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  • 1.
    Godinho, Jose
    Stockholm University, Faculty of Science, Department of Geological Sciences.
    Direct observations of the structures developed on fluorite surfaces with different orientations during dissolutionArticle in journal (Other academic)
  • 2.
    Godinho, Jose R. A.
    et al.
    Stockholm University, Faculty of Science, Department of Geological Sciences. Oak Ridge National Laboratory, United States.
    Putnis, Christine V.
    Piazolo, Sandra
    Stockholm University, Faculty of Science, Department of Geological Sciences. Macquarie University, Australia.
    Direct Observations of the Dissolution of Fluorite Surfaces with Different Orientations2014In: Crystal Growth & Design, ISSN 1528-7483, E-ISSN 1528-7505, Vol. 14, no 1, p. 69-77Article in journal (Refereed)
    Abstract [en]

    Atomic force microscopy has been used to observe the surface dynamics during dissolution of polished fluorite surfaces with different orientations. These surfaces, with an initially high density of atomic scale defects, showed fast changes during the first seconds in contact with a solution. Different types of structures developed on each surface, depending on its initial orientation and solution composition. These structures dissolved slower than the main surface persisting for at least 67.5 days of continuous dissolution. A new interpretation of traditional kinetic and thermodynamic models of dissolution applied to surfaces with a high density of steps is proposed to explain the observations. The new model includes the following: (a) fast initial dissolution at defect sites, (b) formation of a fluid boundary layer at the mineral solution interface enriched in the dissolving ions, and (c) precipitation of more stable fluorite structures nucleated at surface defects. This model highlights the importance of considering surface defects and crystal orientation for advancing our understanding of processes happening at the mineral solution interface and for developing more accurate kinetic dissolution and crystal growth models essential in Earth and material sciences.

  • 3.
    Godinho, José
    Stockholm University, Faculty of Science, Department of Geological Sciences.
    Effect of surface structure for the development of topography during dissolution of fluorite surfacesArticle in journal (Other academic)
  • 4.
    Godinho, José R. A.
    et al.
    Stockholm University, Faculty of Science, Department of Geological Sciences.
    Piazolo, Sandra
    Stockholm University, Faculty of Science, Department of Geological Sciences.
    Evins, L. Z.
    Effect of surface orientation on dissolution rates and topography of caf22012In: Geochimica et Cosmochimica Acta, ISSN 0016-7037, E-ISSN 1872-9533, Vol. 86, p. 392-403Article in journal (Refereed)
    Abstract [en]

    This paper reports how during dissolution differences in surface chemistry affect the evolution of topography of CaF2 pellets with a microstructure similar to UO2 spent nuclear fuel. 3D confocal profilometry and atomic force microscopy were used to quantify retreat rates and analyze topography changes on surfaces with different orientations as dissolution proceeds up to 468 h. A NaClO4 (0.05 M) solution with pH 3.6 which was far from equilibrium relative to CaF2 was used. Measured dissolution rates depend directly on the orientation of the exposed planes. The {111} is the most stable plane with a dissolution rate of (1.2 +/- 0.8) x 10(-9) mol m(-2) s(-1), and {112} the least stable plane with a dissolution rate 33 times faster that {111}. Surfaces that expose both Ca and F atoms in the same plane dissolve faster. Dissolution rates were found to be correlated to surface orientation which is characterized by a specific surface chemistry and therefore related to surface energy. It is proposed that every surface is characterized by the relative proportions of the three reference planes {111}, {100} and {110}, and by the high energy sites at their interceptions. Based on the different dissolution rates observed we propose a dissolution model to explain changes of topography during dissolution. Surfaces with slower dissolution rate, and inferred lower surface energy, tend to form while dissolution proceeds leading to an increase of roughness and surface area. This adjustment of the surface suggests that dissolution rates during early stages of dissolution are different from the later stages. The time-dependency of this dynamic system needs to be taken into consideration when predicting long-term dissolution rates.

