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Sample records for hydride nucleation kinetics

  1. Erbium hydride decomposition kinetics.

    Energy Technology Data Exchange (ETDEWEB)

    Ferrizz, Robert Matthew

    2006-11-01

    Thermal desorption spectroscopy (TDS) is used to study the decomposition kinetics of erbium hydride thin films. The TDS results presented in this report are analyzed quantitatively using Redhead's method to yield kinetic parameters (E{sub A} {approx} 54.2 kcal/mol), which are then utilized to predict hydrogen outgassing in vacuum for a variety of thermal treatments. Interestingly, it was found that the activation energy for desorption can vary by more than 7 kcal/mol (0.30 eV) for seemingly similar samples. In addition, small amounts of less-stable hydrogen were observed for all erbium dihydride films. A detailed explanation of several approaches for analyzing thermal desorption spectra to obtain kinetic information is included as an appendix.

  2. Decomposition kinetics of plutonium hydride

    Energy Technology Data Exchange (ETDEWEB)

    Haschke, J.M.; Stakebake, J.L.

    1979-01-01

    Kinetic data for decomposition of PuH/sub 1/ /sub 95/ provides insight into a possible mechanism for the hydriding and dehydriding reactions of plutonium. The fact that the rate of the hydriding reaction, K/sub H/, is proportional to P/sup 1/2/ and the rate of the dehydriding process, K/sub D/, is inversely proportional to P/sup 1/2/ suggests that the forward and reverse reactions proceed by opposite paths of the same mechanism. The P/sup 1/2/ dependence of hydrogen solubility in metals is characteristic of the dissociative absorption of hydrogen; i.e., the reactive species is atomic hydrogen. It is reasonable to assume that the rates of the forward and reverse reactions are controlled by the surface concentration of atomic hydrogen, (H/sub s/), that K/sub H/ = c'(H/sub s/), and that K/sub D/ = c/(H/sub s/), where c' and c are proportionality constants. For this surface model, the pressure dependence of K/sub D/ is related to (H/sub s/) by the reaction (H/sub s/) reversible 1/2H/sub 2/(g) and by its equilibrium constant K/sub e/ = (H/sub 2/)/sup 1/2//(H/sub s/). In the pressure range of ideal gas behavior, (H/sub s/) = K/sub e//sup -1/(RT)/sup -1/2/ and the decomposition rate is given by K/sub D/ = cK/sub e/(RT)/sup -1/2/P/sup 1/2/. For an analogous treatment of the hydriding process with this model, it can be readily shown that K/sub H/ = c'K/sub e//sup -1/(RT)/sup -1/2/P/sup 1/2/. The inverse pressure dependence and direct temperature dependence of the decomposition rate are correctly predicted by this mechanism which is most consistent with the observed behavior of the Pu--H system.

  3. Lithium hydride hydrolysis: experimental and kinetic study

    International Nuclear Information System (INIS)

    Charton, S.; Maupoix, C.; Brevet, A.; Delaunay, F.; Heintz, O.; Saviot, L.

    2006-01-01

    In this work has been studied the contribution of various analyses techniques in the framework, on the one hand of revealing the mechanisms implied in lithium hydride hydrolysis, and on the other hand of studying the kinetics of hydrogen production. Among the methods recently investigated, Raman spectroscopy, XPS and SIMS seem to be particularly attractive. (O.M.)

  4. The role of chemical free energy and elastic strain in the nucleation of zirconium hydride

    International Nuclear Information System (INIS)

    Barrow, A.T.W.; Toffolon-Masclet, C.; Almer, J.; Daymond, M.R.

    2013-01-01

    In this work a combination of synchrotron X-ray diffraction and thermodynamic modelling has been used to study the dissolution and precipitation of zirconium hydride in α-Zr establishing the role of elastic misfit strain and chemical free energy in the α → α + δ phase transformation. The nucleation of zirconium hydride is dominated by the chemical free energy where the chemical driving force for hydride precipitation is proportional to the terminal-solid solubility for precipitation and can be predicted by a function that is analogous to the universal nucleation parameter for the bainite transformation in ferrous alloys. The terminal-solid solubility for precipitation was found to be kinetically limited ⩾287 °C at a cooling rate of 5 °C min −1 or greater. The terminal solubilities were established using an offset method applied to the lattice strain data where a resolution of ∼10 wppm H can be achieved in the 〈c〉-direction. This is aided by the introduction of intra-granular strains in the 〈c〉-direction during cooling as a result of the thermal expansion anisotropy which increases the anisotropy associated with the misfitting H atoms within the α-Zr lattice

  5. The influence of surface morphology and oxide microstructure on the nucleation and growth of uranium hydride on alpha uranium

    International Nuclear Information System (INIS)

    Hanrahan, R.J. Jr.; Hawley, M.E.; Brown, G.W.

    1998-01-01

    While the bulk kinetics of the uranium-hydrogen reaction are well understood, the mechanisms underlying the initial nucleation of uranium hydride on uranium remain controversial. In this study, the authors have employed environmental cell optical microscopy, Scanning Electron Microscopy (SEM) and Atomic Force Microscopy, (AFM) in an attempt to relate the structure of the surface and the microstructure of the substrate with the susceptibility and site of hydride nucleation. Samples have been investigated with varying grain size, inclusion (carbide) concentration, and thermal history. There is a clear correlation to heat treatment immediately prior to hydrogen exposure. Susceptibility to hydride formation also appears to be related to impurities in the uranium. The oxidized surface is very complex, exhibiting wide variations in thickness and topography between samples, between grains in the same sample, and within individual grains. It is, however, very difficult to relate this fine scale variability to the relatively sparse hydride initiation sites. Therefore, the surface oxide layer itself does not appear to control the sites where hydride attack is initiated, although it must play a role in the induction period prior to hydride initiation

  6. The influence of surface morphology and oxide microstructure on the nucleation and growth of uranium hydride on alpha uranium

    Energy Technology Data Exchange (ETDEWEB)

    Hanrahan, R.J. Jr.; Hawley, M.E.; Brown, G.W. [Los Alamos National Lab., NM (United States). Materials Science and Technology Div.

    1998-12-31

    While the bulk kinetics of the uranium-hydrogen reaction are well understood, the mechanisms underlying the initial nucleation of uranium hydride on uranium remain controversial. In this study the authors have employed environmental cell optical microscopy, Scanning Electron Microscopy (SEM) and Atomic Force Microscopy, (AFM) in an attempt to relate the structure of the surface and the microstructure of the substrate with the susceptibility and site of hydride nucleation. Samples have been investigated with varying grain size, inclusion (carbide) concentration, and thermal history. There is a clear correlation to heat treatment immediately prior to hydrogen exposure. Susceptibility to hydride formation also appears to be related to impurities in the uranium. The oxidized surface is very complex, exhibiting wide variations in thickness and topography between samples, between grains in the same sample, and within individual grains. It is, however, very difficult to relate this fine scale variability to the relatively sparse hydride initiation sites. Therefore, the surface oxide layer itself does not appear to control the sites where hydride attack is initiated, although it must play a role in the induction period prior to hydride initiation.

  7. The influence of surface morphology and oxide microstructure on the nucleation and growth of uranium hydride on alpha uranium

    Energy Technology Data Exchange (ETDEWEB)

    Hanrahan, R.J. Jr.; Hawley, M.E.; Brown, G.W.

    1998-12-31

    While the bulk kinetics of the uranium-hydrogen reaction are well understood, the mechanisms underlying the initial nucleation of uranium hydride on uranium remain controversial. In this study, the authors have employed environmental cell optical microscopy, Scanning Electron Microscopy (SEM) and Atomic Force Microscopy, (AFM) in an attempt to relate the structure of the surface and the microstructure of the substrate with the susceptibility and site of hydride nucleation. Samples have been investigated with varying grain size, inclusion (carbide) concentration, and thermal history. There is a clear correlation to heat treatment immediately prior to hydrogen exposure. Susceptibility to hydride formation also appears to be related to impurities in the uranium. The oxidized surface is very complex, exhibiting wide variations in thickness and topography between samples, between grains in the same sample, and within individual grains. It is, however, very difficult to relate this fine scale variability to the relatively sparse hydride initiation sites. Therefore, the surface oxide layer itself does not appear to control the sites where hydride attack is initiated, although it must play a role in the induction period prior to hydride initiation.

  8. Effects of gas phase impurities on the topochemical-kinetic behaviour of uranium hydride development

    International Nuclear Information System (INIS)

    Bloch, J.; Brami, D.; Kremner, A.; Mintz, M.H.; Ben-Gurion Univ. of the Negev, Beersheba

    1988-01-01

    The hydriding kinetics of bulk uranium and U-0.1 wt.% Cr, in the presence of oxidizing gaseous impurities (oxygen and CO), were studied by combined rate measurements and metallographic examinations of partially reacted samples. The effect of the gaseous impurity (type and concentration) was examined metallographically, and the kinetic data were discussed in relation to these examinations. Below about 100 0 C the reaction of uranium with pure hydrogen consists of the following sequence of steps: (i) Surface nucleation; (ii) homogeneous growth (pitting); (iii) relatively fast lateral growth leading to the formation of a reaction front which penetrates into the sample at a constant rate. The effects of oxygen and CO on the hydriding kinetics were related to their abilities to block hydrogen penetration into the uranium. Thus, it was found that oxygen affects only the penetration through the oxide layer, whereas CO affects the penetration through both the oxide and hydride layers. (orig.)

  9. Probabilistic approach to lysozyme crystal nucleation kinetics.

    Science.gov (United States)

    Dimitrov, Ivaylo L; Hodzhaoglu, Feyzim V; Koleva, Dobryana P

    2015-09-01

    Nucleation of lysozyme crystals in quiescent solutions at a regime of progressive nucleation is investigated under an optical microscope at conditions of constant supersaturation. A method based on the stochastic nature of crystal nucleation and using discrete time sampling of small solution volumes for the presence or absence of detectable crystals is developed. It allows probabilities for crystal detection to be experimentally estimated. One hundred single samplings were used for each probability determination for 18 time intervals and six lysozyme concentrations. Fitting of a particular probability function to experimentally obtained data made possible the direct evaluation of stationary rates for lysozyme crystal nucleation, the time for growth of supernuclei to a detectable size and probability distribution of nucleation times. Obtained stationary nucleation rates were then used for the calculation of other nucleation parameters, such as the kinetic nucleation factor, nucleus size, work for nucleus formation and effective specific surface energy of the nucleus. The experimental method itself is simple and adaptable and can be used for crystal nucleation studies of arbitrary soluble substances with known solubility at particular solution conditions.

  10. Activation and discharge kinetics of metal hydride electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Johnsen, Stein Egil

    2003-07-01

    Potential step chronoamperometry and Electrochemical Impedance Spectroscopy (eis) measurements were performed on single metal hydride particles. For the {alpha}-phase, the bulk diffusion coefficient and the absorption/adsorption rate parameters were determined. Materials produced by atomisation, melt spinning and conventional casting were investigated. The melt spun and conventional cast materials were identical and the atomised material similar in composition. The particles from the cast and the melt spun material were shaped like parallelepipeds. A corresponding equation, for this geometry, for diffusion coupled to an absorption/adsorption reaction was developed. It was found that materials produced by melt spinning exhibited lower bulk diffusion (1.7E-14 m2/s) and absorption/adsorption reaction rate (1.0E-8 m/s), compared to materials produced by conventionally casting (1.1E-13 m2/s and 5.5E-8 m/s respectively). In addition, the influence of particle active surface and relative diffusion length were discussed. It was concluded that there are uncertainties connected to these properties, which may explain the large distribution in the kinetic parameters measured on metal hydride particles. Activation of metal hydride forming materials has been studied and an activation procedure, for porous electrodes, was investigated. Cathodic polarisation of the electrode during a hot alkaline surface treatment gave the maximum discharge capacity on the first discharge of the electrode. The studied materials were produced by gas atomisation and the spherical shape was retained during the activation. Both an AB{sub 5} and an AB{sub 2} alloy was successfully activated and discharge rate properties determined. The AB{sub 2} material showed a higher maximum discharge capacity, but poor rate properties, compared to the AB{sub 5} material. Reduction of surface oxides, and at the same time protection against corrosion of active metallic nickel, can explain the satisfying results of

  11. Nucleation and Growth Kinetics from LaMer Burst Data.

    Science.gov (United States)

    Chu, Daniel B K; Owen, Jonathan S; Peters, Baron

    2017-10-12

    In LaMer burst nucleation, the individual nucleation events happen en masse, quasi-simultaneously, and at nearly identical homogeneous conditions. These properties make LaMer burst nucleation important for applications that require monodispersed particles and also for theoretical analyses. Sugimoto and co-workers predicted that the number of nuclei generated during a LaMer burst depends only on the solute supply rate and the growth rate, independent of the nucleation kinetics. Some experiments confirm that solute supply kinetics control the number of nuclei, but flaws in the original theoretical analysis raise questions about the predicted roles of growth and nucleation kinetics. We provide a rigorous analysis of the coupled equations that govern concentrations of nuclei and solutes. Our analysis confirms that the number of nuclei is largely determined by the solute supply and growth rates, but our predicted relationship differs from that of Sugimoto et al. Moreover, we find that additional nucleus size dependent corrections should emerge in systems with slow growth kinetics. Finally, we show how the nucleation kinetics determine the particle size distribution. We suggest that measured particle size distributions might therefore provide ways to test theoretical models of homogeneous nucleation kinetics.

  12. Modelling the role of compositional fluctuations in nucleation kinetics

    International Nuclear Information System (INIS)

    Ženíšek, J.; Kozeschnik, E.; Svoboda, J.; Fischer, F.D.

    2015-01-01

    The classical nucleation theory of precipitate nucleation in interstitial/substitutional alloys is applied to account for the influence of spatial A–B composition fluctuations in an A–B–C matrix on the kinetics of nucleation of (A,B) 3 C precipitates. A and B are substitutional elements in the matrix and C is an interstitial component, assumed to preferentially bind to B atoms. All lattice sites are considered as potential nucleation sites. The fluctuations of chemical composition result in a local variation of the nucleation probability. The nucleation sites are eliminated from the system if they are located in a C-depleted diffusion zone belonging to an already nucleated and growing precipitate. The chemistry is that of an Fe–Cr–C system, and the specific interface energy is treated as a free parameter. Random, regular and homogeneous A–B distributions in the matrix are simulated and compared for various values of the interface energy. An increasing enhancement of the role of compositional fluctuations on nucleation kinetics with increasing interface energy and decreasing chemical driving force is observed

  13. Focus: Nucleation kinetics of shear bands in metallic glass.

    Science.gov (United States)

    Wang, J Q; Perepezko, J H

    2016-12-07

    The development of shear bands is recognized as the primary mechanism in controlling the plastic deformability of metallic glasses. However, the kinetics of the nucleation of shear bands has received limited attention. The nucleation of shear bands in metallic glasses (MG) can be investigated using a nanoindentation method to monitor the development of the first pop-in event that is a signature of shear band nucleation. The analysis of a statistically significant number of first pop-in events demonstrates the stochastic behavior that is characteristic of nucleation and reveals a multimodal behavior associated with local spatial heterogeneities. The shear band nucleation rate of the two nucleation modes and the associated activation energy, activation volume, and site density were determined by loading rate experiments. The nucleation activation energy is very close to the value that is characteristic of the β relaxation in metallic glass. The identification of the rate controlling kinetics for shear band nucleation offers guidance for promoting plastic flow in metallic glass.

  14. A unified kinetic approach to binary nucleation

    Energy Technology Data Exchange (ETDEWEB)

    Kevrekidis, P.G. [Department of Physics, Rutgers University, 136 Frelinghuysen Road]|[E.O.H.S.I., Rutgers University]|[UMDNJ, 170 Frelinghuysen Road, Piscataway, New Jersey 08854-8019 (United States); Lazaridis, M. [Norwegian Institute for Air Research (NILU), Instittutvein 18, P. O. Box 100, N-2007 Kjeller (Norway); Drossinos, Y. [European Commission, Joint Research Centre, I-21020 Ispra (Vatican City State, Holy See) (Italy); Georgopoulos, P.G. [E.O.H.S.I., Rutgers University]|[UMDNJ, 170 Frelinghuysen Road, Piscataway, New Jersey 08854 (United States)

    1999-11-01

    Two different methods to calculate the steady-state nucleation rate in heteromolecular systems proposed by Stauffer (1976) and Langer (1969) are analyzed. Their mathematical equivalence is explicitly demonstrated, thereby obtaining a generic expression for the rate of binary nucleation. Its numerical evaluation does not entail rotation of the coordinate system at the saddle point, but it only requires data in the natural coordinate system of number fluctuations, namely molecular impingement rates, the droplet free energy and its second order derivatives at the saddle point, and the total density of condensible vapors. {copyright} {ital 1999 American Institute of Physics.}

  15. Crystal nucleation kinetics in confined systems

    Czech Academy of Sciences Publication Activity Database

    Kožíšek, Zdeněk

    2013-01-01

    Roč. 15, č. 12 (2013), 2269-2274 ISSN 1466-8033 R&D Projects: GA ČR GAP108/12/0891 Institutional support: RVO:68378271 Keywords : nucleation * phase transtion Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 3.858, year: 2013

  16. Hydrogen desorption kinetics from zirconium hydride and zirconium metal in vacuum

    International Nuclear Information System (INIS)

    Hu, Xunxiang; Terrani, Kurt A.; Wirth, Brian D.

    2014-01-01

    The kinetics of hydrogen desorption from zirconium hydride is important in many nuclear design and safety applications. In this paper, a coordinated experimental and modeling study has been used to explicitly demonstrate the applicability of existing kinetic theories for hydrogen desorption from zirconium hydride and α-zirconium. A static synthesis method was used to produce δ-zirconium hydride, and the crystallographic phases of the zirconium hydride were confirmed by X-ray diffraction (XRD). Three obvious stages, involving δ-zirconium hydride, a two-phase region, and α-zirconium, were observed in the hydrogen desorption spectra of two zirconium hydride specimens with H/Zr ratios of 1.62 and 1.64, respectively, which were obtained using thermal desorption spectroscopy (TDS). A continuous, one-dimensional, two-phase moving boundary model, coupled with the zero- and second-order kinetics of hydrogen desorption from δ-zirconium hydride and α-zirconium, respectively, has been developed to reproduce the TDS experimental results. A comparison of the modeling predictions with the experimental results indicates that a zero-order kinetic model is valid for description of hydrogen flux away from the δ-hydride phase, and that a second-order kinetic model works well for hydrogen desorption from α-Zr if the activation energy of desorption is optimized to be 70% of the value reported in the literature

  17. Quantifying the Effect of Stress on Sn Whisker Nucleation Kinetics

    Science.gov (United States)

    Chason, Eric; Vasquez, Justin; Pei, Fei; Jain, Nupur; Hitt, Andrew

    2018-01-01

    Although Sn whiskers have been studied extensively, there is still a need to understand the driving forces behind whisker nucleation and growth. Many studies point to the role of stress, but confirming this requires a quantitative comparison between controlled stress and the resulting whisker evolution. Recent experimental studies applied stress to a Sn layer via thermal cycling and simultaneously monitored the evolution of the temperature, stress and number of nuclei. In this work, we analyze these nucleation kinetics in terms of classical nucleation theory to relate the observed behavior to underlying mechanisms including a stress dependent activation energy and a temperature and stress-dependent whisker growth rate. Non-linear least squares fitting of the data taken at different temperatures and strain rates to the model shows that the results can be understood in terms of stress decreasing the barrier for whisker nucleation.

  18. Binary nucleation kinetics. III. Transient behavior and time lags

    International Nuclear Information System (INIS)

    Wyslouzil, B.E.; Wilemski, G.

    1996-01-01

    Transient binary nucleation is more complex than unary because of the bidimensionality of the cluster formation kinetics. To investigate this problem qualitatively and quantitatively, we numerically solved the birth-death equations for vapor-to-liquid phase transitions. Our previous work showed that the customary saddle point and growth path approximations are almost always valid in steady state gas phase nucleation and only fail if the nucleated solution phase is significantly nonideal. Now, we demonstrate that in its early transient stages, binary nucleation rarely, if ever, occurs via the saddle point. This affects not only the number of particles forming but their composition and may be important for nucleation in glasses and other condensed mixtures for which time scales are very long. Before reaching the state of saddle point nucleation, most binary systems pass through a temporary stage in which the region of maximum flux extends over a ridge on the free energy surface. When ridge crossing nucleation is the steady state solution, it thus arises quite naturally as an arrested intermediate state that normally occurs in the development of saddle point nucleation. While the time dependent and steady state distributions of the fluxes and concentrations for each binary system are strongly influenced by the gas composition and species impingement rates, the ratio of nonequilibrium to equilibrium concentrations has a quasiuniversal behavior that is determined primarily by the thermodynamic properties of the liquid mixture. To test our quantitive results of the transient behavior, we directly calculated the time lag for the saddle point flux and compared it with the available analytical predictions. Although the analytical results overestimate the time lag by factors of 1.2-5, they should be adequate for purposes of planning experiments. We also found that the behavior of the saddle point time lag can indicate when steady state ridge crossing nucleation will occur

  19. Recent developments in the kinetic theory of nucleation.

    Science.gov (United States)

    Ruckenstein, E; Djikaev, Y S

    2005-12-30

    A review of recent progress in the kinetics of nucleation is presented. In the conventional approach to the kinetic theory of nucleation, it is necessary to know the free energy of formation of a new-phase particle as a function of its independent variables at least for near-critical particles. Thus the conventional kinetic theory of nucleation is based on the thermodynamics of the process. The thermodynamics of nucleation can be examined by using various approaches, such as the capillarity approximation, density functional theory, and molecular simulation, each of which has its own advantages and drawbacks. Relatively recently a new approach to the kinetics of nucleation was proposed [Ruckenstein E, Nowakowski B. J Colloid Interface Sci 1990;137:583; Nowakowski B, Ruckenstein E. J Chem Phys 1991;94:8487], which is based on molecular interactions and does not employ the traditional thermodynamics, thus avoiding such a controversial notion as the surface tension of tiny clusters involved in nucleation. In the new kinetic theory the rate of emission of molecules by a new-phase particle is determined with the help of a mean first passage time analysis. This time is calculated by solving the single-molecule master equation for the probability distribution function of a surface layer molecule moving in a potential field created by the rest of the cluster. The new theory was developed for both liquid-to-solid and vapor-to-liquid phase transitions. In the former case the single-molecule master equation is the Fokker-Planck equation in the phase space which can be reduced to the Smoluchowski equation owing to the hierarchy of characteristic time scales. In the latter case, the starting master equation is a Fokker-Planck equation for the probability distribution function of a surface layer molecule with respect to both its energy and phase coordinates. Unlike the case of liquid-to-solid nucleation, this Fokker-Planck equation cannot be reduced to the Smoluchowski equation

  20. A deformation and thermodynamic model for hydride precipitation kinetics in spent fuel cladding

    International Nuclear Information System (INIS)

    Stout, R.B.

    1989-10-01

    Hydrogen is contained in the Zircaloy cladding of spent fuel rods from nuclear reactors. All the spent fuel rods placed in a nuclear waste repository will have a temperature history that decreases toward ambient; and as a result, most all of the hydrogen in the Zircaloy will eventually precipitate as zirconium hydride platelets. A model for the density of hydride platelets is a necessary sub-part for predicting Zircaloy cladding failure rate in a nuclear waste repository. A model is developed to describe statistically the hydride platelet density, and the density function includes the orientation as a physical attribute. The model applies concepts from statistical mechanics to derive probable deformation and thermodynamic functionals for cladding material response that depend explicitly on the hydride platelet density function. From this model, hydride precipitation kinetics depend on a thermodynamic potential for hydride density change and on the inner product of a stress tensor and a tensor measure for the incremental volume change due to hydride platelets. The development of a failure response model for Zircaloy cladding exposed to the expected conditions in a nuclear waste repository is supported by the US DOE Yucca Mountain Project. 19 refs., 3 figs

  1. Oxidation kinetics of hydride-bearing uranium metal corrosion products

    Science.gov (United States)

    Totemeier, Terry C.; Pahl, Robert G.; Frank, Steven M.

    The oxidation behavior of hydride-bearing uranium metal corrosion products from Zero Power Physics Reactor (ZPPR) fuel plates was studied using thermo-gravimetric analysis (TGA) in environments of Ar-4%O 2, Ar-9%O 2, and Ar-20%O 2. Ignition of corrosion product samples from two moderately corroded plates was observed between 125°C and 150°C in all environments. The rate of oxidation above the ignition temperature was found to be dependent only on the net flow rate of oxygen in the reacting gas. Due to the higher net oxygen flow rate, burning rates increased with increasing oxygen concentration. Oxidation rates below the ignition temperature were much slower and decreased with increasing test time. The hydride contents of the TGA samples from the two moderately corroded plates, determined from the total weight gain achieved during burning, were 47-61 wt% and 29-39 wt%. Samples from a lightly corroded plate were not reactive; X-ray diffraction (XRD) confirmed that they contained little hydride.

  2. Oxidation kinetics of hydride-bearing uranium metal corrosion products

    International Nuclear Information System (INIS)

    Totemeier, T.C.; Pahl, R.G.; Frank, S.M.

    1998-01-01

    The oxidation behavior of hydride-bearing uranium metal corrosion products from zero power physics reactor (ZPPR) fuel plates was studied using thermo-gravimetric analysis (TGA) in environments of Ar-4%O 2 , Ar-9%O 2 , and Ar-20%O 2 . Ignition of corrosion product samples from two moderately corroded plates was observed between 125 C and 150 C in all environments. The rate of oxidation above the ignition temperature was found to be dependent only on the net flow rate of oxygen in the reacting gas. Due to the higher net oxygen flow rate, burning rates increased with increasing oxygen concentration. Oxidation rates below the ignition temperature were much slower and decreased with increasing test time. The hydride contents of the TGA samples from the two moderately corroded plates, determined from the total weight gain achieved during burning, were 47-61 wt% and 29-39 wt%. Samples from a lightly corroded plate were not reactive; X-ray diffraction (XRD) confirmed that they contained little hydride. (orig.)

  3. In-situ study of hydriding kinetics in Pd-based thin film systems

    Energy Technology Data Exchange (ETDEWEB)

    Delmelle, Renaud; Proost, Joris [Univ. Catholique de Louvain, Louvain-la-Neuve (Belgium). Div. of Materials and Process Engineering

    2010-07-01

    The hydriding kinetics of Pd thin films has been investigated in detail. The key experimental technique used in this work consists of a high resolution curvature measurement setup, which continuously monitors the reflections of multiple laser beams coming off a cantilevered sample. After mounting the sample inside a vacuum chamber, a H-containing gas mixture is introduced to instantaneously generate a given hydrogen partial pressure (p{sub H2}) inside the chamber. The resulting interaction of H with the Pd layer then leads to a volume expansion of the thin film system. This induces in turn changes in the sample curvature as a result of internal stresses developing in the Pd film during a hydriding cycle. Based on such curvature date obtained in-situ at different p{sub H2}, a two-step model for the kinetics of Pd-hydride formation has been proposed and expressions for the hydrogen adsorption and absorption velocities have been derived. The rate-limiting steps have been identified by studying the p{sub H2}-dependence of these velocities. Furthermore, from our in-situ experimental data, relevant kinetic parameters have been calculated. The effect of dry air exposure of the Pd films on the hydriding kinetics has been considered as well. (orig.)

  4. Kinetic behaviour of low-Co AB5-type metal hydride electrodes

    International Nuclear Information System (INIS)

    Tliha, M.; Boussami, S.; Mathlouthi, H.; Lamloumi, J.; Percheron-Guegan, A.

    2010-01-01

    The kinetic behaviour of the LaNi 3.55 Mn 0.4 Al 0.3 Co 0.4 Fe 0.35 metal hydride, used as a negative electrode in the nickel/metal hydride (Ni/MH) batteries, was investigated using electrochemical impedance spectroscopy (EIS) at different state of charge (SOC). Impedance measurements were performed in the frequency range from 50 kHz to 1 mHz. Electrochemical impedance spectrum of the metal hydride electrode was interpreted by an equivalent circuit including the different electrochemical processes taking place on the interface between the MH electrode and the electrolyte. Electrochemical kinetic parameters such as the charge-transfer resistance R tc , the exchange current density I 0 and the hydrogen diffusion coefficient D H were determined at different state of charge. The results of EIS measurements indicate that the electrochemical reaction activity of the LaNi 3.55 Mn 0.4 Al 0.3 Co 0.4 Fe 0.35 metal hydride electrode was markedly improved with increasing state of charge (SOC). The transformation α-β is probably a limiting step in the mechanisms of hydrogenation of metal hydride electrode.

  5. Kinetics of the isothermal decomposition of zirconium hydride: terminal solid solubility for precipitation and dissolution

    Science.gov (United States)

    Denisov, E. A.; Kompaniets, T. N.; Voyt, A. P.

    2018-05-01

    The hydrogen permeation technique in the surface-limited regime (SLR) was first used to study the isothermal decomposition of zirconium hydride. It is shown that under isothermal conditions, the hydrogen terminal solid solubility in the α-phase for hydride precipitation (TSSp) and dissolution (TSSd) differ only by 6%, in contrast to the 20-30% indicated in the available literature. It is demonstrated that even the minimum heating/cooling rate (1 C/min) used in the traditional methods of studying TSSp and TSSd is too high to exclude the effect of kinetics on the results obtained.

  6. Titanium tritide radioisotope heat source development: palladium-coated titanium hydriding kinetics and tritium loading tests

    International Nuclear Information System (INIS)

    Van Blarigan, Peter; Shugard, Andrew D.; Walters, R. Tom

    2012-01-01

    We have found that a 180 nm palladium coating enables titanium to be loaded with hydrogen isotopes without the typical 400-500 C vacuum activation step. The hydriding kinetics of Pd coated Ti can be described by the Mintz-Bloch adherent film model, where the rate of hydrogen absorption is controlled by diffusion through an adherent metal-hydride layer. Hydriding rate constants of Pd coated and vacuum activated Ti were found to be very similar. In addition, deuterium/tritium loading experiments were done on stacks of Pd coated Ti foil in a representative-size radioisotope heat source vessel. The experiments demonstrated that such a vessel could be loaded completely, at temperatures below 300 C, in less than 10 hours, using existing department-of-energy tritium handling infrastructure.

  7. Kinetics of thermal decomposition of aluminium hydride: I-non-isothermal decomposition under vacuum and in inert atmosphere (argon)

    International Nuclear Information System (INIS)

    Ismail, I.M.K.; Hawkins, T.

    2005-01-01

    Recently, interest in aluminium hydride (alane) as a rocket propulsion ingredient has been renewed due to improvements in its manufacturing process and an increase in thermal stability. When alane is added to solid propellant formulations, rocket performance is enhanced and the specific impulse increases. Preliminary work was performed at AFRL on the characterization and evaluation of two alane samples. Decomposition kinetics were determined from gravimetric TGA data and volumetric vacuum thermal stability (VTS) results. Chemical analysis showed the samples had 88.30% (by weight) aluminium and 9.96% hydrogen. The average density, as measured by helium pycnometery, was 1.486 g/cc. Scanning electron microscopy showed that the particles were mostly composed of sharp edged crystallographic polyhedral such as simple cubes, cubic octahedrons and hexagonal prisms. Thermogravimetric analysis was utilized to investigate the decomposition kinetics of alane in argon atmosphere and to shed light on the mechanism of alane decomposition. Two kinetic models were successfully developed and used to propose a mechanism for the complete decomposition of alane and to predict its shelf-life during storage. Alane decomposes in two steps. The slowest (rate-determining) step is solely controlled by solid state nucleation of aluminium crystals; the fastest step is due to growth of the crystals. Thus, during decomposition, hydrogen gas is liberated and the initial polyhedral AlH 3 crystals yield a final mix of amorphous aluminium and aluminium crystals. After establishing the kinetic model, prediction calculations indicated that alane can be stored in inert atmosphere at temperatures below 10 deg. C for long periods of time (e.g., 15 years) without significant decomposition. After 15 years of storage, the kinetic model predicts ∼0.1% decomposition, but storage at higher temperatures (e.g. 30 deg. C) is not recommended

  8. Tailoring Thermodynamics and Kinetics for Hydrogen Storage in Complex Hydrides towards Applications.

    Science.gov (United States)

    Liu, Yongfeng; Yang, Yaxiong; Gao, Mingxia; Pan, Hongge

    2016-02-01

    Solid-state hydrogen storage using various materials is expected to provide the ultimate solution for safe and efficient on-board storage. Complex hydrides have attracted increasing attention over the past two decades due to their high gravimetric and volumetric hydrogen densities. In this account, we review studies from our lab on tailoring the thermodynamics and kinetics for hydrogen storage in complex hydrides, including metal alanates, borohydrides and amides. By changing the material composition and structure, developing feasible preparation methods, doping high-performance catalysts, optimizing multifunctional additives, creating nanostructures and understanding the interaction mechanisms with hydrogen, the operating temperatures for hydrogen storage in metal amides, alanates and borohydrides are remarkably reduced. This temperature reduction is associated with enhanced reaction kinetics and improved reversibility. The examples discussed in this review are expected to provide new inspiration for the development of complex hydrides with high hydrogen capacity and appropriate thermodynamics and kinetics for hydrogen storage. © 2015 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Kinetics of heterogeneous nucleation of gas-atomized Sn-5 mass%Pb droplets

    International Nuclear Information System (INIS)

    Li Shu; Wu Ping; Zhou Wei; Ando, Teiichi

    2008-01-01

    A method for predicting the nucleation kinetics of gas-atomized droplets has been developed by combining models predicting the nucleation temperature of cooling droplets with a model simulating the droplet motion and cooling in gas atomization. Application to a Sn-5 mass%Pb alloy has yielded continuous-cooling transformation (CCT) diagrams for the heterogeneous droplet nucleation in helium gas atomization. Both internal nucleation caused by a catalyst present in the melt and surface nucleation caused by oxidation are considered. Droplets atomized at a high atomizing gas velocity get around surface oxidation and nucleate internally at high supercoolings. Low atomization gas velocities promote oxidation-catalyzed nucleation which leads to lower supercoolings. The developed method enables improved screening of atomized powders for critical applications where stringent control of powder microstructure is required

  10. Improved hydrogen sorption kinetics in wet ball milled Mg hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Meng, Li

    2011-05-04

    In this work, wet ball milling method is used in order to improve hydrogen sorption behaviour due to its improved microstructure of solid hydrogen materials. Compared to traditional ball milling method, wet ball milling has benefits on improvement of MgH{sub 2} microstructure and further influences on its hydrogen sorption behavior. With the help of solvent tetrahydrofuran (THF), wet ball milled MgH{sub 2} powder has much smaller particle size and its specific surface area is 7 times as large as that of dry ball milled MgH{sub 2} powder. Although after ball milling the grain size is decreased a lot compared to as-received MgH{sub 2} powder, the grain size of wet ball milled MgH{sub 2} powder is larger than that of dry ball milled MgH{sub 2} powder due to the lubricant effect of solvent THF during wet ball milling. The improved particle size and specific surface area of wet ball milled MgH{sub 2} powder is found to be determining its hydrogen sorption kinetics especially at relatively low temperatures. And it also shows good cycling sorption behavior, which decides on its industrial applicability. With three different catalysts MgH{sub 2} powder shows improved hydrogen sorption behavior as well as the cyclic sorption behavior. Among them, the Nb{sub 2}O{sub 5} catalyst is found to be the most effective one in this work. Compared to the wet ball milled MgH{sub 2} powder, the particle size and specific surface area of the MgH{sub 2} powder with catalysts are similar to the previous ones, while the grain size of the MgH{sub 2} with catalysts is much finer. In this case, two reasons for hydrogen sorption improvement are suggested: one is the reduction of the grain size. The other may be as pointed out in some literatures that formation of new oxidation could enhance the hydrogen sorption kinetics, which is also the reason why its hydrogen capacity is decreased compared to without catalysts. After further ball milling, the specific surface area of wet ball milled Mg

  11. Nucleation and growth kinetics of zirconium hydroxide by precipitation with ammonium hydroxide

    International Nuclear Information System (INIS)

    Carleson, T.E.; Chipman, N.A.

    1987-01-01

    The results of a study of the nucleation and growth kinetics of the precipitation of zirconium hydroxide from the reaction of hexafluorozirconate solution with ammonium hydroxide are reported. The McCabe linear growth rate model was used to correlate the results. The growth rate decreased with residence time and supersaturation for studies with 7 residence times (3.5 - 90 minutes and two supersaturation ratios (0.03 - 0.04, and 0.4). The nucleation rate increased with residence time and supersaturation. A negative kinetic order of nucleation was observed that may be due to the inhibition of particle growth by adsorption of reacting species on the crystal surfaces

  12. Theoretical Studies Of Nucleation Kinetics And Nanodroplet Microstructure

    International Nuclear Information System (INIS)

    Wilemski, Gerald

    2009-01-01

    The goals of this project were to (1) explore ways of bridging the gap between fundamental molecular nucleation theories and phenomenological approaches based on thermodynamic reasoning, (2) test and improve binary nucleation theory, and (3) provide the theoretical underpinning for a powerful new experimental technique, small angle neutron scattering (SANS) from nanodroplet aerosols, that can probe the compositional structure of nanodroplets. This report summarizes the accomplishments of this project in realizing these goals. Publications supported by this project fall into three general categories: (1) theoretical work on nucleation theory (2) experiments and modeling of nucleation and condensation in supersonic nozzles, and (3) experimental and theoretical work on nanodroplet structure and neutron scattering. These publications are listed and briefly summarized in this report.

  13. Kinetics of transformations nucleated on random parallel planes: analytical modelling and computer simulation

    International Nuclear Information System (INIS)

    Rios, Paulo R; Assis, Weslley L S; Ribeiro, Tatiana C S; Villa, Elena

    2012-01-01

    In a classical paper, Cahn derived expressions for the kinetics of transformations nucleated on random planes and lines. He used those as a model for nucleation on the boundaries, edges and vertices of a polycrystal consisting of equiaxed grains. In this paper it is demonstrated that Cahn's expression for random planes may be used in situations beyond the scope envisaged in Cahn's original paper. For instance, we derived an expression for the kinetics of transformations nucleated on random parallel planes that is identical to that formerly obtained by Cahn considering random planes. Computer simulation of transformations nucleated on random parallel planes is carried out. It is shown that there is excellent agreement between simulated results and analytical solutions. Such an agreement is to be expected if both the simulation and the analytical solution are correct. (paper)

  14. Microstructure development in Kolmogorov, Johnson-Mehl, and Avrami nucleation and growth kinetics

    Science.gov (United States)

    Pineda, Eloi; Crespo, Daniel

    1999-08-01

    A statistical model with the ability to evaluate the microstructure developed in nucleation and growth kinetics is built in the framework of the Kolmogorov, Johnson-Mehl, and Avrami theory. A populational approach is used to compute the observed grain-size distribution. The impingement process which delays grain growth is analyzed, and the effective growth rate of each population is estimated considering the previous grain history. The proposed model is integrated for a wide range of nucleation and growth protocols, including constant nucleation, pre-existing nuclei, and intermittent nucleation with interface or diffusion-controlled grain growth. The results are compared with Monte Carlo simulations, giving quantitative agreement even in cases where previous models fail.

  15. Growth Kinetics of the Homogeneously Nucleated Water Droplets: Simulation Results

    International Nuclear Information System (INIS)

    Mokshin, Anatolii V; Galimzyanov, Bulat N

    2012-01-01

    The growth of homogeneously nucleated droplets in water vapor at the fixed temperatures T = 273, 283, 293, 303, 313, 323, 333, 343, 353, 363 and 373 K (the pressure p = 1 atm.) is investigated on the basis of the coarse-grained molecular dynamics simulation data with the mW-model. The treatment of simulation results is performed by means of the statistical method within the mean-first-passage-time approach, where the reaction coordinate is associated with the largest droplet size. It is found that the water droplet growth is characterized by the next features: (i) the rescaled growth law is unified at all the considered temperatures and (ii) the droplet growth evolves with acceleration and follows the power law.

  16. Electrostatics Control Actin Filament Nucleation and Elongation Kinetics*

    Science.gov (United States)

    Crevenna, Alvaro H.; Naredi-Rainer, Nikolaus; Schönichen, André; Dzubiella, Joachim; Barber, Diane L.; Lamb, Don C.; Wedlich-Söldner, Roland

    2013-01-01

    The actin cytoskeleton is a central mediator of cellular morphogenesis, and rapid actin reorganization drives essential processes such as cell migration and cell division. Whereas several actin-binding proteins are known to be regulated by changes in intracellular pH, detailed information regarding the effect of pH on the actin dynamics itself is still lacking. Here, we combine bulk assays, total internal reflection fluorescence microscopy, fluorescence fluctuation spectroscopy techniques, and theory to comprehensively characterize the effect of pH on actin polymerization. We show that both nucleation and elongation are strongly enhanced at acidic pH, with a maximum close to the pI of actin. Monomer association rates are similarly affected by pH at both ends, although dissociation rates are differentially affected. This indicates that electrostatics control the diffusional encounter but not the dissociation rate, which is critical for the establishment of actin filament asymmetry. A generic model of protein-protein interaction, including electrostatics, explains the observed pH sensitivity as a consequence of charge repulsion. The observed pH effect on actin in vitro agrees with measurements of Listeria propulsion in pH-controlled cells. pH regulation should therefore be considered as a modulator of actin dynamics in a cellular environment. PMID:23486468

  17. Electrostatics control actin filament nucleation and elongation kinetics.

    Science.gov (United States)

    Crevenna, Alvaro H; Naredi-Rainer, Nikolaus; Schönichen, André; Dzubiella, Joachim; Barber, Diane L; Lamb, Don C; Wedlich-Söldner, Roland

    2013-04-26

    The actin cytoskeleton is a central mediator of cellular morphogenesis, and rapid actin reorganization drives essential processes such as cell migration and cell division. Whereas several actin-binding proteins are known to be regulated by changes in intracellular pH, detailed information regarding the effect of pH on the actin dynamics itself is still lacking. Here, we combine bulk assays, total internal reflection fluorescence microscopy, fluorescence fluctuation spectroscopy techniques, and theory to comprehensively characterize the effect of pH on actin polymerization. We show that both nucleation and elongation are strongly enhanced at acidic pH, with a maximum close to the pI of actin. Monomer association rates are similarly affected by pH at both ends, although dissociation rates are differentially affected. This indicates that electrostatics control the diffusional encounter but not the dissociation rate, which is critical for the establishment of actin filament asymmetry. A generic model of protein-protein interaction, including electrostatics, explains the observed pH sensitivity as a consequence of charge repulsion. The observed pH effect on actin in vitro agrees with measurements of Listeria propulsion in pH-controlled cells. pH regulation should therefore be considered as a modulator of actin dynamics in a cellular environment.

  18. Kinetics of heterogeneous nucleation on intrinsic nucleants in pure fcc transition metals

    International Nuclear Information System (INIS)

    Wilde, G; Bokeloh, J; Santhaweesuk, C; Perepezko, J H; Sebright, J L

    2009-01-01

    Nucleation during solidification is heterogeneous in nature in an overwhelmingly large fraction of all solidification events. Yet, most often the identity of the heterogeneous nucleants that initiate nucleation remains a matter of speculation. In fact, a series of dedicated experiments needs to be designed in order to verify if nucleation of the material under study is based on one type of heterogeneous nucleant and if the potency of that nucleant is constant, e.g. for a population of individual droplets, or stays constant over time, e.g. throughout repeated melting/solidification cycles. In this work it is demonstrated that one way to circumvent ambiguities and analyze nucleation kinetics under well-defined conditions experimentally is given by performing statistically significant numbers of repeated single-droplet experiments. The application of proper statistics analyses based upon a non-homogeneous Poisson process is shown to yield nucleation rates that are independent of a specific nucleation model. Based upon this approach nucleation undercooling measurements on pure Au, Cu and Ni as model materials have confirmed that the experimental strategy and analysis method are valid. The results are comparable to those obtained by classical nucleation theory applied to experimental data that has been verified to comply with the assertions that are necessary for applying this model framework. However, the results reveal also other complex nucleant-sample interactions such as an initial transient undercooling behavior and impurity removal during repeated cycling treatments. The transient undercooling behavior has been analyzed by a nucleant refining model to provide new insight on the operation of melt fluxing treatments.

  19. Kinetics of hydrogen evolution in the thermal dissociation of the hydride ZrNiH /SUB 2.8/

    International Nuclear Information System (INIS)

    Chernavskii, P.A.; Lunin, V.V.

    1985-01-01

    The kinetics of hydrogen evolution in the thermal decomposition of ZrNiH /SUB 2.8/ has been studied. The kinetic curve has two rate maxima. It is presumed that the second maximum is related to the phenomenon of critical inhibition that accompanies the phase transition. Apparent activation energies were determined for hydrogen evolution in argon and argon-ethylene atmospheres. The apparent energy increases in the argon-ethylene mixture. On the basis of the activation energy measurements it is presumed that the rate-determining step in hydrogen evolution is either the formation of hydrogen molecules from atoms on the surface of the lateral diffusion of atomic hydrogen. In the region of hydrogen concentration in the hydride corresponding to the phase transition, the rate-determining step is hydrogen diffusion in the hydride

  20. Experimental validation of kinetic inhibitor strength on natural gas hydrate nucleation

    DEFF Research Database (Denmark)

    Daraboina, Nagu; Pachitsas, Stylianos; von Solms, Nicolas

    2015-01-01

    The kinetics of natural gas hydrate formation in the presence of dissolved salts (NaCl) and crude oil ( a middle east crude with density 851.5 kg/m3 were investigated by using a standard rocking cell (RC-5) apparatus. The hydrate nucleation temperature was reduced in the presence of NaCl and oil...... management in oil and gas facilities. (C) 2014 Elsevier Ltd. All rights reserved....

  1. Fundamental experiments on hydride reorientation in zircaloy

    Science.gov (United States)

    Colas, Kimberly B.

    In the current study, an in-situ X-ray diffraction technique using synchrotron radiation was used to follow directly the kinetics of hydride dissolution and precipitation during thermomechanical cycles. This technique was combined with conventional microscopy (optical, SEM and TEM) to gain an overall understanding of the process of hydride reorientation. Thus this part of the study emphasized the time-dependent nature of the process, studying large volume of hydrides in the material. In addition, a micro-diffraction technique was also used to study the spatial distribution of hydrides near stress concentrations. This part of the study emphasized the spatial variation of hydride characteristics such as strain and morphology. Hydrided samples in the shape of tensile dog-bones were used in the time-dependent part of the study. Compact tension specimens were used during the spatial dependence part of the study. The hydride elastic strains from peak shift and size and strain broadening were studied as a function of time for precipitating hydrides. The hydrides precipitate in a very compressed state of stress, as measured by the shift in lattice spacing. As precipitation proceeds the average shift decreases, indicating average stress is reduced, likely due to plastic deformation and morphology changes. When nucleation ends the hydrides follow the zirconium matrix thermal contraction. When stress is applied below the threshold stress for reorientation, hydrides first nucleate in a very compressed state similar to that of unstressed hydrides. After reducing the average strain similarly to unstressed hydrides, the average hydride strain reaches a constant value during cool-down to room temperature. This could be due to a greater ease of deforming the matrix due to the applied far-field strain which would compensate for the strains due to thermal contraction. Finally when hydrides reorient, the average hydride strains become tensile during the first precipitation regime and

  2. Nucleation of diindenoperylene and pentacene at thermal and hyperthermal incident kinetic energies

    Energy Technology Data Exchange (ETDEWEB)

    Kish, Edward R.; Desai, Tushar V.; Greer, Douglas R.; Engstrom, James R., E-mail: jre7@cornell.edu [School of Chemical and Biomolecular Engineering, Cornell University, Ithaca, New York 14853 (United States); Woll, Arthur R. [Cornell High Energy Synchrotron Source, Cornell University, Ithaca, New York 14853 (United States)

    2015-05-15

    The authors have examined the nucleation of diindenoperylene (DIP) on SiO{sub 2} employing primarily atomic force microscopy and focusing on the effect of incident kinetic energy employing both thermal and supersonic sources. For all incident kinetic energies examined (E{sub i} = 0.09–11.3 eV), the nucleation of DIP is homogeneous and the dependence of the maximum island density on the growth rate is described by a power law. A critical nucleus of approximately two molecules is implicated by our data. A re-examination of the nucleation of pentacene on SiO{sub 2} gives the same major result that the maximum island density is determined by the growth rate, and it is independent of the incident kinetic energy. These observations are readily understood by factoring in the size of the critical nucleus in each case, and the island density, which indicates that diffusive transport of molecules to the growing islands dominate the dynamics of growth in the submonolayer regime.

