces better compaction, provided that the densification proceeds through diffusion flow. This further suggests to terminate the ball milling process by 20 hrs as the particles size reaches its minimum. The impact of the ball milling process on the mechanical properties was evaluated. EUROFER97 with and without ball milling, with and without oxide addition presents an average density around 99.8%. In the as received state, casted EUROFER97, atomized EUROFER97, ball milled EUROFER97 and ODS Yttria present microstructure morphology typical of tempered martensite, whereas ODS Ti presents a nano sized grain microstructure with an average grain size of 200 nm. Ball milling and HIPping does have a slight influence up to 400°C, due to the higher dislocation density induced by ball milling relative to casted EUROFER97. It becomes negligible above 400°C, since both casted and ball milled EUROFER97 present similar hardness and microstructure. In ODS Yttria, yttria presents an average particle size of 25 nm. In ODS Ti, Y-Ti-O presents an average particle size of 7 nm. In the following the identification of the hardening mechanisms in ODS F/M steels. A new model was developed to quantify the collective hardening due to different obstacles, assuming that they provide independent hardening mechanisms. The model helped identifying the dominating source of hardening in ODS F/M steels. The base of the model is the dispersion barrier strengthening model, which is given by Δσsparticle or defects = Mαμb(Nd)1/2 for the hardening due small defects or oxide particles and is given by Δσd-d = Mαμb(ρ)1/2 for the hardening due to dislocations. In this approximation, the total hardening is then given by Δσtotal = {(Δσd-d)2 + (Δσparticle or defects)2}1/2 . The model is used to explain the hardening due to oxides, dislocations and irradiation induced defects. It appears that dispersed oxides is dominating hardness up to 800°C, while following a heat treatment at 1000°C it is the dislocations that then dominate the hardness. Deformation mechanisms were investigated using differential strain rate experiments. The activation parameters, i.e. the activation volume and activation energy, were calculated. It appears that there is a decrease in the activation volume from room temperature to 400°C, which is less than 3%. At about 500°C there is a sudden drop in the activation volume that reaches a minimum at 600°C. With further increase in temperature, there is a significant raise in the activation volume. This abrupt decrease between 400°C and 600°C hints at a change in dislocation-rate controlling mechanism, marking two regimes, a low temperature one and a high temperature one. In situ TEM observations show that at low temperature the deformation is mainly due to the formation of the Orowan loops around the particle. At high temperature the activation energy is about 3.4 eV for ODS, whereas it is 1.3 eV for EUROFER97. The calculated activation energy corresponds well to the one of dislocation climb mechanism. This indicates that at high temperature the yttria particles could be overcome by climb, while at low temperature they are overcome by the Orowan mechanism. The peculiar response of the yield stress to irradiation for this class of material was rationalized using the total hardening model we developed. At a dose of 2 dpa, irradiation induced defects are higher in number density than the dispersed yttria particles, which although they are weaker than the yttria particles they can explain the significant hardening observed in the material. Conversely, the shallow impact of irradiation on ODS F/M steels at low doses, relative to base F/M steels, is explained by the fact that the amount of dispersoid is found to be higher than the density of irradiation induced defects.

EPFL2008

Etude par microscopie électronique de particules nanostructurées d'oxalate de cobalt précipitées en milieu aqueux