  • 5.
    Godinho, José R. A.
    et al.
    Stockholm University, Faculty of Science, Department of Geological Sciences. Oak Ridge National Laboratory, USA.
    Piazolo, Sandra
    Stockholm University, Faculty of Science, Department of Geological Sciences. Macquarie University, Australia.
    Balic-Zunic, T.
    Importance of surface structure on dissolution of fluorite: Implications for surface dynamics and dissolution rates2014In: Geochimica et Cosmochimica Acta, ISSN 0016-7037, E-ISSN 1872-9533, Vol. 126, p. 398-410Article in journal (Refereed)
    Abstract [en]

    Dissolution rates are usually calculated as a function of surface area, which is assumed to remain constant ignoring the changes occurring on the surface during dissolution. Here we present a study of how topography of natural fluorite surfaces with different orientation changes during up to 3200 h of dissolution. Results are analyzed in terms of changes in surface area, surface reactivity and dissolution rates. All surfaces studied present fast changes in topography during the initial 200 h of dissolution. The controlling factors that cause the development of topography are the stability of the step edges forming the initial surface and its inclination to the closest stable planes, which are specific for each surface orientation. During an initial dissolution regime dissolution rates decrease significantly, even though the total surface area increases. During a second dissolution regime, some surfaces continue to present significant changes in topography, while for others the topography tends to remain approximately constant. The observed variation of dissolution rates are attributed to a decrease of the density of step edges on the surface and the continuous increase in exposure of more stable surfaces. Calculations of dissolution rates, which assume that dissolution rates are directly proportional to surface area, are not valid for the type of surfaces studied. Instead, to develop accurate kinetic dissolution models and more realistic stochastic dissolution simulations the surface reactivity, determined by the relative stability of the planes and type of edges that constitute a surface needs to be considered. Significant differences between dissolution rates calculated based on surface area alone, and based on surface reactivity are expected for materials with the fluorite structure.

  • 6.
    Godinho, José R. A.
    et al.
    Stockholm University, Faculty of Science, Department of Geological Sciences. Oak Ridge National Laboratory, USA.
    Piazolo, Sandra
    Stockholm University, Faculty of Science, Department of Geological Sciences. Macquarie University, Australia.
    Evans, L.
    Simulation of surface dynamics during dissolution as a function of the surface orientation: Implications for non-constant dissolution rates2014In: Earth and Planetary Science Letters, ISSN 0012-821X, E-ISSN 1385-013X, Vol. 408, p. 163-170Article in journal (Refereed)
    Abstract [en]

    An important problem in geochemistry is the understanding of how changes occurring on a surface during dissolution affect the variability of measured dissolution rates. In this study a new approach to study the effect of surface dynamics on dissolution rates is tested by coupling experimental data with a numerical model that simulates the retreat of surface profiles during dissolution. We present specific results from the simulation of dissolution of fluorite surfaces. The equations that determine the retreat of a surface are based on experimentally obtained equations that relate the retreat rate of a surface to a single variable, the crystallographic orientation of the surface. Our results show that depending on the starting orientation, different types of topography are developed, similar to those observed experimentally. During the initial dissolution phase, changes of topography are rapid and associated with fast dissolution rates. The progressively slower dissolution rates are coupled with the development of surface segments with orientations that dissolve at a slower rate. Consequently, the overall retreat rate of a profile decreases during the simulation, and tends to a near-constant value. The results show a close relationship between dissolution rates, surface orientation and surface dynamics, which suggests that the dissolution rate of a specific mineral phase is not constant but varies with dissolution time and surface structure. This variability needs to be considered in the evaluation of experimentally derived dissolution rates, future dissolution experiments, and predictive kinetic models of dissolution.

  • 7.
    Godinho, José R. A.
    et al.
    Stockholm University, Faculty of Science, Department of Geological Sciences.
    Piazolo, Sandra
    Stockholm University, Faculty of Science, Department of Geological Sciences.
    Stennett, Martin C.
    Hyatt, Neil C.
    Sintering of CaF2 pellets as nuclear fuel analog for surface stability experiments2011In: Journal of Nuclear Materials, ISSN 0022-3115, E-ISSN 1873-4820, Vol. 419, no 1-3, p. 46-51Article in journal (Refereed)
    Abstract [en]

    To enable a detailed study of the influence of microstructure and surface properties on the stability of spent nuclear fuel, it is necessary to produce analogs that closely resemble nuclear fuel in terms of crystallography and microstructure. One such analog can be obtained by sintering CaF2 powder.