  3. Study on the effects of titanium oxide based nanomaterials as catalysts on the hydrogen sorption kinetics of magnesium hydride

    Energy Technology Data Exchange (ETDEWEB)

    Pereira, Anderson de Farias; Jardim, Paula Mendes; Santos, Dilson Silva dos, E-mail: anderso.n@poli.ufrj.br [Universidade Federal do Rio de Janeiro (UFRJ), RJ (Brazil); Conceicao, Monique Osorio Talarico da [Centro Universitario de Volta Redonda (UniFOA), RJ (Brazil)

    2016-07-01

    Full text: Magnesium hydride is highly attractive for hydrogen storage in solid state in reason of its high gravimetric capacity (7,6 wt% of H{sub 2}) and low density (1,7 g/cm³), making it a promissory candidate for mobile applications [1]. However, its low sorption kinetics and desorption temperature are the main obstacles for its application. In the present study the catalytic role of TiO{sub 2} based nanomaterials with different morphologies on the sorption kinetics of MgH{sub 2} was evaluated. The additions consisted on titanate nanotubes (TTNT-Low), TiO{sub 2} nanorods (TTNT-550) and nanoparticles (KA-100, TTNT-ACID). Transmission and Scanning Transmission Electron Microscopy (S/TEM) associated with X-ray Energy Dispersive Spectroscopy (XEDS) mapping was used to characterize the catalysts' morphology and crystalline structure and their dispersion within magnesium hydride, altogether with other characterization techniques such as X-ray diffraction (XRD) and BET technique for structure and surface area analysis. The sorption kinetics were evaluated by means of a volumetric gas absorption/desorption (Sievert-type) apparatus. The results indicated that all additives improved the sorption kinetics of MgH{sub 2}, but the samples with TTNT-550 (TiO{sub 2} nanorods) and TTNT-ACID (TiO{sub 2} nanoparticles) presented the best and the second best performances, respectively, suggesting that the 1D morphology may promote a slightly superior kinetics than particulate catalysts. (author)

  4. The Improvement of Dehydriding the Kinetics of NaMgH3 Hydride via Doping with Carbon Nanomaterials

    Directory of Open Access Journals (Sweden)

    Zhong-Min Wang

    2016-12-01

    Full Text Available NaMgH3 perovskite hydride and NaMgH3–carbon nanomaterials (NH-CM composites were prepared via the reactive ball-milling method. To investigate the catalytic effect of CM on the dehydriding kinetic properties of NaMgH3 hydride, multiwall carbon nanotubes (MWCNTs and graphene oxide (GO were used as catalytic additives. It was found that dehydriding temperatures and activation energies (ΔE1 and ΔE2 for two dehydrogenation steps of NaMgH3 hydride can be greatly reduced with a 5 wt. % CM addition. The NH–2.5M–2.5G composite presents better dehydriding kinetics, a lower dehydriding temperature, and a higher hydrogen-desorbed amount (3.64 wt. %, 638 K. ΔE1 and ΔE2 can be reduced by about 67 kJ/mol and 30 kJ/mol, respectively. The results suggest that the combination of MWCNTs and GO is a better catalyst as compared to MWCNTs or GO alone.

  5. Thermodynamics and kinetics of binary nucleation in ideal-gas mixtures.

    Science.gov (United States)

    Alekseechkin, Nikolay V

    2015-08-07

    The nonisothermal single-component theory of droplet nucleation [N. V. Alekseechkin, Physica A 412, 186 (2014)] is extended to binary case; the droplet volume V, composition x, and temperature T are the variables of the theory. An approach based on macroscopic kinetics (in contrast to the standard microscopic model of nucleation operating with the probabilities of monomer attachment and detachment) is developed for the droplet evolution and results in the derived droplet motion equations in the space (V, x, T)—equations for V̇≡dV/dt, ẋ, and Ṫ. The work W(V, x, T) of the droplet formation is obtained in the vicinity of the saddle point as a quadratic form with diagonal matrix. Also, the problem of generalizing the single-component Kelvin equation for the equilibrium vapor pressure to binary case is solved; it is presented here as a problem of integrability of a Pfaffian equation. The equation for Ṫ is shown to be the first law of thermodynamics for the droplet, which is a consequence of Onsager's reciprocal relations and the linked-fluxes concept. As an example of ideal solution for demonstrative numerical calculations, the o-xylene-m-xylene system is employed. Both nonisothermal and enrichment effects are shown to exist; the mean steady-state overheat of droplets and their mean steady-state enrichment are calculated with the help of the 3D distribution function. Some qualitative peculiarities of the nucleation thermodynamics and kinetics in the water-sulfuric acid system are considered in the model of regular solution. It is shown that there is a small kinetic parameter in the theory due to the small amount of the acid in the vapor and, as a consequence, the nucleation process is isothermal.

  6. Estimation of the nucleation kinetics for the anti-solvent crystallisation of paracetamol in methanol/water solutions

    Science.gov (United States)

    Ó'Ciardhá, Clifford T.; Frawley, Patrick J.; Mitchell, Niall A.

    2011-08-01

    In this work the primary nucleation kinetics have been estimated for the anti-solvent crystallisation of paracetamol in methanol-water solutions from metastable zone widths (MSZW) and induction times at 25 °C. Laser back-scattering via a focused beam reflectance Measurement (FBRM ®) is utilised to detect the onset of nucleation. The theoretical approach of Kubota was employed to estimate the nucleation kinetics, which accounts for the sensitivity of the nucleation detection technique. This approach is expanded in this work to analyse the induction time for an anti-solvent crystallisation process. Solvent composition is known to have a significant impact on the measured induction times and MSZW. The induction time in this paper was measured from 40% to 70% mass water and the MSZW is measured from 40% to 60% mass water. The primary focus of the paper was to gauge the extent of how solvent composition affects nucleation kinetics so that this effect may be incorporated into a population balance model. Furthermore, the effects of solvent composition on the estimated nucleation rates are investigated. The primary nucleation rates were found to decrease with dynamic solvent composition, with the extent of their reduction linked to the gradient of the solubility curve. Finally, both MSZW and induction time methods have been found to produce similar estimates for the nucleation parameters.

  7. Kinetic study of nucleation and crystal growth during oxalic precipitation in the nuclear industry

    International Nuclear Information System (INIS)

    Andrieu, Murielle

    1999-01-01

    In spite of an extensive use in chemical industry, most of precipitation processes are based on global and empirical knowledge. However, in the recent years, fundamental and phenomenological theories have been developed and they can be used to better understand the mechanisms of precipitation of plutonium IV oxalate, which is a significant stage of the irradiated fuel reprocessing. For this reason, appropriate methods were developed to study nucleation and crystal growth kinetics in a nuclear environment under a wide range of operating conditions. Each phenomena was studied individually in order to reduce the free parameters of the System. This study bears on the oxalates of plutonium and elements which simulate plutonium behaviour during the precipitation, neodymium III and uranium IV. A compact apparatus of a specific construction was used for nucleation measurements in accordance with the Nielsen's method. The state of the mixing was characterised at the reactor scale (macro-mixing) and at molecular scale (micro-mixing). The experimental results for the studied oxalates are in good agreement with the Volmer and Weber's theory. We propose primary nucleation kinetic laws over a wide range of operating conditions (temperature, non-stoichiometric conditions, acidity...). An original method, using a high seed charge, was developed for the determination of crystal growth kinetics, in a batch crystallizer. The crystal growth rate is first order with respect to the supersaturation and the kinetic constant follows an Arrhenius type relation with activation energies of 14, 29 and 36 kJ.mol -1 for respectively neodymium III, uranium IV and plutonium IV oxalates. The overall growth process is surface integration controlled, with a screw dislocation mechanism. [fr

  8. The Effect of Spatial Heterogeneities on Nucleation Kinetics in Amorphous Aluminum Alloys

    Science.gov (United States)

    Shen, Ye

    The mechanical property of the Al based metallic glass could be enhanced significantly by introducing the high number density of Al-fcc nanocrystals (1021 ˜1023 m-3) to the amorphous matrix through annealing treatments, which motivates the study of the nucleation kinetics for the microstructure control. With the presence of a high number density (1025 m-3) of aluminum-like medium range order (MRO), the Al-Y-Fe metallic glass is considered to be spatially heterogeneous. Combining the classical nucleation theory with the structural configuration, a MRO seeded nucleation model has been proposed and yields theoretical steady state nucleation rates consistent with the experimental results. In addition, this model satisfies all the thermodynamic and kinetic constraints to be reasonable. Compared with the Al-Y-Fe system, the primary crystallization onset temperature decreases significantly and the transient delay time (tau) is shorter in the Al-Y-Fe-Pb(In) systems because the insoluble Pb and In nanoparticles in the amorphous matrix served as extrinsic spatial heterogeneity to provide the nucleation sites for Al-fcc precipitation and the high-resolution transmission electron microscopy (HRTEM) images of the Pb-Al interface revealed a good wetting behavior between the Al and Pb nanoparticles. The study of the transient delay time (tau) could provide insight on the transport behavior during the nucleation and a more convenient approach to evaluate the delay time has been developed by measuring the Al-Y-Fe amorphous alloy glass transition temperature (Tg) shift with the increasing annealing time (tannealing) in FlashDSC. The break point in the Tg vs. log(tannealing) plot has been identified to correspond to the delay time by the TEM characterization. FlashDSC tests with different heating rates and different compositions (Al-Y-Fe-Pb and Zn-Mg-Ca-Yb amorphous alloys) further confirmed the break point and delay time relationship. The amorphous matrix composition and the

  9. Effects of AlN nucleation layers on the growth of AlN films using high temperature hydride vapor phase epitaxy

    International Nuclear Information System (INIS)

    Balaji, M.; Claudel, A.; Fellmann, V.; Gélard, I.; Blanquet, E.; Boichot, R.; Pierret, A.

    2012-01-01

    Highlights: ► Growth of AlN Nucleation layers and its effect on high temperature AlN films quality were investigated. ► AlN nucleation layers stabilizes the epitaxial growth of AlN and improves the surface morphology of AlN films. ► Increasing growth temperature of AlN NLs as well as AlN films improves the structural quality and limits the formation of cracks. - Abstract: AlN layers were grown on c-plane sapphire substrates with AlN nucleation layers (NLs) using high temperature hydride vapor phase epitaxy (HT-HVPE). Insertion of low temperature NLs, as those typically used in MOVPE process, prior to the high temperature AlN (HT-AlN) layers has been investigated. The NLs surface morphology was studied by atomic force microscopy (AFM) and NLs thickness was measured by X-ray reflectivity. Increasing nucleation layer deposition temperature from 650 to 850 °C has been found to promote the growth of c-oriented epitaxial HT-AlN layers instead of polycrystalline layers. The growth of polycrystalline layers has been related to the formation of dis-oriented crystallites. The density of such disoriented crystallites has been found to decrease while increasing NLs deposition temperature. The HT-AlN layers have been characterized by X-ray diffraction θ − 2θ scan and (0 0 0 2) rocking curve measurement, Raman and photoluminescence spectroscopies, AFM and field emission scanning electron microscopy. Increasing the growth temperature of HT-AlN layers from 1200 to 1400 °C using a NL grown at 850 °C improves the structural quality as well as the surface morphology. As a matter of fact, full-width at half-maximum (FWHM) of 0 0 0 2 reflections was improved from 1900 to 864 arcsec for 1200 °C and 1400 °C, respectively. Related RMS roughness also found to decrease from 10 to 5.6 nm.

  10. Exploring bainite formation kinetics distinguishing grain-boundary and autocatalytic nucleation in high and low-Si steels

    International Nuclear Information System (INIS)

    Ravi, Ashwath M.; Sietsma, Jilt; Santofimia, Maria J.

    2016-01-01

    Bainite formation in steels begins with nucleation of bainitic ferrite at austenite grain boundaries (γ/γ interfaces). This leads to creation of bainitic ferrite/austenite interfaces (α/γ interfaces). Bainite formation continues through autocatalysis with nucleation of bainitic ferrite at these newly created α/γ interfaces. The displacive theory of bainite formation suggests that the formation of bainitic ferrite is accompanied by carbon enrichment of surrounding austenite. This carbon enrichment generally leads to carbide precipitation unless such a reaction is thermodynamically or kinetically unfavourable. Each bainitic ferrite nucleation event is governed by an activation energy. Depending upon the interface at which nucleation occurs, a specific activation energy would be related to a specific nucleation mechanism. On the basis of this concept, a model has been developed to understand the kinetics of bainite formation during isothermal treatments. This model is derived under the assumptions of displacive mechanism of bainite formation. The fitting parameters used in this model are physical entities related to nucleation and microstructural dimensions. The model is designed in such a way that the carbon redistribution during bainite formation is accounted for, leading to prediction of transformation kinetics both with and without of carbide precipitation during bainite formation. Furthermore, the model is validated using two different sets of kinetic data published in the literature.

  11. Modifications of the hydriding kinetics of a metallic surface, using ion implantation

    International Nuclear Information System (INIS)

    Crusset, D.

    1992-10-01

    Uranium reacts with hydrogen to form an hydride: this reaction leads to the total destruction of the material. To modify the reactivity of an uranium surface towards hydrogen, ion implantation was selected, among surface treatments techniques. Four elements (carbon, nitrogen, oxygen, sulfur) were implanted to different doses. The results show a modification of the hydriding mechanism and a significant increase in the reaction induction times, notably at high implantation doses. Several techniques (SIMS, X-rays phases analysis and residual stresses determination) were used to characterize the samples and understand the different mechanisms involved

  12. A method for analyzing the non-stationary nucleation and overall transition kinetics: A case of water

    International Nuclear Information System (INIS)

    Mokshin, Anatolii V.; Galimzyanov, Bulat N.

    2014-01-01

    We present the statistical method as a direct extension of the mean first-passage time concept to the analysis of molecular dynamics simulation data of a phase transformation. According to the method, the mean first-passage time trajectories for the first (i = 1) as well as for the subsequent (i = 2, 3, 4,…) nucleation events should be extracted that allows one to calculate the time-dependent nucleation rate, the critical value of the order parameter (the critical size), the waiting times for the nucleation events, and the growth law of the nuclei – i.e., all the terms, which are usually necessary to characterize the overall transition kinetics. There are no restrictions in the application of the method by the specific thermodynamic regions; and the nucleation rate parameters are extracted according to their basic definitions. The method differs from the Wedekind-Bartell scheme and its modification [A. V. Mokshin and B. N. Galimzyanov, J. Phys. Chem. B 116, 11959 (2012)], where the passage-times for the first (largest) nucleus are evaluated only and where the average waiting time for the first nucleation event is accessible instead of the true steady-state nucleation time scale. We demonstrate an efficiency of the method by its application to the analysis of the vapor-to-liquid transition kinetics in water at the different temperatures. The nucleation rate/time characteristics and the droplet growth parameters are computed on the basis of the coarse-grained molecular dynamics simulation data

  13. Stochastic kinetics reveal imperative role of anisotropic interfacial tension to determine morphology and evolution of nucleated droplets in nematogenic films

    Science.gov (United States)

    Bhattacharjee, Amit Kumar

    2017-01-01

    For isotropic fluids, classical nucleation theory predicts the nucleation rate, barrier height and critical droplet size by ac- counting for the competition between bulk energy and interfacial tension. The nucleation process in liquid crystals is less understood. We numerically investigate nucleation in monolayered nematogenic films using a mesoscopic framework, in par- ticular, we study the morphology and kinetic pathway in spontaneous formation and growth of droplets of the stable phase in the metastable background. The parameter κ that quantifies the anisotropic elastic energy plays a central role in determining the geometric structure of the droplets. Noncircular nematic droplets with homogeneous director orientation are nucleated in a background of supercooled isotropic phase for small κ. For large κ, noncircular droplets with integer topological charge, accompanied by a biaxial ring at the outer surface, are nucleated. The isotropic droplet shape in a superheated nematic background is found to depend on κ in a similar way. Identical growth laws are found in the two cases, although an unusual two-stage mechanism is observed in the nucleation of isotropic droplets. Temporal distributions of successive events indi- cate the relevance of long-ranged elasticity-mediated interactions within the isotropic domains. Implications for a theoretical description of nucleation in anisotropic fluids are discussed.

  14. Hydride Transfer versus Deprotonation Kinetics in the Isobutane–Propene Alkylation Reaction: A Computational Study

    Science.gov (United States)

    2017-01-01

    The alkylation of isobutane with light alkenes plays an essential role in modern petrochemical processes for the production of high-octane gasoline. In this study we have employed periodic DFT calculations combined with microkinetic simulations to investigate the complex reaction mechanism of isobutane–propene alkylation catalyzed by zeolitic solid acids. Particular emphasis was given to addressing the selectivity of the alkylate formation versus alkene formation, which requires a high rate of hydride transfer in comparison to the competitive oligomerization and deprotonation reactions resulting in catalyst deactivation. Our calculations reveal that hydride transfer from isobutane to a carbenium ion occurs via a concerted C–C bond formation between a tert-butyl fragment and an additional olefin, or via deprotonation of the tert-butyl fragment to generate isobutene. A combination of high isobutane concentration and low propene concentration at the reaction center favor the selective alkylation. The key reaction step that has to be suppressed to increase the catalyst lifetime is the deprotonation of carbenium intermediates that are part of the hydride transfer reaction cycle. PMID:29226012

  15. Hydride Transfer versus Deprotonation Kinetics in the Isobutane-Propene Alkylation Reaction: A Computational Study.

    Science.gov (United States)

    Liu, Chong; van Santen, Rutger A; Poursaeidesfahani, Ali; Vlugt, Thijs J H; Pidko, Evgeny A; Hensen, Emiel J M

    2017-12-01

    The alkylation of isobutane with light alkenes plays an essential role in modern petrochemical processes for the production of high-octane gasoline. In this study we have employed periodic DFT calculations combined with microkinetic simulations to investigate the complex reaction mechanism of isobutane-propene alkylation catalyzed by zeolitic solid acids. Particular emphasis was given to addressing the selectivity of the alkylate formation versus alkene formation, which requires a high rate of hydride transfer in comparison to the competitive oligomerization and deprotonation reactions resulting in catalyst deactivation. Our calculations reveal that hydride transfer from isobutane to a carbenium ion occurs via a concerted C-C bond formation between a tert -butyl fragment and an additional olefin, or via deprotonation of the tert -butyl fragment to generate isobutene. A combination of high isobutane concentration and low propene concentration at the reaction center favor the selective alkylation. The key reaction step that has to be suppressed to increase the catalyst lifetime is the deprotonation of carbenium intermediates that are part of the hydride transfer reaction cycle.

  16. Colloidal nanoparticle size control: experimental and kinetic modeling investigation of the ligand-metal binding role in controlling the nucleation and growth kinetics.

    Science.gov (United States)

    Mozaffari, Saeed; Li, Wenhui; Thompson, Coogan; Ivanov, Sergei; Seifert, Soenke; Lee, Byeongdu; Kovarik, Libor; Karim, Ayman M

    2017-09-21

    Despite the major advancements in colloidal metal nanoparticles synthesis, a quantitative mechanistic treatment of the ligand's role in controlling their size remains elusive. We report a methodology that combines in situ small angle X-ray scattering (SAXS) and kinetic modeling to quantitatively capture the role of ligand-metal binding (with the metal precursor and the nanoparticle surface) in controlling the synthesis kinetics. We demonstrate that accurate extraction of the kinetic rate constants requires using both, the size and number of particles obtained from in situ SAXS to decouple the contributions of particle nucleation and growth to the total metal reduction. Using Pd acetate and trioctylphosphine in different solvents, our results reveal that the binding of ligands with both the metal precursor and nanoparticle surface play a key role in controlling the rates of nucleation and growth and consequently the final size. We show that the solvent can affect the metal-ligand binding and consequently ligand coverage on the nanoparticles surface which has a strong effect on the growth rate and final size (1.4 nm in toluene and 4.3 nm in pyridine). The proposed kinetic model quantitatively predicts the effects of varying the metal concentration and ligand/metal ratio on nanoparticle size for our work and literature reports. More importantly, we demonstrate that the final size is exclusively determined by the nucleation and growth kinetics at early times and not how they change with time. Specifically, the nanoparticle size in this work and many literature reports can be predicted using a single, model independent kinetic descriptor, (growth-to-nucleation rate ratio) 1/3 , despite the different metals and synthetic conditions. The proposed model and kinetic descriptor could serve as powerful tools for the design of colloidal nanoparticles with specific sizes.

  17. A coupled transport and solid mechanics formulation with improved reaction kinetics parameters for modeling oxidation and decomposition in a uranium hydride bed.

    Energy Technology Data Exchange (ETDEWEB)

    Salloum, Maher N.; Shugard, Andrew D.; Kanouff, Michael P.; Gharagozloo, Patricia E.

    2013-03-01

    Modeling of reacting flows in porous media has become particularly important with the increased interest in hydrogen solid-storage beds. An advanced type of storage bed has been proposed that utilizes oxidation of uranium hydride to heat and decompose the hydride, releasing the hydrogen. To reduce the cost and time required to develop these systems experimentally, a valid computational model is required that simulates the reaction of uranium hydride and oxygen gas in a hydrogen storage bed using multiphysics finite element modeling. This SAND report discusses the advancements made in FY12 (since our last SAND report SAND2011-6939) to the model developed as a part of an ASC-P&EM project to address the shortcomings of the previous model. The model considers chemical reactions, heat transport, and mass transport within a hydride bed. Previously, the time-varying permeability and porosity were considered uniform. This led to discrepancies between the simulated results and experimental measurements. In this work, the effects of non-uniform changes in permeability and porosity due to phase and thermal expansion are accounted for. These expansions result in mechanical stresses that lead to bed deformation. To describe this, a simplified solid mechanics model for the local variation of permeability and porosity as a function of the local bed deformation is developed. By using this solid mechanics model, the agreement between our reacting bed model and the experimental data is improved. Additionally, more accurate uranium hydride oxidation kinetics parameters are obtained by fitting the experimental results from a pure uranium hydride oxidation measurement to the ones obtained from the coupled transport-solid mechanics model. Finally, the coupled transport-solid mechanics model governing equations and boundary conditions are summarized and recommendations are made for further development of ARIA and other Sandia codes in order for them to sufficiently implement the model.

  18. The hydrogen evolution and oxidation kinetics during overdischarging of sealed nickel-metal hydride batteries

    NARCIS (Netherlands)

    Ayeb, A.; Otten, W.M.; Mank, A.J.G.; Notten, P.H.L.

    2006-01-01

    The hydrogen evolution and oxidation kinetics in NiMH batteries have been investigated under temperature-controlled, steady-state, overdischarging conditions within a temperature range of 10 and 50°C and at discharging currents of 1–330 mA (0.0009 to 0.3 C rate). In situ Raman spectroscopic analyses

  19. Nucleation and growth kinetics for intercalated islands during deposition on layered materials with isolated pointlike surface defects

    International Nuclear Information System (INIS)

    Han, Yong; Lii-Rosales, A.; Zhou, Y.; Wang, C.-J.

    2017-01-01

    Theory and stochastic lattice-gas modeling is developed for the formation of intercalated metal islands in the gallery between the top layer and the underlying layer at the surface of layered materials. Our model for this process involves deposition of atoms, some fraction of which then enter the gallery through well-separated pointlike defects in the top layer. Subsequently, these atoms diffuse within the subsurface gallery leading to nucleation and growth of intercalated islands nearby the defect point source. For the case of a single point defect, continuum diffusion equation analysis provides insight into the nucleation kinetics. However, complementary tailored lattice-gas modeling produces a more comprehensive and quantitative characterization. We analyze the large spread in nucleation times and positions relative to the defect for the first nucleated island. We also consider the formation of subsequent islands and the evolution of island growth shapes. The shapes reflect in part our natural adoption of a hexagonal close-packed island structure. As a result, motivation and support for the model is provided by scanning tunneling microscopy observations of the formation of intercalated metal islands in highly-ordered pyrolytic graphite at higher temperatures.

  20. Thermodynamics and Kinetics of Prenucleation Clusters, Classical and Non-Classical Nucleation.

    Science.gov (United States)

    Zahn, Dirk

    2015-07-20

    Recent observations of prenucleation species and multi-stage crystal nucleation processes challenge the long-established view on the thermodynamics of crystal formation. Here, we review and generalize extensions to classical nucleation theory. Going beyond the conventional implementation as has been used for more than a century now, nucleation inhibitors, precursor clusters and non-classical nucleation processes are rationalized as well by analogous concepts based on competing interface and bulk energy terms. This is illustrated by recent examples of species formed prior to/instead of crystal nucleation and multi-step nucleation processes. Much of the discussed insights were obtained from molecular simulation using advanced sampling techniques, briefly summarized herein for both nucleation-controlled and diffusion-controlled aggregate formation. © 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution Non-Commercial NoDerivs License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non-commercial and no modifications or adaptations are made.

  1. Room temperature and thermal decomposition of magnesium hydride/deuteride thin films

    Energy Technology Data Exchange (ETDEWEB)

    Ares, J.R.; Leardini, F.; Bodega, J.; Macia, M.D.; Diaz-Chao, P.; Ferrer, I.J.; Fernandez, J.F.; Sanchez, C. [Universidad Autonoma de Madrid (Spain). Lab. de Materiales de Interes en Energias Renovables

    2010-07-01

    Magnesium hydride (MgH{sub 2}) can be considered an interesting material to store hydrogen as long as two main drawbacks were solved: (i) its high stability and (ii) slow (de)hydriding kinetics. In that context, magnesium hydride films are an excellent model system to investigate the influence of structure, morphology and dimensionality on kinetic and thermodynamic properties. In the present work, we show that desorption mechanism of Pd-capped MgH{sub 2} at room temperature is controlled by a bidimensional interphase mechanism and a similar rate step limiting mechanism is observed during thermal decomposition of MgH{sub 2}. This mechanism is different to that occurring in bulk MgH{sub 2} (nucleation and growth) and obtained activation energies are lower than those reported in bulk MgH{sub 2}. We also investigated the Pd-capping properties upon H-absorption/desorption by means of RBS and isotope experiments. (orig.)

  2. Process optimization and kinetics for leaching of rare earth metals from the spent Ni-metal hydride batteries.

    Science.gov (United States)

    Meshram, Pratima; Pandey, B D; Mankhand, T R

    2016-05-01

    Nickel-metal hydride batteries (Ni-MH) contain not only the base metals, but valuable rare earth metals (REMs) viz. La, Sm, Nd, Pr and Ce as well. In view of the importance of resource recycling and assured supply of the contained metals in such wastes, the present study has focussed on the leaching of the rare earth metals from the spent Ni-MH batteries. The conditions for the leaching of REMs from the spent batteries were optimized as: 2M H2SO4, 348K temperature and 120min of time at a pulp density (PD) of 100g/L. Under this condition, the leaching of 98.1% Nd, 98.4% Sm, 95.5% Pr and 89.4% Ce was achieved. Besides the rare earth metals, more than 90% of base metals (Ni, Co, Mn and Zn) were also leached out in this condition. Kinetic data for the dissolution of all the rare earth metals showed the best fit to the chemical control shrinking core model. The leaching of metals followed the mechanism involving the chemical reaction proceeding on the surface of particles by the lixiviant, which was corroborated by the XRD phase analysis and SEM-EDS studies. The activation energy of 7.6, 6.3, 11.3 and 13.5kJ/mol was acquired for the leaching of neodymium, samarium, praseodymium and cerium, respectively in the temperature range 305-348K. From the leach liquor, the mixed rare earth metals were precipitated at pH∼1.8 and the precipitated REMs was analyzed by XRD and SEM studies to determine the phases and the morphological features. Copyright © 2015. Published by Elsevier Ltd.

  3. Submonolayer nucleation and growth and the initial stage of multilayer kinetic roughening during Ag/Ag (100) homoepitaxy

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, C.

    1996-08-01

    A comprehensive Scanning Tunneling Microscopy (STM) study of submonolayer nucleation and growth of 2D islands in Ag/Ag(100) homoepitaxy for temperature between 295K and 370K is presented. The initial stages of multilayer kinetic roughening is also studied. Analysis of an appropriate model for metal (100) homoepitaxy, produces estimates of 350 meV for the terrace diffusion barrier, 400 meV for the adatom bond energy, and 25 meV for the additional Ehrlich-Schwoebel step-edge barrier.

  4. Electrolytic hydriding and hydride distribution in zircaloy-4

    International Nuclear Information System (INIS)

    Gomes, M.H.L.

    1974-01-01

    A study has been made of the electrolytic hydriding of zircaloy-4 in the range 20-80 0 C, for reaction times from 5 to 30 hours, and the effect of potential, pH and dissolved oxygen has been investigated. The hydriding reaction was more sensitive to time and temperature conditions than to the electrochemical variables. It has been shown that a controlled introduction of hydrides in zircaloy is feasible. Hydrides were found to be plate like shaped and distributed mainly along grain-boundaries. It has been shown that hydriding kinetics do not follow a simple law but may be described by a Johnson-Mehl empirical equation. On the basis of this equation an activation energy of 9.400 cal/mol has been determined, which is close to the activation energy for diffusion of hydrogen in the hydride. (author)

  5. Thermodynamic and kinetic theory of nucleation, deliquescence and efflorescence transitions in the ensemble of droplets on soluble particles.

    Science.gov (United States)

    Shchekin, Alexander K; Shabaev, Ilya V; Hellmuth, Olaf

    2013-02-07

    Thermodynamic and kinetic peculiarities of nucleation, deliquescence and efflorescence transitions in the ensemble of droplets formed on soluble condensation nuclei from a solvent vapor have been considered. The interplay of the effects of solubility and the size of condensation nuclei has been analyzed. Activation barriers for the deliquescence and phase transitions and for the reverse efflorescence transition have been determined as functions of the relative humidity of the vapor-gas atmosphere, initial size, and solubility of condensation nuclei. It has been demonstrated that, upon variations in the relative humidity of the atmosphere, the crossover in thermodynamically stable and unstable variables of the droplet state takes place. The physical meaning of stable and unstable variables has been clarified. The kinetic equations for establishing equilibrium and steady distributions of binary droplets have been solved. The specific times for relaxation, deliquescence and efflorescence transitions have been calculated.

  6. Hydrogen Outgassing from Lithium Hydride

    Energy Technology Data Exchange (ETDEWEB)

    Dinh, L N; Schildbach, M A; Smith, R A; Balazs1, B; McLean II, W

    2006-04-20

    Lithium hydride is a nuclear material with a great affinity for moisture. As a result of exposure to water vapor during machining, transportation, storage and assembly, a corrosion layer (oxide and/or hydroxide) always forms on the surface of lithium hydride resulting in the release of hydrogen gas. Thermodynamically, lithium hydride, lithium oxide and lithium hydroxide are all stable. However, lithium hydroxides formed near the lithium hydride substrate (interface hydroxide) and near the sample/vacuum interface (surface hydroxide) are much less thermally stable than their bulk counterpart. In a dry environment, the interface/surface hydroxides slowly degenerate over many years/decades at room temperature into lithium oxide, releasing water vapor and ultimately hydrogen gas through reaction of the water vapor with the lithium hydride substrate. This outgassing can potentially cause metal hydriding and/or compatibility issues elsewhere in the device. In this chapter, the morphology and the chemistry of the corrosion layer grown on lithium hydride (and in some cases, its isotopic cousin, lithium deuteride) as a result of exposure to moisture are investigated. The hydrogen outgassing processes associated with the formation and subsequent degeneration of this corrosion layer are described. Experimental techniques to measure the hydrogen outgassing kinetics from lithium hydride and methods employing the measured kinetics to predict hydrogen outgassing as a function of time and temperature are presented. Finally, practical procedures to mitigate the problem of hydrogen outgassing from lithium hydride are discussed.

  7. Investigations on the nucleation kinetics of γ-glycine single crystal

    International Nuclear Information System (INIS)

    Yogambal, C.; Rajan Babu, D.; Ezhil Vizhi, R.

    2014-01-01

    Single crystals of γ-glycine were grown by slow evaporation technique. The crystalline system was confirmed by single crystal X-ray diffraction analysis. The optical absorption study has shown that the grown crystal possesses lower cut-off wavelength. Solubility and metastable zone width were estimated for different temperatures. The induction period of title compound was determined by varying the temperature and concentration. Nucleation parameters such as Gibbs volume free energy change (ΔG v ), interfacial tension (γ), critical free energy change of the nucleus (ΔG ⁎ ), nucleation rate (J), number of molecules in the critical nucleus (i ⁎ ) have been calculated for the aqueous solution grown γ-glycine single crystals. The second harmonic generation (SHG) of γ-glycine was confirmed by Q-switched Nd:YAG laser technique

  8. Inference of some pharmacokinetic parameters of the C mitomycin, through the analysis of its micro nucleate polychromatic erythrocytes induction kinetics

    International Nuclear Information System (INIS)

    Morales R, P.; Vallarino K, T.; Cruz V, V.; Delgadillo H, A.

    2003-01-01

    The objective of the present work was to establish pharmacokinetic parameters of the C Mitomycin (MMC) in vivo, comparing its kinetics of induction of polychromatic micro nucleate erythrocytes (EPGMN) with that of the gamma radiation. The used doses were of 0.75; 1.5 and 3. 0 μmoles/kg of MMC. It was observed that the MMC produces MN in the first cycle of cellular division and it is independent of the cytotoxic effect. This agent requires of a relatively long period of latency that is not compatible with her great reactivity, for what the pharmacokinetic values obtained in fact reflect the time that takes the processing of leisure in the DNA and the subsequent induction of ruptures that produce MN. (Author)

  9. Predicting Hydride Donor Strength via Quantum Chemical Calculations of Hydride Transfer Activation Free Energy.

    Science.gov (United States)

    Alherz, Abdulaziz; Lim, Chern-Hooi; Hynes, James T; Musgrave, Charles B

    2018-01-25

    We propose a method to approximate the kinetic properties of hydride donor species by relating the nucleophilicity (N) of a hydride to the activation free energy ΔG ⧧ of its corresponding hydride transfer reaction. N is a kinetic parameter related to the hydride transfer rate constant that quantifies a nucleophilic hydridic species' tendency to donate. Our method estimates N using quantum chemical calculations to compute ΔG ⧧ for hydride transfers from hydride donors to CO 2 in solution. A linear correlation for each class of hydrides is then established between experimentally determined N values and the computationally predicted ΔG ⧧ ; this relationship can then be used to predict nucleophilicity for different hydride donors within each class. This approach is employed to determine N for four different classes of hydride donors: two organic (carbon-based and benzimidazole-based) and two inorganic (boron and silicon) hydride classes. We argue that silicon and boron hydrides are driven by the formation of the more stable Si-O or B-O bond. In contrast, the carbon-based hydrides considered herein are driven by the stability acquired upon rearomatization, a feature making these species of particular interest, because they both exhibit catalytic behavior and can be recycled.

  10. A water activity based model of heterogeneous ice nucleation kinetics for freezing of water and aqueous solution droplets.

    Science.gov (United States)

    Knopf, Daniel A; Alpert, Peter A

    2013-01-01

    Immersion freezing of water and aqueous solutions by particles acting as ice nuclei (IN) is a common process of heterogeneous ice nucleation which occurs in many environments, especially in the atmosphere where it results in the glaciation of clouds. Here we experimentally show, using a variety of IN types suspended in various aqueous solutions, that immersion freezing temperatures and kinetics can be described solely by temperature, T, and solution water activity, a(w), which is the ratio of the vapour pressure of the solution and the saturation water vapour pressure under the same conditions and, in equilibrium, equivalent to relative humidity (RH). This allows the freezing point and corresponding heterogeneous ice nucleation rate coefficient, J(het), to be uniquely expressed by T and a(w), a result we term the a(w) based immersion freezing model (ABIFM). This method is independent of the nature of the solute and accounts for several varying parameters, including cooling rate and IN surface area, while providing a holistic description of immersion freezing and allowing prediction of freezing temperatures, J(het), frozen fractions, ice particle production rates and numbers. Our findings are based on experimental freezing data collected for various IN surface areas, A, and cooling rates, r, of droplets variously containing marine biogenic material, two soil humic acids, four mineral dusts, and one organic monolayer acting as IN. For all investigated IN types we demonstrate that droplet freezing temperatures increase as A increases. Similarly, droplet freezing temperatures increase as the cooling rate decreases. The log10(J(het)) values for the various IN types derived exclusively by Tand a(w), provide a complete description of the heterogeneous ice nucleation kinetics. Thus, the ABIFM can be applied over the entire range of T, RH, total particulate surface area, and cloud activation timescales typical of atmospheric conditions. Lastly, we demonstrate that ABIFM can

  11. Hydride formation on deformation twin in zirconium alloy

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Ju-Seong [Korea Atomic Energy Research Institute, 989-111 Daedeokdaero, Yuseong-gu, Daejeon, 305-353 (Korea, Republic of); Kim, Sung-Dae [Korea Institute of Material Science (KIMS), 797 Changwondaero, Changwon, Gyeongnam, 642-831 (Korea, Republic of); Yoon, Jonghun, E-mail: yooncsmd@gmail.com [Department of Mechanical Engineering, Hanyang University, 1271 Sa3-dong, Sangrok-gu, Ansan-si, Gyeonggi-do, 426-791 (Korea, Republic of)

    2016-12-15

    Hydrides deteriorate the mechanical properties of zirconium (Zr) alloys used in nuclear reactors. Intergranular hydrides that form along grain boundaries have been extensively studied due to their detrimental effects on cracking. However, it has been little concerns on formation of Zr hydrides correlated with deformation twins which is distinctive heterogeneous nucleation site in hexagonal close-packed metals. In this paper, the heterogeneous precipitation of Zr hydrides at the twin boundaries was visualized using transmission electron microscopy. It demonstrates that intragranular hydrides in the twinned region precipitates on the rotated habit plane by the twinning and intergranular hydrides precipitate along the coherent low energy twin boundaries independent of the conventional habit planes. Interestingly, dislocations around the twin boundaries play a substantial role in the nucleation of Zr hydrides by reducing the misfit strain energy.

  12. Dehydrogenation kinetics of pure and nickel-doped magnesium hydride investigated by in situ time-resolved powder X-ray diffraction

    DEFF Research Database (Denmark)

    Jensen, T.R.; Andreasen, A.; Vegge, Tejs

    2006-01-01

    The dehydrogenation kinetics of pure and nickel (Ni)-doped (2w/w%) magnesium hydride (MgH2) have been investigated by in situ time-resolved powder X-ray diffraction (PXD). Deactivated samples, i.e. air exposed, are investigated in order to focus on the effect of magnesium oxide (MgO) surface layers......, which might be unavoidable for magnesium (Mg)-based storage media for mobile applications. A curved position-sensitive detector covering 120 degrees in 20 and a rotating anode X-ray source provide a time resolution of 45 s and up to 90 powder pattems collected during an experiment under isothermal...... by the Johnson-Mehi-Avrami formalism in order to derive rate constants at different temperatures. The apparent activation energies for dehydrogenation of pure and Ni-doped magnesium hydride were E-A approximate to 300 and 250 kJ/mol, respectively. Differential scanning calorimetry gave, E-A = 270 k...

  13. Investigation of nucleation kinetics in H2SO4 vapor through modeling of gas phase kinetics coupled with particle dynamics

    Science.gov (United States)

    Carlsson, Philip T. M.; Zeuch, Thomas

    2018-03-01

    We have developed a new model utilizing our existing kinetic gas phase models to simulate experimental particle size distributions emerging in dry supersaturated H2SO4 vapor homogeneously produced by rapid oxidation of SO2 through stabilized Criegee-Intermediates from 2-butene ozonolysis. We use a sectional method for simulating the particle dynamics. The particle treatment in the model is based on first principles and takes into account the transition from the kinetic to the diffusion-limited regime. It captures the temporal evolution of size distributions at the end of the ozonolysis experiment well, noting a slight underrepresentation of coagulation effects for larger particle sizes. The model correctly predicts the shape and the modes of the experimentally observed particle size distributions. The predicted modes show an extremely high sensitivity to the H2SO4 evaporation rates of the initially formed H2SO4 clusters (dimer to pentamer), which were arbitrarily restricted to decrease exponentially with increasing cluster size. In future, the analysis presented in this work can be extended to allow a direct validation of quantum chemically predicted stabilities of small H2SO4 clusters, which are believed to initiate a significant fraction of atmospheric new particle formation events. We discuss the prospects and possible limitations of the here presented approach.

  14. Dust Effects on Nucleation Kinetics and Nanoparticle Product Size Distributions: Illustrative Case Study of a Prototype Ir(0)n Transition-Metal Nanoparticle Formation System.

    Science.gov (United States)

    Özkar, Saim; Finke, Richard G

    2017-07-05

    The question is addressed if dust is kinetically important in the nucleation and growth of Ir(0) n nanoparticles formed from [Bu 4 N] 5 Na 3 (1,5-COD)Ir I ·P 2 W 15 Nb 3 O 62 (hereafter [(COD)Ir·POM] 8- ), reduced by H 2 in propylene carbonate solvent. Following a concise review of the (often-neglected) literature addressing dust in nucleation phenomena dating back to the late 1800s, the nucleation and growth kinetics of the [(COD)Ir·POM] 8- precatalyst system are examined for the effects of 0.2 μm microfiltration of the solvent and precatalyst solution, of rinsing the glassware with that microfiltered solvent, of silanizing the glass reaction vessel, for the addition of nucleation apparent rate "constant" k 1obs(bimol) is shown to be slowed by a factor of ∼5 to ∼7.6, depending on the precise experiment and its conditions, just by the filtration of the precatalyst solution using a 0.20 μm filter and rinsing the glassware surface with 0.20 μm filtered propylene carbonate solvent; (ii) that simply employing a 0.20 μm filtration step narrows the size distribution of the resulting Ir(0) n nanoparticles by a factor of 2.4 from ±19 to ±8%, a remarkable result; (iii) that the narrower size distribution can be accounted for by the slowed nucleation rate constant, k 1obs(bimol) , and by the unchanged autocatalytic growth rate constant, k 2obs(bimol) , that is, by the increased ratio of k 2obs(bimol) /k 1obs(bimol) that further separates nucleation from growth in time for filtered vs unfiltered solutions; and (iv) that five lines of evidence indicate that the filterable component of the solution, which has nucleation rate-enhancing and size-dispersion broadening effects, is dust.

  15. E-cadherin junction formation involves an active kinetic nucleation process

    Science.gov (United States)

    Biswas, Kabir H.; Hartman, Kevin L.; Yu, Cheng-han; Harrison, Oliver J.; Song, Hang; Smith, Adam W.; Huang, William Y. C.; Lin, Wan-Chen; Guo, Zhenhuan; Padmanabhan, Anup; Troyanovsky, Sergey M.; Dustin, Michael L.; Shapiro, Lawrence; Honig, Barry; Zaidel-Bar, Ronen; Groves, Jay T.

    2015-01-01

    Epithelial (E)-cadherin-mediated cell−cell junctions play important roles in the development and maintenance of tissue structure in multicellular organisms. E-cadherin adhesion is thus a key element of the cellular microenvironment that provides both mechanical and biochemical signaling inputs. Here, we report in vitro reconstitution of junction-like structures between native E-cadherin in living cells and the extracellular domain of E-cadherin (E-cad-ECD) in a supported membrane. Junction formation in this hybrid live cell-supported membrane configuration requires both active processes within the living cell and a supported membrane with low E-cad-ECD mobility. The hybrid junctions recruit α-catenin and exhibit remodeled cortical actin. Observations suggest that the initial stages of junction formation in this hybrid system depend on the trans but not the cis interactions between E-cadherin molecules, and proceed via a nucleation process in which protrusion and retraction of filopodia play a key role. PMID:26290581

  16. Cloud condensation nuclei droplet growth kinetics of ultrafine particles during anthropogenic nucleation events

    Science.gov (United States)

    Shantz, N. C.; Pierce, J. R.; Chang, R. Y.-W.; Vlasenko, A.; Riipinen, I.; Sjostedt, S.; Slowik, J. G.; Wiebe, A.; Liggio, J.; Abbatt, J. P. D.; Leaitch, W. R.

    2012-02-01

    Evolution of the cloud condensation nucleus (CCN) activity of 36 ± 4 nm diameter anthropogenic aerosol particles at a water supersaturation of 1.0 ± 0.1% is examined for particle nucleation and growth. During the early stages of one event, relatively few of the anthropogenic particles at 36 nm were CCN active and their growth rates by water condensation were delayed relative to ammonium sulphate particles. As the event progressed, the particle size distribution evolved to larger sizes and the relative numbers of particles at 36 nm that were CCN active increased until all the 36 nm particles were activating at the end of the event. Based on the chemistry of larger particles and the results from an aerosol chemical microphysics box model, the increase in CCN activity of the particles was most likely the result of the condensation of sulphate in this case. Despite the increased CCN activity, a delay was observed in the initial growth of these particles into cloud droplets, which persisted even when the aerosol was most CCN active later in the afternoon. Simulations show that the delay in water uptake is explained by a reduction of the mass accommodation coefficient assuming that the composition of the 36 nm particles is the same as the measured composition of the 60-100 nm particles.

  17. New Parameterizations for Neutral and Ion-Induced Sulfuric Acid-Water Particle Formation in Nucleation and Kinetic Regimes

    Science.gov (United States)

    Määttänen, Anni; Merikanto, Joonas; Henschel, Henning; Duplissy, Jonathan; Makkonen, Risto; Ortega, Ismael K.; Vehkamäki, Hanna

    2018-01-01

    We have developed new parameterizations of electrically neutral homogeneous and ion-induced sulfuric acid-water particle formation for large ranges of environmental conditions, based on an improved model that has been validated against a particle formation rate data set produced by Cosmics Leaving OUtdoor Droplets (CLOUD) experiments at European Organization for Nuclear Research (CERN). The model uses a thermodynamically consistent version of the Classical Nucleation Theory normalized using quantum chemical data. Unlike the earlier parameterizations for H2SO4-H2O nucleation, the model is applicable to extreme dry conditions where the one-component sulfuric acid limit is approached. Parameterizations are presented for the critical cluster sulfuric acid mole fraction, the critical cluster radius, the total number of molecules in the critical cluster, and the particle formation rate. If the critical cluster contains only one sulfuric acid molecule, a simple formula for kinetic particle formation can be used: this threshold has also been parameterized. The parameterization for electrically neutral particle formation is valid for the following ranges: temperatures 165-400 K, sulfuric acid concentrations 104-1013 cm-3, and relative humidities 0.001-100%. The ion-induced particle formation parameterization is valid for temperatures 195-400 K, sulfuric acid concentrations 104-1016 cm-3, and relative humidities 10-5-100%. The new parameterizations are thus applicable for the full range of conditions in the Earth's atmosphere relevant for binary sulfuric acid-water particle formation, including both tropospheric and stratospheric conditions. They are also suitable for describing particle formation in the atmosphere of Venus.

  18. Equilibrium and Kinetic Studies of Systems of Hydrogen Isotopes, Lithium Hydrides, Aluminum and LiAlO2

    International Nuclear Information System (INIS)

    Owen, J.H.

    2001-01-01

    This paper described measurements of (1) the distribution of tritium and helium throughout both phases of irradiated Li-Al alloy, (2) the migration rate of tritium during moderate heating, (3) equilibrium pressures as functions of temperature of H2, D2, or T2 in contact with lithium hydrides + aluminum, Li-Al alloy, or irradiated Li-Al alloy, (4) the equilibrium constant for the reaction as a function of temperature, and (5) extraction rates of tritium from irradiated LiAlO2 targets at elevated temperatures

  19. Morphology, Nucleation, and Isothermal Crystallization Kinetics of Poly(ε-caprolactone Mixed with a Polycarbonate/MWCNTs Masterbatch

    Directory of Open Access Journals (Sweden)

    Thandi P. Gumede

    2017-12-01

    Full Text Available In this study, nanocomposites were prepared by melt blending poly (ε-caprolactone (PCL with a (polycarbonate (PC/multi-wall carbon nanotubes (MWCNTs masterbatch in a twin-screw extruder. The nanocomposites contained 0.5, 1.0, 2.0, and 4.0 wt % MWCNTs. Even though PCL and PC have been reported to be miscible, our DSC (Differential Scanning Calorimetry, SAXS (Small Angle X-ray Scattering, and WAXS (Wide Angle X-ray Scattering results showed partial miscibility, where two phases were formed (PC-rich and PCL-rich phases. In the PC-rich phase, the small amount of PCL chains included within this phase plasticized the PC component and the PC-rich phase was therefore able to crystallize. In contrast, in the PCL-rich phase the amount of PC chains present generates changes in the glass transition temperature of the PCL phase that were much smaller than those predicted by the Fox equation. The presence of two phases was corroborated by SEM, TEM, and AFM observations where a fair number of MWCNTs diffused from the PC-rich phase to the PCL-rich phase, even though there were some MWCNTs agglomerates confined to PC-rich droplets. Standard DSC measurements demonstrated that the MWCNTs nucleation effects are saturated at a 1 wt % MWCNT concentration on the PCL-rich phase. This is consistent with the dielectric percolation threshold, which was found to be between 0.5 and 1 wt % MWCNTs. However, the nucleating efficiency was lower than literature reports for PCL/MWCNTs, due to limited phase mixing between the PC-rich and the PCL-rich phases. Isothermal crystallization experiments performed by DSC showed an increase in the overall crystallization kinetics of PCL with increases in MWCNTs as a result of their nucleating effect. Nevertheless, the crystallinity degree of the nanocomposite containing 4 wt % MWCNTs decreased by about 15% in comparison to neat PCL. This was attributed to the presence of the PC-rich phase, which was able to crystallize in view of the

  20. Modeling of helium bubble nucleation and growth in austenitic stainless steels using an Object Kinetic Monte Carlo method

    International Nuclear Information System (INIS)

    De Backer, A.; Adjanor, G.; Domain, C.; Lescoat, M.L.; Jublot-Leclerc, S.; Fortuna, F.; Gentils, A.; Ortiz, C.J.; Souidi, A.; Becquart, C.S.