The understanding of material self-assembling and self-organization mechanisms, at mesoscale, is crucial for nanotechnologies development. Such structures, hierarchically organized in superlattices or colloïdal crystals, are observed in inorganic or organo-metallic precipitates. The classical characterization, using electron microscopy and X-ray diffraction, of a synthesized powder is inadequate to describe the hierarchically organized polycrystalline structure of the final particles. Here, we have highlighted the successive steps that lead to the spontaneous formation of a cobalt oxalate dihydrate (COD) colloïdal crystals that precipitate in aqueous media. The characterization of the final particles, made by X-ray and electronic diffraction, has allowed us to determine the controversial crystalline phase of the precipitated COD. The β and γ COD phases has been discriminated by comparing experimental results with simulations of X-ray diffractogram and electron diffraction patterns for these both structures. The precipitated COD corresponds to the γ phase indicating that it comes from solid dehydration of cobalt oxalate tetrahydrate. The final powder characterization, performed by X-ray diffraction (XRD), atomic force microscopy (AFM), low voltage high resolution scanning electron microscopy (LVHRSEM) and transmission electron microscopy (TEM), gives some diverging results about monocrystalline or polycrystalline nature of the precipitates. XRD and AFM analysis show a polycrystalline structure of particles whereas LVHRSEM, TEM and electron diffraction observations indicate a monocrystalline structure. This apparent contradiction has led us to elaborate a new characterization method allowing to follow the growth and the structural evolution of the precipitate as a function of time. The cryo- preparation techniques are well adapted as they allow freezing and direct observation of solid state suspension by electron microscopy. The freeze/drying method has been modified and used for both SEM and TEM, and has allowed us to study the morphological and structural evolution of the COD precipitate from nanoscale to mesoscale. In addition, TEM analysis of samples prepared by classical techniques has been performed to complement cryo-electron microscopy observations. The combination of these two methods show that COD precipitation is a complex multi-step process leading to the formation of a core/shell heterostructure. The anisotropic core is porous and partially crystalline. It is formed by agglomeration of isolated primary particles and agregated ones (15-20 nm sized secondary particles). The crystalline shell corresponds to the final particles faces and is made up by the layer by layer self-assembling and alignment of 5-7 nm sized crystalline primary particles. These nanoparticles are aligned and perfectly ordered in strings of nanograins in the layer structure. The self-assembling occurs in the last step of growth where we have a lower ionic strength and supersaturation inducing slower kinetics of growth and aggregation. Moreover, the crystalline order in the primary and secondary particles increase with the time of reaction consistent with a continuous process of primary particle nucleation and growth. Our results show that self-assembling occurs layer by layer with terraces, kinks and steps that are present on the faces. This reminds the layer by layer crystalline growth models but in this case, the buiding blocks are colloïdal instead of atomic or molecular. Based on these different results, we propose an original model describing the COD precipitate growth. In addition, we have studied the poly(methacrylic acid-sodium salt) effect on the COD precipitation. This additive (PMMA) appeared to be a very good growth inhibitor. The PMMA effect on the final particles morphology is dramatic. Its concentration variation in solution slows down the nanoparticles aggregation rates along a [101] preferential direction. The crystal habit can then be controlled and we have synthesized platelets, cubes and rods with tailored length. The use of cryogenic electron microscopy has been shown to be a powerful tool for the understanding of time dependent aspects of particle growth. The use of such techniques for the study of other systems, where the final precipitate appearance may hide particle substructures, will help to elucidate growth mechanisms and allow finer control of nanostructured materials for many applications. The complex self-assembling and self-organization processes could then be highlighted and studied on a nanometer to micrometer scale.