    This paper reports the microstructures obtained after sintering CaF2 powders at temperatures up to 1240 °C. Pellets with microstructure, density and pore structure similar to that of UO2 spent nuclear fuel pellets were obtained in the temperature range between 900 °C and 1000 °C. When CaF2 was sintered above 1100 °C the formation of CaO at the grain boundaries caused the disintegration of the pellet due to hydration occurring after sintering.

    First results from a novel set-up of dissolution experiments show that changes in roughness, dissolution rate and etch pit shape of fluorite surfaces are strongly dependent on the crystallographic orientation of the expose surface. Consequently, the differences observed for each orientation will affect the overall dissolution rate and will lead to uncertainties in the estimation of dissolution rates of spent nuclear fuel.

  • 8.
    Godinho, José Ricardo Assunção
    Stockholm University, Faculty of Science, Department of Geological Sciences.
    A surface approach to understanding the dissolution of fluorite type materials: Implications for mineral dissolution kinetic models2013Doctoral thesis, comprehensive summary (Other academic)
    Abstract [en]

    Traditional dissolution models are based in the analyses of bulk solution compositions and ignore the fact that different sites of a surface dissolve at different rates. Consequently, the variation of surface area and surface reactivity during dissolution are not considered for the calculation of the overall dissolution rate, which is expected to remain constant with time. The results presented here show the limitations of this approach suggesting that dissolution rates should be calculated as a function of an overall surface reactivity term that accounts for the reactivity of each of the sites that constitute the surface. In contrast to previous studies, here the focus is put on studying the surface at different dissolution times. Significant changes in surface topography of CaF2 were observed during the initial seconds and up to 3200 hours of dissolution. The observed changes include the increase of surface area and progressive exposure of the most stable planes, with consequent decrease in overall reactivity of the surface. The novelty of a proposed dissolution model for fluorite surfaces, when compared with traditional dissolution models, is that it differentiates the reactivity of each characteristic site on a surface, e.g. plane or step edge, and considers the time dynamics. The time dependency of dissolution rates is a major factor of uncertainty when calculating long term dissolution rates using equations derived from dissolution experiments running for short periods of time and using materials with different surface properties. An additional factor of uncertainty is that the initial dissolution times are the most dynamic periods of dissolution, when significant variations of surface area and reactivity occur. The results are expected to have impact in the field of nuclear waste management and to the larger geological and material science community.

  • 9. Maldonado, P.
    et al.
    Godinho, José
    Stockholm University, Faculty of Science, Department of Geological Sciences.
    Evins, L. Z.
    Oppeneeer, P. M.
    Ab Initio Prediction of Surface Stability of Fluorite Materials and Experimental Verification2013In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 117, no 13, p. 6639-6650Article in journal (Refereed)
    Abstract [en]

    Utilizing first-principle simulations [based on density functional theory (DFT) corrected for on-site Coulomb interactions (DFT+U)], we develop a model to explain the experimental stability in solution of materials having the fluorite structure, such as CaF2 and CeO2. It is shown that the stability of a surface is mainly dependent on its atomic structure and the presence of sites where atoms are deficiently bonded. Using as reference planes the surfaces with low surface formation energies, viz., (111), (100), and (110), our results reveal the relation between the surface energy of any Miller-indexed plane and the surface energy of those reference planes, being dependent on the fluorite surface structure only. Therefore, they follow the same trend for CaF2 and CeO2. Comparison with experimental results shows a correlation between the trends of dry surface energies and surface stabilities during dissolution of both CaF2 and CeO2, even though the chemical processes of dissolution of CeO2 and CaF2 are different. A deviation between ab initio predictions and experiments for some surfaces highlights the sensitivity of the developed model to the treatment of surface dipolar moments.

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