    2015-01-01

    Implantation of 10 keV helium in 316L steel thin foils was performed in JANNuS-Orsay facility and modeled using a multiscale approach. Density Functional Theory (DFT) atomistic calculations [1] were used to obtain the properties of He and He-vacancy clusters, and the Binary Collision Approximation based code MARLOWE was applied to determine the damage and He-ion depth profiles as in [2,3]. The processes involved in the homogeneous He bubble nucleation and growth were defined and implemented in the Object Kinetic Monte Carlo code LAKIMOCA [4]. In particular as the He to dpa ratio was high, self-trapping of He clusters and the trap mutation of He-vacancy clusters had to be taken into account. With this multiscale approach, the formation of bubbles was modeled up to nanometer-scale size, where bubbles can be observed by Transmission Electron Microscopy. Their densities and sizes were studied as functions of fluence (up to 5 × 10 19 He/m 2 ) at two temperatures (473 and 723 K) and for different sample thicknesses (25–250 nm). It appears that the damage is not only due to the collision cascades but is also strongly controlled by the He accumulation in pressurized bubbles. Comparison with experimental data is discussed and sensible agreement is achieved

  1. Modeling of helium bubble nucleation and growth in austenitic stainless steels using an Object Kinetic Monte Carlo method

    Energy Technology Data Exchange (ETDEWEB)

    De Backer, A., E-mail: andree.debacker@ccfe.ac.uk [UMET, UMR 8207, Université Lille 1, Villeneuve d’Ascq (France); CCFE, Culham Centre for Fusion Energy, Abingdon, Oxon (United Kingdom); Adjanor, G.; Domain, C.; Lescoat, M.L. [EDF R& D, MMC Centre des Renardières, Moret-sur-Loing (France); Jublot-Leclerc, S.; Fortuna, F.; Gentils, A. [CSNSM, Univ Paris-Sud, CNRS/IN2P3, Orsay (France); Ortiz, C.J. [CIEMAT, Laboratorio Nacional de Fusión por Confinamiento Magnético, Madrid (Spain); Souidi, A. [Université Dr. Tahar Moulay de Saida, Saida (Algeria); Becquart, C.S. [UMET, UMR 8207, Université Lille 1, Villeneuve d’Ascq (France)

    2015-06-01

    Implantation of 10 keV helium in 316L steel thin foils was performed in JANNuS-Orsay facility and modeled using a multiscale approach. Density Functional Theory (DFT) atomistic calculations [1] were used to obtain the properties of He and He-vacancy clusters, and the Binary Collision Approximation based code MARLOWE was applied to determine the damage and He-ion depth profiles as in [2,3]. The processes involved in the homogeneous He bubble nucleation and growth were defined and implemented in the Object Kinetic Monte Carlo code LAKIMOCA [4]. In particular as the He to dpa ratio was high, self-trapping of He clusters and the trap mutation of He-vacancy clusters had to be taken into account. With this multiscale approach, the formation of bubbles was modeled up to nanometer-scale size, where bubbles can be observed by Transmission Electron Microscopy. Their densities and sizes were studied as functions of fluence (up to 5 × 10{sup 19} He/m{sup 2}) at two temperatures (473 and 723 K) and for different sample thicknesses (25–250 nm). It appears that the damage is not only due to the collision cascades but is also strongly controlled by the He accumulation in pressurized bubbles. Comparison with experimental data is discussed and sensible agreement is achieved.

  2. Void nucleation at heterogeneities

    International Nuclear Information System (INIS)

    Seyyedi, S.A.; Hadji-Mirzai, M.; Russell, K.C.

    The energetics and kinetics of void nucleation at dislocations and interfaces are analyzed. These are potential void nucleation sites only when they are not point defect sinks. Both kinds of site are found to be excellent catalysts in the presence of inert gas

  3. Equilibrium and kinetic studies of systems of hydrogen isotopes, lithium hydrides, aluminum, and LiAlO2

    International Nuclear Information System (INIS)

    Owen, J.H.; Randall, D.

    1976-01-01

    Tritium might be bred by the 6 Li(n,α)T reaction in a solid lithium alloy or compound in the blanket of a controlled thermonuclear reactor to avoid problems associated with molten lithium or lithium compounds. Li--Al and LiAlO 2 systems containing hydrogen, deuterium, or tritium were studied 10 to 15 years ago at the Savannah River Laboratory. This paper descibes measurements of (1) the distribution of tritium and helium throughout both α and β phases of irradiated Li--Al alloy, (2) the migration rate of tritium to the β phase during moderate heating, (3) equilibrium pressures as functions of temperature of H 2 , D 2 , or T 2 in contact with lithium hydrides + aluminum, Li--Al alloy, or irradiated Li--Al alloy, (4) the equilibrium constant for the reaction LiH + Al → LiAl + 1 / 2 H 2 as a function of temperature, and (5) extraction rates of tritium from irradiated LiAlO 2 targets at elevated temperatures

  4. Initiation of delayed hydride cracking in zirconium-2.5 wt% niobium

    International Nuclear Information System (INIS)

    Shalabi, A.F.; Meneley, D.A.

    1990-01-01

    Delayed hydride cracking in zirconium alloys is caused by the repeated precipitation and cracking of brittle hydrides. The growth kinetic of the hydrides have been measured to evaluate the critical hydride length for crack initiation. Hydride growth leading to crack initiation follows an approximate (time) 1/3 law on the average; crack propagation proceeds in a stepwise fashion. The critical length of hydride for crack initiation increases with stress and temperature. The fracture criterion for crack initiation predicts the critical hydride length at a give stress level and temperature. The fracture initiation mechanism of the hydride confirms the temperature effects for heating and cooling cycles under services loads. (orig.)

  5. Kinetic, stereochemical, and molecular association factors in the hydralumination of group IV subtituted alkynes. The role of p/sub π/-d/sub π/ conjugation in the addition of diisobutylaluminum hydride to trimethyl(phenylethynyl)silane

    International Nuclear Information System (INIS)

    Eisch, J.J.; Rhee, S.G.

    1975-01-01

    The kinetic, stereochemistry, and molecular association factors for the addition of diisobutylaluminum hydride to trimethyl(phenylethynyl)silane were studied in the temperature range of -10 to 38 0 . Hydralumination was found to have a kinetic true order of essentially one in the alkyne and one-third in the hydride. Although the trans adduct is the predominating product (approximately 99 percent) after completion of the hydralumination, the variation of the proportion of cis adduct and the initial rate law are consistent with a kinetically controlled cis hydralumination by monomeric R 2 'AlH, followed by a rapid isomerization to the trans adduct. The trans adduct formed a complex with l equivalent to the hydride. This complexation had to be taken into account, in order to explain the observed rate retardation and to obtain satisfactory integrated rate expressions for hydraluminations monitored to high conversion. Since in hydralumination this silylacetylene shows a stereospecificity and regiospecificity exactly opposite that of tert-butyl(phenyl)acetylene, as well as a heightened reactivity, a critical consideration of possible p/sub π/--d/sub π/ electronic effects was undertaken. The unusually facile isomerization of the resulting silyl-substituted vinylalanes, however, does seem more persuasive evidence for a p/sub π/--d/sub π/ effect, which promotes isomerization by electrophilic attack of R 2 'AlH on the carbon α to the Me 3 Si group. (U.S.)

  6. Electrochemical modeling of hydrogen storage in hydride-forming electrodes

    NARCIS (Netherlands)

    Ledovskikh, A.; Danilov, D.; Vermeulen, P.; Notten, P.H.L.

    2009-01-01

    An electrochemical kinetic model (EKM) is developed, describing the electrochemical hydrogen storage in hydride-forming materials under equilibrium conditions. This model is based on first principles of electrochemical reaction kinetics and statistical thermodynamics and describes the complex,

  7. Nucleation and growth kinetics of electrodeposited sulfate-doped polypyrrole: determination of the diffusion coefficient of SO(4)(2-) in the polymeric membrane.

    Science.gov (United States)

    Licona-Sánchez, T de J; Alvarez-Romero, G A; Mendoza-Huizar, L H; Galán-Vidal, C A; Palomar-Pardavé, M; Romero-Romo, M; Herrera-Hernández, H; Uruchurtu, J; Juárez-García, J M

    2010-08-05

    A kinetic study for the electrosynthesis of polypyrrole (Ppy) doped with SO(4)(2-) ions is presented. Ppy films were electrochemically polymerized onto a graphite-epoxy resin electrode. Experimental current density transients (j-t) were obtained for three different potentiometric behaviors: anionic, cationic, and a combination. Theoretical models were used to fit the experimental j-t data to determine the nucleation and growth processes controlling the polymer synthesis. It was encountered that, in all cases, pyrrole electropolimerization involves two concomitant processes, namely, a Ppy diffusion limited multiple 3D nucleation and growth and pyrrole electro-oxidation on the growing surface of the Ppy nuclei. SEM analysis of the electrodes surfaces reveals that Ppy deposition occurred over most of the electrode surface by multiple nucleation of hemispheres, as the theoretical model used for the analysis of the current transients required. Hemispherical particles formed the polymeric film displaying different sizes. The order for the particle size was as follows: anionic > anionic-cationic > cationic. These results are congruent with those obtained by theoretical analysis of the corresponding current transients. Analysis of the impedance measurements recorded on the anionic Ppy film, immersed in an aqueous solution with different sulfate ion concentrations evidenced that SO(4)(2-) ions diffuse through the Ppy film provoking a decrease of its electrical resistance and an increase of its dielectric constant. From the Warburg impedance coefficient, the sulfate coefficient of diffusion in the Ppy film was 1.38 x 10(-9) cm(2) s(-1).

  8. Quantifying the stress fields due to a delta-hydride precipitate in alpha-Zr matrix

    Energy Technology Data Exchange (ETDEWEB)

    Tummala, Hareesh [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Capolungo, Laurent [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Tome, Carlos N. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2017-10-19

    This report is a preliminary study on δ-hydride precipitate in zirconium alloy performed using 3D discrete dislocation dynamics simulations. The ability of dislocations in modifying the largely anisotropic stress fields developed by the hydride particle in a matrix phase is addressed for a specific dimension of the hydride. The influential role of probable dislocation nucleation at the hydride-matrix interface is reported. Dislocation nucleation around a hydride was found to decrease the shear stress (S13) and also increase the normal stresses inside the hydride. We derive conclusions on the formation of stacks of hydrides in zirconium alloys. The contribution of mechanical fields due to dislocations was found to have a non-negligible effect on such process.

  9. Nucleation theory with delayed interactions: an application to the early stages of the receptor-mediated adhesion/fusion kinetics of lipid vesicles.

    Science.gov (United States)

    Raudino, Antonio; Pannuzzo, Martina

    2010-01-28

    A semiquantitative theory aimed to describe the adhesion kinetics between soft objects, such as living cells or vesicles, has been developed. When rigid bodies are considered, the adhesion kinetics is successfully described by the classical Derjaguin, Landau, Verwey, and Overbeek (DLVO) picture, where the energy profile of two approaching bodies is given by a two asymmetrical potential wells separated by a barrier. The transition probability from the long-distance to the short-distance minimum defines the adhesion rate. Conversely, soft bodies might follow a different pathway to reach the short-distance minimum: thermally excited fluctuations give rise to local protrusions connecting the approaching bodies. These transient adhesion sites are stabilized by short-range adhesion forces (e.g., ligand-receptor interactions between membranes brought at contact distance), while they are destabilized both by repulsive forces and by the elastic deformation energy. Above a critical area of the contact site, the adhesion forces prevail: the contact site grows in size until the complete adhesion of the two bodies inside a short-distance minimum is attained. This nucleation mechanism has been developed in the framework of a nonequilibrium Fokker-Planck picture by considering both the adhesive patch growth and dissolution processes. In addition, we also investigated the effect of the ligand-receptor pairing kinetics at the adhesion site in the time course of the patch expansion. The ratio between the ligand-receptor pairing kinetics and the expansion rate of the adhesion site is of paramount relevance in determining the overall nucleation rate. The theory enables one to self-consistently include both thermodynamics (energy barrier height) and dynamic (viscosity) parameters, giving rise in some limiting cases to simple analytical formulas. The model could be employed to rationalize fusion kinetics between vesicles, provided the short-range adhesion transition is the rate

  10. Metal hydrides for hydrogen storage in nickel hydrogen batteries

    International Nuclear Information System (INIS)

    Bittner, H.F.; Badcock, C.C.; Quinzio, M.V.

    1984-01-01

    Metal hydride hydrogen storage in nickel hydrogen (Ni/H 2 ) batteries has been shown to increase battery energy density and improve battery heat management capabilities. However the properties of metal hydrides in a Ni/H 2 battery environment, which contains water vapor and oxygen in addition to the hydrogen, have not been well characterized. This work evaluates the use of hydrides in Ni/H 2 batteries by fundamental characterization of metal hydride properties in a Ni/H 2 cell environment. Hydrogen sorption properties of various hydrides have been measured in a Ni/H 2 cell environment. Results of detailed thermodynamic and kinetic studies of hydrogen sorption in LaNi 5 in a Ni/H 2 cell environment are presented. Long-term cycling studies indicate that degradation of the hydride can be minimized by cycling between certain pressure limits. A model describing the mechanism of hydride degradation is presented

  11. Dimers in nucleating vapors

    Science.gov (United States)

    Lushnikov, A. A.; Kulmala, M.

    1998-09-01

    The dimer stage of nucleation may affect considerably the rate of the nucleation process at high supersaturation of the nucleating vapor. Assuming that the dimer formation limits the nucleation rate, the kinetics of the particle formation-growth process is studied starting with the definition of dimers as bound states of two associating molecules. The partition function of dimer states is calculated by summing the Boltzmann factor over all classical bound states, and the equilibrium population of dimers is found for two types of intermolecular forces: the Lennard-Jones (LJ) and rectangular well+hard core (RW) potentials. The principle of detailed balance is used for calculating the evaporation rate of dimers. The kinetics of the particle formation-growth process is then investigated under the assumption that the trimers are stable with respect to evaporation and that the condensation rate is a power function of the particle mass. If the power exponent λ=n/(n+1) (n is a non-negative integer), the kinetics of the process is described by a finite set of moments of particle mass distribution. When the characteristic time of the particle formation by nucleation is much shorter than that of the condensational growth, n+2 universal functions of a nondimensional time define the kinetic process. These functions are calculated for λ=2/3 (gas-to-particle conversion in the free molecular regime) and λ=1/2 (formation of islands on surfaces).

  12. Complex hydrides for hydrogen storage

    Science.gov (United States)

    Zidan, Ragaiy

    2006-08-22

    A hydrogen storage material and process of forming the material is provided in which complex hydrides are combined under conditions of elevated temperatures and/or elevated temperature and pressure with a titanium metal such as titanium butoxide. The resulting fused product exhibits hydrogen desorption kinetics having a first hydrogen release point which occurs at normal atmospheres and at a temperature between 50.degree. C. and 90.degree. C.

  13. Nucleation kinetics and growth aspects of semi organic non-linear optical bis thiourea cadmium acetate single crystals

    International Nuclear Information System (INIS)

    Sankar, R.; Raghavan, C.M.; Jayavel, R.

    2006-01-01

    Nucleation parameters such as metastable zone width, induction period and interfacial energy have been determined for the aqueous solution growth of bis thiourea cadmium acetate (BTCA) single crystals. Solubility of BTCA has been determined for various temperatures. Metastable zone width and induction period values have been estimated in order to optimize the growth parameters. The interfacial tension values derived from experimentally determined induction period are found to be comparable with theoretical values. Bulk crystals of BTCA have been grown using the optimized growth parameters. The grown crystals have been subjected to structural, optical and mechanical property studies. (copyright 2006 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  14. Dehydrogenation kinetics for pure and nickel-doped magnesium hydride investigated by in-situ, time-resolved powder diffraction (poster)

    DEFF Research Database (Denmark)

    Jensen, T.R.; Andreasen, A.; Vegge, T.

    2004-01-01

    temperatures. Apparent activation energies were calculated from Arrhenius plots revealing values of ca. 300 and 250 kJ/mol for the dehydrogenationof pure and nickel-doped magnesium hydride, respectively, in accord with EA= 270 kJ/mol measured by thermal desorption spectroscopy for these non-activated materials...

  15. Crystal plasticity model for BCC iron atomistically informed by kinetics of correlated kinkpair nucleation on screw dislocation

    Science.gov (United States)

    Narayanan, Sankar; McDowell, David L.; Zhu, Ting

    2014-04-01

    The mobility of dislocation in body-centered cubic (BCC) metals is controlled by the thermally activated nucleation of kinks along the dislocation core. By employing a recent interatomic potential and the Nudged Elastic Band method, we predict the atomistic saddle-point state of 1/2 screw dislocation motion in BCC iron that involves the nucleation of correlated kinkpairs and the resulting double superkinks. This unique process leads to a single-humped minimum energy path that governs the one-step activation of a screw dislocation to move into the adjacent {110} Peierls valley, which contrasts with the double-humped energy path and the two-step transition predicted by other interatomic potentials. Based on transition state theory, we use the atomistically computed, stress-dependent kinkpair activation parameters to inform a coarse-grained crystal plasticity flow rule. Our atomistically-informed crystal plasticity model quantitatively predicts the orientation dependent stress-strain behavior of BCC iron single crystals in a manner that is consistent with experimental results. The predicted temperature and strain-rate dependencies of the yield stress agree with experimental results in the 200-350 K temperature regime, and are rationalized by the small activation volumes associated with the kinkpair-mediated motion of screw dislocations.

  16. Morphology, Nucleation, and Isothermal Crystallization Kinetics of Poly(Butylene Succinate Mixed with a Polycarbonate/MWCNT Masterbatch

    Directory of Open Access Journals (Sweden)

    Thandi P. Gumede

    2018-04-01

    Full Text Available In this study, nanocomposites were prepared by melt blending poly(butylene succinate (PBS with a polycarbonate (PC/multi-wall carbon nanotubes (MWCNTs masterbatch, in a twin-screw extruder. The nanocomposites contained 0.5, 1.0, 2.0, and 4.0 wt% MWCNTs. Differential scanning calorimetry (DSC, small angle X-ray scattering (SAXS and wide angle X-ray scattering (WAXS results indicate that the blends are partially miscible, hence they form two phases (i.e., PC-rich and PBS-rich phases. The PC-rich phase contained a small amount of PBS chains that acted as a plasticizer and enabled crystallization of the PC component. In the PBS-rich phase, the amount of the PC chains present gave rise to increases in the glass transition temperature of the PBS phase. The presence of two phases was supported by scanning electron microscopy (SEM and atomic force microscopy (AFM analysis, where most MWCNTs aggregated in the PC-rich phase (especially at the high MWCNTs content of 4 wt% and a small amount of MWCNTs were able to diffuse to the PBS-rich phase. Standard DSC scans showed that the MWCNTs nucleation effects saturated at 0.5 wt% MWCNT content on the PBS-rich phase, above this content a negative nucleation effect was observed. Isothermal crystallization results indicated that with 0.5 wt% MWCNTs the crystallization rate was accelerated, but further increases in MWCNTs loading (and also in PC content resulted in progressive decreases in crystallization rate. The results are explained by increased MWCNTs aggregation and reduced diffusion rates of PBS chains, as the masterbatch content in the blends increased.

  17. Use of triammonium salt of aurin tricarboxylic acid as risk mitigant for aluminum hydride

    Science.gov (United States)

    Cortes-Concepcion, Jose A.; Anton, Donald L.

    2017-08-08

    A process and a resulting product by process of an aluminum hydride which is modified with by physically combining in a ball milling process an aluminum hydride with a triammonium salt of aurin tricarboxylic acid. The resulting product is an aluminum hydride which is resistant to air, ambient moisture, and liquid water while maintaining useful hydrogen storage and release kinetics.

  18. Metal hydrides based high energy density thermal battery

    International Nuclear Information System (INIS)

    Fang, Zhigang Zak; Zhou, Chengshang; Fan, Peng; Udell, Kent S.; Bowman, Robert C.; Vajo, John J.; Purewal, Justin J.; Kekelia, Bidzina

    2015-01-01

    Highlights: • The principle of the thermal battery using advanced metal hydrides was demonstrated. • The thermal battery used MgH 2 and TiMnV as a working pair. • High energy density can be achieved by the use of MgH 2 to store thermal energy. - Abstract: A concept of thermal battery based on advanced metal hydrides was studied for heating and cooling of cabins in electric vehicles. The system utilized a pair of thermodynamically matched metal hydrides as energy storage media. The pair of hydrides that was identified and developed was: (1) catalyzed MgH 2 as the high temperature hydride material, due to its high energy density and enhanced kinetics; and (2) TiV 0.62 Mn 1.5 alloy as the matching low temperature hydride. Further, a proof-of-concept prototype was built and tested, demonstrating the potential of the system as HVAC for transportation vehicles

  19. Metal Hydride Compression

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, Terry A. [Sandia National Lab. (SNL-CA), Livermore, CA (United States); Bowman, Robert [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Smith, Barton [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Anovitz, Lawrence [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Jensen, Craig [Hawaii Hydrogen Carriers LLC, Honolulu, HI (United States)

    2017-07-01

    feed pressure of >50 bar and a delivery pressure ≥ 875 bar of high purity H2 gas using the scheme shown in Figure 1. Progress to date includes the selection of two candidate metal hydrides for each compressor stage, supplier engagement and synthesis of small samples, and the beginning of in-depth characterization of their thermodynamics, kinetics, and hydrogen capacities for optimal performance with respect to energy requirements and efficiency. Additionally, bed design trade studies are underway and will be finalized in FY18. Subsequently, the prototype two-stage compressor will be fabricated, assembled and experimentally evaluated in FY19.

  20. A classical density functional investigation of nucleation

    International Nuclear Information System (INIS)

    Ghosh, Satinath; Ghosh, Swapan K.

    2009-01-01

    Study of nucleation and growth phenomena in condensation is of prime importance in various applications such as crystal growth, nanoparticle synthesis, pattern formation etc. The knowledge of nucleation barrier in condensation is necessary to control the nucleation kinetics, size of the nanoparticles etc. Classical nucleation theory (CNT) assumes the density of the drop as bulk density irrespective of the size of the drop and overestimates the nucleation barrier. Here we are interested in solving the problem analytically using density functional theory (DFT) with square gradient approximation along the lines of Cahn and Hilliard. Nucleation barrier and density profile obtained in this work are consistent with other works based on nonclassical theory. (author)

  1. Steric effects on the primary isotope dependence of secondary kinetic isotope effects in hydride transfer reactions in solution: caused by the isotopically different tunneling ready state conformations?

    Science.gov (United States)

    Maharjan, Binita; Raghibi Boroujeni, Mahdi; Lefton, Jonathan; White, Ormacinda R; Razzaghi, Mortezaali; Hammann, Blake A; Derakhshani-Molayousefi, Mortaza; Eilers, James E; Lu, Yun

    2015-05-27

    The observed 1° isotope effect on 2° KIEs in H-transfer reactions has recently been explained on the basis of a H-tunneling mechanism that uses the concept that the tunneling of a heavier isotope requires a shorter donor-acceptor distance (DAD) than that of a lighter isotope. The shorter DAD in D-tunneling, as compared to H-tunneling, could bring about significant spatial crowding effect that stiffens the 2° H/D vibrations, thus decreasing the 2° KIE. This leads to a new physical organic research direction that examines how structure affects the 1° isotope dependence of 2° KIEs and how this dependence provides information about the structure of the tunneling ready states (TRSs). The hypothesis is that H- and D-tunneling have TRS structures which have different DADs, and pronounced 1° isotope effect on 2° KIEs should be observed in tunneling systems that are sterically hindered. This paper investigates the hypothesis by determining the 1° isotope effect on α- and β-2° KIEs for hydride transfer reactions from various hydride donors to different carbocationic hydride acceptors in solution. The systems were designed to include the interactions of the steric groups and the targeted 2° H/D's in the TRSs. The results substantiate our hypothesis, and they are not consistent with the traditional model of H-tunneling and 1°/2° H coupled motions that has been widely used to explain the 1° isotope dependence of 2° KIEs in the enzyme-catalyzed H-transfer reactions. The behaviors of the 1° isotope dependence of 2° KIEs in solution are compared to those with alcohol dehydrogenases, and sources of the observed "puzzling" 2° KIE behaviors in these enzymes are discussed using the concept of the isotopically different TRS conformations.

  2. Precipitation of γ-zirconium hydride in zirconium

    International Nuclear Information System (INIS)

    Carpenter, G.J.C.

    1978-01-01

    A mechanism for the precipitation of γ-zirconium hydride in zirconium is presented which does not require the diffusion of zirconium. The transformation is completed by shears caused by 1/3 (10 anti 10) Shockley partial dislocations on alternate zirconium basal planes, either by homogeneous nucleation or at lattice imperfections. Homogeneous nucleation is considered least likely in view of the large nucleation barrier involved. Hydrides may form at dislocations by the generation of partials by means of either a pole or ratchet mechanism. The former requires dislocations with a component of Burgers vector along the c-axis, but contrast experiments show that these are not normally observed in annealed zirconium. It is therefore most likely that intragranular hydrides form at the regular 1/3 (11 anti 20) dislocations, possibly by means of a ratchet mechanism. Contrast experiments in the electron microscope show that the precipitates have a shear character consistent with the mechanism suggested. The possibility that the shear dislocations associated with the hydrides are emissary dislocations is considered and a model suggested in which this function is satisfied together with the partial relief of misfit stresses. The large shear strains associated with the precipitation mechanism may play an important role in the preferential orientation of hydrides under stress

  3. Effects of clustered nucleation on recrystallization

    DEFF Research Database (Denmark)

    Storm, Søren; Juul Jensen, Dorte

    2009-01-01

    Computer simulations are used to study effects of an experimentally determined 3D distribution of nucleation sites on the recrystallization kinetics and on the evolution of the recrystallized microstructure as compared to simulations with random nucleation. It is found that although...... the experimentally observed clustering is not very strong, it changes the kinetics and the recrystallized microstructural morphology plus leads to a recrystallized grain size distribution, which is significantly broadened compared to that of random nucleation simulations. (C) 2009 Published by Elsevier Ltd...

  4. Precipitation of hydrides in high purity niobium after different treatments

    Energy Technology Data Exchange (ETDEWEB)

    Barkov, F.; Romanenko, A.; Trenikhina, Y.; Grassellino, A.

    2013-01-01

    Precipitation of lossy non-superconducting niobium hydrides represents a known problem for high purity niobium in superconducting applications. Using cryogenic optical and laser confocal scanning microscopy we have directly observed surface precipitation and evolution of niobium hydrides in samples after different treatments used for superconducting RF cavities for particle acceleration. Precipitation is shown to occur throughout the sample volume, and the growth of hydrides is well described by the fast diffusion-controlled process in which almost all hydrogen is precipitated at $T=140$~K within $\\sim30$~min. 120$^{\\circ}$C baking and mechanical deformation are found to affect hydride precipitation through their influence on the number of nucleation and trapping centers.

  5. Catalitic effect of Co on hydrogen desorption form nanostucturated magnesium hydride

    Directory of Open Access Journals (Sweden)

    Matović Ljiljana Lj.

    2008-01-01

    Full Text Available To study the influence of 3d transition metal addition on desorption kinetics of MgH2 ball milling of MgH2-Co blends was performed under Ar. Microstructural and morphological characterization, performed by XRD and SEM, show a huge correlation with thermal stability and hydrogen desorption properties investigated by DSC. A complex desorption behavior is correlated with the dispersion of the metal additive particles on hydride matrix. The activation energy for H2 desorption from MgH2-Co composite was calculated from both non-isothermal and isothermal methods to be 130 kJ/mol which means that mutually diffusion and nucleation and growth of new phase control the dehydration process.

  6. Computational Replication of the Primary Isotope Dependence of Secondary Kinetic Isotope Effects in Solution Hydride-Transfer Reactions: Supporting the Isotopically Different Tunneling Ready State Conformations.

    Science.gov (United States)

    Derakhshani-Molayousefi, Mortaza; Kashefolgheta, Sadra; Eilers, James E; Lu, Yun

    2016-06-30

    We recently reported a study of the steric effect on the 1° isotope dependence of 2° KIEs for several hydride-transfer reactions in solution (J. Am. Chem. Soc. 2015, 137, 6653). The unusual 2° KIEs decrease as the 1° isotope changes from H to D, and more in the sterically hindered systems. These were explained in terms of a more crowded tunneling ready state (TRS) conformation in D-tunneling, which has a shorter donor-acceptor distance (DAD) than in H-tunneling. To examine the isotopic DAD difference explanation, in this paper, following an activated motion-assisted H-tunneling model that requires a shorter DAD in a heavier isotope transfer process, we computed the 2° KIEs at various H/D positions at different DADs (2.9 Å to 3.5 Å) for the hydride-transfer reactions from 2-propanol to the xanthylium and thioxanthylium ions (Xn(+) and TXn(+)) and their 9-phenyl substituted derivatives (Ph(T)Xn(+)). The calculated 2° KIEs match the experiments and the calculated DAD effect on the 2° KIEs fits the observed 1° isotope effect on the 2° KIEs. These support the motion-assisted H-tunneling model and the isotopically different TRS conformations. Furthermore, it was found that the TRS of the sterically hindered Ph(T)Xn(+) system does not possess a longer DAD than that of the (T)Xn(+) system. This predicts a no larger 1° KIE in the former system than in the latter. The observed 1° KIE order is, however, contrary to the prediction. This implicates the stronger DAD-compression vibrations coupled to the bulky Ph(T)Xn(+) reaction coordinate.

  7. Preparation of beryllium hydride

    International Nuclear Information System (INIS)

    Roberts, C.B.

    1975-01-01

    A process is described for preparing beryllium hydride by the direct reaction of beryllium borohydride and aluminum hydride trimethylamine adduct. Volatile by-products and unreacted reactants are readily removed from the product mass by sublimation and/or evaporation. (U.S.)

  8. Isotope exchange between gaseous hydrogen and uranium hydride powder

    International Nuclear Information System (INIS)

    Shugard, Andrew D.; Buffleben, George M.; Johnson, Terry A.; Robinson, David B.

    2014-01-01

    Highlights: • Isotope exchange between hydrogen gas and uranium hydride powder can be rapid and reversible. • Gas–solid exchange rate is controlled by transport within ∼0.7 μm hydride particles. • Gas chromatographic separation of hydrogen isotopes using uranium hydride is feasible. - Abstract: Isotope exchange between gaseous hydrogen and solid uranium hydride has been studied by flowing hydrogen (deuterium) gas through packed powder beds of uranium deuteride (hydride). We used a residual gas analyzer system to perform real-time analysis of the effluent gas composition. We also developed an exchange and transport model and, by fitting it to the experimental data, extracted kinetic parameters for the isotope exchange reaction. Our results suggest that, from approximately 70 to 700 kPa and 25 to 400 °C, the gas-to-solid exchange rate is controlled by hydrogen and deuterium transport within the ∼0.7 μm diameter uranium hydride particles. We use our kinetic parameters to show that gas chromatographic separation of hydrogen and deuterium using uranium hydride could be feasible

  9. Hydride redistribution and crack growth in Zr-2.5 wt.% Nb stressed in torsion

    International Nuclear Information System (INIS)

    Puls, M.P.; Rogowski, A.J.

    1980-11-01

    The effect of applied shear stresses on zirconium hydride solubility in a zirconium alloy was investigated. Recent studies have shown that zirconium hydride precipiates probably nucleate and grow by means of a shear transformation mechanism. It is postulated that these transformation shear strains can interact with applied shear stress gradients in the same way that the dilatational strains can interact with a dilatational stress gradient, providing a driving force for hydride accumulation, hydride embrittlement and crack propagation. To test this proposition, crack growth experiments were carried out under torsional loading conditions on hydrided, round notched bar specimens of cold-worked Zr-2.5 wt.% Nb cut from Pickering-type pressure tube material. Postmortem metallographic examination of the hydride distribution in these samples showed that, in many cases, the hydrides appeared to have reoriented in response to the applied shear stress and that hydride accumulation at the notch tip had occurred. However, except in a few cases, the rate of accumulation of reoriented hydrides at the notch tip due to applied shear stresses was much less than the rate due to corresponding applied uniaxial stresss. Moreover, the process in shear appears to be more sensitive to the inital hydride size. Attempts to elucidate the fracture mechanism by fractographic examination using scanning and replica transmission electron microscopy proved to be inconclusive because of smearing of the fracture face. (auth)

  10. Modeling of electrochemical hydrogen storage in metal hydride electrodes

    NARCIS (Netherlands)

    Ledovskikh, A.; Danilov, D.; Vermeulen, P.; Notten, P.H.L.

    2010-01-01

    The recently presented Electrochemical Kinetic Model (EKM), describing the electrochemical hydrogen storage in hydride-forming materials, has been extended by the description of the solid/electrolyte interface, i.e. the charge transfer kinetics and electrical double layer charging. A complete set of

  11. Modeling of electrochemical hydrogen storage in metal hydride electrodes

    NARCIS (Netherlands)

    Ledovskikh, A.; Danilov, D.; Vermeulen, P.; Notten, P.H.L.

    2010-01-01

    The recently presented electrochemical kinetic model, describing the electrochemical hydrogen storage in hydride-forming materials, was extended by the description of the solid/electrolyte interface, i.e., the charge-transfer kinetics and electrical double-layer charging. A complete set of equations

  12. Regenerative Hydride Heat Pump

    Science.gov (United States)

    Jones, Jack A.

    1992-01-01

    Hydride heat pump features regenerative heating and single circulation loop. Counterflow heat exchangers accommodate different temperatures of FeTi and LaNi4.7Al0.3 subloops. Heating scheme increases efficiency.

  13. Obtaining zircaloy powder through hydriding

    International Nuclear Information System (INIS)

    Dupim, Ivaldete da Silva; Moreira, Joao M.L.

    2009-01-01

    Zirconium alloys are good options for the metal matrix in dispersion fuels for power reactors due to their low thermal neutron absorption cross-section, good corrosion resistance, good mechanical strength and high thermal conductivity. A necessary step for obtaining such fuels is producing Zr alloy powder for the metal matrix composite material. This article presents results from the Zircaloy-4 hydrogenation tests with the purpose to embrittle the alloy as a first step for comminuting. Several hydrogenation tests were performed and studied through thermogravimetric analysis. They included H 2 pressures of 25 and 50 kPa and temperatures ranging between from 20 to 670 deg C. X-ray diffraction analysis showed in the hydrogenated samples the predominant presence of ZrH 2 and some ZrO 2 . Some kinetics parameters for the Zircaloy-4 hydrogenation reaction were obtained: the time required to reach the equilibrium state at the dwell temperature was about 100 minutes; the hydrogenation rate during the heating process from 20 to 670 deg C was about 21 mg/h, and at constant temperature of 670 deg C, the hydride rate was about 1.15 mg/h. The hydrogenation rate is largest during the heating process and most of it occurs during this period. After hydrogenated, the samples could easily be comminuted indicating that this is a possible technology to obtain Zircaloy powder. The results show that only few minutes of hydrogenation are necessary to reach the hydride levels required for comminuting the Zircaloy. The final hydride stoichiometry was between 2.7 and 2.8 H for each Zr atom in the sample (author)

  14. Tritium removal using vanadium hydride

    International Nuclear Information System (INIS)

    Hill, F.B.; Wong, Y.W.; Chan, Y.N.

    1978-01-01

    The results of an initial examination of the feasibility of separation of tritium from gaseous protium-tritium mixtures using vanadium hydride in cyclic processes is reported. Interest was drawn to the vanadium-hydrogen system because of the so-called inverse isotope effect exhibited by this system. Thus the tritide is more stable than the protide, a fact which makes the system attractive for removal of tritium from a mixture in which the light isotope predominates. The initial results of three phases of the research program are reported, dealing with studies of the equilibrium and kinetics properties of isotope exchange, development of an equilibrium theory of isotope separation via heatless adsorption, and experiments on the performance of a single heatless adsorption stage. In the equilibrium and kinetics studies, measurements were made of pressure-composition isotherms, the HT--H 2 separation factors and rates of HT--H 2 exchange. This information was used to evaluate constants in the theory and to understand the performance of the heatless adsorption experiments. A recently developed equilibrium theory of heatless adsorption was applied to the HT--H 2 separation using vanadium hydride. Using the theory it was predicted that no separation would occur by pressure cycling wholly within the β phase but that separation would occur by cycling between the β and γ phases and using high purge-to-feed ratios. Heatless adsorption experiments conducted within the β phase led to inverse separations rather than no separation. A kinetic isotope effect may be responsible. Cycling between the β and γ phases led to separation but not to the predicted complete removal of HT from the product stream, possibly because of finite rates of exchange. Further experimental and theoretical work is suggested which may ultimately make possible assessment of the feasibility and practicability of hydrogen isotope separation by this approach

  15. Alkali metal hydride formation

    International Nuclear Information System (INIS)

    1976-01-01

    The present invention relates to a method of producing alkali metal hydrides by absorbing hydrogen gas under pressure into a mixture of lower alkyl mono amines and alkali metal alkyl amides selected from sodium and potassium amides formed from said amines. The present invention also includes purification of a mixture of the amines and amides which contain impurities, such as is used as a catalytic exchange liquid in the enrichment of deuterium, involving the formation of the alkali metal hydride

  16. Blistering and hydride embrittlement

    International Nuclear Information System (INIS)

    Louthan, M.R. Jr.

    1975-01-01

    The effects of hydrogen on the mechanical properties of metals have been categorized into several groups. Two of the groups, hydrogen blistering and hydride embrittlement, are reasonably well understood, and problems relating to their occurrence may be avoided if that understanding is used as a basis for selecting alloys for hydrogen service. Blistering and hydride embrittlement are described along with several techniques of materials selection and used to minimize their adverse effects. (U.S.)

  17. Truncated Dual-Cap Nucleation Site Development

    Science.gov (United States)

    Matson, Douglas M.; Sander, Paul J.

    2012-01-01

    During heterogeneous nucleation within a metastable mushy-zone, several geometries for nucleation site development must be considered. Traditional spherical dual cap and crevice models are compared to a truncated dual cap to determine the activation energy and critical cluster growth kinetics in ternary Fe-Cr-Ni steel alloys. Results of activation energy results indicate that nucleation is more probable at grain boundaries within the solid than at the solid-liquid interface.

  18. Non-isothermal crystallization kinetics of Fe{sub 2}O{sub 3}–CaO–SiO{sub 2} glass containing nucleation agent P{sub 2}O{sub 5}/TiO{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Li, Bin, E-mail: stra-ceo@163.com; Wang, Yongya; Luo, Wenqin; Li, Jingfen [Huzhou University, Department of Material Chemistry (China); Li, Jianyou [Huzhou Central Hospital, Orthopedic Department (China)

    2017-03-15

    Fe{sub 2}O{sub 3}–CaO–SiO{sub 2} glass ceramics containing nucleation agent P{sub 2}O{sub 5}/TiO{sub 2} were prepared by sol-gel method. The samples were characterized by X-ray diffraction (XRD) and differential scanning calorimetry (DSC). The activation energy and kinetic parameters for crystallization of the samples were calculated by the Johnson-Mehi-Avrami (JMA) model and Augis-Bennett method according to the results of DSC. The results showed that the crystallization mechanism of Fe{sub 2}O{sub 3}–CaO–SiO{sub 2} glass, whose non-isothermal kinetic parameter n = 2.3, was consistent with surface crystallization of the JMA model. The kinetics model function of Fe{sub 2}O{sub 3}–CaO–SiO{sub 2} glass, f(α) = 2.3(1–α)[–ln(1–α)]{sup 0.57}, was also obtained. The addition of nucleation agent P{sub 2}O{sub 5}/TiO{sub 2} could reduce the activation energy, which made the crystal growth modes change from onedimensional to three-dimensional.

  19. Nanoparticle Nucleation Is Termolecular in Metal and Involves Hydrogen: Evidence for a Kinetically Effective Nucleus of Three {Ir3H2x·P2W15Nb3O62}6- in Ir(0)n Nanoparticle Formation From [(1,5-COD)IrI·P2W15Nb3O62]8- Plus Dihydrogen.

    Science.gov (United States)

    Özkar, Saim; Finke, Richard G

    2017-04-19

    The nucleation process yielding Ir(0) ∼300 nanoparticles from (Bu 4 N) 5 Na 3 [(1,5-COD)Ir·P 2 W 15 Nb 3 O 62 ] (abbreviated hereafter as (COD)Ir·POM 8- , where POM 9- = the polyoxometalate, P 2 W 15 Nb 3 O 62 9- ) under H 2 is investigated to learn the true molecularity, and hence the associated kinetically effective nucleus (KEN), for nanoparticle formation for the first time. Recent work with this prototype transition-metal nanoparticle formation system ( J. Am. Chem. Soc. 2014 , 136 , 17601 - 17615 ) revealed that nucleation in this system is an apparent second-order in the precatalyst, A = (COD)Ir·POM 8- , not the higher order implied by classic nucleation theory and its nA ⇌ A n , "critical nucleus", A n concept. Herein, the three most reasonable more intimate mechanisms of nucleation are tested: bimolecular nucleation, termolecular nucleation, and a mechanism termed "alternative termolecular nucleation" in which 2(COD)Ir + and 1(COD)Ir·POM 8- yield the transition state of the rate-determining step of nucleation. The results obtained definitively rule out a simple bimolecular nucleation mechanism and provide evidence for the alternative termolecular mechanism with a KEN of 3, Ir 3 . All higher molecularity nucleation mechanisms were also ruled out. Further insights into the KEN and its more detailed composition involving hydrogen, {Ir 3 H 2x POM} 6- , are also obtained from the established role of H 2 in the Ir(0) ∼300 formation balanced reaction stoichiometry, from the p(H 2 ) dependence of the kinetics, and from a D 2 /H 2 kinetic isotope effect of 1.2(±0.3). Eight insights and conclusions are presented. A section covering caveats in the current work, and thus needed future studies, is also included.

  20. Hydrogen storage in metallic hydrides: the hydrides of magnesium-nickel alloys

    International Nuclear Information System (INIS)

    Silva, E.P. da.

    1981-01-01

    The massive and common use of hydrogen as an energy carrier requires an adequate solution to the problem of storing it. High pressure or low temperatures are not entirely satisfactory, having each a limited range of applications. Reversible metal hydrides cover a range of applications intermediate to high pressure gas and low temperature liquid hydrogen, retaining very favorable safety and energy density characteristics, both for mobile and stationary applications. This work demonstrates the technical viability of storing hydrogen in metal hydrides of magnesium-nickel alloys. Also, it shows that technology, a product of science, can be generated within an academic environment, of the goal is clear, the demand outstanding and the means available. We review briefly theoretical models relating to metal hydride properties, specially the thermodynamics properties relevant to this work. We report our experimental results on hydrides of magnesium-nickel alloys of various compositions including data on structure, hydrogen storage capacities, reaction kinetics, pressure-composition isotherms. We selected a promising alloy for mass production, built and tested a modular storage tank based on the hydrides of the alloy, with a capacity for storing 10 Nm sup(3) of hydrogen of 1 atm and 20 sup(0)C. The tank weighs 46,3 Kg and has a volume of 21 l. (author)

  1. Metal Hydrides for Rechargeable Batteries

    Energy Technology Data Exchange (ETDEWEB)

    Valoeen, Lars Ole

    2000-03-01

    Rechargeable battery systems are paramount in the power supply of modern electronic and electromechanical equipment. For the time being, the most promising secondary battery systems for the future are the lithium-ion and the nickel metal hydride (NiMH) batteries. In this thesis, metal hydrides and their properties are described with the aim of characterizing and improving those. The thesis has a special focus on the AB{sub 5} type hydrogen storage alloys, where A is a rare earth metal like lanthanum, or more commonly misch metal, which is a mixture of rare earth metals, mainly lanthanum, cerium, neodymium and praseodymium. B is a transition metal, mainly nickel, commonly with additions of aluminium, cobalt, and manganese. The misch metal composition was found to be very important for the geometry of the unit cell in AB{sub 5} type alloys, and consequently the equilibrium pressure of hydrogen in these types of alloys. The A site substitution of lanthanum by misch metal did not decrease the surface catalytic properties of AB{sub 5} type alloys. B-site substitution of nickel with other transition elements, however, substantially reduced the catalytic activity of the alloy. If the internal pressure within the electrochemical test cell was increased using inert argon gas, a considerable increase in the high rate charge/discharge performance of LaNi{sub 5} was observed. An increased internal pressure would enable the utilisation of alloys with a high hydrogen equivalent pressure in batteries. Such alloys often have favourable kinetics and high hydrogen diffusion rates and thus have a potential for improving the high current discharge rates in metal hydride batteries. The kinetic properties of metal hydride electrodes were found to improve throughout their lifetime. The activation properties were found highly dependent on the charge/discharge current. Fewer charge/discharge cycles were needed to activate the electrodes if a small current was used instead of a higher

  2. New mechanism for bubble nucleation: Classical transitions

    International Nuclear Information System (INIS)

    Easther, Richard; Giblin, John T. Jr; Hui Lam; Lim, Eugene A.

    2009-01-01

    Given a scalar field with metastable minima, bubbles nucleate quantum mechanically. When bubbles collide, energy stored in the bubble walls is converted into kinetic energy of the field. This kinetic energy can facilitate the classical nucleation of new bubbles in minima that lie below those of the 'parent' bubbles. This process is efficient and classical, and changes the dynamics and statistics of bubble formation in models with multiple vacua, relative to that derived from quantum tunneling.

  3. Roles of texture in controlling oxidation, hydrogen ingress and hydride formation in Zr alloys

    International Nuclear Information System (INIS)

    Szpunar, Jerzy A.; Qin, Wen; Li, Hualong; Kumar, Kiran

    2011-01-01

    Experimental observations shows that the oxide formed on Zr alloys are strongly textured. The texture and grain-boundary characteristics of oxide are dependent on the texture of metal substrate. Computer simulation and thermodynamic modeling clarify the effect of metal substrate on structure of oxide film, and intrinsic factors affecting the microstructure. Models of diffusion process of hydrogen atoms and oxygen diffusion through oxide are presented. Both intra-granular and inter-granular hydrides were found following (0001) α-Zr //(111) δ-ZrH1.5 relationship. The through-thickness texture inhomogeneity in cladding tubes, the effects of hoop stress on the hydride orientation and the formation of interlinked hydride structure were studied. A thermodynamic model was developed to analyze the nucleation and the stress-induced reorientation of intergranular hydrides. These works provide a framework for understanding the oxidation, the hydrogen ingress and the hydride formation in Zr alloys. (author)

  4. Conference 'Chemistry of hydrides' Proceedings

    International Nuclear Information System (INIS)

    1991-07-01

    This collection of thesis of conference of Chemistry hydrides presents the results of investigations concerning of base questions of chemistry of nonorganic hydrides, including synthesis questions, studying of physical and chemical properties, thermodynamics, analytical chemistry, investigation of structure, equilibriums in the systems of metal-hydrogen, behaviour of nonorganic hydrides in non-water mediums and applying investigations in the chemistry area and technology of nonorganic hydrides

  5. Hydrogen storage material and process using graphite additive with metal-doped complex hydrides

    Science.gov (United States)

    Zidan, Ragaiy [Aiken, SC; Ritter, James A [Lexington, SC; Ebner, Armin D [Lexington, SC; Wang, Jun [Columbia, SC; Holland, Charles E [Cayce, SC

    2008-06-10

    A hydrogen storage material having improved hydrogen absorbtion and desorption kinetics is provided by adding graphite to a complex hydride such as a metal-doped alanate, i.e., NaAlH.sub.4. The incorporation of graphite into the complex hydride significantly enhances the rate of hydrogen absorbtion and desorption and lowers the desorption temperature needed to release stored hydrogen.

  6. Preparation of beryllium hydride

    International Nuclear Information System (INIS)

    Lowrance, B.R.