EPFL2004

Characterization and modeling of twinned dendrite growth

Mario Alberto Salgado Ordorica

The formation of feathery grains during semi-continuous casting of Al-alloys [1, 2] is an interesting problem from both practical and theoretical points of view. These structures are formed by a lamellar sequence of twinned and untwinned regions separated by straight and wavy-like boundaries. Each pair of lamellae contains twinned dendrites split in their trunk center by a coherent {111} twin plane, while lateral arms meet at an incoherent {111} boundary. In practice, feathery grains are considered as defects which reduce the mechanical properties of a solidified ingot. In theory, an understanding of twinned dendrite growth includes different solidification phenomena, e.g., interfacial energy anisotropy, crystallographic growth directions, twinning, growth competition mechanisms, etc. Although several studies have been performed in order to understand the physics leading to the nucleation and growth of twinned dendrites, various questions remain unanswered. In this work, a comprehensive study of twinned dendrite growth has been undertaken, with the main objectives being: i) to study the effect of different alloying elements and solidification conditions on twin formation in binary Al-alloys; ii) to establish a better understanding on the stability of twinned dendrites and the growth kinetic advantage that they exhibit over regular ones; and iii) to elucidate the stable shape of the twinned dendrite tip. In order to study alloying-element effects, binary Al-X alloys (where X = Zn, Mg, Cu and Ni), were produced under Directional Solidification (DS) conditions in the presence of a slight natural convection in the melt. Analysis of these castings has shown that feathery grains can form for all solute elements of interest, but not for all compositions. The probability of forming feathery grains is relatively high when the alloying elements are hcp (Zn or Mg), but decreases for fcc solute elements (Cu or Ni). A study on the effect of forced convection in the melt, performed using different experimental set-ups, confirms previous observations suggesting that it is the shearing components of the liquid slow which induce twin nucleation [3, 4]. However, the poor reproducibility of these experiments and the variable rate of feathery grains formation indicate that twin nucleation is governed by a highly stochastic behavior. The probability of such an event decreases as the melt slow is less complex and the associated Stacking Fault Energy (SFE) of the alloying element is increased. In terms of growth kinetics advantage, a characterization using various metallography techniques and X-ray synchroton tomography has shown that this is in part due to the complex morphology of twinned dendrites. Indeed, it has been confirmed that these dendrites grow along ‹110› directions with ‹110›, and also sometimes ‹100› secondary arms, the primary trunk spacing of these dendrites being much less anisotropic than previously thought [5, 6]. It has been shown that twinned dendrites grow in a stable manner at a lower undercooling than regular ones. In addition, the distribution and orientation of their side arms favors their growth at the expense of less developed regular dendrites. A mechanism to explain the lateral multiplication of twin planes is also proposed in this work. In terms of stability, observations after partial remelting of twinned DS specimens, then re-solidification in a Bridgman furnace, have shown that even if twin planes remain stable during partial remelting, independent regular non-twinned dendrites issued from the twinned and untwinned parts of the seed grow during solidification. This implies that the formation of twinned dendrites is not only related to the ability to nucleate a stacking fault, but also to the imposed solidification conditions. The favorable growth kinetics of twinned dendrites is also explained by their tip morphology. Three hypotheses have been evaluated in this work: i) the grooved tip [7], stabilized by the Young-Laplace equilibrium condition; ii) the doublon [5], i.e., a double tip dendrite that grows with a narrow liquid channel in its center that solidifies at a composition close to C0; and iii) the pointed (or edgy) tip [8], equilibrated by torque terms of γsl when it is too anisotropic. Observations performed at the twinned dendrite tip have revealed the presence of a small groove, which eliminates definitively the hypothesis of the edgy tip. Further examination of the stable growth morphology of twinned dendrites has been done by using a phase field model that reproduces the presence of a twin plane through an appropriate boundary condition. The results of these simulations show that twinned dendrites are doublons that grow with a narrow liquid channel (0.2 to 3 µm width) whose depth depends strongly on the alloy composition and the solidification conditions. In order to validate these simulations, Focused Ion Beam (FIB)-microtomography and X-ray chemical analysis (EDS) in a Scanning Transmission Electron Microscope (STEM) were performed on small specimens extracted from twinned dendrite trunks. These have shown the existence of a positive solute gradient in a region localized within 2 µm around the twin plane, i.e., as expected for a doublon morphology. Additionally, the presence of small particles aligned within the twin plane is in agreement with the formation of small liquid pockets below the doublon root as predicted by the numerical model, but further work is required to explain this remarkable feature. Finally, composition measurements performed after quenching a partially remelted specimen also seem to confirm the existence of a doublon. This work contributes to the understanding on twinned dendrite growth kinetics in several aspects, principally the effect of alloying elements on twin formation, their growth kinetic advantage, their stability and their stable tip morphology. However, further work must be carried out to overcome the limited knowledge on the mechanisms leading to twinned dendrite nucleation. In the same manner, the growth mechanisms of the doublon morphology should also be further investigated in future works.

EPFL2009