    1975-01-01

    A process is described for the preparation of beryllium hydride which comprises pyrolyzing, while in solution in a solvent inert under the reaction conditions, with respect to reactants and products and at a temperature in the range of about 100 0 to about 200 0 C, sufficient to result in the formation of beryllium hydride, a di-t-alkyl beryllium etherate wherein each tertiary alkyl radical contains from 4 to 20 carbon atoms. The pyrolysis is carried out under an atmosphere inert under the reaction conditions, with respect to reactants and products. (U.S.)

  7. Hydridation of Ti-6Al-4V

    International Nuclear Information System (INIS)

    Domizzi, G; Luppo, M.I; Ortiz, M; Vigna, G

    2004-01-01

    The production of Ti pieces or their alloys through powder metallurgy is an economical alternative that replaces the costly methods commonly used. The Ti-6AI-4V alloy is widely used in the aerospace, chemical and medical industries. The use of powder from the alloy instead of using more pure alloyed titanium powders, further simplifies the production process. The presence of V allows the phase β to stabilize at very low temperatures and both alloys alter the Ti-H equilibrium diagram. This work analyzes to what degree these effects influence the obtaining of powders from this alloy from that of hydridation and dehydridation. Although it has slower kinetics, powders can be produced in times similar to those found for grade 2 Ti since the distribution of hydrides in the sample is uniform and the material is fragile enough for concentrations of approximately 0.7 H/Ti (CW)

  8. High pressure hydriding of sponge-Zr in steam-hydrogen mixtures

    International Nuclear Information System (INIS)

    Kim, Y.S.

    1997-01-01

    Hydriding kinetics of thin sponge-Zr layers metallurgically bonded to a Zircaloy disk has been studied by thermogravimetry in the temperature range 350-400 C in 7 MPa hydrogen-steam mixtures. Some specimens were prefilmed with a thin oxide layer prior to exposure to the reactant gas; all were coated with a thin layer of gold to avoid premature reaction at edges. Two types of hydriding were observed in prefilmed specimens, viz., a slow hydrogen absorption process that precedes an accelerated (massive) hydriding. At 7 MPa total pressure, the critical ratio of H 2 /H 2 O above which massive hydriding occurs at 400 C is ∝200. The critical H 2 /H 2 O ratio is shifted to ∝2.5 x 10 3 at 350 C. The slow hydriding process occurs only when conditions for hydriding and oxidation are approximately equally favorable. Based on maximum weight gain, the specimen is completely converted to δ-ZrH 2 by massive hydriding in ∝5 h at a hydriding rate of ∝10 -6 mol H/cm 2 s. Incubation times of 10-20 h prior to the onset of massive hydriding increases with prefilm oxide thickness in the range of 0-10 μm. By changing to a steam-enriched gas, massive hydriding that initially started in a steam-starved condition was arrested by re-formation of a protective oxide scale. (orig.)

  9. Metal hydrides based high energy density thermal battery

    Energy Technology Data Exchange (ETDEWEB)

    Fang, Zhigang Zak, E-mail: zak.fang@utah.edu [Department of Metallurgical Engineering, The University of Utah, 135 South 1460 East, Room 412, Salt Lake City, UT 84112-0114 (United States); Zhou, Chengshang; Fan, Peng [Department of Metallurgical Engineering, The University of Utah, 135 South 1460 East, Room 412, Salt Lake City, UT 84112-0114 (United States); Udell, Kent S. [Department of Metallurgical Engineering, The University of Utah, 50 S. Central Campus Dr., Room 2110, Salt Lake City, UT 84112-0114 (United States); Bowman, Robert C. [Department of Metallurgical Engineering, The University of Utah, 135 South 1460 East, Room 412, Salt Lake City, UT 84112-0114 (United States); Vajo, John J.; Purewal, Justin J. [HRL Laboratories, LLC, 3011 Malibu Canyon Road, Malibu, CA 90265 (United States); Kekelia, Bidzina [Department of Metallurgical Engineering, The University of Utah, 50 S. Central Campus Dr., Room 2110, Salt Lake City, UT 84112-0114 (United States)

    2015-10-05

    Highlights: • The principle of the thermal battery using advanced metal hydrides was demonstrated. • The thermal battery used MgH{sub 2} and TiMnV as a working pair. • High energy density can be achieved by the use of MgH{sub 2} to store thermal energy. - Abstract: A concept of thermal battery based on advanced metal hydrides was studied for heating and cooling of cabins in electric vehicles. The system utilized a pair of thermodynamically matched metal hydrides as energy storage media. The pair of hydrides that was identified and developed was: (1) catalyzed MgH{sub 2} as the high temperature hydride material, due to its high energy density and enhanced kinetics; and (2) TiV{sub 0.62}Mn{sub 1.5} alloy as the matching low temperature hydride. Further, a proof-of-concept prototype was built and tested, demonstrating the potential of the system as HVAC for transportation vehicles.

  10. Preparation of beryllium hydride

    International Nuclear Information System (INIS)

    Bergeron, C.R.; Baker, R.W.

    1975-01-01

    Beryllium hydride of high bulk density, suitable for use as a component of high-energy fuels, is prepared by the pyrolysis, in solution in an inert solvent, of a ditertiary-alkyl beryllium. An agitator introduces mechanical energy into the reaction system, during the pyrolysis, at the rate of 0.002 to 0.30 horsepower per gallon of reaction mixture. (U.S.)

  11. Vapour–to–liquid nucleation: Nucleation theorems for nonisothermal–nonideal case

    Energy Technology Data Exchange (ETDEWEB)

    Malila, J.; McGraw, R.; Napari, I.; Laaksonen, A.

    2010-08-29

    Homogeneous vapour-to-liquid nucleation, a basic process of aerosol formation, is often considered as a type example of nucleation phenomena, while most treatment of the subject introduce several simplifying assumptions (ideal gas phase, incompressible nucleus, isothermal kinetics, size-independent surface free energy...). During last decades, nucleation theorems have provided new insights into properties of critical nuclei facilitating direct comparison between laboratory experiments and molecular simulations. These theorems are, despite of their generality, often applied in forms where the aforementioned assumptions are made. Here we present forms of nucleation theorems that explicitly take into account these effects and allow direct estimation of their importance. Only assumptions are Arrhenius-type kinetics of nucleation process and exclusion carrier gas molecules from the critical nucleus.

  12. Air and metal hydride battery

    Energy Technology Data Exchange (ETDEWEB)

    Lampinen, M.; Noponen, T. [Helsinki Univ. of Technology, Otaniemi (Finland). Lab. of Applied Thermodynamics

    1998-12-31

    The main goal of the air and metal hydride battery project was to enhance the performance and manufacturing technology of both electrodes to such a degree that an air-metal hydride battery could become a commercially and technically competitive power source for electric vehicles. By the end of the project it was possible to demonstrate the very first prototype of the air-metal hydride battery at EV scale, achieving all the required design parameters. (orig.)

  13. Hydriding of metallic thorium

    International Nuclear Information System (INIS)

    Miyake, Masanobu; Katsura, Masahiro; Matsuki, Yuichi; Uno, Masayoshi

    1983-01-01

    Powdered thorium is usually prepared through a combination of hydriding and dehydriding processes of metallic thorium in massive form, in which the hydriding process consists of two steps: the formation of ThH 2 , and the formation of Th 4 H 15 . However, little has yet been known as to on what stage of hydriding process the pulverization takes place. It is found in the present study that the formation of Th 4 H 15 by the reaction of ThH 2 with H 2 is responsible for pulverization. Temperature of 70 deg C adopted in this work for the reaction of formation Th 4 H 15 seems to be much more effective for production of powdered thorium than 200 - 300 deg C in the literature. The pressure-composition-temperature relationships for Th-H system are determined at 200, 300, 350, and 800 deg C. From these results, a tentative equilibrium phase diagram for the Th-H system is proposed, attention being focused on the two-phase region of ThH 2 and Th 4 H 15 . Pulverization process is discussed in terms of the tentative phase diagram. (author)

  14. Dynamics of homogeneous nucleation

    DEFF Research Database (Denmark)

    Toxværd, Søren

    2015-01-01

    The classical nucleation theory for homogeneous nucleation is formulated as a theory for a density fluctuation in a supersaturated gas at a given temperature. But molecular dynamics simulations reveal that it is small cold clusters which initiates the nucleation. The temperature in the nucleating...

  15. Hydride precipitation crack propagation in zircaloy cladding during a decreasing temperature history

    International Nuclear Information System (INIS)

    Stout, R.B.

    2001-01-01

    An assessment of safety, design, and cost tradeoff issues for short (ten to fifty years) and longer (fifty to hundreds of years) interim dry storage of spent nuclear fuel in Zircaloy rods shall address potential failures of the Zircaloy cladding caused by the precipitation response of zirconium hydride platelets. To perform such assessment analyses rigorously and conservatively will be necessarily complex and difficult. For Zircaloy cladding, a model for zirconium hydride induced crack propagation velocity was developed for a decreasing temperature field and for hydrogen, temperature, and stress dependent diffusive transport of hydrogen to a generic hydride platelet at a crack tip. The development of the quasi-steady model is based on extensions of existing models for hydride precipitation kinetics for an isolated hydride platelet at a crack tip. An instability analysis model of hydride-crack growth was developed using existing concepts in a kinematic equation for crack propagation at a constant thermodynamic crack potential subject to brittle fracture conditions. At the time an instability is initiated, the crack propagation is no longer limited by hydride growth rate kinetics, but is then limited by stress rates. The model for slow hydride-crack growth will be further evaluated using existing available data. (authors)

  16. Hydride precipitation crack propagation in zircaloy cladding during a decreasing temperature history

    Energy Technology Data Exchange (ETDEWEB)

    Stout, R.B. [California Univ., Livermore, CA (United States). Lawrence Livermore National Lab

    2001-07-01

    An assessment of safety, design, and cost tradeoff issues for short (ten to fifty years) and longer (fifty to hundreds of years) interim dry storage of spent nuclear fuel in Zircaloy rods shall address potential failures of the Zircaloy cladding caused by the precipitation response of zirconium hydride platelets. To perform such assessment analyses rigorously and conservatively will be necessarily complex and difficult. For Zircaloy cladding, a model for zirconium hydride induced crack propagation velocity was developed for a decreasing temperature field and for hydrogen, temperature, and stress dependent diffusive transport of hydrogen to a generic hydride platelet at a crack tip. The development of the quasi-steady model is based on extensions of existing models for hydride precipitation kinetics for an isolated hydride platelet at a crack tip. An instability analysis model of hydride-crack growth was developed using existing concepts in a kinematic equation for crack propagation at a constant thermodynamic crack potential subject to brittle fracture conditions. At the time an instability is initiated, the crack propagation is no longer limited by hydride growth rate kinetics, but is then limited by stress rates. The model for slow hydride-crack growth will be further evaluated using existing available data. (authors)

  17. Evaporation rate of nucleating clusters.

    Science.gov (United States)

    Zapadinsky, Evgeni

    2011-11-21

    The Becker-Döring kinetic scheme is the most frequently used approach to vapor liquid nucleation. In the present study it has been extended so that master equations for all cluster configurations are included into consideration. In the Becker-Döring kinetic scheme the nucleation rate is calculated through comparison of the balanced steady state and unbalanced steady state solutions of the set of kinetic equations. It is usually assumed that the balanced steady state produces equilibrium cluster distribution, and the evaporation rates are identical in the balanced and unbalanced steady state cases. In the present study we have shown that the evaporation rates are not identical in the equilibrium and unbalanced steady state cases. The evaporation rate depends on the number of clusters at the limit of the cluster definition. We have shown that the ratio of the number of n-clusters at the limit of the cluster definition to the total number of n-clusters is different in equilibrium and unbalanced steady state cases. This causes difference in evaporation rates for these cases and results in a correction factor to the nucleation rate. According to rough estimation it is 10(-1) by the order of magnitude and can be lower if carrier gas effectively equilibrates the clusters. The developed approach allows one to refine the correction factor with Monte Carlo and molecular dynamic simulations.

  18. The effect of sample preparation on uranium hydriding

    International Nuclear Information System (INIS)

    Banos, A.; Stitt, C.A.; Scott, T.B.

    2016-01-01

    Highlights: • Distinct differences in uranium hydride growth rates and characteristics between different surface preparation methods. • The primary difference between the categories of sample preparations is the level of strain present in the surface. • Greater surface-strain, leads to higher nucleation number density, implying a preferred attack of strained vs unstrained metal. • As strain is reduced, surface features such as carbides and grain boundaries become more important in controlling the UH3 location. - Abstract: The influence of sample cleaning preparation on the early stages of uranium hydriding has been examined, by using four identical samples but concurrently prepared using four different methods. The samples were reacted together in the same corrosion cell to ensure identical exposure conditions. From the analysis, it was found that the hydride nucleation rate was proportional to the level of strain exhibiting higher number density for the more strained surfaces. Additionally, microstructure of the metal plays a secondary role regarding initial hydrogen attack on the highly strained surfaces yet starts to dominate the system while moving to more pristine samples.

  19. Microcapsulated rare earth - nickel hydride-forming materials

    International Nuclear Information System (INIS)

    Ishikawa, H.; Oguro, K.; Kato, A.; Suzuki, H.; Ishii, E.

    1985-01-01

    Fine particles of hydride-forming alloys such as LaNi/sub 5/ and MmNi/sub 4.5/Mn/sub 0.5/ (MM : mischmetal) were coated with metallic copper thin layer by chemical plating method. Hydrogen storage capacities of alloys were not appreciably affected by the plating treatment. The capsulated alloy powders were easily pressed into pellets. The pellets obtained had high thermal conductivity and porosity enough to permeate hydrogen, leading to fast reaction kinetics. These were able to withstand more than 5,000 repeated hydriding-dehydriding cycles without disintegrating

  20. Stochastic simulation of nucleation in binary alloys

    Science.gov (United States)

    L’vov, P. E.; Svetukhin, V. V.

    2018-06-01

    In this study, we simulate nucleation in binary alloys with respect to thermal fluctuations of the alloy composition. The simulation is based on the Cahn–Hilliard–Cook equation. We have considered the influence of some fluctuation parameters (wave vector cutoff and noise amplitude) on the kinetics of nucleation and growth of minority phase precipitates. The obtained results are validated by the example of iron–chromium alloys.

  1. Dislocation/hydrogen interaction mechanisms in hydrided nanocrystalline palladium films

    International Nuclear Information System (INIS)

    Amin-Ahmadi, Behnam; Connétable, Damien; Fivel, Marc; Tanguy, Döme; Delmelle, Renaud; Turner, Stuart; Malet, Loic; Godet, Stephane; Pardoen, Thomas; Proost, Joris; Schryvers, Dominique

    2016-01-01

    The nanoscale plasticity mechanisms activated during hydriding cycles in sputtered nanocrystalline Pd films have been investigated ex-situ using advanced transmission electron microscopy techniques. The internal stress developing within the films during hydriding has been monitored in-situ. Results showed that in Pd films hydrided to β-phase, local plasticity was mainly controlled by dislocation activity in spite of the small grain size. Changes of the grain size distribution and the crystallographic texture have not been observed. In contrast, significant microstructural changes were not observed in Pd films hydrided to α-phase. Moreover, the effect of hydrogen loading on the nature and density of dislocations has been investigated using aberration-corrected TEM. Surprisingly, a high density of shear type stacking faults has been observed after dehydriding, indicating a significant effect of hydrogen on the nucleation energy barriers of Shockley partial dislocations. Ab-initio calculations of the effect of hydrogen on the intrinsic stable and unstable stacking fault energies of palladium confirm the experimental observations.

  2. Ion irradiation enhanced crystal nucleation in amorphous Si thin films

    International Nuclear Information System (INIS)

    Im, J.S.; Atwater, H.A.

    1990-01-01

    The nucleation kinetics of the amorphous-to-crystal transition of Si films under 1.5 MeV Xe + irradiation have been investigated by means of in situ transmission electron microscopy in the temperature range T=500--580 degree C. After an incubation period during which negligible nucleation occurs, a constant nucleation rate was observed in steady state, suggesting that homogeneous nucleation occurred. Compared to thermal crystallization, a significant enhancement in the nucleation rate during high-energy ion irradiation (five to seven orders of magnitude) was observed with an apparent activation energy of 3.9±0.75 eV

  3. A Comparative Study of Nucleation Parameterizations: 2. Three-Dimensional Model Application and Evaluation

    Science.gov (United States)

    Following the examination and evaluation of 12 nucleation parameterizations presented in part 1, 11 of them representing binary, ternary, kinetic, and cluster‐activated nucleation theories are evaluated in the U.S. Environmental Protection Agency Community Multiscale Air Quality ...

  4. Zircaloy-4 hydridation

    International Nuclear Information System (INIS)

    Vizcaino, Pablo

    1997-01-01

    The objectives of this work can be summarized as: 1) To reproduce, by heat treatments, matrix microstructures and hydride morphologies similar to those observed in structural components of the CNA-1 and CNE nuclear power plants; 2) To study the evolution of the mechanical properties of the original material with different hydrogen concentrations, such as microhardness, and its capacity to distinguish these materials; 3) To find parameters that allow to estimate the hydrogen content of a material by quantitative metallographic techniques, to be used as complementary in the study of the radioactive materials from reactors

  5. Another Look at the Mechanisms of Hydride Transfer Enzymes with Quantum and Classical Transition Path Sampling.

    Science.gov (United States)

    Dzierlenga, Michael W; Antoniou, Dimitri; Schwartz, Steven D

    2015-04-02

    The mechanisms involved in enzymatic hydride transfer have been studied for years, but questions remain due, in part, to the difficulty of probing the effects of protein motion and hydrogen tunneling. In this study, we use transition path sampling (TPS) with normal mode centroid molecular dynamics (CMD) to calculate the barrier to hydride transfer in yeast alcohol dehydrogenase (YADH) and human heart lactate dehydrogenase (LDH). Calculation of the work applied to the hydride allowed for observation of the change in barrier height upon inclusion of quantum dynamics. Similar calculations were performed using deuterium as the transferring particle in order to approximate kinetic isotope effects (KIEs). The change in barrier height in YADH is indicative of a zero-point energy (ZPE) contribution and is evidence that catalysis occurs via a protein compression that mediates a near-barrierless hydride transfer. Calculation of the KIE using the difference in barrier height between the hydride and deuteride agreed well with experimental results.

  6. Hydride embrittlement in zircaloy components

    Energy Technology Data Exchange (ETDEWEB)

    Lobo, Raquel M.; Andrade, Arnaldo H.P.; Castagnet, Mariano, E-mail: rmlobo@ipen.br [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil)

    2011-07-01

    Zirconium alloys are used in nuclear reactor cores under high-temperature water environment. During service, hydrogen is generated by corrosion processes, and it is readily absorbed by these materials. When hydrogen concentration exceeds the terminal solid solubility, the excess hydrogen precipitates as zirconium hydride (ZrH{sub 2}) platelets or needles. Zirconium alloys components can fail by hydride cracking if they contain large flaws and are highly stressed. Zirconium alloys are susceptible to a mechanism for crack initiation and propagation termed delayed hydride cracking (DHC). The presence of brittle hydrides, with a K{sub Ic} fracture toughness of only a few MPa{radical}m, results in a severe loss in ductility and toughness when platelet normal is oriented parallel to the applied stress. In plate or tubing, hydrides tend to form perpendicular to the thickness direction due to the texture developed during fabrication. Hydrides in this orientation do not generally cause structural problems because applied stresses in the through-thickness direction are very low. However, the high mobility of hydrogen in a zirconium lattice enables redistribution of hydrides normal to the applied stress direction, which can result in localized embrittlement. When a platelet reaches a critical length it ruptures. If the tensile stress is sufficiently great, crack initiation starts at some of these hydrides. Crack propagation occurs by repeating the same process at the crack tip. Delayed hydride cracking can degrade the structural integrity of zirconium alloys during reactor service. The paper focuses on the fracture mechanics and fractographic aspects of hydride material. (author)

  7. A kinetic Monte Carlo simulation method of van der Waals epitaxy for atomistic nucleation-growth processes of transition metal dichalcogenides.

    Science.gov (United States)

    Nie, Yifan; Liang, Chaoping; Cha, Pil-Ryung; Colombo, Luigi; Wallace, Robert M; Cho, Kyeongjae

    2017-06-07

    Controlled growth of crystalline solids is critical for device applications, and atomistic modeling methods have been developed for bulk crystalline solids. Kinetic Monte Carlo (KMC) simulation method provides detailed atomic scale processes during a solid growth over realistic time scales, but its application to the growth modeling of van der Waals (vdW) heterostructures has not yet been developed. Specifically, the growth of single-layered transition metal dichalcogenides (TMDs) is currently facing tremendous challenges, and a detailed understanding based on KMC simulations would provide critical guidance to enable controlled growth of vdW heterostructures. In this work, a KMC simulation method is developed for the growth modeling on the vdW epitaxy of TMDs. The KMC method has introduced full material parameters for TMDs in bottom-up synthesis: metal and chalcogen adsorption/desorption/diffusion on substrate and grown TMD surface, TMD stacking sequence, chalcogen/metal ratio, flake edge diffusion and vacancy diffusion. The KMC processes result in multiple kinetic behaviors associated with various growth behaviors observed in experiments. Different phenomena observed during vdW epitaxy process are analysed in terms of complex competitions among multiple kinetic processes. The KMC method is used in the investigation and prediction of growth mechanisms, which provide qualitative suggestions to guide experimental study.

  8. Mechanisms of hydrogen induced delayed cracking in hydride forming materials

    International Nuclear Information System (INIS)

    Dutton, R.; Nuttall, K.; Puls, M.P.; Simpson, L.A.

    1977-01-01

    Mechanisms which have been formulated to describe delayed hydrogen cracking in hydride-forming metals are reviewed and discussed. Particular emphasis is placed on the commercial alloy Zr--2.5% Nb (Cb) which is extensively used in nuclear reactor core components. A quantitative model for hydrogen cracking in this material is presented and compared with available experimental data. The kinetics of crack propagation are controlled by the growth of hydrides at the stressed crack tip by the diffusive ingress of hydrogen into this region. The driving force for the diffusion flux is provided by the local stress gradient which interacts with both hydrogen atoms in solution and hydrogen atoms being dissolved and reprecipitated at the crack tip. The model is developed using concepts of elastoplastic fracture mechanics. Stage I crack growth is controlled by hydrides growing in the elastic stress gradient, while Stage II is controlled by hydride growth in the plastic zone at the crack tip. Recent experimental observations are presented which indicate that the process occurs in an intermittent fashion; hydride clusters accumulate at the crack tip followed by unstable crack advance and subsequent crack arrest in repeated cycles

  9. Mechanisms of hydrogen induced delayed cracking in hydride forming materials

    International Nuclear Information System (INIS)

    Dutton, R.; Nuttall, K.; Puls, M.P.; Simpson, L.A.

    1977-01-01

    Mechanisms which have been formulated to describe delayed hydrogen cracking in hydride-forming metals are reviewed and discussed. Particular emphasis is placed on the commercial alloy Zr-2.5 pct Nb which is extensively used in nuclear reactor core components. A quantitative model for hydrogen cracking in this material is presented and compared with available experimental data. The kinetics of crack propagation are controlled by the growth of hydrides at the stressed crack tip by the diffusive ingress of hydrogen into this region. The driving force for the diffusion flux is provided by the local stress gradient which interacts with both hydrogen atoms in solution and hydrogen atoms being dissolved and reprecipitated at the crack tip. The model is developed using concepts of elastoplastic fracture mechanics. Stage I crack growth is controlled by hydrides growing in the elastic stress gradient, while Stage II is controlled by hydride growth in the plastic zone at the crack tip. Recent experimental observations are presented which indicate that the process occurs in an intermittent fashion; hydride clusters accumulate at the crack tip followed by unstable crack advance and subsequent crack arrest in repeated cycles. 55 refs., 6 figs

  10. Gas hydrate nucleation

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1997-12-31

    The overall aim of the project was to gain more knowledge about the kinetics of gas hydrate formation especially the early growth phase. Knowledge of kinetics of gas hydrate formation is important and measurements of gas hydrate particle size and concentration can contribute to improve this knowledge. An experimental setup for carrying out experimental studies of the nucleation and growth of gas hydrates has been constructed and tested. Multi wavelength extinction (MWE) was the experimental technique selected for obtaining particle diameter and concentration. The principle behind MWE is described as well as turbidity spectrum analysis that in an initial stage of the project was considered as an alternative experimental technique. Details of the experimental setup and its operation are outlined. The measuring cell consists of a 1 litre horizontal tube sustaining pressures up to 200 bar. Laser light for particle size determination can be applied through sapphire windows. A description of the various auxiliary equipment and of another gas hydrate cell used in the study are given. A computer program for simulation and analysis of gas hydrate experiments is based on the gas hydrate kinetics model proposed by Skovborg and Rasmussen (1993). Initial measurements showed that knowledge of the refractive index of gas hydrates was important in order to use MWE. An experimental determination of the refractive index of methane and natural gas hydrate is described. The test experiments performed with MWE on collectives of gas hydrate particles and experiments with ethane, methane and natural gas hydrate are discussed. Gas hydrate particles initially seem to grow mainly in size and at latter stages in number. (EG) EFP-94; 41 refs.

  11. Gas hydrate nucleation

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1998-12-31

    The overall aim of the project was to gain more knowledge about the kinetics of gas hydrate formation especially the early growth phase. Knowledge of kinetics of gas hydrate formation is important and measurements of gas hydrate particle size and concentration can contribute to improve this knowledge. An experimental setup for carrying out experimental studies of the nucleation and growth of gas hydrates has been constructed and tested. Multi wavelength extinction (MWE) was the experimental technique selected for obtaining particle diameter and concentration. The principle behind MWE is described as well as turbidity spectrum analysis that in an initial stage of the project was considered as an alternative experimental technique. Details of the experimental setup and its operation are outlined. The measuring cell consists of a 1 litre horizontal tube sustaining pressures up to 200 bar. Laser light for particle size determination can be applied through sapphire windows. A description of the various auxiliary equipment and of another gas hydrate cell used in the study are given. A computer program for simulation and analysis of gas hydrate experiments is based on the gas hydrate kinetics model proposed by Skovborg and Rasmussen (1993). Initial measurements showed that knowledge of the refractive index of gas hydrates was important in order to use MWE. An experimental determination of the refractive index of methane and natural gas hydrate is described. The test experiments performed with MWE on collectives of gas hydrate particles and experiments with ethane, methane and natural gas hydrate are discussed. Gas hydrate particles initially seem to grow mainly in size and at latter stages in number. (EG) EFP-94; 41 refs.

  12. Low-Cost Metal Hydride Thermal Energy Storage System for Concentrating Solar Power Systems

    Energy Technology Data Exchange (ETDEWEB)

    Zidan, Ragaiy [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Hardy, B. J. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Corgnale, C. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Teprovich, J. A. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Ward, P. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Motyka, Ted [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

    2016-01-31

    The objective of this research was to evaluate and demonstrate a metal hydride-based TES system for use with a CSP system. A unique approach has been applied to this project that combines our modeling experience with the extensive material knowledge and expertise at both SRNL and Curtin University (CU). Because of their high energy capacity and reasonable kinetics many metal hydride systems can be charged rapidly. Metal hydrides for vehicle applications have demonstrated charging rates in minutes and tens of minutes as opposed to hours. This coupled with high heat of reaction allows metal hydride TES systems to produce very high thermal power rates (approx. 1kW per 6-8 kg of material). A major objective of this work is to evaluate some of the new metal hydride materials that have recently become available. A problem with metal hydride TES systems in the past has been selecting a suitable high capacity low temperature metal hydride material to pair with the high temperature material. A unique aspect of metal hydride TES systems is that many of these systems can be located on or near dish/engine collectors due to their high thermal capacity and small size. The primary objective of this work is to develop a high enthalpy metal hydride that is capable of reversibly storing hydrogen at high temperatures (> 650 °C) and that can be paired with a suitable low enthalpy metal hydride with low cost materials. Furthermore, a demonstration of hydrogen cycling between the two hydride beds is desired.

  13. Thermal enhancement cartridge heater modified tritium hydride bed development, Part 2 - Experimental validation of key conceptual design features

    Energy Technology Data Exchange (ETDEWEB)

    Heroux, K.J.; Morgan, G.A. [Savannah River Laboratory, Aiken, SC (United States)

    2015-03-15

    The Thermal Enhancement Cartridge Heater Modified (TECH Mod) tritium hydride bed is an interim replacement for the first generation (Gen1) process hydride beds currently in service in the Savannah River Site (SRS) Tritium Facilities. 3 new features are implemented in the TECH Mod hydride bed prototype: internal electric cartridge heaters, porous divider plates, and copper foam discs. These modifications will enhance bed performance and reduce costs by improving bed activation and installation processes, in-bed accountability measurements, end-of-life bed removal, and He-3 recovery. A full-scale hydride bed test station was constructed at the Savannah River National Laboratory (SRNL) in order to evaluate the performance of the prototype TECH Mod hydride bed. Controlled hydrogen (H{sub 2}) absorption/ desorption experiments were conducted to validate that the conceptual design changes have no adverse effects on the gas transfer kinetics or H{sub 2} storage/release properties compared to those of the Gen1 bed. Inert gas expansions before, during, and after H{sub 2} flow tests were used to monitor changes in gas transfer rates with repeated hydriding/de-hydriding of the hydride material. The gas flow rates significantly decreased after initial hydriding of the material; however, minimal changes were observed after repeated cycling. The data presented herein confirm that the TECH Mod hydride bed would be a suitable replacement for the Gen1 bed with the added enhancements expected from the advanced design features. (authors)

  14. Nucleation in ZBLAN glasses

    NARCIS (Netherlands)

    de Leede, G.L.A.; Waal, de H.

    1989-01-01

    Nucleation rates were detd. in a ZrF4-BaF2-NaF-LaF3-AlF3 glass (ZBLAN) using an optical method. The results were compared with a similar glass having a slightly different compn. The difference in the nucleation rate is explained by classical nucleation theory using calcd. free-energy differences

  15. The effect of stress state on zirconium hydride reorientation

    Science.gov (United States)

    Cinbiz, Mahmut Nedim

    correlating the finite element stress-state results with the spatial distribution of hydride microstructures observed within the optical micrographs for each sample. Experiments showed that the hydride reorientation was enhanced as the stress biaxiality increased. The threshold stress decreased from 150 MPa to 80 MPa when stress biaxiality ratio increased from uniaxial tension to near-equibiaxial tension. This behavior was also predicted by classical nucleation theory based on the Gibbs free energy of transformation being assisted by the far-field stress. An analysis of in situ X-ray diffraction data obtained during a thermo-mechanical cycle typical of vacuum drying showed a complex lattice-spacing behavior of the hydride phase during the dissolution and precipitation. The in-plane hydrides showed bilinear lattice expansion during heating with the intrinsic thermal expansion rate of the hydrides being observed only at elevated temperatures as they dissolve. For radial hydrides that precipitate during cooling under stress, the spacing of the close-packed {111} planes oriented normal to the maximum applied stress was permanently higher than the corresponding {111} plane spacing in the other directions. This behavior is believed to be a result of a complex stress state within the precipitating plate-like hydrides that induces a strain component within the hydrides normal to its "plate" face (i.e., the applied stress direction) that exceeds the lattice spacing strains in the other directions. During heat-up, the lattice spacing of these same "plate" planes actually contract due to the reversion of the stress state within the plate-like hydrides as they dissolve. The presence of radial hydrides and their connectivity with in-plane hydrides was shown to increase the ductile-to-brittle transition temperature during tensile testing. This behavior can be understood in terms of the role of radial hydrides in promoting the initiation of a long crack that subsequently propagates under

  16. Thermodynamics and statistical mechanics of some hydrides of the lanthanides and actinides

    International Nuclear Information System (INIS)

    Mintz, M.H.

    1976-06-01

    This work deals mainly with the thermodynamic and physical properties of the hydrides of the lanthanides and actinides. In addition, statistical models have been developed and applied to metal-hydrogen systems. A kinetic study of the uranium-hydrogen system was performed. The thermodynamic properties of the hydrides of neptunium, thorium, praseodymium, neodymium, samarium and europium were determined. In addition the samarium-europium-hydrogen ternary system was investigated. Moessbauer effect measurements of cubic neptunium hydrides were interpreted according to a model presented. A comparison. (author)

  17. Anodematerials for Metal Hydride Batteries

    DEFF Research Database (Denmark)

    Jensen, Jens Oluf

    1997-01-01

    This report describes the work on development of hydride forming alloys for use as electrode materials in metal hydride batteries. The work has primarily been concentrated on calcium based alloys derived from the compound CaNi5. This compound has a higher capacity compared with alloys used in today......’s hydride batteries, but a much poorer stability towards repeated charge/discharge cycling. The aim was to see if the cycleability of CaNi5 could be enhanced enough by modifications to make the compound a suitable electrode material. An alloying method based on mechanical alloying in a planetary ball mill...

  18. Nucleation behavior of glutathione polymorphs in water

    International Nuclear Information System (INIS)

    Chen, Zhi; Dang, Leping; Li, Shuai; Wei, Hongyuan

    2013-01-01

    Nucleation behavior of glutathione (GSH) polymorphs in water was investigated by experimental method combined with classical nucleation theory. The solubility of α and β forms GSH in water at different temperatures, and the nucleation induction period at various supersaturations and temperatures were determined experimentally. The results show that, in a certain range of supersaturation, the nucleation of β form predominates at relatively higher temperature, while α form will be obtained at lower temperature. The nucleation kinetics parameters of α and β form were then calculated. To understand the crucial role of temperature on crystal forms, “hypothetic” nucleation parameters of β form at 283.15 K were deduced based on extrapolation method. The results show that the interfacial tension, critical free energy, critical nucleus radius and nucleus number of α form are smaller than that of β form in the same condition at 283.15 K, which implies that α form nucleates easier than β form at low temperature. This work may be useful for the control and optimization of GSH crystallization process in industry

  19. Nucleation of voids - the impurity effect

    International Nuclear Information System (INIS)

    Chen, I-W; Taiwo, A.

    1984-01-01

    Nucleation of voids under irradiation in multicomponent alloys remains an unsolved theoretical problem. Of particular interest are the effects of nonequilibrium solute segregation phenomena on the critical nucleus and the nucleation rate. The resolution of the multicomponent nucleation in a dissipative system also has broader implication to the field of irreversible thermodynamics. The present paper describes a recent study of solute segregation effects in void nucleation. We begin with a thermodynamic model for a nonequilibrium void with interfacial segregation. The thermodynamic model is coupled with kinetic considerations of solute/solvent diffusion under a bias, which is itself related to segregation by the coating effect, to assess the stability of void embryos. To determine nucleation rate, we develop a novel technique by extending the most probable path method in statistical mechanics for nonequilibrium steady state to simulate large fluctuation with nonlinear dissipation. The path of nucleation is determined by solving an analogous problem on particle trajectory in classical dynamics. The results of both the stability analysis and the fluctuation analysis establish the paramount significance of the impurity effect via the mechanism of nonequilibrium segregation. We conclude that over-segregation is probably the most general cause for the apparently low nucleation barriers that are responsible for nearly ubiquitous occurrence of void swelling in common metals

  20. Hydrogen storage in complex hydrides

    International Nuclear Information System (INIS)

    Lupu, D.; Biris, A. R.; Misan, I.

    2005-01-01

    Full text: Hydrogen storage is a key enabling technology for the advancement of hydrogen and fuel cell power technologies in mobile and stationary applications. A relevant role of the fuel cell powered vehicles on the market of the transportation systems will be achieved only if the research and development of on-board vehicular hydrogen storage are able to allow a driving range of at least 500 km. The on-board hydrogen storage systems are more challenging due to the space, weight and cost limitations. This range of autonomy between refueling requires materials able to store at least 6.5% weight hydrogen, available at moderate pressures, at the working temperature of the fuel cells and with acceptable cycling stability. The intensive research on the hydrogen storage in alloys and intermetallic of the LaNi 5 , FeTi or Laves phase type compounds, which started more than three decades ago did not resulted in materials of more than about 3% H storage capacities. The 7.5% H content of the Mg hydride is still of attracting interest but though the absorption has been achieved at lower temperatures by ball milling magnesium with various amounts of nickel, the desorption can not be attained at 1 bar H 2 below 280 deg. C and the kinetics of the process is too slow. In the last decade, the attention is focused on another class of compounds, the complex hydrides of aluminum with alkali metals (alanates), due to their high hydrogen content. It was found that doping with Ti-based catalysts improve the hydrogenation/dehydrogenation conditions of NaAlH 4 . Later on, it was shown that ball milling with solid state catalysts greatly improve the hydrogen desorption kinetics of NaAlH 4 , and this also helps to the rehydriding process. The hydrogen desorption from NaAlH 4 occurs in three steps, it shows a reversible storage capacity of 5.5% H and this led to further research work for a better knowledge of its application relating properties. In this work, ball milling experiments on Na

  1. Nucleation in the atmosphere

    International Nuclear Information System (INIS)

    Hegg, D A; Baker, M B

    2009-01-01

    Small particles play major roles in modulating radiative and hydrological fluxes in the atmosphere and thus they impact both climate (IPCC 2007) and weather. Most atmospheric particles outside clouds are created in situ through nucleation from gas phase precursors and most ice particles within clouds are formed by nucleation, usually from the liquid. Thus, the nucleation process is of great significance in the Earth's atmosphere. The theoretical examination of nucleation in the atmosphere has been based mostly on classical nucleation theory. While diagnostically very useful, the prognostic skill demonstrated by this approach has been marginal. Microscopic approaches such as molecular dynamics and density functional theory have also proven useful in elucidating various aspects of the process but are not yet sufficiently refined to offer a significant prognostic advantage to the classical approach, due primarily to the heteromolecular nature of atmospheric nucleation. An important aspect of the nucleation process in the atmosphere is that the degree of metastability of the parent phase for the nucleation is modulated by a number of atmospheric processes such as condensation onto pre-existing particles, updraft velocities that are the main driving force for supersaturation of water (a major factor in all atmospheric nucleation), and photochemical production rates of nucleation precursors. Hence, atmospheric nucleation is both temporally and spatially inhomogeneous

  2. Complex Hydrides for Hydrogen Storage

    Energy Technology Data Exchange (ETDEWEB)

    Slattery, Darlene; Hampton, Michael

    2003-03-10

    This report describes research into the use of complex hydrides for hydrogen storage. The synthesis of a number of alanates, (AIH4) compounds, was investigated. Both wet chemical and mechano-chemical methods were studied.

  3. Nucleation versus instability race in strained films

    Science.gov (United States)

    Liu, Kailang; Berbezier, Isabelle; David, Thomas; Favre, Luc; Ronda, Antoine; Abbarchi, Marco; Voorhees, Peter; Aqua, Jean-Noël

    2017-10-01

    Under the generic term "Stranski-Krastanov" are grouped two different growth mechanisms of SiGe quantum dots. They result from the self-organized Asaro-Tiller-Grinfel'd (ATG) instability at low strain, while at high strain, from a stochastic nucleation. While these regimes are well known, we elucidate here the origin of the transition between these two pathways thanks to a joint theoretical and experimental work. Nucleation is described within the master equation framework. By comparing the time scales for ATG instability development and three-dimensional (3D) nucleation onset, we demonstrate that the transition between these two regimes is simply explained by the crossover between their divergent evolutions. Nucleation exhibits a strong exponential deviation at low strain while ATG behaves only algebraically. The associated time scale varies with exp(1 /x4) for nucleation, while it only behaves as 1 /x8 for the ATG instability. Consequently, at high (low) strain, nucleation (instability) occurs faster and inhibits the alternate evolution. It is then this different kinetic evolution which explains the transition from one regime to the other. Such a kinetic view of the transition between these two 3D growth regimes was not provided before. The crossover between nucleation and ATG instability is found to occur both experimentally and theoretically at a Ge composition around 50% in the experimental conditions used here. Varying the experimental conditions and/or the system parameters does not allow us to suppress the transition. This means that the SiGe quantum dots always grow via ATG instability at low strain and nucleation at high strain. This result is important for the self-organization of quantum dots.

  4. Hydrogen storage in sodium aluminum hydride.

    Energy Technology Data Exchange (ETDEWEB)

    Ozolins, Vidvuds; Herberg, J.L. (Lawrence Livermore National Laboratories, Livermore, CA); McCarty, Kevin F.; Maxwell, Robert S. (Lawrence Livermore National Laboratories, Livermore, CA); Stumpf, Roland Rudolph; Majzoub, Eric H.

    2005-11-01

    Sodium aluminum hydride, NaAlH{sub 4}, has been studied for use as a hydrogen storage material. The effect of Ti, as a few mol. % dopant in the system to increase kinetics of hydrogen sorption, is studied with respect to changes in lattice structure of the crystal. No Ti substitution is found in the crystal lattice. Electronic structure calculations indicate that the NaAlH{sub 4} and Na{sub 3}AlH{sub 6} structures are complex-ionic hydrides with Na{sup +} cations and AlH{sub 4}{sup -} and AlH{sub 6}{sup 3-} anions, respectively. Compound formation studies indicate the primary Ti-compound formed when doping the material at 33 at. % is TiAl{sub 3} , and likely Ti-Al compounds at lower doping rates. A general study of sorption kinetics of NaAlH{sub 4}, when doped with a variety of Ti-halide compounds, indicates a uniform response with the kinetics similar for all dopants. NMR multiple quantum studies of solution-doped samples indicate solvent interaction with the doped alanate. Raman spectroscopy was used to study the lattice dynamics of NaAlH{sub 4}, and illustrated the molecular ionic nature of the lattice as a separation of vibrational modes between the AlH{sub 4}{sup -} anion-modes and lattice-modes. In-situ Raman measurements indicate a stable AlH{sub 4}{sup -} anion that is stable at the melting temperature of NaAlH{sub 4}, indicating that Ti-dopants must affect the Al-H bond strength.

  5. First-principles calculations of niobium hydride formation in superconducting radio-frequency cavities

    Science.gov (United States)

    Ford, Denise C.; Cooley, Lance D.; Seidman, David N.

    2013-09-01

    Niobium hydride is suspected to be a major contributor to degradation of the quality factor of niobium superconducting radio-frequency (SRF) cavities. In this study, we connect the fundamental properties of hydrogen in niobium to SRF cavity performance and processing. We modeled several of the niobium hydride phases relevant to SRF cavities and present their thermodynamic, electronic, and geometric properties determined from calculations based on density functional theory. We find that the absorption of hydrogen from the gas phase into niobium is exothermic and hydrogen becomes somewhat anionic. The absorption of hydrogen by niobium lattice vacancies is strongly preferred over absorption into interstitial sites. A single vacancy can accommodate six hydrogen atoms in the symmetrically equivalent lowest energy sites and additional hydrogen in the nearby interstitial sites affected by the strain field: this indicates that a vacancy can serve as a nucleation center for hydride phase formation. Small hydride precipitates may then occur near lattice vacancies upon cooling. Vacancy clusters and extended defects should also be enriched in hydrogen, potentially resulting in extended hydride phase regions upon cooling. We also assess the phase changes in the niobium-hydrogen system based on charge transfer between niobium and hydrogen, the strain field associated with interstitial hydrogen, and the geometry of the hydride phases. The results of this study stress the importance of not only the hydrogen content in niobium, but also the recovery state of niobium for the performance of SRF cavities.

  6. First-principles calculations of niobium hydride formation in superconducting radio-frequency cavities

    International Nuclear Information System (INIS)

    Ford, Denise C; Cooley, Lance D; Seidman, David N

    2013-01-01

    Niobium hydride is suspected to be a major contributor to degradation of the quality factor of niobium superconducting radio-frequency (SRF) cavities. In this study, we connect the fundamental properties of hydrogen in niobium to SRF cavity performance and processing. We modeled several of the niobium hydride phases relevant to SRF cavities and present their thermodynamic, electronic, and geometric properties determined from calculations based on density functional theory. We find that the absorption of hydrogen from the gas phase into niobium is exothermic and hydrogen becomes somewhat anionic. The absorption of hydrogen by niobium lattice vacancies is strongly preferred over absorption into interstitial sites. A single vacancy can accommodate six hydrogen atoms in the symmetrically equivalent lowest energy sites and additional hydrogen in the nearby interstitial sites affected by the strain field: this indicates that a vacancy can serve as a nucleation center for hydride phase formation. Small hydride precipitates may then occur near lattice vacancies upon cooling. Vacancy clusters and extended defects should also be enriched in hydrogen, potentially resulting in extended hydride phase regions upon cooling. We also assess the phase changes in the niobium–hydrogen system based on charge transfer between niobium and hydrogen, the strain field associated with interstitial hydrogen, and the geometry of the hydride phases. The results of this study stress the importance of not only the hydrogen content in niobium, but also the recovery state of niobium for the performance of SRF cavities. (paper)

  7. Modeling of hydrogen isotopes separation in a metal hydride bed

    International Nuclear Information System (INIS)

    Charton, S.; Corriou, J.P.; Schweich, D.

    1999-01-01

    A predictive model for hydrogen isotopes separation in a non-isothermal bed of unsupported palladium hydride particles is derived. It accounts for the non-linear adsorption-dissociation equilibrium, hydrodynamic dispersion, pressure drop, mass transfer kinetics, heat of sorption and heat losses at the bed wall. Using parameters from the literature or estimated with classical correlations, the model gives simulated curves in agreement with previously published experiments without any parameter fit. The non-isothermal behavior is shown to be responsible for drastic changes of the mass transfer rate which is controlled by diffusion in the solid-phase lattice. For a feed at 300 K and atmospheric pressure, the endothermic hydride-to-deuteride exchange is kinetically controlled, whereas the reverse exothermic exchange is nearly at equilibrium. Finally, a simple and efficient thermodynamic model for the dissociative equilibrium between a metal and a diatomic gas is proposed. (Copyright (c) 1999 Elsevier Science B.V., Amsterdam. All rights reserved.)

  8. Elastoplastic phase-field modeling of ζ-hydride precipitation in zirconium alloy: dynamics evolution in inhomogeneous elasticity

    International Nuclear Information System (INIS)

    Oum, G.; Thuinet, L.; Legris, A.

    2015-07-01

    A phase-field (PF) model was developed within the framework of homogeneous and heterogeneous elasticity theory to study the precipitation of ζ-hydride in zirconium. By coupling crystal plasticity to PF we show that plastic strain participates in lowering the transformation stresses, and therefore induces changes in nucleation, growth and morphology evolution of the precipitates. (authors)

  9. Hydriding failure in water reactor fuel elements

    International Nuclear Information System (INIS)

    Sah, D.N.; Ramadasan, E.; Unnikrishnan, K.

    1980-01-01

    Hydriding of the zircaloy cladding has been one of the important causes of failure in water reactor fuel elements. This report reviews the causes, the mechanisms and the methods for prevention of hydriding failure in zircaloy clad water reactor fuel elements. The different types of hydriding of zircaloy cladding have been classified. Various factors influencing zircaloy hydriding from internal and external sources in an operating fuel element have been brought out. The findings of post-irradiation examination of fuel elements from Indian reactors, with respect to clad hydriding and features of hydriding failure are included. (author)

  10. Nanometer-scale mapping of irreversible electrochemical nucleation processes on solid Li-ion electrolytes

    OpenAIRE

    Kumar, Amit; Arruda, Thomas M.; Tselev, Alexander; Ivanov, Ilia N.; Lawton, Jamie S.; Zawodzinski, Thomas A.; Butyaev, Oleg; Zayats, Sergey; Jesse, Stephen; Kalinin, Sergei V.

    2013-01-01

    Electrochemical processes associated with changes in structure, connectivity or composition typically proceed via new phase nucleation with subsequent growth of nuclei. Understanding and controlling reactions requires the elucidation and control of nucleation mechanisms. However, factors controlling nucleation kinetics, including the interplay between local mechanical conditions, microstructure and local ionic profile remain inaccessible. Furthermore, the tendency of current probing technique...

  11. Principles of nucleation theory

    International Nuclear Information System (INIS)

    Clement, C.F.; Wood, M.H.

    1980-01-01

    The nucleation of small stable species is described in the problem of void growth by discrete rate equations. When gas is being produced the problem reduces to one of calculating the incubation dose for the gas bubble to void transition. A general expression for the steady state nucleation rate is derived for the case when voids are formed by vacancy fluctuations which enable an effective nucleation barrier to be crossed. (author)

  12. Mechanical properties and fracture of titanium hydrides

    International Nuclear Information System (INIS)

    Koketsu, Hideyuki; Taniyama, Yoshihiro; Yonezu, Akio; Cho, Hideo; Ogawa, Takeshi; Takemoto, Mikio; Nakayama, Gen

    2006-01-01

    Titanium hydrides tend to suffer fracture when their thicknesses reach a critical thickness. Morphology and mechanical property of the hydrides are, however, not well known. The study aims to reveal the hydride morphology and fracture types of the hydrides. Chevron shaped plate hydrides were found to be produced on the surface of pure titanium (Grade 1) and Grade 7 titanium absorbing hydrogen. There were tree types of fracture of the hydrides, i.e., crack in hydride layer, exfoliation of the layer and shear-type fracture of the hydride plates, during the growth of the hydrides and deformation. We next estimated the true stress-strain curves of the hydrides on Grade 1 and 7 titanium using the dual Vickers indentation method, and the critical strain causing the Mode-I fine crack by indentation. Fracture strength and strain of the hydrides in Grade 1 titanium were estimated as 566 MPa and 4.5%, respectively. Those of the hydride in Grade 7 titanium were 498 MPa and 16%. Though the fracture strains estimated from the plastic instability of true stress-strain curves were approximately the half of those estimated by finite element method, the titanium hydrides were estimated to possess some extent of toughness or plastic deformation capability. (author)

  13. On void nucleation

    International Nuclear Information System (INIS)

    Subbotin, A.V.

    1978-01-01

    Nucleation of viable voids in irradiated materials is considered. The mechanism of evaporation and absorption of interstitials and vacancies disregarding the possibility of void merging is laid down into the basis of the discussion. The effect of irradiated material structure on void nucleation is separated from the effect of the properties of supersaturated solutions of vacancies and interstitials. An analytical expression for the nucleation rate is obtained and analyzed in different cases. The interstitials are concluded to effect severely the nucleation rate of viable voids

  14. High-pressure hydriding of Zircaloy

    International Nuclear Information System (INIS)

    Kim, Y.S.

    1996-01-01

    The hydriding characteristics of Zircaloy-2(Zry), sponge zirconium (as a liner on Zry plate), and crystal-bar zirconium exposed to pure H 2 at 0.1 MPa or 7 MPa and 400 C were determined in a thermogravimetric apparatus. The morphology of the hydrided specimens was also examined by optical microscopy. For all specimen types, the rate of hydriding in 7 MPa H 2 was two orders of magnitude greater than in 0.1 MPa H 2 . For Zry, uniform bulk hydriding was revealed by hydride precipitates at room temperature and on one occasion, a sunburst hydride. In addition, all specimen types exhibited a hydride surface layer. In a duplex Zry/sponge-Zr specimen, Zry is more heavily hydrided than the sponge Zr layer. (orig.)

  15. Hydride Olefin complexes of tantalum and niobium

    NARCIS (Netherlands)

    Klazinga, Aan Hendrik

    1979-01-01

    This thesis describes investigations on low-valent tantalum and niobium hydride and alkyl complexes, particularly the dicyclopentadienyl tantalum hydride olefin complexes Cp2Ta(H)L (L=olefin). ... Zie: Summary

  16. Glass-crystal transformation under non-isothermal conditions: Kinetic analysis of the Ag{sub 0.16}As{sub 0.38}Se{sub 0.46} glassy alloy by using a new theoretical method based on nucleation and growth processes, which depend on time as a power law

    Energy Technology Data Exchange (ETDEWEB)

    Vazquez, J., E-mail: jose.vazquez@uca.e [Departamento de Fisica de la Materia Condensada, Facultad de Ciencias, Universidad de Cadiz, Apartado 40, 11510, Puerto Real (Cadiz) (Spain); Cardenas-Leal, J.L.; Garcia-G Barreda, D.; Gonzalez-Palma, R.; Lopez-Alemany, P.L.; Villares, P. [Departamento de Fisica de la Materia Condensada, Facultad de Ciencias, Universidad de Cadiz, Apartado 40, 11510, Puerto Real (Cadiz) (Spain)

    2010-11-01

    A theoretical method, which we have published in two previous works, has been applied to the study of the glass-crystal transformation of the Ag{sub 0.16}As{sub 0.38}Se{sub 0.46} semiconductor glass under non-isothermal conditions. This method allows one to obtain an evolution equation with temperature for the actual volume fraction, to calculate the kinetic parameters of the quoted transformation, to establish the thermal process type, to determine the dimensionality of the crystal growth and to evaluate the exponents of the power laws of the time-dependence both for the nucleation frequency and for the crystal growth rate in non-isothermal transformations. The quoted method assumes the concept of extended volume of the transformed material, the condition of randomly located nuclei and the supposition of mutual interference of regions growing from separated nuclei, considering moreover the case presented in the practice of a kinetic exponent with a value larger than 4. To study the quoted case it is proposed that both the nucleation frequency and the crystal growth rate depend on time as a power law. The above-mentioned Ag{sub 0.16}As{sub 0.38}Se{sub 0.46} glassy alloy presents two exothermic peaks. The second peak gives for the kinetic exponent a value large enough than 4 and it is necessary to resort to the hypotheses of the considered method to justify the unexpectedly high value of the kinetic exponent. Following the quoted method it has been found that the thermal process type is continuous nucleation with three-dimensional growth for the two peaks of crystallization of the studied alloy. Moreover, the experimental curve of the transformed fraction shows a satisfactory agreement with the theoretical curve corresponding to the considered method, confirming the reliability of the quoted method in order to analyze the transformation kinetics of the above-mentioned alloy.

  17. Influence of temperature and hydrogen content on stress-induced radial hydride precipitation in Zircaloy-4 cladding

    Energy Technology Data Exchange (ETDEWEB)

    Desquines, J., E-mail: jean.desquines@irsn.fr; Drouan, D.; Billone, M.; Puls, M.P.; March, P.; Fourgeaud, S.; Getrey, C.; Elbaz, V.; Philippe, M.

    2014-10-15

    Radial hydride precipitation in stress relieved Zircaloy-4 fuel claddings is studied using a new thermal–mechanical test. Two maximum temperatures for radial hydride precipitation heat treatment are studied, 350 and 450 °C with hydrogen contents ranging between 50 and 600 wppm. The new test provides two main results of interest: the minimum hoop stress required to precipitate radial hydrides and a maximum stress above which, all hydrides precipitate in the radial direction. Based on these two extreme stress conditions, a model is derived to determine the stress level required to obtain a given fraction of radial hydrides after high temperature thermal–mechanical heat treatment. The proposed model is validated using metallographic observation data on pressurized tubes cooled down under constant pressure. Most of the samples with reoriented hydrides are further subjected to a ductility test. Using finite element modeling, the test results are analyzed in terms of crack nucleation within radial hydrides at the outer diameter and crack growth through the thickness of the tubular samples. The combination of test results shows that samples with hydrogen contents of about 100 wppm had the lowest ductility.

  18. A nucleator arms race: cellular control of actin assembly.

    Science.gov (United States)

    Campellone, Kenneth G; Welch, Matthew D

    2010-04-01

    For over a decade, the actin-related protein 2/3 (ARP2/3) complex, a handful of nucleation-promoting factors and formins were the only molecules known to directly nucleate actin filament formation de novo. However, the past several years have seen a surge in the discovery of mammalian proteins with roles in actin nucleation and dynamics. Newly recognized nucleation-promoting factors, such as WASP and SCAR homologue (WASH), WASP homologue associated with actin, membranes and microtubules (WHAMM), and junction-mediating regulatory protein (JMY), stimulate ARP2/3 activity at distinct cellular locations. Formin nucleators with additional biochemical and cellular activities have also been uncovered. Finally, the Spire, cordon-bleu and leiomodin nucleators have revealed new ways of overcoming the kinetic barriers to actin polymerization.

  19. Nucleation barrier reconstruction via the seeding method in a lattice model with competing nucleation pathways.

    Science.gov (United States)

    Lifanov, Yuri; Vorselaars, Bart; Quigley, David

    2016-12-07

    We study a three-species analogue of the Potts lattice gas model of nucleation from solution in a regime where partially disordered solute is a viable thermodynamic phase. Using a multicanonical sampling protocol, we compute phase diagrams for the system, from which we determine a parameter regime where the partially disordered phase is metastable almost everywhere in the temperature-fugacity plane. The resulting model shows non-trivial nucleation and growth behaviour, which we examine via multidimensional free energy calculations. We consider the applicability of the model in capturing the multi-stage nucleation mechanisms of polymorphic biominerals (e.g., CaCO 3 ). We then quantitatively explore the kinetics of nucleation in our model using the increasingly popular "seeding" method. We compare the resulting free energy barrier heights to those obtained via explicit free energy calculations over a wide range of temperatures and fugacities, carefully considering the propagation of statistical error. We find that the ability of the "seeding" method to reproduce accurate free energy barriers is dependent on the degree of supersaturation, and severely limited by the use of a nucleation driving force Δμ computed for bulk phases. We discuss possible reasons for this in terms of underlying kinetic assumptions, and those of classical nucleation theory.

  20. Nucleation reactions during deformation and crystallization of metallic glass

    International Nuclear Information System (INIS)

    Perepezko, J.H.; Imhoff, S.D.; Chen, M.W.; Gonzalez, S.; Inoue, A.

    2012-01-01

    Highlights: ► New approach to the examination and analysis of shear band nucleation. ► Discovery of multiple shear band nucleation sites. ► Identification of a method of using transient kinetic behavior to provide a more realistic evaluation of the diffusivity that is relevant to nucleation. - Abstract: Nucleation reactions play a central role in the synthesis of both bulk metallic glasses and nanostructured materials. For nanostructured materials it is necessary to promote a high nucleation density without significant growth or coarsening. Beyond crystallization reactions nucleation of shear bands is critical for promoting a homogeneous flow and useful ductility for structural applications of bulk metallic glass. The study and analysis of nucleation reactions for these different situations requires a consideration of the stochastic nature of nucleation, the influence of heterogeneous sites, and the controlling transport properties. For shear band nucleation, the stochastic nature can be effectively probed by instrumented nanoindentation tests. The analysis of a statistically significant number of measurements of the first pop-in shear band nucleation events reveals at least two main nucleation sites. In nanostructured composites, the initial nucleation stage is influenced by transient effects as reflected in the delay time prior to steady state nucleation and by heterogeneous nucleation sites that are related to medium range order regions in Al-base amorphous alloys. Moreover, the early growth characteristics are linked to the maximum achievable particle density. The new developments and insight on the fundamental understanding of nanostructure reaction mechanisms offer valuable guidance for control of nanoscale microstructures and for promoting ductile deformation behavior.

  1. Metal hydride compositions and lithium ion batteries

    Energy Technology Data Exchange (ETDEWEB)

    Young, Kwo; Nei, Jean

    2018-04-24

    Heterogeneous metal hydride (MH) compositions comprising a main region comprising a first metal hydride and a secondary region comprising one or more additional components selected from the group consisting of second metal hydrides, metals, metal alloys and further metal compounds are suitable as anode materials for lithium ion cells. The first metal hydride is for example MgH.sub.2. Methods for preparing the composition include coating, mechanical grinding, sintering, heat treatment and quenching techniques.

  2. Corrosion behavior of Zircaloy 4 cladding material. Evaluation of the hydriding effect

    International Nuclear Information System (INIS)

    Blat, M.

    1997-04-01

    In this work, particular attention has been paid to the hydriding effect in PIE and laboratory test to validate a detrimental hydrogen contribution on Zircaloy 4 corrosion behavior at high burnup. Laboratory corrosion tests results confirm that hydrides have a detrimental role on corrosion kinetics. This effect is particularly significant for cathodic charged samples with a massive hydride outer layer before corrosion test. PIE show that at high burnup a hydride layer is formed underneath the metal/oxide interface. The results of the metallurgical examinations are discussed with respect to the possible mechanisms involved in this detrimental effect of hydrogen. Therefore, according to the laboratory tests results and PIE, hydrogen could be a strong contributor to explain the increase in corrosion rate at high burnup. (author)

  3. Modelling the effect of acoustic waves on nucleation

    Energy Technology Data Exchange (ETDEWEB)

    Haqshenas, S. R., E-mail: seyyed.haqshenas.12@ucl.ac.uk; Saffari, N., E-mail: n.saffari@ucl.ac.uk [Department of Mechanical Engineering, University College London, Gower Street, London WC1E 7JE (United Kingdom); Ford, I. J., E-mail: i.ford@ucl.ac.uk [Department of Physics and Astronomy, University College London, Gower Street, London WC1E 6BT (United Kingdom)

    2016-07-14

    A phase transformation in a metastable phase can be affected when it is subjected to a high intensity ultrasound wave. In this study we determined the effect of oscillation in pressure and temperature on a phase transformation using the Gibbs droplet model in a generic format. The developed model is valid for both equilibrium and non-equilibrium clusters formed through a stationary or non-stationary process. We validated the underlying model by comparing the predicted kinetics of water droplet formation from the gas phase against experimental data in the absence of ultrasound. Our results demonstrated better agreement with experimental data in comparison with classical nucleation theory. Then, we determined the thermodynamics and kinetics of nucleation and the early stage of growth of clusters in an isothermal sonocrystallisation process. This new contribution shows that the effect of pressure on the kinetics of nucleation is cluster size-dependent in contrast to classical nucleation theory.

  4. Diamond Nucleation Using Polyethene

    Science.gov (United States)

    Morell, Gerardo (Inventor); Makarov, Vladimir (Inventor); Varshney, Deepak (Inventor); Weiner, Brad (Inventor)

    2013-01-01

    The invention presents a simple, non-destructive and non-abrasive method of diamond nucleation using polyethene. It particularly describes the nucleation of diamond on an electrically viable substrate surface using polyethene via chemical vapor deposition (CVD) technique in a gaseous environment.

  5. Effects of shear flow on phase nucleation and crystallization.

    Science.gov (United States)

    Mura, Federica; Zaccone, Alessio

    2016-04-01

    Classical nucleation theory offers a good framework for understanding the common features of new phase formation processes in metastable homogeneous media at rest. However, nucleation processes in liquids are ubiquitously affected by hydrodynamic flow, and there is no satisfactory understanding of whether shear promotes or slows down the nucleation process. We developed a classical nucleation theory for sheared systems starting from the molecular level of the Becker-Doering master kinetic equation and we analytically derived a closed-form expression for the nucleation rate. The theory accounts for the effect of flow-mediated transport of molecules to the nucleus of the new phase, as well as for the mechanical deformation imparted to the nucleus by the flow field. The competition between flow-induced molecular transport, which accelerates nucleation, and flow-induced nucleus straining, which lowers the nucleation rate by increasing the nucleation energy barrier, gives rise to a marked nonmonotonic dependence of the nucleation rate on the shear rate. The theory predicts an optimal shear rate at which the nucleation rate is one order of magnitude larger than in the absence of flow.

  6. Accommodation stresses in hydride precipitates by synchrotron x-ray diffraction

    International Nuclear Information System (INIS)

    Santisteban, J R; Vicente, M A; Vizcaino, P; Banchik, A D; Almer, J

    2012-01-01

    Hydride-forming materials (Zr, Ti, Nb, etc) are affected by a sub-critical crack growth mechanism that involves the diffusion of H to the stressed region ahead of a crack, followed by nucleation and fracture of hydrides at the crack tip [1]. The phenomenon is intermittent, with the crack propagating through the hydride and stopping when it reaches the matrix. By repeating these processes, the crack propagates through a component at a rate that is highly dependent on the temperature history of the component. Most research effort to understand this phenomenon has occurred within the nuclear industry, as it affects the safe operation of pressure tubes (Zr2.5%Nb) and the long-term storage of nuclear fuel (Zircaloy cladding). Stress-induced hydride formation is a consequence of the volume dilatation that accompanies hydride formation (of the order of 15%), which is elastoplastically accommodated by the matrix and precipitate. Compressive stresses are expected within hydride precipitates due to the constraint imposed by the matrix. Such 'accommodation' stresses are essential ingredients in all theoretical models developed to assess the crack growth rate dependence on operational variables such as temperature, applied stress intensity factor, or overall H concentration [2]. Yet little experimental information is available about the magnitude and directionality of such accommodation stresses. Synchrotron X-ray diffraction is the only technique capable of quantifying such stresses. Here we briefly describe the fundaments of the technique, when used through an area detector placed in transmission geometry. The results of the experiments have allowed us to produce a comprehensive picture about the magnitude and origin of accommodation stresses in δ zirconium hydride platelets (author)

  7. Thermal coupling of a high temperature PEM fuel cell with a complex hydride tank

    DEFF Research Database (Denmark)

    Pfeifer, P.; Wall, C.; Jensen, Jens Oluf

    2009-01-01

    the possibilities of a thermal coupling of a high temperature PEM fuel cell operating at 160-200 degrees C. The starting temperatures and temperature hold-times before starting fuel cell operation, the heat transfer characteristics of the hydride storage tanks, system temperature, fuel cell electrical power......Sodium alanate doped with cerium catalyst has been proven to have fast kinetics for hydrogen ab- and de-sorption as well as a high gravimetric storage density around 5 wt%. The kinetics of hydrogen sorption can be improved by preparing the alanate as nanocrystalline material. However, the second...... decomposition step, i.e. the decomposition of the hexahydride to sodium hydride and aluminium which refers to 1.8 wt% hydrogen is supposed to happen above 110 degrees C. The discharge of the material is thus limited by the level of heat supplied to the hydride storage tank. Therefore, we evaluated...

  8. Interaction of electrons with light metal hydrides in the transmission electron microscope.

    Science.gov (United States)

    Wang, Yongming; Wakasugi, Takenobu; Isobe, Shigehito; Hashimoto, Naoyuki; Ohnuki, Somei

    2014-12-01

    Transmission electron microscope (TEM) observation of light metal hydrides is complicated by the instability of these materials under electron irradiation. In this study, the electron kinetic energy dependences of the interactions of incident electrons with lithium, sodium and magnesium hydrides, as well as the constituting element effect on the interactions, were theoretically discussed, and electron irradiation damage to these hydrides was examined using in situ TEM. The results indicate that high incident electron kinetic energy helps alleviate the irradiation damage resulting from inelastic or elastic scattering of the incident electrons in the TEM. Therefore, observations and characterizations of these materials would benefit from increased, instead decreased, TEM operating voltage. © The Author 2014. Published by Oxford University Press on behalf of The Japanese Society of Microscopy. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

  9. Improving solid-state hydriding and dehydriding properties of the LiBH{sub 4} plus MgH{sub 2} system with the addition of Mn and V dopants

    Energy Technology Data Exchange (ETDEWEB)

    Crosby, Kyle; Wan, Xuefei; Shaw, Leon L. [Department of Chemical, Materials and Biomolecular Engineering, University of Connecticut, 97 North Eagleville Road, U-3136, Storrs, CT 06269 (United States)

    2010-11-01

    The hydriding process of the 2LiH + MgB{sub 2} mixture is controlled by outward diffusion of Mg and inward diffusion of Li and H within MgB{sub 2} crystals to form LiBH{sub 4}. This study explores the feasibility of using transition metal dopants, such as Mn and V, to enhance the diffusion rate and thus the hydriding kinetics. It is found that Mn can indeed enhance the hydriding kinetics of the 2LiH + MgB{sub 2} mixture, while V does not. The major factor in enhancing the diffusion rate and thus the hydriding kinetics is related to the dopant's ability to induce the lattice distortion of MgB{sub 2} crystals. This study demonstrates that the kinetics of the diffusion controlled solid-state hydriding process can be improved by doping if the dopant is properly selected. (author)

  10. Modelling the gas transport and chemical processes related to clad oxidation and hydriding

    Energy Technology Data Exchange (ETDEWEB)

    Montgomery, R O; Rashid, Y R [ANATECH Research Corp., San Diego, CA (United States)

    1997-08-01

    Models are developed for the gas transport and chemical processes associated with the ingress of steam into a LWR fuel rod through a small defect. These models are used to determine the cladding regions in a defective fuel rod which are susceptible to massive hydriding and the creation of sunburst hydrides. The brittle nature of zirconium hydrides (ZrH{sub 2}) in these susceptible regions produces weak spots in the cladding which can act as initiation sites for cladding cracks under certain cladding stress conditions caused by fuel cladding mechanical interaction. The modeling of the axial gas transport is based on gaseous bimolar diffusion coupled with convective mass transport using the mass continuity equation. Hydrogen production is considered from steam reaction with cladding inner surface, fission products and internal components. Eventually, the production of hydrogen and its diffusion along the length results in high hydrogen concentration in locations remote from the primary defect. Under these conditions, the hydrogen can attack the cladding inner surface and breakdown the protective ZrO{sub 2} layer locally, initiating massive localized hydriding leading to sunburst hydride. The developed hydrogen evolution model is combined with a general purpose fuel behavior program to integrate the effects of power and burnup into the hydriding kinetics. Only in this manner can the behavior of a defected fuel rod be modeled to determine the conditions the result in fuel rod degradation. (author). 14 refs, 6 figs.

  11. Effect of strain on surface diffusion and nucleation

    DEFF Research Database (Denmark)

    Brune, Harald; Bromann, Karsten; Röder, Holger

    1995-01-01

    The influence of strain on diffusion and nucleation has been studied by means of scanning tunneling microscopy and effective-medium theory for Ag self-diffusion on strained and unstrained (111) surfaces. Experimentally, the diffusion barrier is observed to be substantially lower on a pseudomorphic...... effect on surface diffusion and nucleation in heteroepitaxy and are thus of significance for the film morphology in the kinetic growth regime....

  12. Nucleation of strange matter in dense stellar cores

    International Nuclear Information System (INIS)

    Horvath, J.E.; Benvenuto, O.G.; Vucetich, H.

    1992-01-01

    We investigate the nucleation of strange quark matter inside hot, dense nuclear matter. Applying Zel'dovich's kinetic theory of nucleation we find a lower limit of the temperature T for strange-matter bubbles to appear, which happens to be satisfied inside the Kelvin-Helmholtz cooling era of a compact star life but not much after it. Our bounds thus suggest that a prompt conversion could be achieved, giving support to earlier expectations for nonstandard type-II supernova scenarios

  13. Tritium processing using metal hydrides

    International Nuclear Information System (INIS)

    Mallett, M.W.

    1986-01-01

    E.I. duPont de Nemours and Company is commissioned by the US Department of Energy to operate the Savannah River Plant and Laboratory. The primary purpose of the plant is to produce radioactive materials for national defense. In keeping with current technology, new processes for the production of tritium are being developed. Three main objectives of this new technology are to ease the processing of, ease the storage of, and to reduce the operating costs of the tritium production facility. Research has indicated that the use of metal hydrides offers a viable solution towards satisfying these objectives. The Hydrogen and Fuels Technology Division has the responsibility to conduct research in support of the tritium production process. Metal hydride technology and its use in the storage and transportation of hydrogen will be reviewed

  14. Hydride Molecules towards Nearby Galaxies

    Science.gov (United States)

    Monje, Raquel R.; La, Ngoc; Goldsmith, Paul

    2018-06-01

    Observations carried out by the Herschel Space Observatory revealed strong spectroscopic signatures from light hydride molecules within the Milky Way and nearby active galaxies. To better understand the chemical and physical conditions of the interstellar medium, we conducted the first comprehensive survey of hydrogen fluoride (HF) and water molecular lines observed through the SPIRE Fourier Transform Spectrometer. By collecting and analyzing the sub-millimeter spectra of over two hundred sources, we found that the HF J = 1 - 0 rotational transition which occurs at approximately 1232 GHz was detected in a total of 39 nearby galaxies both in absorption and emission. The analysis will determine the main excitation mechanism of HF in nearby galaxies and provide steady templates of the chemistry and physical conditions of the ISM to be used in the early universe, where observations of hydrides are more scarce.

  15. Rechargeable metal hydrides for spacecraft application

    Science.gov (United States)

    Perry, J. L.

    1988-01-01

    Storing hydrogen on board the Space Station presents both safety and logistics problems. Conventional storage using pressurized bottles requires large masses, pressures, and volumes to handle the hydrogen to be used in experiments in the U.S. Laboratory Module and residual hydrogen generated by the ECLSS. Rechargeable metal hydrides may be competitive with conventional storage techniques. The basic theory of hydride behavior is presented and the engineering properties of LaNi5 are discussed to gain a clear understanding of the potential of metal hydrides for handling spacecraft hydrogen resources. Applications to Space Station and the safety of metal hydrides are presented and compared to conventional hydride storage. This comparison indicates that metal hydrides may be safer and require lower pressures, less volume, and less mass to store an equivalent mass of hydrogen.

  16. Nanostructured, complex hydride systems for hydrogen generation

    Directory of Open Access Journals (Sweden)

    Robert A. Varin

    2015-02-01

    Full Text Available Complex hydride systems for hydrogen (H2 generation for supplying fuel cells are being reviewed. In the first group, the hydride systems that are capable of generating H2 through a mechanical dehydrogenation phenomenon at the ambient temperature are discussed. There are few quite diverse systems in this group such as lithium alanate (LiAlH4 with the following additives: nanoiron (n-Fe, lithium amide (LiNH2 (a hydride/hydride system and manganese chloride MnCl2 (a hydride/halide system. Another hydride/hydride system consists of lithium amide (LiNH2 and magnesium hydride (MgH2, and finally, there is a LiBH4-FeCl2 (hydride/halide system. These hydride systems are capable of releasing from ~4 to 7 wt.% H2 at the ambient temperature during a reasonably short duration of ball milling. The second group encompasses systems that generate H2 at slightly elevated temperature (up to 100 °C. In this group lithium alanate (LiAlH4 ball milled with the nano-Fe and nano-TiN/TiC/ZrC additives is a prominent system that can relatively quickly generate up to 7 wt.% H2 at 100 °C. The other hydride is manganese borohydride (Mn(BH42 obtained by mechano-chemical activation synthesis (MCAS. In a ball milled (2LiBH4 + MnCl2 nanocomposite, Mn(BH42 co-existing with LiCl can desorb ~4.5 wt.% H2 at 100 °C within a reasonable duration of dehydrogenation. Practical application aspects of hydride systems for H2 generation/storage are also briefly discussed.

  17. Use of reversible hydrides for hydrogen storage

    Science.gov (United States)

    Darriet, B.; Pezat, M.; Hagenmuller, P.

    1980-01-01

    The addition of metals or alloys whose hydrides have a high dissociation pressure allows a considerable increase in the hydrogenation rate of magnesium. The influence of temperature and hydrogen pressure on the reaction rate were studied. Results concerning the hydriding of magnesium rich alloys such as Mg2Ca, La2Mg17 and CeMg12 are presented. The hydriding mechanism of La2Mg17 and CeMg12 alloys is given.

  18. Metal hydride-based thermal energy storage systems

    Science.gov (United States)

    Vajo, John J.; Fang, Zhigang

    2017-10-03

    The invention provides a thermal energy storage system comprising a metal-containing first material with a thermal energy storage density of about 1300 kJ/kg to about 2200 kJ/kg based on hydrogenation; a metal-containing second material with a thermal energy storage density of about 200 kJ/kg to about 1000 kJ/kg based on hydrogenation; and a hydrogen conduit for reversibly transporting hydrogen between the first material and the second material. At a temperature of 20.degree. C. and in 1 hour, at least 90% of the metal is converted to the hydride. At a temperature of 0.degree. C. and in 1 hour, at least 90% of the metal hydride is converted to the metal and hydrogen. The disclosed metal hydride materials have a combination of thermodynamic energy storage densities and kinetic power capabilities that previously have not been demonstrated. This performance enables practical use of thermal energy storage systems for electric vehicle heating and cooling.

  19. Hydrogen Storage using Metal Hydrides in a Stationary Cogeneration System

    International Nuclear Information System (INIS)

    Botzung, Maxime; Chaudourne, Serge; Perret, Christian; Latroche, Michel; Percheron-Guegan, Annick; Marty Philippe

    2006-01-01

    In the frame of the development of a hydrogen production and storage unit to supply a 40 kW stationary fuel cell, a metal hydride storage tank was chosen according to its reliability and high energetic efficiency. The study of AB5 compounds led to the development of a composition adapted to the project needs. The absorption/desorption pressures of the hydride at 75 C (2 / 1.85 bar) are the most adapted to the specifications. The reversible storage capacity (0.95 %wt) has been optimized to our work conditions and chemical kinetics is fast. The design of the Combined Heat and Power CHP system requires 5 kg hydrogen storage but in a first phase, only a 0.1 kg prototype has been realised and tested. Rectangular design has been chosen to obtain good compactness with an integrated plate fin type heat exchanger designed to reach high absorption/desorption rates. In this paper, heat and mass transfer characteristics of the Metal Hydride tank (MH tank) during absorption/desorption cycles are given. (authors)

  20. NMR study of hydride systems

    International Nuclear Information System (INIS)

    Peretz, M.

    1980-02-01

    The hydrides of thorium (ThH 2 , Th 4 H 15 and Th 4 D 15 ) and the intermetallic compound system (Zr(Vsub(1-x)Cosub(x)) 2 and its hydrides were investigated using the nuclear magnetic resonance (NMR) technique. From the results for the thorium hydride samples it was concluded that the density of states at the Fermi level n(Esub(f)) is higher in Th 4 H 15 than in ThH 2 ; there is an indirect reaction between the protons and the d electrons belonging to the Th atoms in Th 4 H 15 ; n(E) has a sharp structure near Esub(f). It was also found that the hydrogen diffusion mechanism changes with temperature. From the results for the intermetallic compound system conclusions were drawn concerning variations in the electronic structure, which explain the behavior of the system. In hydrogen diffusion studies in several samples it was found that Co atoms slow the diffusion rate. Quadrupole spectra obtained at low temperatures show that the H atoms preferably occupy tetrahedral sites formed by three V atoms and one Z atom. (H.K.)

  1. Hydrogen generation using silicon nanoparticles and their mixtures with alkali metal hydrides

    Science.gov (United States)

    Patki, Gauri Dilip

    mole of Si. We compare our silicon nanoparticles (˜10nm diameter) with commercial silicon nanopowder (rate upon decreasing the particle size to 10 nm was even greater than would be expected based upon the increase in surface area. While specific surface area increased by a factor of 6 in going from rate increased by a factor of 150. However, in all cases, silicon requires a base (e.g. NaOH, KOH, hydrazine) to catalyze its reaction with water. Metal hydrides are also promising hydrogen storage materials. The optimum metal hydride would possess high hydrogen storage density at moderate temperature and pressure, release hydrogen safely and controllably, and be stable in air. Alkali metal hydrides have high hydrogen storage density, but exhibit high uncontrollable reactivity with water. In an attempt to control this explosive nature while maintaining high storage capacity, we mixed our silicon nanoparticles with the hydrides. This has dual benefits: (1) the hydride- water reaction produces the alkali hydroxide needed for base-catalyzed silicon oxidation, and (2) dilution with 10nm coating by, the silicon may temper the reactivity of the hydride, making the process more controllable. Initially, we analyzed hydrolysis of pure alkali metal hydrides and alkaline earth metal hydrides. Lithium hydride has particularly high hydrogen gravimetric density, along with faster reaction kinetics than sodium hydride or magnesium hydride. On analysis of hydrogen production we found higher hydrogen yield from the silicon nanoparticle—metal hydride mixture than from pure hydride hydrolysis. The silicon-hydride mixtures using our 10nm silicon nanoparticles produced high hydrogen yield, exceeding the theoretical yield. Some evidence of slowing of the hydride reaction rate upon addition of silicon nanoparticles was observed.

  2. Dependency of Delayed Hydride Crack Velocity on the Direction of an Approach to Test Temperatures in Zirconium Alloys

    International Nuclear Information System (INIS)

    Kim, Young Suk; Kim, Kang Soo; Im, Kyung Soo; Ahn, Sang Bok; Cheong, Yong Moo

    2005-01-01

    Recently, Kim proposed a new DHC model where a driving force for the DHC is a supersaturated hydrogen concentration as a result of a hysteresis of the terminal solid solubility (TSS) of hydrogen in zirconium alloys upon a heating and a cooling. This model was demonstrated to be valid through a model experiment where the prior plastic deformation facilitated nucleation of the reoriented hydrides, thus reducing the supersaturated hydrogen concentration at the plastic zone ahead of the crack tip and causing hydrogen to move to the crack tip from the bulk region. Thus, an approach to the test temperature by a cooling is required to create a supersaturation of hydrogen, which is a driving force for the DHC of zirconium alloys. However, despite the absence of the supersaturation of hydrogen due to an approach to the test temperature by a heating, DHC is observed to occur in zirconium alloys at the test temperatures below 180 .deg. C. As to this DHC phenomenon, Kim proposed that stress-induced transformation from γ-hydrides to δ-hydrides is likely to be a cause of this, based on Root's observation that the γ-hydride is a stable phase at temperatures lower than 180 .deg. C. In other words, the hydrides formed at the crack tip would be δ-hydrides due to the stressinduced transformation while the bulk region still maintains the initial hydride phase or γ-hydrides. It should be noted that Ambler has also assumed the crack tip hydrides to be δ-hydrides. When the δ-hydrides or ZrH1.66 are precipitated at the crack tip due to the transformation of the γ-hydrides or ZrH, the crack tip will have a decreased concentration of dissolved hydrogen in zirconium, considering the atomic ratio of hydrogen and zirconium in the γ- and δ-hydrides. In contrast, due to no stress-induced transformation of hydrides, the bulk region maintains the initial concentration of dissolved hydrogen. Hence, there develops a difference in the hydrogen concentration or .C between the bulk and the

  3. Dependency of Delayed Hydride Crack Velocity on the Direction of an Approach to Test Temperatures in Zirconium Alloys

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Young Suk; Kim, Kang Soo; Im, Kyung Soo; Ahn, Sang Bok; Cheong, Yong Moo [Korea Atomic Energy Research Institute, Taejon (Korea, Republic of)

    2005-07-01

    Recently, Kim proposed a new DHC model where a driving force for the DHC is a supersaturated hydrogen concentration as a result of a hysteresis of the terminal solid solubility (TSS) of hydrogen in zirconium alloys upon a heating and a cooling. This model was demonstrated to be valid through a model experiment where the prior plastic deformation facilitated nucleation of the reoriented hydrides, thus reducing the supersaturated hydrogen concentration at the plastic zone ahead of the crack tip and causing hydrogen to move to the crack tip from the bulk region. Thus, an approach to the test temperature by a cooling is required to create a supersaturation of hydrogen, which is a driving force for the DHC of zirconium alloys. However, despite the absence of the supersaturation of hydrogen due to an approach to the test temperature by a heating, DHC is observed to occur in zirconium alloys at the test temperatures below 180 .deg. C. As to this DHC phenomenon, Kim proposed that stress-induced transformation from {gamma}-hydrides to {delta}-hydrides is likely to be a cause of this, based on Root's observation that the {gamma}-hydride is a stable phase at temperatures lower than 180 .deg. C. In other words, the hydrides formed at the crack tip would be {delta}-hydrides due to the stressinduced transformation while the bulk region still maintains the initial hydride phase or {gamma}-hydrides. It should be noted that Ambler has also assumed the crack tip hydrides to be {delta}-hydrides. When the {delta}-hydrides or ZrH1.66 are precipitated at the crack tip due to the transformation of the {gamma}-hydrides or ZrH, the crack tip will have a decreased concentration of dissolved hydrogen in zirconium, considering the atomic ratio of hydrogen and zirconium in the {gamma}- and {delta}-hydrides. In contrast, due to no stress-induced transformation of hydrides, the bulk region maintains the initial concentration of dissolved hydrogen. Hence, there develops a difference in the

  4. Thermokinetics of heterogeneous droplet nucleation on conically textured substrates.

    Science.gov (United States)

    Singha, Sanat K; Das, Prasanta K; Maiti, Biswajit

    2015-11-28

    Within the framework of the classical theory of heterogeneous nucleation, a thermokinetic model is developed for line-tension-associated droplet nucleation on conical textures considering growth or shrinkage of the formed cluster due to both interfacial and peripheral monomer exchange and by considering different geometric configurations. Along with the principle of free energy extremization, Katz kinetic approach has been employed to study the effect of substrate conicity and wettability on the thermokinetics of heterogeneous water droplet nucleation. Not only the peripheral tension is found to have a considerable effect on the free energy barrier but also the substrate hydrophobicity and hydrophilicity are observed to switch over their roles between conical crest and trough for different growth rates of the droplet. Besides, the rate of nucleation increases and further promotes nucleation for negative peripheral tension as it diminishes the free energy barrier appreciably. Moreover, nucleation inhibition can be achievable for positive peripheral tension due to the enhancement of the free energy barrier. Analyzing all possible geometric configurations, the hydrophilic narrower conical cavity is found to be the most preferred nucleation site. These findings suggest a physical insight into the context of surface engineering for the promotion or the suppression of nucleation on real or engineered substrates.

  5. Nucleation path of helium bubbles in metals during irradiation

    International Nuclear Information System (INIS)

    Morishita, Kazunori

    2008-01-01

    Thermodynamical formalization is made for description of the nucleation and growth of helium bubbles in metals during irradiation. The proposed formalization is available or evaluating both microstructural changes in fusion first wall materials where helium is produced by (n, α) nuclear transmutation reactions, and those in fusion divertor materials where helium particles with low energy are directly implanted. Calculated nucleation barrier is significantly reduced by the presence of helium, showing that a helium bubble with an appropriate number of helium atoms depending on bubble size can nucleate without any large nucleation barriers, even at a condition where an empty void has very large nucleation barrier without helium. With the proposed thermodynamical formalization, the nucleation and growth process of helium bubbles in iron during irradiation is simulated by the kinetic Monte-Carlo (KMC) technique. It shows the nucleation path of a helium bubble on the (N He , N V ) space as functions of temperatures and the concentration of helium in the matrix, where N He and N V are the number of helium atoms and vacancies in the helium bubble, respectively. Bubble growth rates depend on the nucleation path and suggest that two different mechanisms operate for bubble growth: one is controlled by vacancy diffusion and the other is controlled by interstitial helium diffusion. (author)

  6. Protein Polymerization into Fibrils from the Viewpoint of Nucleation Theory.

    Science.gov (United States)

    Kashchiev, Dimo

    2015-11-17

    The assembly of various proteins into fibrillar aggregates is an important phenomenon with wide implications ranging from human disease to nanoscience. Using general kinetic results of nucleation theory, we analyze the polymerization of protein into linear or helical fibrils in the framework of the Oosawa-Kasai (OK) model. We show that while within the original OK model of linear polymerization the process does not involve nucleation, within a modified OK model it is nucleation-mediated. Expressions are derived for the size of the fibril nucleus, the work for fibril formation, the nucleation barrier, the equilibrium and stationary fibril size distributions, and the stationary fibril nucleation rate. Under otherwise equal conditions, this rate decreases considerably when the short (subnucleus) fibrils lose monomers much more frequently than the long (supernucleus) fibrils, a feature that should be born in mind when designing a strategy for stymying or stimulating fibril nucleation. The obtained dependence of the nucleation rate on the concentration of monomeric protein is convenient for experimental verification and for use in rate equations accounting for nucleation-mediated fibril formation. The analysis and the results obtained for linear fibrils are fully applicable to helical fibrils whose formation is describable by a simplified OK model. Copyright © 2015 Biophysical Society. Published by Elsevier Inc. All rights reserved.

  7. Secondary hydriding of defected zircaloy-clad fuel rods

    International Nuclear Information System (INIS)

    Olander, D.R.; Vaknin, S.

    1993-01-01

    The phenomenon of secondary hydriding in LWR fuel rods is critically reviewed. The current understanding of the process is summarized with emphasis on the sources of hydrogen in the rod provided by chemical reaction of water (steam) introduced via a primary defect in the cladding. As often noted in the literature, the role of hydrogen peroxide produced by steam radiolysis is to provide sources of hydrogen by cladding and fuel oxidation that are absent without fission-fragment irradiation of the gas. Quantitative description of the evolution of the chemical state inside the fuel rod is achieved by combining the chemical kinetics of the reactions between the gas and the fuel and cladding with the transport by diffusion of components of the gas in the gap. The chemistry-gas transport model provides the framework into which therate constants of the reactions between the gases in the gap and the fuel and cladding are incorporated. The output of the model calculation is the H 2 0/H 2 ratio in the gas and the degree of claddingand fuel oxidation as functions of distance from the primary defect. This output, when combined with a criterion for the onset of massive hydriding of the cladding, can provide a prediction of the time and location of a potential secondary hydriding failure. The chemistry-gas transport model is the starting point for mechanical and H-in-Zr migration analyses intended to determine the nature of the cladding failure caused by the development of the massive hydride on the inner wall

  8. Return to nucleate boiling

    International Nuclear Information System (INIS)

    Shumway, R.W.

    1985-01-01

    This paper presents a collection of TMIN (temperature of return to nucleate boiling) correlations, evaluates them under several conditions, and compares them with a wide range of data. Purpose is to obtain the best one for use in a water reactor safety computer simulator known as TRAC-B. Return to nucleate boiling can occur in a reactor accident at either high or low pressure and flow rates. Most of the correlations yield unrealistic results under some conditions. A new correlation is proposed which overcomes many of the deficiencies

  9. Nonequilibrium thermodynamics of nucleation

    NARCIS (Netherlands)

    Schweizer, M.; Sagis, L.M.C.

    2014-01-01

    We present a novel approach to nucleation processes based on the GENERIC framework (general equation for the nonequilibrium reversible-irreversible coupling). Solely based on the GENERIC structure of time-evolution equations and thermodynamic consistency arguments of exchange processes between a

  10. Manufacture of titanium and zirconium hydrides

    International Nuclear Information System (INIS)

    Mares, F.; Hanslik, T.

    1973-01-01

    A method is described of manufacturing titanium and zirconium hydrides by hydrogenation of said metals characterized by the reaction temperature ranging between 250 to 500 degC, hydrogen pressure of 20 to 300 atm and possibly by the presence of a hydride of the respective metal. (V.V.)

  11. Hydride effect on crack instability of Zircaloy cladding

    Energy Technology Data Exchange (ETDEWEB)

    Tseng, Che-Chung, E-mail: cctseng@iner.gov.tw [Institute of Nuclear Energy Research, No. 1000, Wunhua Road, Jiaan Village, Lungtan, Township, Taoyuan County 32546, Taiwan (China); Sun, Ming-Hung [Institute of Nuclear Energy Research, No. 1000, Wunhua Road, Jiaan Village, Lungtan, Township, Taoyuan County 32546, Taiwan (China); Chao, Ching-Kong [Department of Mechanical Engineering, National Taiwan University of Science and Technology, 43 Keelung Road, Section 4, Taipei 106, Taiwan (China)

    2014-04-01

    Highlights: • Radial hydrides near the crack tip had a significant effect on crack propagation. • For radial hydrides off the crack line vertically, the effect on crack propagation was notably reduced. • The longer hydride platelet resulted in a remarkable effect on crack propagation. • A long split in the radial hydride precipitate would enhance crack propagation. • The presence of circumferential hydride among radial hydrides may play an important role in crack propagation. - Abstract: A methodology was proposed to investigate the effect of hydride on the crack propagation in fuel cladding. The analysis was modeled based on an outside-in crack with radial hydrides located near its crack tip. The finite element method was used in the calculation; both stress intensity factor K{sub I} and J integral were applied to evaluate the crack stability. The parameters employed in the analysis included the location of radial hydride, hydride dimensions, number of hydrides, and the presence of circumferential hydride, etc. According to our study, the effective distance between a radial hydride and the assumed cladding surface crack for the enhancement of crack propagation proved to be no greater than 0.06 mm. For a hydride not on the crack line, it would induce a relatively minor effect on crack propagation if the vertical distance was beyond 0.05 mm. However, a longer hydride precipitate as well as double radial hydrides could have a remarkable effect on crack propagation. A combined effect of radial and circumferential hydrides was also discussed.

  12. High Density Hydrogen Storage System Demonstration Using NaAlH4 Based Complex Compound Hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Daniel A. Mosher; Xia Tang; Ronald J. Brown; Sarah Arsenault; Salvatore Saitta; Bruce L. Laube; Robert H. Dold; Donald L. Anton

    2007-07-27

    This final report describes the motivations, activities and results of the hydrogen storage independent project "High Density Hydrogen Storage System Demonstration Using NaAlH4 Based Complex Compound Hydrides" performed by the United Technologies Research Center under the Department of Energy Hydrogen Program, contract # DE-FC36-02AL67610. The objectives of the project were to identify and address the key systems technologies associated with applying complex hydride materials, particularly ones which differ from those for conventional metal hydride based storage. This involved the design, fabrication and testing of two prototype systems based on the hydrogen storage material NaAlH4. Safety testing, catalysis studies, heat exchanger optimization, reaction kinetics modeling, thermochemical finite element analysis, powder densification development and material neutralization were elements included in the effort.

  13. Metal hydrides: an innovative and challenging conversion reaction anode for lithium-ion batteries

    Directory of Open Access Journals (Sweden)

    Luc Aymard

    2015-08-01

    Full Text Available The state of the art of conversion reactions of metal hydrides (MH with lithium is presented and discussed in this review with regard to the use of these hydrides as anode materials for lithium-ion batteries. A focus on the gravimetric and volumetric storage capacities for different examples from binary, ternary and complex hydrides is presented, with a comparison between thermodynamic prediction and experimental results. MgH2 constitutes one of the most attractive metal hydrides with a reversible capacity of 1480 mA·h·g−1 at a suitable potential (0.5 V vs Li+/Li0 and the lowest electrode polarization (2, TiH2, complex hydrides Mg2MHx and other Mg-based hydrides. The reversible conversion reaction mechanism of MgH2, which is lithium-controlled, can be extended to others hydrides as: MHx + xLi+ + xe− in equilibrium with M + xLiH. Other reaction paths—involving solid solutions, metastable distorted phases, and phases with low hydrogen content—were recently reported for TiH2 and Mg2FeH6, Mg2CoH5 and Mg2NiH4. The importance of fundamental aspects to overcome technological difficulties is discussed with a focus on conversion reaction limitations in the case of MgH2. The influence of MgH2 particle size, mechanical grinding, hydrogen sorption cycles, grinding with carbon, reactive milling under hydrogen, and metal and catalyst addition to the MgH2/carbon composite on kinetics improvement and reversibility is presented. Drastic technological improvement in order to the enhance conversion process efficiencies is needed for practical applications. The main goals are minimizing the impact of electrode volume variation during lithium extraction and overcoming the poor electronic conductivity of LiH. To use polymer binders to improve the cycle life of the hydride-based electrode and to synthesize nanoscale composite hydride can be helpful to address these drawbacks. The development of high-capacity hydride anodes should be inspired by the emergent

  14. Metal hydrides: an innovative and challenging conversion reaction anode for lithium-ion batteries.

    Science.gov (United States)

    Aymard, Luc; Oumellal, Yassine; Bonnet, Jean-Pierre

    2015-01-01

    The state of the art of conversion reactions of metal hydrides (MH) with lithium is presented and discussed in this review with regard to the use of these hydrides as anode materials for lithium-ion batteries. A focus on the gravimetric and volumetric storage capacities for different examples from binary, ternary and complex hydrides is presented, with a comparison between thermodynamic prediction and experimental results. MgH2 constitutes one of the most attractive metal hydrides with a reversible capacity of 1480 mA·h·g(-1) at a suitable potential (0.5 V vs Li(+)/Li(0)) and the lowest electrode polarization (lithium are subsequently detailed for MgH2, TiH2, complex hydrides Mg2MH x and other Mg-based hydrides. The reversible conversion reaction mechanism of MgH2, which is lithium-controlled, can be extended to others hydrides as: MH x + xLi(+) + xe(-) in equilibrium with M + xLiH. Other reaction paths-involving solid solutions, metastable distorted phases, and phases with low hydrogen content-were recently reported for TiH2 and Mg2FeH6, Mg2CoH5 and Mg2NiH4. The importance of fundamental aspects to overcome technological difficulties is discussed with a focus on conversion reaction limitations in the case of MgH2. The influence of MgH2 particle size, mechanical grinding, hydrogen sorption cycles, grinding with carbon, reactive milling under hydrogen, and metal and catalyst addition to the MgH2/carbon composite on kinetics improvement and reversibility is presented. Drastic technological improvement in order to the enhance conversion process efficiencies is needed for practical applications. The main goals are minimizing the impact of electrode volume variation during lithium extraction and overcoming the poor electronic conductivity of LiH. To use polymer binders to improve the cycle life of the hydride-based electrode and to synthesize nanoscale composite hydride can be helpful to address these drawbacks. The development of high-capacity hydride anodes should

  15. Zirconium hydride containing explosive composition

    Science.gov (United States)

    Walker, Franklin E.; Wasley, Richard J.

    1981-01-01

    An improved explosive composition is disclosed and comprises a major portion of an explosive having a detonation velocity between about 1500 and 10,000 meters per second and a minor amount of a donor additive comprising a non-explosive compound or mixture of non-explosive compounds which when subjected to an energy fluence of 1000 calories/cm.sup.2 or less is capable of releasing free radicals each having a molecular weight between 1 and 120. Exemplary donor additives are dibasic acids, polyamines and metal hydrides.

  16. Homogeneous crystal nucleation in polymers.

    Science.gov (United States)

    Schick, C; Androsch, R; Schmelzer, J W P

    2017-11-15

    The pathway of crystal nucleation significantly influences the structure and properties of semi-crystalline polymers. Crystal nucleation is normally heterogeneous at low supercooling, and homogeneous at high supercooling, of the polymer melt. Homogeneous nucleation in bulk polymers has been, so far, hardly accessible experimentally, and was even doubted to occur at all. This topical review summarizes experimental findings on homogeneous crystal nucleation in polymers. Recently developed fast scanning calorimetry, with cooling and heating rates up to 10 6 K s -1 , allows for detailed investigations of nucleation near and even below the glass transition temperature, including analysis of nuclei stability. As for other materials, the maximum homogeneous nucleation rate for polymers is located close to the glass transition temperature. In the experiments discussed here, it is shown that polymer nucleation is homogeneous at such temperatures. Homogeneous nucleation in polymers is discussed in the framework of the classical nucleation theory. The majority of our observations are consistent with the theory. The discrepancies may guide further research, particularly experiments to progress theoretical development. Progress in the understanding of homogeneous nucleation is much needed, since most of the modelling approaches dealing with polymer crystallization exclusively consider homogeneous nucleation. This is also the basis for advancing theoretical approaches to the much more complex phenomena governing heterogeneous nucleation.

  17. Effect of an Excess of Iron and Hydriding on the Metallurgical Properties of Zircaloy-4

    International Nuclear Information System (INIS)

    Ghilarducci, Ada; Ramos, R; Martin, E; Peretti, Hernan; Corso Hugo

    2000-01-01

    Results are presented of mechanical properties and microstructure morphologies obtained in samples of zircaloy-4 of modified composition by an excess in the content of alloying elements as well as hydrides.This work is focused mainly on the effect of 1000 wt. ppm additional Fe as compared to the standard composition alloy.The study is carried out by means of tensile tests at room temperature and at 240 0 C, by hardness tests, by SEM observations and EDS microanalysis.The results indicate that precipitates concentrate along grain boundaries in all cases, and that for higher contents of alloying elements corresponds a higher quantity of precipitates and smaller grain sizes.Except for the hydrided sample, the fracture is ductile with cavities nucleated at precipitates. Finally it is concluded that an increase in Fe content affect the mechanical properties

  18. Do protein crystals nucleate within dense liquid clusters?

    International Nuclear Information System (INIS)

    Maes, Dominique; Vorontsova, Maria A.; Potenza, Marco A. C.; Sanvito, Tiziano; Sleutel, Mike; Giglio, Marzio; Vekilov, Peter G.

    2015-01-01

    The evolution of protein-rich clusters and nucleating crystals were characterized by dynamic light scattering (DLS), confocal depolarized dynamic light scattering (cDDLS) and depolarized oblique illumination dark-field microscopy. Newly nucleated crystals within protein-rich clusters were detected directly. These observations indicate that the protein-rich clusters are locations for crystal nucleation. Protein-dense liquid clusters are regions of high protein concentration that have been observed in solutions of several proteins. The typical cluster size varies from several tens to several hundreds of nanometres and their volume fraction remains below 10 −3 of the solution. According to the two-step mechanism of nucleation, the protein-rich clusters serve as locations for and precursors to the nucleation of protein crystals. While the two-step mechanism explained several unusual features of protein crystal nucleation kinetics, a direct observation of its validity for protein crystals has been lacking. Here, two independent observations of crystal nucleation with the proteins lysozyme and glucose isomerase are discussed. Firstly, the evolutions of the protein-rich clusters and nucleating crystals were characterized simultaneously by dynamic light scattering (DLS) and confocal depolarized dynamic light scattering (cDDLS), respectively. It is demonstrated that protein crystals appear following a significant delay after cluster formation. The cDDLS correlation functions follow a Gaussian decay, indicative of nondiffusive motion. A possible explanation is that the crystals are contained inside large clusters and are driven by the elasticity of the cluster surface. Secondly, depolarized oblique illumination dark-field microscopy reveals the evolution from liquid clusters without crystals to newly nucleated crystals contained in the clusters to grown crystals freely diffusing in the solution. Collectively, the observations indicate that the protein-rich clusters in

  19. The combined effect of thermodynamic promoters tetrahydrofuran and cyclopentane on the kinetics of flue gas hydrate formation

    DEFF Research Database (Denmark)

    Daraboina, Nagu; von Solms, Nicolas

    2015-01-01

    ) hydrate formation using a rocking cell apparatus. Hydrate formation and decomposition kinetics were investigated by constant cooling (hydrate nucleation temperature) and isothermal (hydrate nucleation time) methods. Improved (synergistic) hydrate formation kinetics (hydrate nucleation and growth) were...... of these two promoters is favorable both thermodynamically and kinetically for hydrate formation from flue gas....

  20. Hydrides blister formation and induced embrittlement on zircaloy-4 cladding tubes in reactivity initiated conditions

    International Nuclear Information System (INIS)

    Hellouin-De-Menibus, A.

    2012-01-01

    Our aim is to study the cladding fracture with mechanical tests more representative of RIA conditions, taking into account the hydrides blisters, representative strain rates and stress states. To obtain hydride blisters, we developed a thermodiffusion setup that reproduces blister growth in reactor conditions. By metallography, nano-hardness, XRD and ERDA, we showed that they are constituted by 80% to 100% of δ hydrides in a Zircaloy-4 matrix, and that the zirconium beneath has some radially oriented hydrides. We modeled the blister growth kinetics taking into account the hysteresis of the hydrogen solubility limit and defined the thermal gradient threshold for blister growth. The modeling of the dilatometric behavior of hydrided zirconium indicates the important role of the material crystallographic texture, which could explain differences in the blister shape. Mechanical tests monitored with an infrared camera showed that significant local heating occurred at strain rates higher than 0.1/s. In parallel, the Expansion Due to Compression test was optimized to increase the bi-axiality level from uniaxial stress to plane strain (HB-EDC and VHB-EDC tests). This increase in loading bi-axiality lowers greatly the fracture strain at 25 C and 350 C only in homogeneous material without blister. Eventually, the ductility decrease of unirradiated Zircaloy-4 cladding tube in function of the blister depth was quantified. (author) [fr

  1. Hydrogen-storing hydride complexes

    Science.gov (United States)

    Srinivasan, Sesha S [Tampa, FL; Niemann, Michael U [Venice, FL; Goswami, D Yogi [Tampa, FL; Stefanakos, Elias K [Tampa, FL

    2012-04-10

    A ternary hydrogen storage system having a constant stoichiometric molar ratio of LiNH.sub.2:MgH.sub.2:LiBH.sub.4 of 2:1:1. It was found that the incorporation of MgH.sub.2 particles of approximately 10 nm to 20 nm exhibit a lower initial hydrogen release temperature of 150.degree. C. Furthermore, it is observed that the particle size of LiBNH quaternary hydride has a significant effect on the hydrogen sorption concentration with an optimum size of 28 nm. The as-synthesized hydrides exhibit two main hydrogen release temperatures, one around 160.degree. C. and the other around 300.degree. C., with the main hydrogen release temperature reduced from 310.degree. C. to 270.degree. C., while hydrogen is first reversibly released at temperatures as low as 150.degree. C. with a total hydrogen capacity of 6 wt. % to 8 wt. %. Detailed thermal, capacity, structural and microstructural properties have been demonstrated and correlated with the activation energies of these materials.

  2. Activated aluminum hydride hydrogen storage compositions and uses thereof

    Science.gov (United States)

    Sandrock, Gary; Reilly, James; Graetz, Jason; Wegrzyn, James E.

    2010-11-23

    In one aspect, the invention relates to activated aluminum hydride hydrogen storage compositions containing aluminum hydride in the presence of, or absence of, hydrogen desorption stimulants. The invention particularly relates to such compositions having one or more hydrogen desorption stimulants selected from metal hydrides and metal aluminum hydrides. In another aspect, the invention relates to methods for generating hydrogen from such hydrogen storage compositions.

  3. Hydrogen adsorption on palladium and palladium hydride at 1 bar

    DEFF Research Database (Denmark)

    Johansson, Martin; Skulason, Egill; Nielsen, Gunver

    2010-01-01

    strongly to Pd hydride than to Pd. The activation barrier for desorption at a H coverage of one mono layer is slightly lower on Pd hydride, whereas the activation energy for adsorption is similar on Pd and Pd hydride. It is concluded that the higher sticking probability on Pd hydride is most likely caused...

  4. Cyclopentadiene-mediated hydride transfer from rhodium complexes.

    Science.gov (United States)

    Pitman, C L; Finster, O N L; Miller, A J M

    2016-07-12

    Attempts to generate a proposed rhodium hydride catalytic intermediate instead resulted in isolation of (Cp*H)Rh(bpy)Cl (1), a pentamethylcyclopentadiene complex, formed by C-H bond-forming reductive elimination from the fleeting rhodium hydride. The hydride transfer ability of diene 1 was explored through thermochemistry and hydride transfer reactions, including the reduction of NAD(+).

  5. Effects of Cooling Rates on Hydride Reorientation and Mechanical Properties of Zirconium Alloy Claddings under Interim Dry Storage Conditions

    International Nuclear Information System (INIS)

    Min, Su-Jeong; Kim, Myeong-Su; Won, Chu-chin; Kim, Kyu-Tae

    2013-01-01

    As-received Zr-Nb cladding tubes and 600 ppm hydrogen-charged tubes were employed to evaluate the effects of cladding cooling rates on the extent of hydride reorientation from circumferential hydrides to radial ones and mechanical property degradations with the use of cooling rates of 2, 4 and 15 °C/min from 400 °C to room temperature simulating cladding cooling under interim dry storage conditions. The as-received cladding tubes generated nearly the same ultimate tensile strengths and plastic elongations, regardless of the cooling rates, because of a negligible hydrogen content in the cladding. The 600 ppm-H cladding tubes indicate that the slower cooling rate generated the larger radial hydride fraction and the longer radial hydrides, which resulted in greater mechanical performance degradations. The cooling rate of 2 °C/min generates an ultimate tensile strength of 758 MPa and a plastic elongation of 1.0%, whereas the cooling rate of 15 °C/min generates an ultimate tensile strength of 825 MPa and a plastic elongation of 15.0%. These remarkable mechanical property degradations of the 600 ppm-H cladding tubes with the slowest cooling rate may be characterized by cleavage fracture surface appearance enhanced by longer radial hydrides and their higher fraction that have been precipitated through a relatively larger nucleation and growth rate.

  6. Energies controlling nucleation and growth processes: The case of Ag/W(110)

    DEFF Research Database (Denmark)

    Jones, G. W.; Marcano, J. M.; Nørskov, Jens Kehlet

    1990-01-01

    The nucleation density Nx(T) of Ag islands on the 2-monolayer-thick silver intermediate layer on W(110) is measured by UHV scanning electron microscopy and compared with kinetic nucleation equations. This yields a well-determined value of Ed+2Eb=0.65±0.03 eV, with pair-binding energy Eb=0...

  7. Overview: Nucleation of clathrate hydrates.

    Science.gov (United States)

    Warrier, Pramod; Khan, M Naveed; Srivastava, Vishal; Maupin, C Mark; Koh, Carolyn A

    2016-12-07

    Molecular level knowledge of nucleation and growth of clathrate hydrates is of importance for advancing fundamental understanding on the nature of water and hydrophobic hydrate formers, and their interactions that result in the formation of ice-like solids at temperatures higher than the ice-point. The stochastic nature and the inability to probe the small length and time scales associated with the nucleation process make it very difficult to experimentally determine the molecular level changes that lead to the nucleation event. Conversely, for this reason, there have been increasing efforts to obtain this information using molecular simulations. Accurate knowledge of how and when hydrate structures nucleate will be tremendously beneficial for the development of sustainable hydrate management strategies in oil and gas flowlines, as well as for their application in energy storage and recovery, gas separation, carbon sequestration, seawater desalination, and refrigeration. This article reviews various aspects of hydrate nucleation. First, properties of supercooled water and ice nucleation are reviewed briefly due to their apparent similarity to hydrates. Hydrate nucleation is then reviewed starting from macroscopic observations as obtained from experiments in laboratories and operations in industries, followed by various hydrate nucleation hypotheses and hydrate nucleation driving force calculations based on the classical nucleation theory. Finally, molecular simulations on hydrate nucleation are discussed in detail followed by potential future research directions.

  8. Overview: Nucleation of clathrate hydrates

    Science.gov (United States)

    Warrier, Pramod; Khan, M. Naveed; Srivastava, Vishal; Maupin, C. Mark; Koh, Carolyn A.

    2016-12-01

    Molecular level knowledge of nucleation and growth of clathrate hydrates is of importance for advancing fundamental understanding on the nature of water and hydrophobic hydrate formers, and their interactions that result in the formation of ice-like solids at temperatures higher than the ice-point. The stochastic nature and the inability to probe the small length and time scales associated with the nucleation process make it very difficult to experimentally determine the molecular level changes that lead to the nucleation event. Conversely, for this reason, there have been increasing efforts to obtain this information using molecular simulations. Accurate knowledge of how and when hydrate structures nucleate will be tremendously beneficial for the development of sustainable hydrate management strategies in oil and gas flowlines, as well as for their application in energy storage and recovery, gas separation, carbon sequestration, seawater desalination, and refrigeration. This article reviews various aspects of hydrate nucleation. First, properties of supercooled water and ice nucleation are reviewed briefly due to their apparent similarity to hydrates. Hydrate nucleation is then reviewed starting from macroscopic observations as obtained from experiments in laboratories and operations in industries, followed by various hydrate nucleation hypotheses and hydrate nucleation driving force calculations based on the classical nucleation theory. Finally, molecular simulations on hydrate nucleation are discussed in detail followed by potential future research directions.

  9. Heterogeneous ice nucleation

    Energy Technology Data Exchange (ETDEWEB)

    Bogdan, A. [Helsinki Univ. (Finland). Dept. of Physics

    1994-12-31

    The classical theory of heterogenous ice nucleation is reviewed in detail. The modelling of ice nucleation in the adsorbed water films on natural particles by analogous ice nucleation in adsorbed water films on the walls of porous media is discussed. Ice nucleation in adsorbed films of purewater and the HNO{sub 3}/H{sub 2}0 binary system on the surface of porous aerosol (SiO{sub 2}) was investigated using the method of NMR spectroscopy. The median freezing temperature and freezing temperature region were shown to be highly sensitive both to the average thickness of the adsorbed films and to the amount of adsorbed nitric acid. The character of the ice phase formation tends to approach that of bulk liquid with increasing adsorbed film thickness. Under the given conditions the thickness of the adsorbed films decreases with an increasing amount of adsorbed nitric acid molecules The molar concentration of nitric acid in the adsorbed films is very small (of the order of 10{sup -}3 10{sup -}2 (M/l)). Nitric acid molecules tend to adsorb on the surface of aerosol to a greater extent than in subsequent layers. The concentration is greatest in layers situated close to the surface and sharply decreases with the distance from the surface. The difference between the median freezing temperatures for adsorbed pure water and for the binary system was found to be about 9 K for films of equal thickness. This is about 150 times greater than the difference between the median freezing temperatures of bulk pure water and a solution with the same concentration of nitric acid. (orig.)

  10. Nucleation in Synoptically Forced Cirrostratus

    Science.gov (United States)

    Lin, R.-F.; Starr, D. OC.; Reichardt, J.; DeMott, P. J.

    2004-01-01

    Formation and evolution of cirrostratus in response to weak, uniform and constant synoptic forcing is simulated using a one-dimensional numerical model with explicit microphysics, in which the particle size distribution in each grid box is fully resolved. A series of tests of the model response to nucleation modes (homogeneous-freezing-only/heterogeneous nucleation) and heterogeneous nucleation parameters are performed. In the case studied here, nucleation is first activated in the prescribed moist layer. A continuous cloud-top nucleation zone with a depth depending on the vertical humidity gradient and one of the nucleation parameters is developed afterward. For the heterogeneous nucleation cases, intermittent nucleation zones in the mid-upper portion of the cloud form where the relative humidity is on the rise, because existent ice crystals do not uptake excess water vapor efficiently, and ice nuclei (IN) are available. Vertical resolution as fine as 1 m is required for realistic simulation of the homogeneous-freezing-only scenario, while the model resolution requirement is more relaxed in the cases where heterogeneous nucleation dominates. Bulk microphysical and optical properties are evaluated and compared. Ice particle number flux divergence, which is due to the vertical gradient of the gravity-induced particle sedimentation, is constantly and rapidly changing the local ice number concentration, even in the nucleation zone. When the depth of the nucleation zone is shallow, particle number concentration decreases rapidly as ice particles grow and sediment away from the nucleation zone. When the depth of the nucleation zone is large, a region of high ice number concentration can be sustained. The depth of nucleation zone is an important parameter to be considered in parametric treatments of ice cloud generation.

  11. Enhancement of Hydrogen Storage Behavior of Complex Hydrides via Bimetallic Nanocatalysts Doping

    Directory of Open Access Journals (Sweden)

    Prakash C. Sharma

    2012-10-01

    Full Text Available Pristine complex quaternary hydride (LiBH4/2LiNH2 and its destabilized counterpart (LiBH4/2LiNH2/nanoMgH2 have recently shown promising reversible hydrogen storage capacity under moderate operating conditions. The destabilization of complex hydride via nanocrystalline MgH2 apparently lowers the thermodynamic heat values and thus enhances the reversible hydrogen storage behavior at moderate temperatures. However, the kinetics of these materials is rather low and needs to be improved for on-board vehicular applications. Nanocatalyst additives such as nano Ni, nano Fe, nano Co, nano Mn and nano Cu at low concentrations on the complex hydride host structures have demonstrated a reduction in the decomposition temperature and overall increase in the hydrogen desorption reaction rates. Bi-metallic nanocatalysts such as the combination of nano Fe and nano Ni have shown further pronounced kinetics enhancement in comparison to their individual counterparts. Additionally, the vital advantage of using bi-metallic nanocatalysts is to enable the synergistic effects and characteristics of the two transitional nanometal species on the host hydride matrix for the optimized hydrogen storage behavior.

  12. Identification and characterization of a new Zirconium hydride

    International Nuclear Information System (INIS)

    Zhao, Z.

    2007-01-01

    In order to control the integrity of the fuel clad, alloy of zirconium, it is necessary to predict the behavior of zirconium hydrides in the environment (temperature, stress...), at a microscopic scale. A characterization study by TEM of hydrides has been realized. It shows little hydrides about 500 nm, in hydride Zircaloy 4. Then a more detailed study identified a new hydride phase presented in this paper. (A.L.B.)

  13. Hydride heat pump with heat regenerator

    Science.gov (United States)

    Jones, Jack A. (Inventor)

    1991-01-01

    A regenerative hydride heat pump process and system is provided which can regenerate a high percentage of the sensible heat of the system. A series of at least four canisters containing a lower temperature performing hydride and a series of at least four canisters containing a higher temperature performing hydride is provided. Each canister contains a heat conductive passageway through which a heat transfer fluid is circulated so that sensible heat is regenerated. The process and system are useful for air conditioning rooms, providing room heat in the winter or for hot water heating throughout the year, and, in general, for pumping heat from a lower temperature to a higher temperature.

  14. A procedure for preparing alkali metal hydrides

    International Nuclear Information System (INIS)

    Lemieux, R.U.; Sanford, C.E.; Prescott, J.F.

    1976-01-01

    A plain low cost, procedure for the continuous, low temperature preparation of sodium or potassium hydrides using cheap reagents is presented. Said invention is especially concerned with a process of purifying of a catalytic exchange liquid used for deuterium enrichment, in which an alkali metal hydride is produced as intermediate product. The procedure for producing the sodium and potassium hydrides consists in causing high pressure hydrogen to be absorbed by a mixture of at least a lower monoalkylamine and an alkylamide of an alkali metal from at least one of said amines [fr

  15. Hydride observations using the neutrography technique

    International Nuclear Information System (INIS)

    Meyer, G.; Baruj, A.; Borzone, E.M.; Cardenas, R.; Szames, E.; Somoza, J.; Rivas, S.; Sanchez, F.A.; Marin, J.

    2012-01-01

    Neutron radiography observations were performed at the RA-6 experimental nuclear facility in Bariloche. Images from a prototype of a hydride-based hydrogen storage device have been obtained. The technique allows visualizing the inner hydride space distribution. The hydride appeared compacted at the lower part of the prototype after several cycles of hydrogen charge and discharge. The technique has also been applied to the study of Zr/ZrH 2 samples. There is a linear relation between the sample width/hydrogen concentration and the photograph grey scale. This information could be useful for the study of nuclear engineering materials and to determine their possible degradation by hydrogen pick up (author)

  16. The Oxidation Products of Aluminum Hydride and Boron Aluminum Hydride Clusters

    Science.gov (United States)

    2016-01-04

    AFRL-AFOSR-VA-TR-2016-0075 The Oxidation Products of Aluminum Hydride and Boron Aluminum Hydride Clusters KIT BOWEN JOHNS HOPKINS UNIV BALTIMORE MD...2. REPORT TYPE Final Performance 3. DATES COVERED (From - To) 30-09-2014 to 29-09-2015 4. TITLE AND SUBTITLE The Oxidation Products of Aluminum ...Hydride and Boron Aluminum Hydride Clusters 5a.  CONTRACT NUMBER 5b.  GRANT NUMBER FA9550-14-1-0324 5c.  PROGRAM ELEMENT NUMBER 61102F 6. AUTHOR(S) KIT

  17. On the Ice Nucleation Spectrum

    Science.gov (United States)

    Barahona, D.

    2012-01-01

    This work presents a novel formulation of the ice nucleation spectrum, i.e. the function relating the ice crystal concentration to cloud formation conditions and aerosol properties. The new formulation is physically-based and explicitly accounts for the dependency of the ice crystal concentration on temperature, supersaturation, cooling rate, and particle size, surface area and composition. This is achieved by introducing the concepts of ice nucleation coefficient (the number of ice germs present in a particle) and nucleation probability dispersion function (the distribution of ice nucleation coefficients within the aerosol population). The new formulation is used to generate ice nucleation parameterizations for the homogeneous freezing of cloud droplets and the heterogeneous deposition ice nucleation on dust and soot ice nuclei. For homogeneous freezing, it was found that by increasing the dispersion in the droplet volume distribution the fraction of supercooled droplets in the population increases. For heterogeneous ice nucleation the new formulation consistently describes singular and stochastic behavior within a single framework. Using a fundamentally stochastic approach, both cooling rate independence and constancy of the ice nucleation fraction over time, features typically associated with singular behavior, were reproduced. Analysis of the temporal dependency of the ice nucleation spectrum suggested that experimental methods that measure the ice nucleation fraction over few seconds would tend to underestimate the ice nuclei concentration. It is shown that inferring the aerosol heterogeneous ice nucleation properties from measurements of the onset supersaturation and temperature may carry significant error as the variability in ice nucleation properties within the aerosol population is not accounted for. This work provides a simple and rigorous ice nucleation framework where theoretical predictions, laboratory measurements and field campaign data can be

  18. Inference of some pharmacokinetic parameters of the C mitomycin, through the analysis of its micro nucleate polychromatic erythrocytes induction kinetics; Inferencia de algunos parametros farmacocineticos de la mitomicina C, mediante el analisis de su cinetica de induccion de eritrocitos policromaticos micronucleados

    Energy Technology Data Exchange (ETDEWEB)

    Morales R, P.; Vallarino K, T.; Cruz V, V.; Delgadillo H, A. [ININ, 52045 Ocoyoacac, Estado de Mexico (Mexico)

    2003-07-01

    The objective of the present work was to establish pharmacokinetic parameters of the C Mitomycin (MMC) in vivo, comparing its kinetics of induction of polychromatic micro nucleate erythrocytes (EPGMN) with that of the gamma radiation. The used doses were of 0.75; 1.5 and 3. 0 {mu}moles/kg of MMC. It was observed that the MMC produces MN in the first cycle of cellular division and it is independent of the cytotoxic effect. This agent requires of a relatively long period of latency that is not compatible with her great reactivity, for what the pharmacokinetic values obtained in fact reflect the time that takes the processing of leisure in the DNA and the subsequent induction of ruptures that produce MN. (Author)

  19. Disposal of tritium-exposed metal hydrides

    International Nuclear Information System (INIS)

    Nobile, A.; Motyka, T.

    1991-01-01

    A plan has been established for disposal of tritium-exposed metal hydrides used in Savannah River Site (SRS) tritium production or Materials Test Facility (MTF) R ampersand D operations. The recommended plan assumes that the first tritium-exposed metal hydrides will be disposed of after startup of the Solid Waste Disposal Facility (SWDF) Expansion Project in 1992, and thus the plan is consistent with the new disposal requiremkents that will be in effect for the SWDF Expansion Project. Process beds containing tritium-exposed metal hydride powder will be disposed of without removal of the powder from the bed; however, disposal of tritium-exposed metal hydride powder that has been removed from its process vessel is also addressed

  20. Method of making alkali metal hydrides

    Science.gov (United States)

    Pecharsky, Vitalij K.; Gupta, Shalabh; Pruski, Marek; Hlova, Ihor; Castle, Andra

    2017-05-30

    A method is provided for making alkali metal hydrides by mechanochemically reacting alkali metal and hydrogen gas under mild temperature (e.g room temperature) and hydrogen pressure conditions without the need for catalyst, solvent, and intentional heating or cooling.

  1. Nucleation phenomena at Suzuki phases

    International Nuclear Information System (INIS)

    Acosta-Najarro, D.; Jose Y, M.

    1982-01-01

    Crystal of NaCl doped with Mn present regions with an increase in nucleation densities when observed by surface gold decoration; this increase is related to the nucleation of the Suzuki phases which are induced by cooling of the crystal matrix. Calculations based on atomistic nucleation theory are developed to explain the increased nucleation density. Experiments were made to compare with the theoretical results. In particular the density of nuclei was measured as a function of the rate or arrival of atoms to the surface. Therefore, the changes in the nucleation densities are explained in terms of change in migration energies between the Suzuki phase and the NaCl matrix excluding the possibility of nucleation induced by point defects. (author)

  2. Predicting formation enthalpies of metal hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Andreasen, A.

    2004-12-01

    In order for the hydrogen based society viz. a society in which hydrogen is the primary energy carrier to become realizable an efficient way of storing hydrogen is required. For this purpose metal hydrides are serious candidates. Metal hydrides are formed by chemical reaction between hydrogen and metal and for the stable hydrides this is associated with release of heat ({delta}H{sub f} ). The more thermodynamically stable the hydride, the larger {delta}H{sub f}, and the higher temperature is needed in order to desorp hydrogen (reverse reaction) and vice versa. For practical application the temperature needed for desorption should not be too high i.e. {delta}H{sub f} should not be too large. If hydrogen desorption is to be possible below 100 deg C (which is the ultimate goal if hydrogen storage in metal hydrides should be used in conjunction with a PEM fuel cell), {delta}H{sub f} should not exceed -48 kJ/mol. Until recently only intermetallic metal hydrides with a storage capacity less than 2 wt.% H{sub 2} have met this criterion. However, discovering reversible hydrogen storage in complex metal hydrides such as NaAlH{sub 4} (5.5 wt. % reversible hydrogen capacity) have revealed a new group of potential candiates. However, still many combination of elements from the periodic table are yet to be explored. Since experimental determination of thermodynamic properties of the vast combinations of elements is tedious it may be advantagous to have a predictive tool for this task. In this report different ways of predicting {delta}H{sub f} for binary and ternary metal hydrides are reviewed. Main focus will be on how well these methods perform numerically i.e. how well experimental results are resembled by the model. The theoretical background of the different methods is only briefly reviewed. (au)

  3. Influence of hydrides orientation on strain, damage and failure of hydrided zircaloy-4

    International Nuclear Information System (INIS)

    Racine, A.

    2005-09-01

    In pressurized water reactors of nuclear power plants, fuel pellets are contained in cladding tubes, made of Zirconium alloy, for instance Zircaloy-4. During their life in the primary water of the reactor (155 bars, 300 C), cladding tubes are oxidized and consequently hydrided. A part of the hydrogen given off precipitates as Zirconium hydrides in the bulk material and embrittles the material. This embrittlement depends on many parameters, among which hydrogen content and orientation of hydrides with respect to the applied stress. This investigation is devoted to the influence of the orientation of hydrides with respect to the applied stress on strain, damage and failure mechanisms. Macroscopic and SEM in-situ ring tensile tests are performed on cladding tube material (unirradiated cold worked stress-relieved Zircaloy-4) hydrided with about 200 and 500 wppm hydrogen, and with different main hydrides orientation: either parallel or perpendicular to the circumferential tensile direction. We get the mechanical response of the material as a function of hydride orientation and hydrogen content and we investigate the deformation, damage and failure mechanisms. In both cases, digital image correlation techniques are used to estimate local and global strain distributions. Neither the tensile stress-strain response nor the global and local strain modes are significantly affected by hydrogen content or hydride orientation, but the failure modes are strongly modified. Indeed, only 200 wppm radial hydrides embrittle Zy-4: sample fail in the elastic domain at about 350 MPa before strain bands could develop; whereas in other cases sample reach at least 750 MPa before necking and final failure, in ductile or brittle mode. To model this particular heterogeneous material behavior, a non-coupled damage approach which takes into account the anisotropic distribution of the hydrides is proposed. Its parameters are identified from the macroscopic strain field measurements and a

  4. Multi-scale characterization of nanostructured sodium aluminum hydride

    Science.gov (United States)

    NaraseGowda, Shathabish

    Complex metal hydrides are the most promising candidate materials for onboard hydrogen storage. The practicality of this class of materials is counter-poised on three critical attributes: reversible hydrogen storage capacity, high hydrogen uptake/release kinetics, and favorable hydrogen uptake/release thermodynamics. While a majority of modern metallic hydrides that are being considered are those that meet the criteria of high theoretical storage capacity, the challenges lie in addressing poor kinetics, thermodynamics, and reversibility. One emerging strategy to resolve these issues is via nanostructuring or nano-confinement of complex hydrides. By down-sizing and scaffolding them to retain their nano-dimensions, these materials are expected to improve in performance and reversibility. This area of research has garnered immense interest lately and there is active research being pursued to address various aspects of nanostructured complex hydrides. The research effort documented here is focused on a detailed investigation of the effects of nano-confinement on aspects such as the long range atomic hydrogen diffusivities, localized hydrogen dynamics, microstructure, and dehydrogenation mechanism of sodium alanate. A wide variety of microporous and mesoporous materials (metal organic frameworks, porous silica and alumina) were investigated as scaffolds and the synthesis routes to achieve maximum pore-loading are discussed. Wet solution infiltration technique was adopted using tetrahydrofuran as the medium and the precursor concentrations were found to have a major role in achieving maximum pore loading. These concentrations were optimized for each scaffold with varying pore sizes and confinement was quantitatively characterized by measuring the loss in specific surface area. This work is also aimed at utilizing neutron and synchrotron x-ray characterization techniques to study and correlate multi-scale material properties and phenomena. Some of the most advanced

  5. Nucleate boiling heat transfer

    Energy Technology Data Exchange (ETDEWEB)

    Saiz Jabardo, J.M. [Universidade da Coruna (Spain). Escola Politecnica Superior], e-mail: mjabardo@cdf.udc.es

    2009-07-01

    Nucleate boiling heat transfer has been intensely studied during the last 70 years. However boiling remains a science to be understood and equated. In other words, using the definition given by Boulding, it is an 'insecure science'. It would be pretentious of the part of the author to explore all the nuances that the title of the paper suggests in a single conference paper. Instead the paper will focus on one interesting aspect such as the effect of the surface microstructure on nucleate boiling heat transfer. A summary of a chronological literature survey is done followed by an analysis of the results of an experimental investigation of boiling on tubes of different materials and surface roughness. The effect of the surface roughness is performed through data from the boiling of refrigerants R-134a and R-123, medium and low pressure refrigerants, respectively. In order to investigate the extent to which the surface roughness affects boiling heat transfer, very rough surfaces (4.6 {mu}m and 10.5 {mu}m ) have been tested. Though most of the data confirm previous literature trends, the very rough surfaces present a peculiar behaviour with respect to that of the smoother surfaces (Ra<3.0 {mu}m). (author)

  6. Nucleate boiling heat transfer

    International Nuclear Information System (INIS)

    Saiz Jabardo, J.M.

    2009-01-01

    Nucleate boiling heat transfer has been intensely studied during the last 70 years. However boiling remains a science to be understood and equated. In other words, using the definition given by Boulding, it is an 'insecure science'. It would be pretentious of the part of the author to explore all the nuances that the title of the paper suggests in a single conference paper. Instead the paper will focus on one interesting aspect such as the effect of the surface microstructure on nucleate boiling heat transfer. A summary of a chronological literature survey is done followed by an analysis of the results of an experimental investigation of boiling on tubes of different materials and surface roughness. The effect of the surface roughness is performed through data from the boiling of refrigerants R-134a and R-123, medium and low pressure refrigerants, respectively. In order to investigate the extent to which the surface roughness affects boiling heat transfer, very rough surfaces (4.6 μm and 10.5 μm ) have been tested. Though most of the data confirm previous literature trends, the very rough surfaces present a peculiar behaviour with respect to that of the smoother surfaces (Ra<3.0 μm). (author)

  7. Monomer-dependent secondary nucleation in amyloid formation.

    Science.gov (United States)

    Linse, Sara

    2017-08-01

    Secondary nucleation of monomers on the surface of an already existing aggregate that is formed from the same kind of monomers may lead to autocatalytic amplification of a self-assembly process. Such monomer-dependent secondary nucleation occurs during the crystallization of small molecules or proteins and self-assembled materials, as well as in protein self-assembly into fibrous structures. Indications of secondary nucleation may come from analyses of kinetic experiments starting from pure monomers or monomers supplemented with a low concentration of pre-formed aggregates (seeds). More firm evidence requires additional experiments, for example those employing isotope labels to distinguish new aggregates arising from the monomer from those resulting from fragmentation of the seed. In cases of amyloid formation, secondary nucleation leads to the formation of toxic oligomers, and inhibitors of secondary nucleation may serve as starting points for therapeutic developments. Secondary nucleation displays a high degree of structural specificity and may be enhanced by mutations or screening of electrostatic repulsion.

  8. The Nucleation of Protein Aggregates - From Crystals to Amyloid Fibrils.

    Science.gov (United States)

    Buell, Alexander K

    2017-01-01

    The condensation and aggregation of individual protein molecules into dense insoluble phases is of relevance in such diverse fields as materials science, medicine, structural biology and pharmacology. A common feature of these condensation phenomena is that they usually are nucleated processes, i.e. the first piece of the condensed phase is energetically costly to create and hence forms slowly compared to its subsequent growth. Here we give a compact overview of the differences and similarities of various protein nucleation phenomena, their theoretical description in the framework of colloid and polymer science and their experimental study. Particular emphasis is put on the nucleation of a specific type of filamentous protein aggregates, amyloid fibrils. The current experimentally derived knowledge on amyloid fibril nucleation is critically assessed, and we argue that it is less advanced than is generally believed. This is due to (I) the lack of emphasis that has been put on the distinction between homogeneous and heterogeneous nucleation in experimental studies (II) the use of oversimplifying and/or inappropriate theoretical frameworks for the analysis of kinetic data of amyloid fibril nucleation. A strategy is outlined and advocated of how our understanding of this important class of processes can be improved in the future. © 2017 Elsevier Inc. All rights reserved.

  9. Microchip power compensated calorimetry applied to metal hydride characterization

    Energy Technology Data Exchange (ETDEWEB)

    Sepulveda, A.; Lopeandia, A.F.; Domenech-Ferrer, R.; Garcia, G.; Pi, F.; Rodriguez-Viejo, J. [Nanomaterials and Microsystems Group, Physics Department, Universitat Autonoma de Barcelona, 08193 Bellaterra (Spain); Munoz, F.J. [Instituto de Microelectronica de Barcelona, Centro Nacional de Microelectronica, Campus UAB, 08193 Bellaterra (Spain)

    2008-06-15

    In this work, we show the suitability of the thin film membrane-based calorimetric technique to measure kinetically limited phase transitions such as the dehydrogenation of metallic hydrides. Different compounds such as Mg, Mg/Al and Mg{sub 80}Ti{sub 20} have been deposited over the active area of the microchip by electron beam evaporation. After several hydrogenation treatments at different temperatures to induce the hydride formation, calorimetric measurements on the dehydrogenation process of those thin films, either in vacuum or in air, are performed at a heating rate of 10 C/min. We observe a significant reduction in the onset of dehydrogenation for Mg{sub 80}Ti{sub 20} compared with pure Mg or Mg/Al layers, which confirms the beneficial effect of Ti on dehydrogenation. We also show the suitability of the membrane-based nanocalorimeters to be used in parallel with optical methods. Quantification of the energy released during hydrogen desorption remains elusive due to the semi-insulating to metallic transition of the film which affects the calorimetric trace. (author)

  10. Early stage crystallization kinetics in metallic glass-forming alloys

    International Nuclear Information System (INIS)

    Louzguine-Luzgin, Dmitri V.

    2014-01-01

    Highlights: • Heterogeneous nucleation may precede the homogeneous one in an alloy. • High kinetic constants and the nucleation rate at the initial stage. • Metallic glasses have heterogeneous nucleation sites which saturate later. -- Abstract: The crystallization kinetics and structural changes of a few metallic glassy alloys were monitored using X-ray diffraction, transmission electron microscopy, differential scanning and isothermal calorimetry methods. Microstructural observations were used to estimate the nucleation and growth rates. A clear comparison of the differences in the crystallization kinetics in the metallic glassy samples is observed at the early and later crystallization stages

  11. gamma-Zr-Hydride Precipitate in Irradiated Massive delta- Zr-Hydride

    DEFF Research Database (Denmark)

    Warren, M. R.; Bhattacharya, D. K.

    1975-01-01

    During examination of A Zircaloy-2-clad fuel pin, which had been part of a test fuel assembly in a boiling water reactor, several regions of severe internal hydriding were noticed in the upper-plenum end of the pin. Examination of similar fuel pins has shown that hydride of this type is caused by...... to irradiation-induced swelling....

  12. Nature of Y1Ba2Cu3O7 nucleation centers on ceria buffers

    International Nuclear Information System (INIS)

    Solovyov, Vyacheslav F; Li Qiang; Qing Jie; Zhou Juan; Develos-Bagarinao, Katherine

    2010-01-01

    The purpose of this study is to enhance properties of the second-generation wires by increasing the density of Y 1 Ba 2 Cu 3 O 7 (YBCO) nucleation centers on the surface of the ceria buffer. To identify the nature of the nucleation centers, we compare nucleation kinetics and performance of YBCO layers deposited by the metal-organic process on a standard RABiTS tape to YBCO on ceria buffers with well-controlled structure and surface morphology. The structure of the YBCO layer at the early stage of nucleation and growth is determined by high-flux synchrotron x-ray diffraction. It is shown that the best buffers exhibit high YBCO nucleation rates and produce YBCO nuclei with the least cation disorder. The high YBCO nucleation rate is associated with a high density of threading dislocation outcrops. A strategy for buffer optimization is identified.

  13. The Effect of Hydrogen and Hydrides on the Integrity of Zirconium Alloy Components Delayed Hydride Cracking

    CERN Document Server

    Puls, Manfred P

    2012-01-01

    By drawing together the current theoretical and experimental understanding of the phenomena of delayed hydride cracking (DHC) in zirconium alloys, The Effect of Hydrogen and Hydrides on the Integrity of Zirconium Alloy Components: Delayed Hydride Cracking provides a detailed explanation focusing on the properties of hydrogen and hydrides in these alloys. Whilst the focus lies on zirconium alloys, the combination of both the empirical and mechanistic approaches creates a solid understanding that can also be applied to other hydride forming metals.   This up-to-date reference focuses on documented research surrounding DHC, including current methodologies for design and assessment of the results of periodic in-service inspections of pressure tubes in nuclear reactors. Emphasis is placed on showing that our understanding of DHC is supported by progress across a broad range of fields. These include hysteresis associated with first-order phase transformations; phase relationships in coherent crystalline metallic...

  14. Homogeneous versus heterogeneous zeolite nucleation

    NARCIS (Netherlands)

    Dokter, W.H.; Garderen, van H.F.; Beelen, T.P.M.; Santen, van R.A.; Bras, W.

    1995-01-01

    Aggregates of fractal dimension were found in the intermediate gel phases that organize prior to nucleation and crystallization (shown right) of silicalite from a homogeneous reaction mixture. Small- and wide-angle X-ray scattering studies prove that for zeolites nucleation may be homogeneous or

  15. On Capillary Rise and Nucleation

    Science.gov (United States)

    Prasad, R.

    2008-01-01

    A comparison of capillary rise and nucleation is presented. It is shown that both phenomena result from a balance between two competing energy factors: a volume energy and a surface energy. Such a comparison may help to introduce nucleation with a topic familiar to the students, capillary rise. (Contains 1 table and 3 figures.)

  16. Theory and Simulation of Nucleation

    NARCIS (Netherlands)

    Kuipers, J.|info:eu-repo/dai/nl/304832049

    2009-01-01

    Nucleation is the process where a stable nucleus spontaneously emerges in a metastable environment. Examples of nucleation abound, for instance the formation of droplets in undercooled gasses and of crystals in undercooled liquids. The process is thermally activated and is key to understanding

  17. Controlling the crystal polymorph by exploiting the time dependence of nucleation rates.

    Science.gov (United States)

    Little, Laurie J; King, Alice A K; Sear, Richard P; Keddie, Joseph L

    2017-10-14

    Most substances can crystallise into two or more different crystal lattices called polymorphs. Despite this, there are no systems in which we can quantitatively predict the probability of one competing polymorph forming instead of the other. We address this problem using large scale (hundreds of events) studies of the competing nucleation of the alpha and gamma polymorphs of glycine. In situ Raman spectroscopy is used to identify the polymorph of each crystal. We find that the nucleation kinetics of the two polymorphs is very different. Nucleation of the alpha polymorph starts off slowly but accelerates, while nucleation of the gamma polymorph starts off fast but then slows. We exploit this difference to increase the purity with which we obtain the gamma polymorph by a factor of ten. The statistics of the nucleation of crystals is analogous to that of human mortality, and using a result from medical statistics, we show that conventional nucleation data can say nothing about what, if any, are the correlations between competing nucleation processes. Thus we can show that with data of our form it is impossible to disentangle the competing nucleation processes. We also find that the growth rate and the shape of a crystal depend on it when nucleated. This is new evidence that nucleation and growth are linked.

  18. A dynamical theory of nucleation

    Science.gov (United States)

    Lutsko, James F.

    2013-05-01

    A dynamical theory of nucleation based on fluctuating hydrodynamics is described. It is developed in detail for the case of diffusion-limited nucleation appropriate to colloids and macro-molecules in solution. By incorporating fluctuations, realistic fluid-transport and realistic free energy models the theory is able to give a unified treatment of both the pre-critical development of fluctuations leading to a critical cluster as well as of post-critical growth. Standard results from classical nucleation theory are shown to follow in the weak noise limit while the generality of the theory allows for many extensions including the description of very high supersaturations (small clusters), multiple order parameters and strong-noise effects to name a few. The theory is applied to homogeneous and heterogeneous nucleation of a model globular protein in a confined volume and it is found that nucleation depends critically on the existence of long-wavelength, small-amplitude density fluctuations.

  19. Direct hydride shift mechanism and stereoselectivity of P450nor confirmed by QM/MM calculations.

    Science.gov (United States)

    Krámos, Balázs; Menyhárd, Dóra K; Oláh, Julianna

    2012-01-19

    Nitric oxide reductase (P450(nor)) found in Fusarium oxysporum catalyzes the reduction of nitric oxide to N(2)O in a multistep process. The reducing agent, NADH, is bound in the distal pocket of the enzyme, and direct hydride transfer occurs from NADH to the nitric oxide bound heme enzyme, forming intermediate I. Here we studied the possibility of hydride transfer from NADH to both the nitrogen and oxygen of the heme-bound nitric oxide, using quantum chemical and combined quantum mechanics/molecular mechanics (QM/MM) calculations, on two different protein models, representing both possible stereochemistries, a syn- and an anti-NADH arrangement. All calculations clearly favor hydride transfer to the nitrogen of nitric oxide, and the QM-only barrier and kinetic isotope effects are good agreement with the experimental values of intermediate I formation. We obtained higher barriers in the QM/MM calculations for both pathways, but hydride transfer to the nitrogen of nitric oxide is still clearly favored. The barriers obtained for the syn, Pro-R conformation of NADH are lower and show significantly less variation than the barriers obtained in the case of anti conformation. The effect of basis set and wide range of functionals on the obtained results are also discussed.

  20. Synthesis of Nano-Light Magnesium Hydride for Hydrogen Storage ...

    African Journals Online (AJOL)

    Abstract. Nano-light magnesium hydride that has the capability for hydrogen storage was synthesized from treatment of magnesium ribbon with hydrogen peroxide. The optimum time for complete hydrogenation of the magnesium hydride was 5 hours.

  1. High H⁻ ionic conductivity in barium hydride.

    Science.gov (United States)

    Verbraeken, Maarten C; Cheung, Chaksum; Suard, Emmanuelle; Irvine, John T S

    2015-01-01

    With hydrogen being seen as a key renewable energy vector, the search for materials exhibiting fast hydrogen transport becomes ever more important. Not only do hydrogen storage materials require high mobility of hydrogen in the solid state, but the efficiency of electrochemical devices is also largely determined by fast ionic transport. Although the heavy alkaline-earth hydrides are of limited interest for their hydrogen storage potential, owing to low gravimetric densities, their ionic nature may prove useful in new electrochemical applications, especially as an ionically conducting electrolyte material. Here we show that barium hydride shows fast pure ionic transport of hydride ions (H(-)) in the high-temperature, high-symmetry phase. Although some conductivity studies have been reported on related materials previously, the nature of the charge carriers has not been determined. BaH2 gives rise to hydride ion conductivity of 0.2 S cm(-1) at 630 °C. This is an order of magnitude larger than that of state-of-the-art proton-conducting perovskites or oxide ion conductors at this temperature. These results suggest that the alkaline-earth hydrides form an important new family of materials, with potential use in a number of applications, such as separation membranes, electrochemical reactors and so on.

  2. Economic analysis of hydride fueled BWR

    International Nuclear Information System (INIS)

    Ganda, F.; Shuffler, C.; Greenspan, E.; Todreas, N.

    2009-01-01

    The economic implications of designing BWR cores with hydride fuels instead of conventional oxide fuels are analyzed. The economic analysis methodology adopted is based on the lifetime levelized cost of electricity (COE). Bracketing values (1970 and 3010 $/kWe) are used for the overnight construction costs and for the power scaling factors (0.4 and 0.8) that correlate between a change in the capital cost to a change in the power level. It is concluded that a newly constructed BWR reactor could substantially benefit from the use of 10 x 10 hydride fuel bundles instead of 10 x 10 oxide fuel bundles design presently in use. The cost saving would depend on the core pressure drop constraint that can be implemented in newly constructed BWRs - it is between 2% and 3% for a core pressure drop constraint as of the reference BWR, between 9% and 15% for a 50% higher core pressure drop, and between 12% and 21% higher for close to 100% core pressure. The attainable cost reduction was found insensitive to the specific construction cost but strongly dependent on the power scaling factor. The cost advantage of hydride fuelled cores as compared to that of the oxide reference core depends only weakly on the uranium and SWU prices, on the 'per volume base' fabrication cost of hydride fuels, and on the discount rate used. To be economically competitive, the uranium enrichment required for the hydride fuelled core needs to be around 10%.

  3. Hydrogen vacancies facilitate hydrogen transport kinetics in sodium hydride nanocrystallites

    NARCIS (Netherlands)

    Singh, S.; Eijt, S.W.H.

    2008-01-01

    We report ab initio calculations based on density-functional theory, of the vacancy-mediated hydrogen migration energy in bulk NaH and near the NaH(001) surface. The estimated rate of the vacancy mediated hydrogen transport, obtained within a hopping diffusion model, is consistent with the reaction

  4. Experimental investigation of strain, damage and failure of hydrided zircaloy-4 with various hydride orientations

    International Nuclear Information System (INIS)

    Racine, A; Catherine, C.S.; Cappelaere, C.; Bornert, M.; Caldemaison, D.

    2005-01-01

    This experimental investigation is devoted to the influence of the orientation of hydrides on the mechanical response of Zircaloy-4. Ring tensile tests are performed on unirradiated CWSR Zircaloy-4, charged with about 200 or 500wppm hydrogen. Hydrides are oriented either parallel ('tangential'), or perpendicular ('radial') to the circumferential tensile direction. Tangential hydrides are usually observed in cladding tubes, however, hydrides can be reoriented after cooling under stress to become radial and then trigger brittle behavior. In this investigation, we perform, 'macroscopic' or SEM in-situ tensile tests on smooth rings, at room temperature. We get the mechanical response of the material as a function of hydride orientation and hydrogen content and we investigate the deformation, damage and failure mechanisms. In both cases, digital image correlation techniques are used to estimate local and global strain distributions. The results lead to the following conclusions: neither the tensile stress-strain response nor the strain modes are affected by hydrogen content or hydride orientation, but the failure modes are. Indeed, only 200wppm radial hydrides embrittle Zy-4: sample fails in the elastic domain at about 350 MPa before strain bands could develop; whereas in other cases samples reach at least 750 MPa before failure, with ductile or brittle mode. (authors)

  5. Protein crystal nucleation in pores.

    Science.gov (United States)

    Nanev, Christo N; Saridakis, Emmanuel; Chayen, Naomi E

    2017-01-16

    The most powerful method for protein structure determination is X-ray crystallography which relies on the availability of high quality crystals. Obtaining protein crystals is a major bottleneck, and inducing their nucleation is of crucial importance in this field. An effective method to form crystals is to introduce nucleation-inducing heterologous materials into the crystallization solution. Porous materials are exceptionally effective at inducing nucleation. It is shown here that a combined diffusion-adsorption effect can increase protein concentration inside pores, which enables crystal nucleation even under conditions where heterogeneous nucleation on flat surfaces is absent. Provided the pore is sufficiently narrow, protein molecules approach its walls and adsorb more frequently than they can escape. The decrease in the nucleation energy barrier is calculated, exhibiting its quantitative dependence on the confinement space and the energy of interaction with the pore walls. These results provide a detailed explanation of the effectiveness of porous materials for nucleation of protein crystals, and will be useful for optimal design of such materials.

  6. Mathematical model of a NiOOH/metal hydride cell. Final report, September 15, 1993--November 14, 1996

    Energy Technology Data Exchange (ETDEWEB)

    White, R.E.; Popov, B.N.

    1996-12-31

    One of the objectives of work on the nickel/metal hydride cell has been to develop a mathematical model of the performance of the cell. This is a summary of work to date and is meant to be a Final Report of the BES project. Mathematical model of the nickel/metal hydride cell depends on the kinetics, thermodynamics, and transport properties of the metal hydride electrode. Consequently, investigations were carried out to determine: (1) the exchange current density and the equilibrium potential as a function of hydrogen content in the electrode; (2) the hydrogen diffusion coefficient in the bulk of the alloy; (3) the hydrogen reaction rate order; (4) the symmetry factor for hydrogen evolution reaction and (5) to determine the reaction mechanisms of the hydrogen charge and discharge processes including overcharge and overdischarge mechanism.

  7. Climate Impacts of Ice Nucleation

    Science.gov (United States)

    Gettelman, Andrew; Liu, Xiaohong; Barahona, Donifan; Lohmann, Ulrike; Chen, Celia

    2012-01-01

    Several different ice nucleation parameterizations in two different General Circulation Models (GCMs) are used to understand the effects of ice nucleation on the mean climate state, and the Aerosol Indirect Effects (AIE) of cirrus clouds on climate. Simulations have a range of ice microphysical states that are consistent with the spread of observations, but many simulations have higher present-day ice crystal number concentrations than in-situ observations. These different states result from different parameterizations of ice cloud nucleation processes, and feature different balances of homogeneous and heterogeneous nucleation. Black carbon aerosols have a small (0.06 Wm(exp-2) and not statistically significant AIE when included as ice nuclei, for nucleation efficiencies within the range of laboratory measurements. Indirect effects of anthropogenic aerosols on cirrus clouds occur as a consequence of increasing anthropogenic sulfur emissions with different mechanisms important in different models. In one model this is due to increases in homogeneous nucleation fraction, and in the other due to increases in heterogeneous nucleation with coated dust. The magnitude of the effect is the same however. The resulting ice AIE does not seem strongly dependent on the balance between homogeneous and heterogeneous ice nucleation. Regional effects can reach several Wm2. Indirect effects are slightly larger for those states with less homogeneous nucleation and lower ice number concentration in the base state. The total ice AIE is estimated at 0.27 +/- 0.10 Wm(exp-2) (1 sigma uncertainty). This represents a 20% offset of the simulated total shortwave AIE for ice and liquid clouds of 1.6 Wm(sup-2).

  8. The growth of crystals of erbium hydride

    International Nuclear Information System (INIS)

    Grimshaw, J.A.; Spooner, F.J.; Wilson, C.G.; McQuillan, A.D.

    1981-01-01

    Crystals of the rare-earth hydride ErH 2 have been produced with face areas greater than a square millimetre and corresponding volumes exceeding those of earlier crystals by orders of magnitude. The hydride, which was produced in bulk polycrystalline form by hydriding erbium metal at 950 0 C, has been examined by optical and X-ray techniques. For material of composition ErH 2 and ErHsub(1.8) the size of the grains and their degree of strain appears to depend more on oxygen contamination during formation and on the subsequent cooling procedure, than on the size of erbium metal crystals in the starting material. (author)

  9. Superheating in nucleate boiling calculated by the heterogeneous nucleation theory

    International Nuclear Information System (INIS)

    Gerum, E.; Straub, J.; Grigull, U.

    1979-01-01

    With the heterogeneous nucleation theory the superheating of the liquid boundary layer in nucleate boiling is described not only for the onset of nuclear boiling but also for the boiling crisis. The rate of superheat depends on the thermodynamic stability of the metastable liquid, which is influenced by the statistical fluctuations in the liquid and the nucleation at the solid surface. Because of the fact that the cavities acting as nuclei are too small for microscopic observation, the size and distribution function of the nuclei on the surface necessary for the determination of the probability of bubble formation cannot be detected by measuring techniques. The work of bubble formation reduced by the nuclei can be represented by a simple empirical function whose coefficients are determined from boiling experiments. Using this the heterogeneous nucleation theory describes the superheating of the liquid. Several fluids including refrigerants, liquid gases, organic liquids and water were used to check the theory. (author)

  10. Metadynamics studies of crystal nucleation

    Science.gov (United States)

    Giberti, Federico; Salvalaglio, Matteo; Parrinello, Michele

    2015-01-01

    Crystallization processes are characterized by activated events and long timescales. These characteristics prevent standard molecular dynamics techniques from being efficiently used for the direct investigation of processes such as nucleation. This short review provides an overview on the use of metadynamics, a state-of-the-art enhanced sampling technique, for the simulation of phase transitions involving the production of a crystalline solid. In particular the principles of metadynamics are outlined, several order parameters are described that have been or could be used in conjunction with metadynamics to sample nucleation events and then an overview is given of recent metadynamics results in the field of crystal nucleation. PMID:25866662

  11. Metadynamics studies of crystal nucleation

    Directory of Open Access Journals (Sweden)

    Federico Giberti

    2015-03-01

    Full Text Available Crystallization processes are characterized by activated events and long timescales. These characteristics prevent standard molecular dynamics techniques from being efficiently used for the direct investigation of processes such as nucleation. This short review provides an overview on the use of metadynamics, a state-of-the-art enhanced sampling technique, for the simulation of phase transitions involving the production of a crystalline solid. In particular the principles of metadynamics are outlined, several order parameters are described that have been or could be used in conjunction with metadynamics to sample nucleation events and then an overview is given of recent metadynamics results in the field of crystal nucleation.

  12. Review: The nucleation of disorder

    International Nuclear Information System (INIS)

    Cahn, R.W.; Johnson, W.L.

    1986-01-01

    Four types of phase transformation that involve the conversion of crystalline phases into more disordered forms are reviewed: melting, disordering of superlattices, amorphization by diffusion between crystalline phases, and irradation amorphization. In the review emphasis is placed on evidence for the heterogeneous nucleation of the product phases; in this connection, the role of surfaces, antiphase domain boundaries, dislocations, vacancies, and grain boundaries is specifically discussed. All of these features have been either observed, or hypothesized, to play a role as heterogeneous nucleation sites in one or more of the four transformations. An attempt is made to draw parallels between nucleation mechanisms in the various processes

  13. Stress induced reorientation of vanadium hydride

    International Nuclear Information System (INIS)

    Beardsley, M.B.

    1977-10-01

    The critical stress for the reorientation of vanadium hydride was determined for the temperature range 180 0 to 280 0 K using flat tensile samples containing 50 to 500 ppM hydrogen by weight. The critical stress was observed to vary from a half to a third of the macroscopic yield stress of pure vanadium over the temperature range. The vanadium hydride could not be stress induced to precipitate above its stress-free precipitation temperature by uniaxial tensile stresses or triaxial tensile stresses induced by a notch

  14. Novel Design Integrating a Microwave Applicator into a Crystallizer for Rapid Temperature Cycling. A Direct Nucleation Control Study

    NARCIS (Netherlands)

    Kacker, R.; Radoiu, Marilena; Kramer, H.J.M.

    2017-01-01

    The control of nucleation in crystallization processes is a challenging task due to the often lacking knowledge on the process kinetics. Inflexible (predetermined) control strategies fail to grow the nucleated crystals to the desired quality because of the variability in the process conditions,

  15. OPTIMIZATION OF INTERNAL HEAT EXCHANGERS FOR HYDROGEN STORAGE TANKS UTILIZING METAL HYDRIDES

    Energy Technology Data Exchange (ETDEWEB)

    Garrison, S.; Tamburello, D.; Hardy, B.; Anton, D.; Gorbounov, M.; Cognale, C.; van Hassel, B.; Mosher, D.

    2011-07-14

    Two detailed, unit-cell models, a transverse fin design and a longitudinal fin design, of a combined hydride bed and heat exchanger are developed in COMSOL{reg_sign} Multiphysics incorporating and accounting for heat transfer and reaction kinetic limitations. MatLab{reg_sign} scripts for autonomous model generation are developed and incorporated into (1) a grid-based and (2) a systematic optimization routine based on the Nelder-Mead downhill simplex method to determine the geometrical parameters that lead to the optimal structure for each fin design that maximizes the hydrogen stored within the hydride. The optimal designs for both the transverse and longitudinal fin designs point toward closely-spaced, small cooling fluid tubes. Under the hydrogen feed conditions studied (50 bar), a 25 times improvement or better in the hydrogen storage kinetics will be required to simultaneously meet the Department of Energy technical targets for gravimetric capacity and fill time. These models and methodology can be rapidly applied to other hydrogen storage materials, such as other metal hydrides or to cryoadsorbents, in future work.

  16. Stereo-specificity for pro-(R) hydrogen of NAD(P)H during enzyme-catalyzed hydride transfer to CL-20

    International Nuclear Information System (INIS)

    Bhushan, Bharat; Halasz, Annamaria; Hawari, Jalal

    2005-01-01

    A dehydrogenase from Clostridium sp. EDB2 and a diaphorase from Clostridium kluyveri were reacted with CL-20 to gain insights into the enzyme-catalyzed hydride transfer to CL-20, and the enzyme's stereo-specificity for either pro-R or pro-S hydrogens of NAD(P)H. Both enzymes biotransformed CL-20 at rates of 18.5 and 24 nmol/h/mg protein, using NADH and NADPH as hydride-source, respectively, to produce a N-denitrohydrogenated product with a molecular weight of 393 Da. In enzyme kinetics studies using reduced deuterated pyridine nucleotides, we found a kinetic deuterium isotopic effect of 2-fold on CL-20 biotransformation rate using dehydrogenase enzyme against (R)NADD as a hydride-source compared to either (S)NADD or NADH. Whereas, in case of diaphorase, the kinetic deuterium isotopic effect of about 1.5-fold was observed on CL-20 biotransformation rate using (R)NADPD as hydride-source. In a comparative study with LC-MS, using deuterated and non-deuterated NAD(P)H, we found a positive mass-shift of 1 Da in the N-denitrohydrogenated product suggesting the involvement of a deuteride (D - ) transfer from NAD(P)D. The present study thus revealed that both dehydrogenase and diaphorase enzymes from the two Clostridium species catalyzed a hydride transfer to CL-20 and showed stereo-specificity for pro-R hydrogen of NAD(P)H

  17. Computer simulation of chemical nucleation

    International Nuclear Information System (INIS)

    Turner, J.S.

    1979-01-01

    The problem of nucleation at chemical instabilities is investigated by means of microscopic computer simulation. The first-order transition of interest involves a new kind of nucleation arising from chemical transformations rather than physical forces. Here it is the chemical state of matter, and not matter itself, which is spatially localized to form the nucleus for transition between different chemical states. First, the concepts of chemical instability, nonequilibrium phase transition, and dissipative structure are reviewed briefly. Then recently developed methods of reactive molecular dynamics are used to study chemical nucleation in a simple model chemical reactions. Finally, the connection of these studies to nucleation and condensation processes involving physical and chemical interactions is explored. (orig.)

  18. In situ hydride formation in titanium during focused ion milling.

    Science.gov (United States)

    Ding, Rengen; Jones, Ian P

    2011-01-01

    It is well known that titanium and its alloys are sensitive to electrolytes and thus hydrides are commonly observed in electropolished foils. In this study, focused ion beam (FIB) milling was used to prepare thin foils of titanium and its alloys for transmission electron microscopy. The results show the following: (i) titanium hydrides were observed in pure titanium, (ii) the preparation of a bulk sample in water or acid solution resulted in the formation of more hydrides and (iii) FIB milling aids the precipitation of hydrides, but there were never any hydrides in Ti64 and Ti5553.

  19. Effects of δ-hydride precipitation at a crack tip on crack propagation in delayed hydride cracking of Zircaloy-2

    Energy Technology Data Exchange (ETDEWEB)

    Kubo, T., E-mail: kubo@nfd.co.jp [Nippon Nuclear Fuel Development Co., Ltd., 2163 Narita-cho, Oarai-machi, Ibaraki 311-1313 (Japan); Kobayashi, Y. [M.O.X. Co., Ltd., 1828-520 Hirasu-cho, Mito, Ibaraki 311-0853 (Japan)

    2013-08-15

    Highlights: • Steady state crack velocity of delayed hydride cracking in Zircaloy-2 was analyzed. • A large stress peak is induced at an end of hydride by volume expansion of hydride. • Hydrogen diffuses to the stress peak, thereby accelerating steady hydride growth. • Crack velocity was estimated from the calculated hydrogen flux into the stress peak. • There was good agreement between calculation results and experimental data. -- Abstract: Delayed hydride cracking (DHC) of Zircaloy-2 is one possible mechanism for the failure of boiling water reactor fuel rods in ramp tests at high burnup. Analyses were made for hydrogen diffusion around a crack tip to estimate the crack velocity of DHC in zirconium alloys, placing importance on effects of precipitation of δ-hydride. The stress distribution around the crack tip is significantly altered by precipitation of hydride, which was strictly analyzed using a finite element computer code. Then, stress-driven hydrogen diffusion under the altered stress distribution was analyzed by a differential method. Overlapping of external stress and hydride precipitation at a crack tip induces two stress peaks; one at a crack tip and the other at the front end of the hydride precipitate. Since the latter is larger than the former, more hydrogen diffuses to the front end of the hydride precipitate, thereby accelerating hydride growth compared with that in the absence of the hydride. These results indicated that, after hydride was formed in front of the crack tip, it grew almost steadily accompanying the interaction of hydrogen diffusion, hydride growth and the stress alteration by hydride precipitation. Finally, crack velocity was estimated from the calculated hydrogen flux into the crack tip as a function of temperature, stress intensity factor and material strength. There was qualitatively good agreement between calculation results and experimental data.

  20. Influence of silicon on void nucleation in irradiated alloys

    International Nuclear Information System (INIS)

    Esmailzadeh, B.; Kumar, A.; Garner, F.A.

    1984-01-01

    The addition of silicon to pure nickel, Ni-Cr alloys and Fe-Ni-Cr alloys raises the diffusivity of each of the alloy components. The resultant increase in the effective vacancy diffusion coefficient causes large reductions in the nucleation rate of voids during irradiation. This extends the transient regime of swelling, which is controlled not only by the amount of silicon in solution but also by the precipitation kinetics of precipitates rich in nickel and silicon

  1. Aluminum hydride as a hydrogen and energy storage material: Past, present and future

    Energy Technology Data Exchange (ETDEWEB)

    Graetz, J., E-mail: graetz@bnl.gov [Sustainable Energy Technologies Department, Brookhaven National Laboratory, Upton, NY (United States); Reilly, J.J. [Sustainable Energy Technologies Department, Brookhaven National Laboratory, Upton, NY (United States); Yartys, V.A.; Maehlen, J.P. [Institute for Energy Technology, Kjeller (Norway); Bulychev, B.M. [Department of Chemistry, Lomonosov Moscow State University, Moscow (Russian Federation); Antonov, V.E. [Institute of Solid State Physics, Russian Academy of Sciences, Chernogolovka (Russian Federation); Tarasov, B.P. [Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka (Russian Federation); Gabis, I.E. [Department of Physics, Saint-Petersburg State University, St. Petersburg (Russian Federation)

    2011-09-15

    Aluminum hydride (AlH{sub 3}) and its associated compounds make up a fascinating class of materials that have motivated considerable scientific and technological research over the past 50 years. Due primarily to its high energy density, AlH{sub 3} has become a promising hydrogen and energy storage material that has been used (or proposed for use) as a rocket fuel, explosive, reducing agent and as a hydrogen source for portable fuel cells. This review covers the past, present and future research on aluminum hydride and includes the latest research developments on the synthesis of {alpha}-AlH{sub 3} and the other polymorphs (e.g., microcrystallization reaction, batch and continuous methods), crystallographic structures, thermodynamics and kinetics (e.g., as a function of crystallite size, catalysts and surface coatings), high-pressure hydrogenation experiments and possible regeneration routes.

  2. Characterisation of hydrides in a zirconium alloy, by EBSD

    International Nuclear Information System (INIS)

    Ubhi, H.S.; Larsen, K.

    2012-01-01

    Zirconium alloys are used in nuclear reactors owing to their low capture cross-section for thermal neutrons and good mechanical and corrosion properties. However, they do suffer from delayed hydrogen cracking (DHC) due to formation of hydride particles. This study shows how the electron back-scatter diffraction (EBSD) technique can be used to characterise hydrides and their orientation relationship with the matrix. Hydrided EB weld specimens were prepared by electro-polishing, characterised using Oxford instruments AZtecHKL EBSD apparatus and software attached to a FEG SEM. Hydrides were found to exist as fine intra granular plates and having the Blackburn orientation relationship, i.e. (0002)Zr//(111)hydride and (1120)Zr//(1-10)hydride. The hydrides were also found to contain sigma 3 boundaries as well as local misorientations. (author)

  3. Role of nucleation in nanodiamond film growth

    International Nuclear Information System (INIS)

    Lifshitz, Y.; Lee, C.H.; Wu, Y.; Zhang, W.J.; Bello, I.; Lee, S.T.

    2006-01-01

    Nanodiamond films were deposited using different microwave plasma chemical vapor deposition schemes following several nucleation pretreatment methods. The nucleation efficiency and the films structure were investigated using scanning and transmission electron microscopy and Raman spectroscopy. C 2 dimer growth (CH 4 and H 2 in 90% Ar) cannot nucleate diamond and works only on existing diamond surfaces. The methyl radical process (up to 20% CH 4 in H 2 ) allows some nucleation probability on appropriate substrates. Prolonged bias enhanced nucleation initiates both diamond nucleation and growth. C 2 dimer growth results in pure nanodiamond free of amorphous carbon, while prolonged bias enhanced nucleation forms an amorphous carbon/nanodiamond composite

  4. Preparation and nucleation of spherical metallic droplet

    Directory of Open Access Journals (Sweden)

    Bing-ge Zhao

    2015-03-01

    Full Text Available The preparation and solidification of metallic droplets attract more and more attention for their significance in both engineering and scientific fields. In this paper, the preparation and characterization of Sn-based alloy droplets using different methods such as atomization and consumable electrode direct current arc (CDCA technique are reviewed. The morphology and structure of these droplets were determined by optical microscopy, X-ray diffraction (XRD and scanning electron microscopy (SEM. The solidification behavior of single droplet was systematically studied by means of scanning calorimetry (DSC, and the nucleation kinetics was also calculated. In particular, the development of fast scanning calorimetry (FSC made it possible to investigate the evolution of undercooling under ultrafast but controllable heating and cooling conditions. The combination of CDCA technique and FSC measurements opens up a new door for quantitative studies on droplet solidification, which is accessible to demonstrate some theories by experiments.

  5. A Study on the Radial Hydride Assisted Delayed Hydride Cracking of Zircaloy

    Energy Technology Data Exchange (ETDEWEB)

    Jeong, Jin-Ho; Lee, Ji-Min; Kim, Yong-Soo [Hanyang University, Seoul (Korea, Republic of)

    2015-05-15

    Extensive studies have been done on understanding of DHC(Delayed hydride cracking) phenomenon since several zirconium alloy pressure tubes failed in nuclear reactor in the 1970s. Recently, long-term dry storage strategy has been considered seriously in order to manage spent nuclear fuel in Korea and other countries around the world. Consequentially, many researches have been investigated the degradation mechanisms which will threaten the spent fuel integrity during dry storage and showed that hydrogen related phenomenon such as hydride reorientation and DHC are the critical factors. Especially, DHC is the direct cracking mechanism which can cause not only a through-wall defect but also a radiation leak to the environment. In addition, DHC can be enhanced by radial hydride as reported by Kim who demonstrate that radial hydrides clearly act as crack linkage path. This phenomenon is known as the radial hydride assisted DHC (RHA-DHC). Therefore, study on DHC is essential to ensure the safety of spent fuel. Finite element analysis will be carried out for the stress gradient evaluation around notch tip. A variation in thermal cycle which leads to change in hydrogen solid solution trajectory may be required. If the radial hydride precipitates at notch tip, we will investigate what conditions should be met. Ultimately, we will suggest the regulation criteria for long-term dry storage of spent nuclear fuel.

  6. Method for preparation of uranium hydride

    International Nuclear Information System (INIS)

    Gorski, M.S.; Goncalves, Miriam; Mirage, A.; Lima, W. de.

    1985-01-01

    A method for preparation of Uranium Hydride starting from Hidrogen and Uranium is described. In the temperature range of 250 0 up to 350 0 C, and pressures above 10torr, Hydrogen reacts smoothly with Uranium turnings forming a fine black or dark gray powder (UH 3 ). Samples containing a significant amount of oxides show a delay before the reaction begging. (Author) [pt

  7. Hydrogen isotope exchange in metal hydride columns

    International Nuclear Information System (INIS)

    Wiswall, R.; Reilly, J.; Bloch, F.; Wirsing, E.

    1977-01-01

    Several metal hydrides were shown to act as chromatographic media for hydrogen isotopes. The procedure was to equilibrate a column of hydride with flowing hydrogen, inject a small quantity of tritium tracer, and observe its elution behavior. Characteristic retention times were found. From these and the extent of widening of the tritium band, the heights equivalent to a theoretical plate could be calculated. Values of around 1 cm were obtained. The following are the metals whose hydrides were studied, together with the temperature ranges in which chromatographic behavior was observed: vanadium, 0 to 70 0 C; zirconium, 500 to 600 0 C; LaNi 5 , -78 to +30 0 C; Mg 2 Ni, 300 to 375 0 C; palladium, 0 to 70 0 C. A dual-temperature isotope separation process based on hydride chromatography was demonstrated. In this, a column was caused to cycle between two temperatures while being supplied with a constant stream of tritium-traced hydrogen. Each half-cycle was continued until ''breakthrough,'' i.e., until the tritium concentration in the effluent was the same as that in the feed. Up to that point, the effluent was enriched or depleted in tritium, by up to 20%

  8. Magnesium hydrides and their phase transitions

    Czech Academy of Sciences Publication Activity Database

    Paidar, Václav

    2016-01-01

    Roč. 41, č. 23 (2016), s. 9769-9773 ISSN 0360-3199 R&D Projects: GA MŠk(CZ) LD13069 Institutional support: RVO:68378271 Keywords : hydrogen * magnesium and transition metal hydrides * crystal structure stability * displacive phase transformations Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 3.582, year: 2016

  9. Are RENiAl hydrides metallic?

    Czech Academy of Sciences Publication Activity Database

    Eichinger, K.; Havela, L.; Prokleška, J.; Stelmakhovych, O.; Daniš, S.; Šantavá, Eva; Miliyanchuk, K.

    2009-01-01

    Roč. 100, č. 9 (2009), s. 1200-1202 ISSN 1862-5282 Grant - others:GA ČR(CZ) GA202/07/0418 Institutional research plan: CEZ:AV0Z10100520 Keywords : rare earth metals * magnetism * hydrides Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 0.862, year: 2009

  10. Influence of mixing and solid concentration on sodium bicarbonate secondary nucleation rate in stirred tank

    Energy Technology Data Exchange (ETDEWEB)

    Wylock, C.; Debaste, F.; Haut, B. [Transfers, Interfaces and Processes - Chemical Engineering Unit, ULB, Brussels (Belgium); Gutierrez, V.; Delplancke-Ogletree, M.P. [Chemicals and Materials Department, ULB, Brussels (Belgium); Cartage, T. [Solvay SA, Brussels (Belgium)

    2010-09-15

    This work aims to investigate the influence of the solid concentration in suspension on the contact secondary nucleation rate of sodium bicarbonate crystallization in a stirred tank crystallizer and to show the necessity of a local description of the mixing for a nucleation rate influence study. Experiments and computational fluid dynamics (CFD) simulations are realized. Crystallization kinetic parameters are extracted from experimental data using a mass distribution fitting approach. CFD and the experimental results allow identifying that a mixing property correlated with the measurements of the secondary nucleation rate in the stirred tank crystallizer appears to be the turbulent dissipation rate on the edge of the impeller. Its influence and the influence of the solid concentration in the suspension on the secondary nucleation rate are estimated by the evaluation of their exponents in a kinetic law. The obtained exponent values are then discussed qualitatively. (copyright 2010 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  11. Nanometer-scale mapping of irreversible electrochemical nucleation processes on solid Li-ion electrolytes

    Science.gov (United States)

    Kumar, Amit; Arruda, Thomas M.; Tselev, Alexander; Ivanov, Ilia N.; Lawton, Jamie S.; Zawodzinski, Thomas A.; Butyaev, Oleg; Zayats, Sergey; Jesse, Stephen; Kalinin, Sergei V.

    2013-01-01

    Electrochemical processes associated with changes in structure, connectivity or composition typically proceed via new phase nucleation with subsequent growth of nuclei. Understanding and controlling reactions requires the elucidation and control of nucleation mechanisms. However, factors controlling nucleation kinetics, including the interplay between local mechanical conditions, microstructure and local ionic profile remain inaccessible. Furthermore, the tendency of current probing techniques to interfere with the original microstructure prevents a systematic evaluation of the correlation between the microstructure and local electrochemical reactivity. In this work, the spatial variability of irreversible nucleation processes of Li on a Li-ion conductive glass-ceramics surface is studied with ~30 nm resolution. An increased nucleation rate at the boundaries between the crystalline AlPO4 phase and amorphous matrix is observed and attributed to Li segregation. This study opens a pathway for probing mechanisms at the level of single structural defects and elucidation of electrochemical activities in nanoscale volumes. PMID:23563856

  12. Homogeneous nucleation limit on the bulk formation of metallic glasses

    International Nuclear Information System (INIS)

    Drehman, A.J.

    1983-01-01

    Glassy Pd 82 Si 18 spheres, of up to 1 mm diameter, were formed in a drop tube filled with He gas. The largest spheres were successfully cooled to a glass using a cooling rate of less than 800 K/sec. Even at this low cooling rate, crystallization (complete or partial) was the result of heterogeneous nucleation at a high temperature, relative to the temperature at which copious homogeneous nucleation would commence. Bulk underscoring experiments demonstrated that this alloy could be cooled to 385 K below its eutectic melting temperature (1083 K) without the occurrence of crystallization. If heterogeneous nucleation can be avoided, it is estimated that a cooling rate of at most 100 K/sec would be required to form this alloy in the glassy state. Ingots of glassy Pd 40 Ni 40 P 20 were formed from the liquid by cooling at a rate of only 1 K/sec. It was found that glassy samples of this alloy could be heated well above the glass transition temperature without the occurrence of rapid divitrification. This is a result due, in part of the low density of pre-existing nuclei, but, more importantly, due to the low homogeneous nucleation rate and the slow crystal growth kinetics. Based on the observed devitrification kinetics, the steady-state homogeneous nucleation rate is approximately 1 nuclei/cm 3 sec at 590 K (the temperature at which the homogeneous nucleation rate is estimated to be a maximum). Two iron-nickel based glass-forming alloys (Fe 40 Ni 40 P 14 B 6 and Fe 40 Ni 40 B 20 , were not successfully formed into glassy spheres, however, microstructural examination indicates that crystallization was not the result of copious homogeneous nucleation. In contrast, glass forming iron based alloys (Fe 80 B 20 and Fe/sub 79.3/B/sub 16.4/Si/sub 4.0/C/sub 0.3/) exhibit copious homogeneous nucleation when cooled at approximately the same rate

  13. Arsenic flux dependence of island nucleation on InAs(001)

    International Nuclear Information System (INIS)

    Grosse, Frank; Barvosa-Carter, William; Zinck, Jenna; Wheeler, Matthew; Gyure, Mark F.

    2002-01-01

    The initial stages of InAs(001) homoepitaxial growth are investigated using a combination of kinetic Monte Carlo simulations based on ab initio density functional theory and scanning tunneling microscopy. In the two dimensional island nucleation mode investigated, the island number density is found to decrease with increasing As. This behavior is explained by a suppression of the effective In-adatom density leading to a reduction in island nucleation. The relevant microscopic processes responsible for this reduction are identified

  14. Steady-state molecular dynamics simulation of vapor to liquid nucleation with Mc Donald's demon

    International Nuclear Information System (INIS)

    Horsch, M.; Miroshnichenko, S.; Vrabec, J.

    2009-01-01

    Grand canonical MD with McDonald's demon is discussed in the present contribution and applied for sampling both nucleation kinetics and steady-state properties of a supersaturated vapor. The idea behind the new approach is to simulate the production of clusters up to a given size for a specified supersaturation. The classical nucleation theory is found to overestimate the free energy of cluster formation and deviate by two orders of magnitude from the nucleation rate below the triple point at high supersaturations.

  15. A computational fluid dynamics approach to nucleation in the water-sulfuric acid system.

    Science.gov (United States)

    Herrmann, E; Brus, D; Hyvärinen, A-P; Stratmann, F; Wilck, M; Lihavainen, H; Kulmala, M

    2010-08-12

    This study presents a computational fluid dynamics modeling approach to investigate the nucleation in the water-sulfuric acid system in a flow tube. On the basis of an existing experimental setup (Brus, D.; Hyvärinen, A.-P.; Viisanen, Y.; Kulmala, M.; Lihavainen, H. Atmos. Chem. Phys. 2010, 10, 2631-2641), we first establish the effect of convection on the flow profile. We then proceed to simulate nucleation for relative humidities of 10, 30, and 50% and for sulfuric acid concentration between 10(9) to 3 x 10(10) cm(-3). We describe the nucleation zone in detail and determine how flow rate and relative humidity affect its characteristics. Experimental nucleation rates are compared to rates gained from classical binary and kinetic nucleation theory as well as cluster activation theory. For low RH values, kinetic theory yields the best agreement with experimental results while binary nucleation best reproduces the experimental nucleation behavior at 50% relative humidity. Particle growth is modeled for an example case at 50% relative humidity. The final simulated diameter is very close to the experimental result.

  16. Deviation from equilibrium conditions in molecular dynamic simulations of homogeneous nucleation.

    Science.gov (United States)

    Halonen, Roope; Zapadinsky, Evgeni; Vehkamäki, Hanna

    2018-04-28

    We present a comparison between Monte Carlo (MC) results for homogeneous vapour-liquid nucleation of Lennard-Jones clusters and previously published values from molecular dynamics (MD) simulations. Both the MC and MD methods sample real cluster configuration distributions. In the MD simulations, the extent of the temperature fluctuation is usually controlled with an artificial thermostat rather than with more realistic carrier gas. In this study, not only a primarily velocity scaling thermostat is considered, but also Nosé-Hoover, Berendsen, and stochastic Langevin thermostat methods are covered. The nucleation rates based on a kinetic scheme and the canonical MC calculation serve as a point of reference since they by definition describe an equilibrated system. The studied temperature range is from T = 0.3 to 0.65 ϵ/k. The kinetic scheme reproduces well the isothermal nucleation rates obtained by Wedekind et al. [J. Chem. Phys. 127, 064501 (2007)] using MD simulations with carrier gas. The nucleation rates obtained by artificially thermostatted MD simulations are consistently lower than the reference nucleation rates based on MC calculations. The discrepancy increases up to several orders of magnitude when the density of the nucleating vapour decreases. At low temperatures, the difference to the MC-based reference nucleation rates in some cases exceeds the maximal nonisothermal effect predicted by classical theory of Feder et al. [Adv. Phys. 15, 111 (1966)].

  17. Investigating heterogeneous nucleation in peritectic materials via the phase-field method

    International Nuclear Information System (INIS)

    Emmerich, Heike; Siquieri, Ricardo

    2006-01-01

    Here we propose a phase-field approach to investigate the influence of convection on peritectic growth as well as the heterogeneous nucleation kinetics of peritectic systems. For this purpose we derive a phase-field model for peritectic growth taking into account fluid flow in the melt, which is convergent to the underlying sharp interface problem in the thin interface limit (Karma and Rappel 1996 Phys. Rev. E 53 R3017). Moreover, we employ our new phase-field model to study the heterogeneous nucleation kinetics of peritectic material systems. Our approach is based on a similar approach towards homogeneous nucleation in Granasy et al (2003 Interface and Transport Dynamics (Springer Lecture Notes in Computational Science and Engineering vol 32) ed Emmerich et al (Berlin: Springer) p 190). We applied our model successfully to extend the nucleation rate predicted by classical nucleation theory for an additional morphological term relevant for peritectic growth. Further applications to understand the mechanisms and consequences of heterogeneous nucleation kinetics in more detail are discussed

  18. A note on the nucleation with multiple steps: Parallel and series nucleation

    OpenAIRE

    Iwamatsu, Masao

    2012-01-01

    Parallel and series nucleation are the basic elements of the complex nucleation process when two saddle points exist on the free-energy landscape. It is pointed out that the nucleation rates follow formulas similar to those of parallel and series connection of resistors or conductors in an electric circuit. Necessary formulas to calculate individual nucleation rates at the saddle points and the total nucleation rate are summarized and the extension to the more complex nucleation process is su...

  19. Enhancement of the droplet nucleation in a dense supersaturated Lennard-Jones vapor

    Energy Technology Data Exchange (ETDEWEB)

    Zhukhovitskii, D. I., E-mail: dmr@ihed.ras.ru [Joint Institute of High Temperatures, Russian Academy of Sciences, Izhorskaya 13, Bd. 2, 125412 Moscow (Russian Federation)

    2016-05-14

    The vapor–liquid nucleation in a dense Lennard-Jones system is studied analytically and numerically. A solution of the nucleation kinetic equations, which includes the elementary processes of condensation/evaporation involving the lightest clusters, is obtained, and the nucleation rate is calculated. Based on the equation of state for the cluster vapor, the pre-exponential factor is obtained. The latter diverges as a spinodal is reached, which results in the nucleation enhancement. The work of critical cluster formation is calculated using the previously developed two-parameter model (TPM) of small clusters. A simple expression for the nucleation rate is deduced and it is shown that the work of cluster formation is reduced for a dense vapor. This results in the nucleation enhancement as well. To verify the TPM, a simulation is performed that mimics a steady-state nucleation experiments in the thermal diffusion cloud chamber. The nucleating vapor with and without a carrier gas is simulated using two different thermostats for the monomers and clusters. The TPM proves to match the simulation results of this work and of other studies.

  20. Nucleation and cavitation in parahydrogen

    International Nuclear Information System (INIS)

    Pi, Martí; Barranco, Manuel; Navarro, Jesús; Ancilotto, Francesco

    2012-01-01

    Highlights: ► We have constructed a density functional (DF) for parahydrogen between 14 and 32 K. ► The experimental equation of state and the surface tension are well reproduced. ► We have investigated nucleation and cavitations processes in the metastable phase. ► We have obtained the electron bubble explosion within the capillary model. - Abstract: We have used a density functional approach to investigate thermal homogeneous nucleation and cavitation in parahydrogen. The effect of electrons as seeds of heterogeneous cavitation in liquid parahydrogen is also discussed within the capillary model.

  1. Nucleation behavior of melted Bi films at cooling rates from 101 to 104 K/s studied by combining scanning AC and DC nano-calorimetry techniques

    International Nuclear Information System (INIS)

    Xiao, Kechao; Vlassak, Joost J.

    2015-01-01

    Highlights: • We proposed a general data reduction scheme that combines scanning AC and DC calorimetry results for the study of reaction kinetics. • Calorimetry measurements at cooling rates ranging from 30 K/s to 20,000 K/s were achieved. • Upon initial melting, the Bi thin-film sample breaks up into thousands of isolated islands, and highly repeatable nucleation behavior is observed. • The nucleation rate of melted Bi is calculated, which can be well described by classical nucleation theory over a wide range of cooling rates. - Abstract: We study the nucleation behavior of undercooled liquid Bi at cooling rates ranging from 10 1 to 10 4 K/s using a combination of scanning DC and AC nano-calorimetry techniques. Upon initial melting, the Bi thin-film sample breaks up into silicon nitride-coated isolated islands. The number of islands in a typical sample is sufficiently large that highly repeatable nucleation behavior is observed, despite the stochastic nature of the nucleation process. We establish a data reduction technique to evaluate the nucleation rate from DC and AC calorimetry results. The results show that the driving force for the nucleation of melted Bi is well described by classical nucleation theory over a wide range of cooling rates. The proposed technique provides a unique and efficient way to examine nucleation kinetics with cooling rates over several orders of magnitude. The technique is quite general and can be used to evaluate reaction kinetics in other materials

  2. SYNTHESIS AND STRUCTURE OF BIS(PHENYLTETRAMETHYLCYCLOPENTADIENYL)TITANIUM(III) HYDRIDE - THE FIRST MONOMERIC BIS(CYCLOPENTADIENYL)TITANIUM(III) HYDRIDE : The First Monomeric Bis(cyclopentadienyl)titanium(III) Hydride

    NARCIS (Netherlands)

    de Wolf, J.M.; Meetsma, A.; Teuben, J.H

    1995-01-01

    The first structurally characterized monomeric bis(cyclopentadienyl)titanium(III) hydride, (C(5)PhMe(4))(2)TiH (4), was synthesized by hydrogenolysis of (C(5)PhMe(4))(2)TiMe (5). Hydride 4 was found to be a monomeric bent sandwich by X-ray diffraction methods, and the pentamethylcyclopentadienyl

  3. Development of delayed hydride cracking resistant-pressure tube

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Young Suk; Kwon, Sang Chul; Kim, S. S.; Yim, K. S

    2000-10-01

    For the first time, we demonstrate that the pattern of nucleation and growth of a DHC crack is governed by the precipitation of hydrides so that the DHC velocity and K{sub IH} are determined by an angle of the cracking plane and the hydride habit plane 10.7. Since texture controls the distribution of the 10.7 habit plane in Zr-2.5Nb pressure tube, we draw a conclusion that a textural change in Zr-2.5Nb tube from a strong tangential texture to the radial texture shall increase the threshold stress intensity factor, K{sub IH}, and decrease the delayed hydride cracking velocity. This conclusion is also verified by a complimentary experiment showing a linear dependence of DHCV and K{sub IH} with an increase in the basal component in the cracking plane. On the basis of the study on the DHC mechanism and the effect of manufacturing processes on the properties of Zr-2.5Nb tube, we have established a manufacturing procedure to make pressure tubes with improved DHC resistance. The main features of the established manufacturing process consist in the two step-cold pilgering process and the intermediate heat treatment in the {alpha} + {beta} phase for Zr-2.5Nb alloy and in the {alpha} phase for Zr-1Nb-1.2Sn-0.4Fe alloy. The manufacturing of DHC resistant-pressure tubes of Zr-2.5Nb and Zr-1N-1.2Sn-0.4Fe was made in the ChMP zirconium plant in Russia under a joint research with Drs. Nikulina and Markelov in VNIINM (Russia). Zr-2.5Nb pressure tube made with the established manufacturing process has met all the specification requirements put by KAERI. Chracterization tests have been jointly conducted by VNIINM and KAERI. As expected, the Zr-2.5Nb tube made with the established procedure has improved DHC resistance compared to that of CANDU Zr-2.5Nb pressure tube used currently. The measured DHC velocity of the Zr-2.5Nb tube meets the target value (DHCV <5x10{sup -8} m/s) and its other properties also were equivalent to those of the CANDU Zr-2.5Nb tube used currently. The Zr-1Nb-1

  4. The electrochemical impedance of metal hydride electrodes

    DEFF Research Database (Denmark)

    Valøen, Lars Ole; Lasia, Andrzej; Jensen, Jens Oluf

    2002-01-01

    The electrochemical impedance responses for different laboratory type metal hydride electrodes were successfully modeled and fitted to experimental data for AB5 type hydrogen storage alloys as well as one MgNi type electrode. The models fitted the experimental data remarkably well. Several AC......, explaining the experimental impedances in a wide frequency range for electrodes of hydride forming materials mixed with copper powder, were obtained. Both charge transfer and spherical diffusion of hydrogen in the particles are important sub processes that govern the total rate of the electrochemical...... hydrogen absorption/desorption reaction. To approximate the experimental data, equations describing the current distribution in porous electrodes were needed. Indications of one or more parallel reduction/oxidation processes competing with the electrochemical hydrogen absorption/desorption reaction were...

  5. Hydrides and Borohydrides of Light Elements

    Science.gov (United States)

    1947-12-04

    Troy, Attn: Inst. of Naval Science (30) Solar Aircraft Cu,, San Diego, Attn: Dr. M. A. Williamson " (31) INSMAT. N. J. for Itandard Oil Co., Esso Lab...with the other# iLD F.Re p. 8 ilt -ms" #61ggSotod that.. ir addition to thc impurity in the t~y..thr, an impurkty, prosumably aluminum hydride, in

  6. Facile Synthesis of Permethyl Yttrocene Hydride

    NARCIS (Netherlands)

    Haan, Klaas H. den; Teuben, Jan H.

    1984-01-01

    A convenient three step synthesis of (Cp*2YH)n (Cp* = C5Me5) is described starting with YCl3.3thf, in which Cp*2YCl.thf and Cp*2YCH(SiMe3)2 are intermediates, which could be isolated and characterized. The hydride is active in the activation of sp2 and sp3 C-H bonds as was demonstrated by the H-D

  7. HYDRIDE-RELATED DEGRADATION OF SNF CLADDING UNDER REPOSITORY CONDITIONS

    International Nuclear Information System (INIS)

    McCoy, K.

    2000-01-01

    The purpose and scope of this analysis/model report is to analyze the degradation of commercial spent nuclear fuel (CSNF) cladding under repository conditions by the hydride-related metallurgical processes, such as delayed hydride cracking (DHC), hydride reorientation and hydrogen embrittlement, thereby providing a better understanding of the degradation process and clarifying which aspects of the process are known and which need further evaluation and investigation. The intended use is as an input to a more general analysis of cladding degradation

  8. Atomistic modeling of zirconium hydride precipitation: methodology for deriving a tight-binding potential

    International Nuclear Information System (INIS)

    Dufresne, Alice

    2014-01-01

    The zirconium-hydrogen system is of nuclear safety interest, as the hydride precipitation leads to the cladding embrittlement, which is made of zirconium-based alloys. The cladding is the first safety barrier confining the radioactive products: its integrity shall be kept during the entire fuel-assemblies life, in reactor, including accidental situation, and post-operation (transport and storage). Many uncertainties remain regarding the hydrides precipitation kinetics and the local stress impact on their precipitation. The atomic scale modeling of this system would bring clarifications on the relevant mechanisms. The usual atomistic modeling methods are based on thermo-statistic approaches, whose precision and reliability depend on the interatomic potential used. However, there was no potential allowing a rigorous study of the Zr-H system. The present work has indeed addressed this issue: a new tight-binding potential for zirconium hydrides modeling is now available. Moreover, this thesis provides a detailed manual for deriving such potentials accounting for spd hybridization, and fitted here on DFT results. This guidebook has be written in light of modeling a pure transition metal followed by a metal-covalent coupling (metallic carbides, nitrides and silicides). (author)

  9. Investigation of the thermodynamics governing metal hydride synthesis in the molten state process

    International Nuclear Information System (INIS)

    Stowe, Ashley C.; Berseth, Polly A.; Farrell, Thomas P.; Laughlin, Laura; Anton, Donald; Zidan, Ragaiy

    2008-01-01

    This work is aimed at utilizing a new synthetic technique to form novel complex hydrides for hydrogen storage. This technique is based on fusing different complex hydrides at elevated temperatures and pressures to form new species with improved hydrogen storage properties. Under conditions of elevated hydrogen overpressures and temperatures the starting materials can reach melting or near-melting point without decomposing (molten state processing), allowing for enhanced diffusion and exchange of elements among the starting materials. The formation and stabilization of these compounds, using the molten state process, is driven by the thermodynamic and kinetic properties of the starting and resulting compounds. Complex hydrides (e.g. NaK 2 AlH 6 , Mg(AlH 4 ) 2 ) were formed, structurally characterized and their hydrogen desorption properties were tested. In this paper we report on investigations of the thermodynamic aspects governing the process and products. We also report on the role of molar ratio in determining the final products. The effectiveness of the molten state process is compared with chemomechanical synthetic methods (ball milling)

  10. Ultrapure hydrogen thermal compressor based on metal hydrides for fuel cells and hybrid vehicles

    International Nuclear Information System (INIS)

    Almasan, V.; Biris, A.; Coldea, I.; Lupu, D.; Misan, I.; Popeneciu, G.; Ardelean, O.

    2007-01-01

    Full text: In hydrogen economy, efficient compressors are indispensable elements in the storage, transport and distribution of the produced hydrogen. Energetic efficient technologies can contribute to H 2 pipelines transport to the point of use and to distribute H 2 by refuelling stations. Characteristic for metal hydrides systems is the wide area of possibilities to absorb hydrogen at low pressure from any source of hydrogen, to store and deliver it hydrogen at high pressure (compression ratio more than 30). On the basis of innovative concepts and advanced materials for H 2 storage/compression (and fast thermal transfer), a fast mass (H 2 ) and heat transfer unit will be developed suitable to be integrated in a 3 stage thermal compressor. Metal hydrides used for a three stage hydrogen compression system must have different equilibrium pressures, namely: for stage 1, low pressure H 2 absorption and resistant to poisoning with impurities of hydrogen, for stage 2, medium pressure H 2 absorption and for stage 3, high pressure hydrogen delivery (120 bar). In the case of compression device based on metallic hydrides the most important properties are the hydrogen absorption/desorption rate, a smaller process enthalpy and a great structural stability on long term hydrogen absorption/desorption cycling. These properties require metal hydrides with large differences between the hydrogen absorption and desorption pressures at equilibrium, within a rather small temperature range. The main goal of this work is to search and develop metal hydride integrated systems for hydrogen purification, storage and compression. After a careful screening three hydrogen absorbing alloys will be selected. After selection, the work up of the alloys composition on the bases of detailed solid state studies, new multi-component alloys will be developed, with suitable thermodynamic and kinetic properties for a hydrogen compressor. The results of the study are the following: new types of hydrogen

  11. Influence of titanium oxide films on copper nucleation during electrodeposition

    International Nuclear Information System (INIS)

    Chang, Hyun K.; Choe, Byung-Hak; Lee, Jong K.

    2005-01-01

    Copper electrodeposition has an important industrial role because of various interconnects used in electronic devices such as printed wire boards. With an increasing trend in device miniaturization, in demand are void-free, thin copper foils of 10 μm thick or less with a very low surface profile. In accordance, nucleation kinetics of copper was studied with titanium cathodes that were covered with thin, passive oxide films of 2-3 nm. Such an insulating oxide layer with a band gap of 3 eV is supposed to nearly block charge transfer from the cathode to the electrolyte. However, significant nucleation rates of copper were observed. Pipe tunneling mechanism along a dislocation core is reasoned to account for the high nucleation kinetics. A dislocation core is proposed to be a high electron tunneling path with a reduced energy barrier and a reduced barrier thickness. In supporting the pipe tunneling mechanism, both 'in situ' and 'ex situ' scratch tests were performed to introduce extra dislocations into the cathode surface, that is, more high charge paths via tunneling, before electrodeposition

  12. Heterogeneous Nucleation and Growth of Nanoparticles at Environmental Interfaces.

    Science.gov (United States)

    Jun, Young-Shin; Kim, Doyoon; Neil, Chelsea W

    2016-09-20

    Mineral nucleation is a phase transformation of aqueous components to solids with an accompanying creation of new surfaces. In this evolutional, yet elusive, process, nuclei often form at environmental interfaces, which provide remarkably reactive sites for heterogeneous nucleation and growth. Naturally occurring nucleation processes significantly contribute to the biogeochemical cycles of important components in the Earth's crust, such as iron and manganese oxide minerals and calcium carbonate. However, in recent decades, these cycles have been significantly altered by anthropogenic activities, which affect the aqueous chemistry and equilibrium of both surface and subsurface systems. These alterations can trigger the dissolution of existing minerals and formation of new nanoparticles (i.e., nucleation and growth) and consequently change the porosity and permeability of geomedia in subsurface environments. Newly formed nanoparticles can also actively interact with components in natural and engineered aquatic systems, including those posing a significant hazard such as arsenic. These interactions can bilaterally influence the fate and transport of both newly formed nanoparticles and aqueous components. Due to their importance in natural and engineered processes, heterogeneous nucleation at environmental interfaces has started to receive more attention. However, a lack of time-resolved in situ analyses makes the evaluation of heterogeneous nucleation challenging because the physicochemical properties of both the nuclei and surfaces significantly and dynamically change with time and aqueous chemistry. This Account reviews our in situ kinetic studies of the heterogeneous nucleation and growth behaviors of iron(III) (hydr)oxide, calcium carbonate, and manganese (hydr)oxide minerals in aqueous systems. In particular, we utilized simultaneous small-angle and grazing incidence small-angle X-ray scattering (SAXS/GISAXS) to investigate in situ and in real-time the effects of

  13. Nuclear fragmentation by nucleation approach

    International Nuclear Information System (INIS)

    Chung, K.C.

    1992-01-01

    The nucleation model is used to simulate nuclear fragmentation processes. The critical value of the effective interaction radius is shown to vary linearly with the expansion factor α. The calculated mass and charge distributions are compared with some experimental data. (author)

  14. Effect of an Excess of Chromium and Hydriding on Zircaloy-4

    International Nuclear Information System (INIS)

    Soldati, A.; Ghilarducci, A. A; Corso, H.L.; Peretti, H.A.; Bolcich, J.C

    2003-01-01

    Results of mechanical properties and microstructure morphologies of zircaloy-4 are presented.They were obtained in several laboratory made samples of chemical composition modified with respect to the ASTM B 350 by the addition of alloying elements as well as hydrides.This work is focused mainly on the effect of 900 ppm of additional Cr in excess as compared with the standard composition alloy and with two other laboratory alloys studied before, containing 250 ppm of Ni in excess and 1000 ppm of Fe in excess, respectively.The study is carried out by means of tensile tests at room temperature and at 240C, hardness tests, SEM observations and EDS microanalysis.The neutron irradiation was carried out at Bariloche in the RA6-CNEA reactor.The results indicate that precipitates concentrate along grain boundaries in all cases, and that for higher contents of alloying elements corresponds a higher quantity of precipitates and smaller grain sizes.Except for the hydrided sample, the fracture is ductile with cavities nucleated at precipitates

  15. The nature of γ-hydride in crept zirconium single crystals

    International Nuclear Information System (INIS)

    Akhtar, A.

    1977-01-01

    Single crystals prepared from crystal bar zirconium have been subjected to uniaxial tensile-creep under a vacuum of 10 -4 Pa for 160 h. Transmission electron microscopy of crept crystals has revealed the presence of thin fct γ-zirconium hydride platelets lying parallel to (1100) planes and elongated along the [1120]sub(α) direction. The platelets maintain the following lattice relationship with the hcp (α) matrix: [1120]sub(α)//[110]sub(γ), (0001)sub(α)//(001)sub(γ). This relationship is different from that obtained for needle γ-hydride generally observed in quenched samples. Lattice misfit calculations indicate that the platelets have a large positive misfit normal to the plane of the disc and a small misfit in the plane of the disc, which remains parallel to (1010)sub(α). Displacement fringe contrast is observed inside the platelets under conditions consistent with the lattice misfit. It is proposed that the nucleation of these precipitates occurs at stacking faults in the presence of applied stress. (Auth.)

  16. Spectrophotometric determination of volautile inorganic hydrides in binary gaseous mixtures

    International Nuclear Information System (INIS)

    Rezchikov, V.G.; Skachkova, I.N.; Kuznetsova, T.S.; Khrushcheva, V.V.

    1985-01-01

    A study was made on possibility of single and continuons analysis of binary mixtures (hydride-gas) for the content of volatile inorganic hydrides (VIH) from absorption spectra in the 185-280 nm band. Dependences of the percentage of VIH transmission on the wavelength are presented. It is shown that the maximum of their absorption depends on the element-hydrogen the bond length and binding energy. Detection limit for boron hydride was established to be n x 10 -3 % vol at 185-190 nm wavelength. Technique for spectrophotometric hydride determination in binary mixtures with hydrogen, argon, helium was developed. The technique provides the continuous control of gaseous mixture composition

  17. Identification of the zirconium hydrides metallography in zircaloy-2

    International Nuclear Information System (INIS)

    Garcia Gonzalez, F.

    1968-01-01

    Technique for the Identification of the zirconium hydrides in metallographic specimens have been developed. Microhardness, quantitative estimation and relative orientation of the present hydrides as well as grain size determination of the different Zircaloy-2 tube specimens have also been made. The specimens used were corrosion- tested in water during various periods of time at 300 degree castrating, prior to the metallographic examination. Reference specimens, as received, and heavily hydride specimens in a hydrogen atmosphere at 800 degree centigrees, have been used in the previous stages of the work. No difficulties have been met in this early stage of acquaintanceship with the zirconium hydrides. (Author) 5 refs

  18. Nucleation, growth and transport modelling of helium bubbles under nuclear irradiation in lead–lithium with the self-consistent nucleation theory and surface tension corrections

    International Nuclear Information System (INIS)

    Fradera, J.; Cuesta-López, S.

    2013-01-01

    Highlights: • The work presented in this manuscript provides a reliable computational tool to quantify the He complex phenomena in a HCLL. • A model based on the self-consistent nucleation theory (SCT) is exposed. It includes radiation induced nucleation modelling and surface tension corrections. • Results informed reinforce the necessity of conducting experiments to determine nucleation conditions and bubble transport parameters in LM breeders. • Our findings and model provide a good qualitative insight into the helium nucleation phenomenon in LM systems for fusion technology and can be used to identify key system parameters. -- Abstract: Helium (He) nucleation in liquid metal breeding blankets of a DT fusion reactor may have a significant impact regarding system design, safety and operation. Large He production rates are expected due to tritium (T) fuel self-sufficiency requirement, as both, He and T, are produced at the same rate. Low He solubility, local high concentrations, radiation damage and fluid discontinuities, among other phenomena, may yield the necessary conditions for He nucleation. Hence, He nucleation may have a significant impact on T inventory and may lower the T breeding ratio. A model based on the self-consistent nucleation theory (SCT) with a surface tension curvature correction model has been implemented in OpenFOAM ® CFD code. A modification through a single parameter of the necessary nucleation condition is proposed in order to take into account all the nucleation triggering phenomena, specially radiation induced nucleation. Moreover, the kinetic growth model has been adapted so as to allow for the transition from a critical cluster to a macroscopic bubble with a diffusion growth process. Limitations and capabilities of the models are shown by means of zero-dimensional simulations and sensitivity analyses to key parameters under HCLL breeding unit conditions. Results provide a good qualitative insight into the helium nucleation

  19. Nucleation, growth and transport modelling of helium bubbles under nuclear irradiation in lead–lithium with the self-consistent nucleation theory and surface tension corrections

    Energy Technology Data Exchange (ETDEWEB)

    Fradera, J., E-mail: jfradera@ubu.es; Cuesta-López, S., E-mail: scuesta@ubu.es

    2013-12-15

    Highlights: • The work presented in this manuscript provides a reliable computational tool to quantify the He complex phenomena in a HCLL. • A model based on the self-consistent nucleation theory (SCT) is exposed. It includes radiation induced nucleation modelling and surface tension corrections. • Results informed reinforce the necessity of conducting experiments to determine nucleation conditions and bubble transport parameters in LM breeders. • Our findings and model provide a good qualitative insight into the helium nucleation phenomenon in LM systems for fusion technology and can be used to identify key system parameters. -- Abstract: Helium (He) nucleation in liquid metal breeding blankets of a DT fusion reactor may have a significant impact regarding system design, safety and operation. Large He production rates are expected due to tritium (T) fuel self-sufficiency requirement, as both, He and T, are produced at the same rate. Low He solubility, local high concentrations, radiation damage and fluid discontinuities, among other phenomena, may yield the necessary conditions for He nucleation. Hence, He nucleation may have a significant impact on T inventory and may lower the T breeding ratio. A model based on the self-consistent nucleation theory (SCT) with a surface tension curvature correction model has been implemented in OpenFOAM{sup ®} CFD code. A modification through a single parameter of the necessary nucleation condition is proposed in order to take into account all the nucleation triggering phenomena, specially radiation induced nucleation. Moreover, the kinetic growth model has been adapted so as to allow for the transition from a critical cluster to a macroscopic bubble with a diffusion growth process. Limitations and capabilities of the models are shown by means of zero-dimensional simulations and sensitivity analyses to key parameters under HCLL breeding unit conditions. Results provide a good qualitative insight into the helium

  20. Behavior and failure of uniformly hydrided Zircaloy-4 fuel claddings between 25 C and 480 C under various stress states, including RIA loading conditions

    International Nuclear Information System (INIS)

    Le Saux, M.; Carassou, S.; Averty, X.; Le Saux, M.; Besson, J.; Poussard, C.

    2010-01-01

    The anisotropic plastic behavior and the fracture of as-received and hydrided Cold-Worked Stress Relieved Zircaloy-4 cladding tubes are investigated under thermal-mechanical loading conditions representative of Pellet-Clad Mechanical Interaction during Reactivity Initiated Accidents in Pressurized Water Reactors. In order to study the combined effects of temperature, hydrogen content, loading direction and stress state, Axial Tensile, Hoop Tensile, Expansion Due to Compression and hoop Plane Strain Tensile tests are performed at room temperature, 350 C and 480 C on the material containing various hydrogen contents up to 1200 wt. ppm (hydrides are circumferential and homogeneously distributed). These tests are combined with digital image correlation and metallographic and fractographic observations at different scales. The flow stress of the material decreases with increasing temperature. The material is either strengthened or softened by hydrogen depending on temperature and hydrogen content. Plastic anisotropy depends on temperature but not on hydrogen content. The ductility of the material decreases with increasing hydrogen content at room temperature due to damage nucleation by hydride cracking. The plastic strain that leads to hydride fracture at room temperature decreases with increasing hydrogen content. The influence of stress triaxiality on hydride cracking is negligible in the studied range. The influence of hydrogen on material ductility is negligible at 350 C and 480 C since hydrides do not crack at these temperatures. The ductility of the material increases with increasing temperature. The evolution of material ductility is associated with a change in both the macroscopic fracture mode of the specimens and the microscopic failure mechanisms. (authors)

  1. Alloys for hydrogen storage in nickel/hydrogen and nickel/metal hydride batteries

    Science.gov (United States)

    Anani, Anaba; Visintin, Arnaldo; Petrov, Konstantin; Srinivasan, Supramaniam; Reilly, James J.; Johnson, John R.; Schwarz, Ricardo B.; Desch, Paul B.

    1993-01-01

    Since 1990, there has been an ongoing collaboration among the authors in the three laboratories to (1) prepare alloys of the AB(sub 5) and AB(sub 2) types, using arc-melting/annealing and mechanical alloying/annealing techniques; (2) examine their physico-chemical characteristics (morphology, composition); (3) determine the hydrogen absorption/desorption behavior (pressure-composition isotherms as a function of temperature); and (4) evaluate their performance characteristics as hydride electrodes (charge/discharge, capacity retention, cycle life, high rate capability). The work carried out on representative AB(sub 5) and AB(sub 2) type modified alloys (by partial substitution or with small additives of other elements) is presented. The purpose of the modification was to optimize the thermodynamics and kinetics of the hydriding/dehydriding reactions and enhance the stabilities of the alloys for the desired battery applications. The results of our collaboration, to date, demonstrate that (1) alloys prepared by arc melting/annealing and mechanical alloying/annealing techniques exhibit similar morphology, composition and hydriding/dehydriding characteristics; (2) alloys with the appropriate small amounts of substituent or additive elements: (1) retain the single phase structure, (2) improve the hydriding/dehydriding reactions for the battery applications, and (3) enhance the stability in the battery environment; and (3) the AB(sub 2) type alloys exhibit higher energy densities than the AB(sub 5) type alloys but the state-of-the-art, commercialized batteries are predominantly manufactured using Ab(sub 5) type alloys.

  2. Ice nucleation properties of mineral dusts

    OpenAIRE

    Steinke, Isabelle

    2013-01-01

    Ice nucleation in clouds has a significant impact on the global hydrological cycle as well as on the radiative budget of the Earth. The AIDA cloud chamber was used to investigate the ice nucleation efficiency of various atmospherically relevant mineral dusts. From experiments with Arizona Test Dust (ATD) a humidity and temperature dependent ice nucleation active surface site density parameterization was developed to describe deposition nucleation at temperatures above 220 K. Based...

  3. Nucleation in Polymers and Soft Matter

    Science.gov (United States)

    Xu, Xiaofei; Ting, Christina L.; Kusaka, Isamu; Wang, Zhen-Gang

    2014-04-01

    Nucleation is a ubiquitous phenomenon in many physical, chemical, and biological processes. In this review, we describe recent progress on the theoretical study of nucleation in polymeric fluids and soft matter, including binary mixtures (polymer blends, polymers in poor solvents, compressible polymer-small molecule mixtures), block copolymer melts, and lipid membranes. We discuss the methodological development for studying nucleation as well as novel insights and new physics obtained in the study of the nucleation behavior in these systems.

  4. Mechanistic aspects of dinitrogen cleavage and hydrogenation to produce ammonia in catalysis and organometallic chemistry: relevance of metal hydride bonds and dihydrogen.

    Science.gov (United States)

    Jia, Hong-Peng; Quadrelli, Elsje Alessandra

    2014-01-21

    Dinitrogen cleavage and hydrogenation by transition-metal centers to produce ammonia is central in industry and in Nature. After an introductory section on the thermodynamic and kinetic challenges linked to N2 splitting, this tutorial review discusses three major classes of transition-metal systems (homogeneous, heterogeneous and biological) capable of achieving dissociation and hydrogenation of dinitrogen. Molecular complexes, solid-state Haber-Bosch catalytic systems, silica-supported tantalum hydrides and nitrogenase will be discussed. Emphasis is focused on the reaction mechanisms operating in the process of dissociation and hydrogenation of dinitrogen, and in particular on the key role played by metal hydride bonds and by dihydrogen in such reactions.

  5. Homogeneous nucleation of water in synthetic air

    NARCIS (Netherlands)

    Fransen, M.A.L.J.; Sachteleben, E.; Hruby, J.; Smeulders, D.M.J.; DeMott, P.J.; O'Dowd, C.D.

    2013-01-01

    Homogeneous nucleation rates for water vapor in synthetic air are measured by means of a Pulse-Expansion Wave Tube (PEWT). A comparison of the experimental nucleation rates with the Classical Nucleation Theory (CNT) shows that a more elaborated model is necessary to describe supercooled water

  6. A classical view on nonclassical nucleation

    NARCIS (Netherlands)

    Smeets, P.J.M.; Finney, A.R.; Habraken, W.J.E.M.; Nudelman, F.; Friedrich, H.; Laven, J.; De Yoreo, J.J.; Rodger, P.M.; Sommerdijk, N.A.J.M.

    2017-01-01

    Understanding and controlling nucleation is important for many crystallization applications. Calcium carbonate (CaCO3) is often used as a model system to investigate nucleation mechanisms. Despite its great importance in geology, biology, and many industrial applications, CaCO3 nucleation is still a

  7. Numerical Simulation of the Kinetic Critical Nucleus

    OpenAIRE

    Sanada, Masaaki; Nishioka, Kazumi; Okada, Masahumi; Maksimov, Igor, L.

    1997-01-01

    Our main interest is to see whether the number density indicates a peak at the kinetically stable critical nucleus due to its kinetical stability. We have numerically calculated the time evolution of the number densities of clusters in the case of water vapor nucleation. We employ the condition in which the difference between the size of the thermodynamic crtitical nucleus and that of the kinetic one is appreciable. The results show that the peak does not appear in the number densities of clu...

  8. Effect of amorphous Mg50Ni50 on hydriding and dehydriding behavior of Mg2Ni alloy

    International Nuclear Information System (INIS)

    Guzman, D.; Ordonez, S.; Fernandez, J.F.; Sanchez, C.; Serafini, D.; Rojas, P.A.; Aguilar, C.; Tapia, P.

    2011-01-01

    Composite Mg 2 Ni (25 wt.%) amorphous Mg 50 Ni 50 was prepared by mechanical milling starting with nanocrystalline Mg 2 Ni and amorphous Mg 50 Ni 50 powders, by using a SPEX 8000 D mill. The morphological and microstructural characterization of the powders was performed via scanning electron microscopy and X-ray diffraction. The hydriding characterization of the composite was performed via a solid gas reaction method in a Sievert's-type apparatus at 363 K under an initial hydrogen pressure of 2 MPa. The dehydriding behavior was studied by differential thermogravimetry. On the basis of the results, it is possible to conclude that amorphous Mg 50 Ni 50 improved the hydriding and dehydriding kinetics of Mg 2 Ni alloy upon cycling. A tentative rationalization of experimental observations is proposed. - Research Highlights: → First study of the hydriding behavior of composite Mg 2 Ni (25 wt.%) amorphous Mg 50 Ni 50 . → Microstructural characterization of composite material using XRD and SEM was obtained. → An improved effect of Mg 50 Ni 50 on the Mg 2 Ni hydriding behavior was verified. → The apparent activation energy for the hydrogen desorption of composite was obtained.

  9. Transformation kinetics for nucleus clusters

    International Nuclear Information System (INIS)

    Villa, Elena; Rios, Paulo R.

    2009-01-01

    A rigorous mathematical approach based on stochastic geometry concepts is presented to extend previous Johnson-Mehl, Avrami, Kolmogorov treatment of transformation kinetics to situations in which nuclei are not homogeneously located in space but are located in clusters. An exact analytical solution is presented here for the first time assuming that nucleation sites follow a Matern cluster process. The influence of Matern cluster process parameters on subsequent growth kinetics and the microstructural path are illustrated by means of numerical examples. Moreover, using the superposition principle, exact analytical solutions are also obtained when nucleation takes place by a combination of a Matern cluster process and an inhomogeneous Poisson point process. The new solutions presented here significantly increase the number of exactly solvable cases available to formal kinetics.

  10. The kinetics of hydrogen removal from liquid sodium

    International Nuclear Information System (INIS)

    Gwyther, J.R.; Whittingham, A.C.

    1981-01-01

    The rates of hydrogen removal from liquid sodium-sodium hydride mixtures have been measured as a function of sodium stirring rate at temperatures up to 420 0 C. Two techniques have been employed - removal under continuous evacuation in which hydrogen flow rates were measured using a capillary flow technique and by argon purging in which hydrogen concentrations in the argon carrier gas were measured by gas chromatography. The results have been used to assess the feasibility of thermal decomposition of sodium hydride for the regeneration of hydride-laden LMFBR cold traps. Studies on the kinetics of desorption of hydrogen from solution in liquid sodium at temperatures up to 400 0 C are also presented and possible kinetic mechanisms discussed. (orig.)

  11. Atomistic simulation of hydrogen dynamics near dislocations in vanadium hydrides

    International Nuclear Information System (INIS)

    Ogawa, Hiroshi

    2015-01-01

    Highlights: • Hydrogen–dislocation interaction was simulated by molecular dynamics method. • Different distribution of H atoms were observed at edge and screw dislocation. • Planner distribution of hydrogen may be caused by partialized edge dislocation. • Hydrogen diffusivity was reduced in both edge and screw dislocation models. • Pipe diffusion was observed for edge dislocation but not for screw dislocation. - Abstract: Kinetics of interstitial hydrogen atoms near dislocation cores were analyzed by atomistic simulation. Classical molecular dynamics method was applied to model structures of edge and screw dislocations in α-phase vanadium hydride. Simulation showed that hydrogen atoms aggregate near dislocation cores. The spatial distribution of hydrogen has a planner shape at edge dislocation due to dislocation partialization, and a cylindrical shape at screw dislocation. Simulated self-diffusion coefficients of hydrogen atoms in dislocation models were a half- to one-order lower than that of dislocation-free model. Arrhenius plot of self-diffusivity showed slightly different activation energies for edge and screw dislocations. Directional dependency of hydrogen diffusion near dislocation showed high and low diffusivity along edge and screw dislocation lines, respectively, hence so called ‘pipe diffusion’ possibly occur at edge dislocation but does not at screw dislocation

  12. Unloading Effect on Delayed Hydride Cracking in Zirconium Alloys

    International Nuclear Information System (INIS)

    Kim, Young Suk; Kim, Sung Soo

    2010-01-01

    It is well-known that a tensile overload retards not only the crack growth rate (CGR) in zirconium alloys during the delayed hydride cracking (DHC) tests but also the fatigue crack growth rate in metals, the cause of which is unclear to date. A considerable decrease in the fatigue crack growth rate due to overload is suggested to occur due either to the crack closure or to compressive stresses or strains arising from unloading of the overload. However, the role of the crack closure or the compressive stress in the crack growth rate remains yet to be understood because of incomplete understanding of crack growth kinetics. The aim of this study is to resolve the effect of unloading on the CGR of zirconium alloys, which comes in last among the unresolved issues as listed above. To this end, the CGRs of the Zr-2.5Nb tubes were determined at a constant temperature under the cyclic load with the load ratio, R changing from 0.13 to 0.66 where the extent of unloading became higher at the lower R. More direct evidence for the effect of unloading after an overload is provided using Simpson's experiment investigating the effect on the CGR of a Zr-2.5Nb tube of the stress states of the prefatigue crack tip by unloading or annealing after the formation of a pre-fatigue crack

  13. Hydrogen storage in the form of metal hydrides

    Science.gov (United States)

    Zwanziger, M. G.; Santana, C. C.; Santos, S. C.

    1984-01-01

    Reversible reactions between hydrogen and such materials as iron/titanium and magnesium/ nickel alloy may provide a means for storing hydrogen fuel. A demonstration model of an iron/titanium hydride storage bed is described. Hydrogen from the hydride storage bed powers a converted gasoline electric generator.

  14. Pyrophoric behaviour of uranium hydride and uranium powders

    Science.gov (United States)

    Le Guyadec, F.; Génin, X.; Bayle, J. P.; Dugne, O.; Duhart-Barone, A.; Ablitzer, C.

    2010-01-01

    Thermal stability and spontaneous ignition conditions of uranium hydride and uranium metal fine powders have been studied and observed in an original and dedicated experimental device placed inside a glove box under flowing pure argon. Pure uranium hydride powder with low amount of oxide (Oxidation mechanisms are proposed.

  15. Electrocatalytic hydride-forming compounds for rechageable batteries

    NARCIS (Netherlands)

    Notten, P.H.L.; Einerhand, R.E.F.

    1991-01-01

    Non-toxic intermetallic hydride-forming compounds are attractive alternatives to cadmium as the negative electrode materials in the new generation of Ni/metal hydride rechargeable batteries. High exchange currents and discharge efficiencies even at low temperatures can be achieved using highly

  16. Ultra-sonic observation in niobium hydride precipitation

    International Nuclear Information System (INIS)

    Florencio, O.; Pinatti, Dyonisio G.

    1982-01-01

    The hidrogen embrittlement of exothermic ocluders, had been considered as due to applied stress induced hydride precipitates leading to brittle fracture. The results of simultaneous measurements of macroscopic deformation and elastic change due to hydride precipitation, using the ultrasonic pulse-echo technique are showed. THen it was tested the possibility of kinectis precipitation parameters evoluation. (Author) [pt

  17. Creating nanoshell on the surface of titanium hydride bead

    Directory of Open Access Journals (Sweden)

    PAVLENKO Vyacheslav Ivanovich

    2016-12-01

    Full Text Available The article presents data on the modification of titanium hydride bead by creating titanium nanoshell on its surface by ion-plasma vacuum magnetron sputtering. To apply titanium nanoshell on the titanium hydride bead vacuum coating plant of multifunctional nanocomposite coatings QVADRA 500 located in the center of high technology was used. Analysis of the micrographs of the original surface of titanium hydride bead showed that the microstructure of the surface is flat, smooth, in addition the analysis of the microstructure of material surface showed the presence of small porosity, roughness, mainly cavities, as well as shallow longitudinal cracks. The presence of oxide film in titanium hydride prevents the free release of hydrogen and fills some micro-cracks on the surface. Differential thermal analysis of both samples was conducted to determine the thermal stability of the initial titanium hydride bead and bead with applied titanium nanoshell. Hydrogen thermal desorption spectra of the samples of the initial titanium hydride bead and bead with applied titanium nanoshell show different thermal stability of compared materials in the temperature range from 550 to 860о C. Titanium nanoshells applied in this way allows increasing the heat resistance of titanium hydride bead – the temperature of starting decomposition is 695о C and temperature when decomposition finishes is more than 1000о C. Modified in this way titanium hydride bead can be used as a filler in the radiation protective materials used in the construction or upgrading biological protection of nuclear power plants.

  18. Ice nucleation activity of polysaccharides

    Science.gov (United States)

    Bichler, Magdalena; Felgitsch, Laura; Haeusler, Thomas; Seidl-Seiboth, Verena; Grothe, Hinrich

    2015-04-01

    Heterogeneous ice nucleation is an important process in the atmosphere. It shows direct impact on our climate by triggering ice cloud formation and therefore it has much influence on the radiation balance of our planet (Lohmann et al. 2002; Mishchenko et al. 1996). The process itself is not completely understood so far and many questions remain open. Different substances have been found to exhibit ice nucleation activity (INA). Due to their vast differences in chemistry and morphology it is difficult to predict what substance will make good ice nuclei and which will not. Hence simple model substances must be found and be tested regarding INA. Our work aims at gaining to a deeper understanding of heterogeneous ice nucleation. We intend to find some reference standards with defined chemistry, which may explain the mechanisms of heterogeneous ice nucleation. A particular focus lies on biological carbohydrates in regards to their INA. Biological carbohydrates are widely distributed in all kingdoms of life. Mostly they are specific for certain organisms and have well defined purposes, e.g. structural polysaccharides like chitin (in fungi and insects) and pectin (in plants), which has also water-binding properties. Since they are widely distributed throughout our biosphere and mostly safe to use for nutrition purposes, they are well studied and easily accessible, rendering them ideal candidates as proxies. In our experiments we examined various carbohydrates, like the already mentioned chitin and pectin, as well as their chemical modifications. Lohmann U.; A Glaciation Indirect Aerosol Effect Caused by Soot Aerosols; J. Geoph. Res.; Vol. 24 No.4; pp 11-1 - 11-4; 2002 Mishchenko M.I., Rossow W.B., Macke A., Lacis A. A.; Sensitivity of Cirrus Cloud Albedo, Bidirectional Reflectance and Optical Thickness Retrieval Accuracy to Ice Particle Shape, J. Geoph. Res.; Vol. 101, No D12; pp. 16,973 - 16,985; 1996

  19. Revision of nucleated boiling mechanisms

    International Nuclear Information System (INIS)

    Converti, J.; Balino, J.L.

    1987-01-01

    The boiling occurrence plays an important role in the power reactors energy transfer. But still, there is not a final theory on the boiling mechanisms. This paper presents a critical analysis of the most important nucleated boiling models that appear in literature. The conflicting points are identified and experiments are proposed to clear them up. Some of these experiments have been performed at the Thermohydraulics laboratory (Bariloche Atomic Center). (Author)

  20. Mechanisms of nucleation in flashing flows

    International Nuclear Information System (INIS)

    Yan, F.; Giot, M.

    1989-01-01

    The mechanisms of nucleation have been analysed. Starting from the assumption that the activation of micro-cavities in the wall surfaces is the most probable nucleation mechanism in practical flashing system, the authors study in detail the nucleation in a micro-cavity. A three step nucleation criterion is proposed, namely: trapping cavity, activable cavity and active cavity. Then, a new nucleation model is presented. The output of the model is the prediction of the bubble departure frequency versus the thermodynamic state of the liquid and the geometry of the cavity. The model can also predict the nucleation site density if the nature of the wall and the surface roughness are know. The prediction have been successfully compared with some preliminary experimental results. By combining the present model with Jones'theory, the flashing inception is correctly predicted. The use of this nucleation model for the complete modelling of a flashing non-equilibrium flow is in progress

  1. Preferred hydride growth orientations on oxide-coated gadolinium surfaces

    International Nuclear Information System (INIS)

    Benamar, G.M.; Schweke, D.; Kimmel, G.; Mintz, M.H.

    2012-01-01

    Highlights: ► The preferred hydride growth orientations on gadolinium metal coated by a thin oxide layer are presented. ► A preferred growth of the (1 0 0) h plane of the face centered cubic (FCC) GdH 2 is observed for the hydride spots forming below the oxidation layer. ► A change to the (1 1 1) h plane of the cubic hydride dominates for the hydride's Growth Centers. ► The texture change is attributed to the surface normal compressive stress component exerted by the oxidation layer on the developing hydride. - Abstract: The initial development of hydrides on polycrystalline gadolinium (Gd), as on some other hydride forming metals, is characterized by two sequential steps. The first step involves the rapid formation of a dense pattern of small hydride spots (referred to as the “small family” of hydrides) below the native oxidation layer. The second stage takes place when some of the “small family” nucleants (referred to as “growth centers”, GCs) break the oxide layer, leading to their rapid growth and finally to the massive hydriding of the sample. In the present study, the texture of the two hydride families was studied, by combining X-ray diffraction (XRD) analysis with a microscopic analysis of the hydride, using scanning electron microscopy (SEM) and atomic force microscopy (AFM). It has been observed that for the “small family”, a preferred growth of the (1 0 0) h plane of the cubic GdH 2 takes place, whereas for the GCs, a change to the (1 1 1) h plane of the cubic hydride dominates. These preferred growth orientations were analyzed by their structure relation with the (0 0 .1) m basal plane of the Gd metal. It has been concluded that the above texture change is due to the surface normal compressive stress component exerted by the oxidation overlayer on the developing hydride, preventing the (0 0 .1) m ||(1 1 1) h growth orientation. This stress is relieved upon the rupture of that overlayer and the development of the GCs, leading to

  2. Growth and decomposition of Lithium and Lithium hydride on Nickel

    DEFF Research Database (Denmark)

    Engbæk, Jakob; Nielsen, Gunver; Nielsen, Jane Hvolbæk

    2006-01-01

    In this paper we have investigated the deposition, structure and decomposition of lithium and lithium-hydride films on a nickel substrate. Using surface sensitive techniques it was possible to quantify the deposited Li amount, and to optimize the deposition procedure for synthesizing lithium......-hydride films. By only making thin films of LiH it is possible to study the stability of these hydride layers and compare it directly with the stability of pure Li without having any transport phenomena or adsorbed oxygen to obscure the results. The desorption of metallic lithium takes place at a lower...... temperature than the decomposition of the lithium-hydride, confirming the high stability and sintering problems of lithium-hydride making the storage potential a challenge. (c) 2006 Elsevier B.V. All rights reserved....

  3. Minimizing hydride cracking in zirconium alloys

    International Nuclear Information System (INIS)

    Coleman, C.E.; Cheadle, B.A.; Ambler, J.F.R.; Eadie, R.L.

    1985-01-01

    Zirconium alloy components can fail by hydride cracking if they contain large flaws and are highly stressed. If cracking in such components is suspected, crack growth can be minimized by following two simple operating rules: components should be heated up from at least 30K below any operating temperature above 450K, and when the component requires cooling to room temperature from a high temperature, any tensile stress should be reduced as much and as quickly as is practical during cooling. This paper describes the physical basis for these rules

  4. Tritium immobilization and packaging using metal hydrides

    International Nuclear Information System (INIS)

    Holtslander, W.J.; Yaraskavitch, J.M.

    1981-04-01

    Tritium recovered from CANDU heavy water reactors will have to be packaged and stored in a safe manner. Tritium will be recovered in the elemental form, T 2 . Metal tritides are effective compounds in which to immobilize the tritium as a stable non-reactive solid with a high tritium capacity. The technology necessary to prepare hydrides of suitable metals, such as titanium and zirconium, have been developed and the properties of the prepared materials evaluated. Conceptual designs of packages for containing metal tritides suitable for transportation and long-term storage have been made and initial testing started. (author)

  5. Low-frequency excitations in zirconium hydrides

    International Nuclear Information System (INIS)

    Radulescu, A.; Padureanu, I.; Rapeanu, S.N.; Beldiman, A.; Kozlov, Zh.A.; Semenov, V.A.

    1999-01-01

    The slow inelastic neutron scattering (INS) on ZrH x systems (x = 0.38, 0.52) revealed new excitations located within the energy range 2-10 MeV. Besides the acoustic vibrations specific to α-HCP Zr and γ-FCO Zr hydride the fine structure of these excitations is clearly observed. The origin of the new observed peaks is not very clear but a proton tunneling or a resonance effect in α-Zr lattice could be taken into account

  6. Novel hydrogen storage materials: A review of lightweight complex hydrides

    International Nuclear Information System (INIS)

    Jain, I.P.; Jain, Pragya; Jain, Ankur

    2010-01-01

    review article the fundamental understanding of the physical, chemical and structural properties of light weight hydride materials, e.g. Alanates, Borohydrides, Amide Borohydrides, Amide-Imide system, Amineborane and Alane for hydrogen storage has been presented. Lot of details of these materials has been incorporated such as synthesis, crystal structure, thermodynamics and kinetics of hydrogenation-dehydrogenation processes, reversibility and hydrogen storage capacity has been presented.

  7. Hydrides formation In Zircaloy-4 irradiated with neutrons

    International Nuclear Information System (INIS)

    Vizcaino, P; Flores, A V; Vicente Alvarez, M A; Banchik, A.D; Tolley, A; Condo, A; Santisteban, J R

    2012-01-01

    Under reactor operating conditions zirconium components go through transformations which affect their original properties. Two phenomena of significant consequences for the integrity of the components are hydrogen uptake and radiation damage, since both contribute to the material fragilization. In the case of the Atucha I nuclear power reactor, the cooling channels, Zircaloy-4 tubular structural components about 6 meters long, were designed to withstand the entire lifetime of the reactor. Inside them, fuel elements 5.3 meters long are located. The fuel elements are cooled by a heavy water flow which circulates from the bottom (250 o ) to the top of the reactor (305 o C). The channels are affected by a fast neutron flux (En>1 Mev), increasing from a nominal value of 1.35 x 10 13 neutrons/cm 2 sec at the bottom to 1.69 x 10 13 neutrons/cm 2 sec at the top, reaching a maximum value of 3.76 x 10 13 neutrons/cm 2 sec at the center of the channels. However, due to the reactor operating conditions, they are replaced after about 10 effective full power years, time at which they reach 10 22 neutrons/cm 2 at the most neutronically active regions of the reactor. Studies on cooling channels are meaningful from many points of view. The channels are structural components which do not work under internal pressure or any other type of structural stress. The typical temperature of the cladding tubes in the reactor is about 350 o C, at which many types of irradiation defects are annealed [1]. The temperature range of the cooling channels lies between 200 o C-235 o C (outer foil of the channels) and 260 o C-300 o C (internal tube), a difference which makes the defect recovery kinetics slower. In the present context, following the program developed in the research contract 15810, we continue with the work started on the effects of the radiation on the hydride formation focusing on the dislocation loops in the zirconium matrix and its possible role as preferential sites for hydride

  8. Nanoindentation measurements of the mechanical properties of zirconium matrix and hydrides in unirradiated pre-hydrided nuclear fuel cladding

    International Nuclear Information System (INIS)

    Rico, A.; Martin-Rengel, M.A.; Ruiz-Hervias, J.; Rodriguez, J.; Gomez-Sanchez, F.J.

    2014-01-01

    It is well known that the mechanical properties of the nuclear fuel cladding may be affected by the presence of hydrides. The average mechanical properties of hydrided cladding have been extensively investigated from a macroscopic point of view. In addition, the mechanical and fracture properties of bulk hydride samples fabricated from zirconium plates have also been reported. In this paper, Young’s modulus, hardness and yield stress are measured for each phase, namely zirconium hydrides and matrix, of pre-hydrided nuclear fuel cladding. To this end, nanoindentation tests were performed on ZIRLO samples in as-received state, on a hydride blister and in samples with 150 and 1200 ppm of hydrogen homogeneously distributed along the hoop direction of the cladding. The results show that the measured mechanical properties of the zirconium hydrides and ZIRLO matrix (Young’s modulus, hardness and yield stress) are rather similar. From the experimental data, the hydride volume fraction in the cladding samples with 150 and 1200 ppm was estimated and the average mechanical properties were calculated by means of the rule of mixtures. These values were compared with those obtained from ring compression tests. Good agreement between the results obtained by both methods was found

  9. A UNIFIED KINETIC APPROACH TO BINARY NUCLEATION. (R826768)

    Science.gov (United States)

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  10. Nonlinear Dynamics and Nucleation Kinetics in Near-Critical Liquids

    Science.gov (United States)

    Patashinski, Alexander Z.; Ratner, Mark A.; Pines, Vladimir

    1996-01-01

    The objective of our study is to model the nonlinear behavior of a near-critical liquid following a rapid change of the temperature and/or other thermodynamic parameters (pressure, external electric or gravitational field). The thermodynamic critical point is manifested by large, strongly correlated fluctuations of the order parameter (particle density in liquid-gas systems, concentration in binary solutions) in the critical range of scales. The largest critical length scale is the correlation radius r(sub c). According to the scaling theory, r(sub c) increases as r(sub c) = r(sub 0)epsilon(exp -alpha) when the nondimensional distance epsilon = (T - T(sub c))/T(sub c) to the critical point decreases. The normal gravity alters the nature of correlated long-range fluctuations when one reaches epsilon approximately equal to 10(exp -5), and correspondingly the relaxation time, tau(r(sub c)), is approximately equal to 10(exp -3) seconds; this time is short when compared to the typical experimental time. Close to the critical point, a rapid, relatively small temperature change may perturb the thermodynamic equilibrium on many scales. The critical fluctuations have a hierarchical structure, and the relaxation involves many length and time scales. Above the critical point, in the one-phase region, we consider the relaxation of the liquid following a sudden temperature change that simultaneously violates the equilibrium on many scales. Below T(sub c), a non-equilibrium state may include a distribution of small scale phase droplets; we consider the relaxation of such a droplet following a temperature change that has made the phase of the matrix stable.

  11. Nucleation and growth kinetics of palladium nanoparticles on thin ...

    African Journals Online (AJOL)

    transmission electron microscopy (TEM), related to the first quantitative study on the ... density of clusters decreases when the substrate temperature increases following Arrhenius law. ... in two terms classical thermodynamics and atomistic.

  12. Li4FeH6: Iron-containing complex hydride with high gravimetric hydrogen density

    Directory of Open Access Journals (Sweden)

    Hiroyuki Saitoh

    2014-07-01

    Full Text Available Li4FeH6, which has the highest gravimetric hydrogen density of iron-containing complex hydrides reported so far, is synthesized by hydrogenation of a powder mixture of iron and LiH above 6.1 GPa at 900 °C. In situ synchrotron radiation X-ray diffraction measurements reveal that while kinetics require high temperature and thus high pressure for the synthesis, Li4FeH6 is expected to be thermodynamically stable slightly below room temperature at ambient pressure; further synthetic studies to suppress the kinetic effects may enable us to synthesize Li4FeH6 at moderate pressures. Li4FeH6 can be recovered at ambient conditions where Li4FeH6 is metastable.

  13. Thermodynamic and Dynamic Aspects of Ice Nucleation

    Science.gov (United States)

    Barahona, Donifan

    2018-01-01

    It is known that ice nucleating particles (INP) immersed within supercooled droplets promote the formation of ice. Common theoretical models used to represent this process assume that the immersed particle lowers the work of ice nucleation without significantly affecting the dynamics of water in the vicinity of the particle. This is contrary to evidence showing that immersed surfaces significantly affect the viscosity and diffusivity of vicinal water. To study how this may affect ice formation this work introduces a model linking the ice nucleation rate to the modification of the dynamics and thermodynamics of vicinal water by immersed particles. It is shown that INP that significantly reduce the work of ice nucleation also pose strong limitations to the growth of the nascent ice germs. This leads to the onset of a new ice nucleation regime, called spinodal ice nucleation, where the dynamics of ice germ growth instead of the ice germ size determines the nucleation rate. Nucleation in this regime is characterized by an enhanced sensitivity to particle area and cooling rate. Comparison of the predicted ice nucleation rate against experimental measurements for a diverse set of species relevant to cloud formation suggests that spinodal ice nucleation may be common in nature.

  14. Application of acoustic emission to hydride cracking

    International Nuclear Information System (INIS)

    Sagat, S.; Ambler, J.F.R.; Coleman, C.E.

    1986-07-01

    Acoustic emission has been used for over a decade to study delayed hydride cracking (DHC) in zirconium alloys. At first acoustic emission was used primarily to detect the onset of DHC. This was possible because DHC was accompanied by very little plastic deformation of the material and furthermore the amplitudes of the acoustic pulses produced during cracking of the brittle hydride phase were much larger than those from dislocation motion and twinning. Acoustic emission was also used for measuring crack growth when it was found that for a suitable amplitude threshold, the total number of acoustic emission counts was linearly related to the cracked area. Once the proportionality constant was established, the acoustic counts could be converted to the crack length. Now the proportionality between the count rate and the crack growth rate is used to provide feedback between the crack length and the applied load, using computer technology. In such a system, the stress at the crack tip can be maintained constant during the test by adjusting the applied load as the crack progresses, or it can be changed in a predetermined manner, for example, to measure the threshold stress for cracking

  15. NATO Advanced Study Institute on Metal Hydrides

    CERN Document Server

    1981-01-01

    In the last five years, the study of metal hydrides has ex­ panded enormously due to the potential technological importance of this class of materials in hydrogen based energy conversion schemes. The scope of this activity has been worldwide among the industrially advanced nations. There has been a consensus among researchers in both fundamental and applied areas that a more basic understanding of the properties of metal/hydrogen syster;,s is required in order to provide a rational basis for the selection of materials for specific applications. The current worldwide need for and interest in research in metal hydrides indicated the timeliness of an Advanced Study Insti­ tute to provide an in-depth view of the field for those active in its various aspects. The inclusion of speakers from non-NATO coun­ tries provided the opportunity for cross-fertilization of ideas for future research. While the emphasis of the Institute was on basic properties, there was a conscious effort to stimulate interest in the applic...

  16. Critical Nuclei Size, Rate, and Activation Energy of H2 Gas Nucleation.

    Science.gov (United States)

    German, Sean R; Edwards, Martin A; Ren, Hang; White, Henry S

    2018-03-21

    Electrochemical measurements of the nucleation rate of individual H 2 bubbles at the surface of Pt nanoelectrodes (radius = 7-41 nm) are used to determine the critical size and geometry of H 2 nuclei leading to stable bubbles. Precise knowledge of the H 2 concentration at the electrode surface, C H 2 surf , is obtained by controlled current reduction of H + in a H 2 SO 4 solution. Induction times of single-bubble nucleation events are measured by stepping the current, to control C H 2 surf , while monitoring the voltage. We find that gas nucleation follows a first-order rate process; a bubble spontaneously nucleates after a stochastic time delay, as indicated by a sudden voltage spike that results from impeded transport of H + to the electrode. Hundreds of individual induction times, at different applied currents and using different Pt nanoelectrodes, are used to characterize the kinetics of phase nucleation. The rate of bubble nucleation increases by four orders of magnitude (0.3-2000 s -1 ) over a very small relative change in C H 2 surf (0.21-0.26 M, corresponding to a ∼0.025 V increase in driving force). Classical nucleation theory yields thermodynamic radii of curvature for critical nuclei of 4.4 to 5.3 nm, corresponding to internal pressures of 330 to 270 atm, and activation energies for nuclei formation of 14 to 26 kT, respectively. The dependence of nucleation rate on H 2 concentration indicates that nucleation occurs by a heterogeneous mechanism, where the nuclei have a contact angle of ∼150° with the electrode surface and contain between 35 and 55 H 2 molecules.

  17. Transmission Electron Microscopy Studies on Titanium-doped Sodium Aluminum Hydride

    Science.gov (United States)

    Culnane, Lance F.

    Hydrogen fuel cells play an important role in today's diverse and blossoming alternative energy industry. One of the greatest technological barriers for vehicular applications is the storage of hydrogen (which is required to power hydrogen fuel cells). Storing hydrogen as a gas is not volume efficient, and storing it as a liquid is not cost effective, therefore solid-state storage of hydrogen, such as in metal hydrides offers the most potential for success since many metal hydrides have attractive qualities for hydrogen storage such as: high volumetric capacity, cost efficiency, weight efficiency, low refueling times, and most importantly, high safety. Unfortunately, a compound has not been discovered which contains all of the attractive hydrogen storage qualities for vehicular applications. Sodium aluminum hydride (NaAlH 4) is one of the few compounds which is close to meeting requirements for car manufacturers, and has perhaps been researched the most extensively out of all metal hydrides in the last 15 years. This arises from the remarkable discovery by Bogdanovic who found that doping NaAlH4 with Ti dopants enabled the reversible dehydrogenation and hydrogenation of NaAlH 4 at mild conditions. Various evidence and theories have been proposed to suggest explanations for the enhanced kinetic effect that Ti-doping and ball-milling provide. However, the research community has not reached a consensus as to the exact role of Ti-dopants. If the role of titanium in the NaAlH4 dehydrogenation/hydrogenation mechanism could be understood, then more attractive metal hydrides could be designed. To this end, we conducted Transmission Electron Microscopy (TEM) studies to explain the role of the Ti dopants. The first known thorough particle size analysis of the NaAlH4 system was conducted, as well as TEM-EELS (Electron Energy Loss Spectroscopy), TEM-EDS (Energy Dispersive X-ray Spectroscopy), and in-situ imaging studies. Preparation methods were found to be important for the

  18. A note on the nucleation with multiple steps: parallel and series nucleation.

    Science.gov (United States)

    Iwamatsu, Masao

    2012-01-28

    Parallel and series nucleation are the basic elements of the complex nucleation process when two saddle points exist on the free-energy landscape. It is pointed out that the nucleation rates follow formulas similar to those of parallel and series connection of resistors or conductors in an electric circuit. Necessary formulas to calculate individual nucleation rates at the saddle points and the total nucleation rate are summarized, and the extension to the more complex nucleation process is suggested. © 2012 American Institute of Physics

  19. Intermediate Nucleation State of GaN Growth

    Science.gov (United States)

    Zheng, L. X.; Xie, M. H.; Tong, S. Y.

    2001-03-01

    Homoexpitaxial nucleation of GaN during molecular-beam epitaxy is followed by scanning tunneling microcopy (STM). We observe a metastable nucleation state, which manifests as “ghost” islands in STM images. These “ghost” islands can be irreversibly driven into normal islands by continuous STM imaging. It is further established that the “ghost” island formation is related to the presence of excess Ga atoms on the surface: Normal islands are only seen under the N-rich or stoichiometric flux condition, whereas “ghost” islands are observed under Ga-rich conditions. For intermediate excess-Ga coverages, both normal and “ghost” islands are present, however, they show distinctly different sizes, suggesting different nucleation states for the two. A growth model is proposed to account for the formation of metastable, “ghost” islands. Kinetic Monte Carlo simulation is carried out and main features of the surface are reproduced. We acknowledge financial support from HK RGC under grant Nos. 7396/00P, 7142/99P, and 7121/00P.

  20. Homogeneous nucleation in liquid nitrogen at negative pressures

    Energy Technology Data Exchange (ETDEWEB)

    Baidakov, V. G., E-mail: baidakov@itp.uran.ru; Vinogradov, V. E.; Pavlov, P. A. [Russian Academy of Sciences, Institute of Thermal Physics, Ural Branch (Russian Federation)

    2016-10-15

    The kinetics of spontaneous cavitation in liquid nitrogen at positive and negative pressures has been studied in a tension wave formed by a compression pulse reflected from the liquid–vapor interface on a thin platinum wire heated by a current pulse. The limiting tensile stresses (Δp = p{sub s}–p, where p{sub s} is the saturation pressure), the corresponding bubble nucleation frequencies J (10{sup 20}–10{sup 22} s{sup –1} m{sup –3}), and temperature induced nucleation frequency growth rate G{sub T} = dlnJ/dT have been experimentally determined. At T = 90 K, the limiting tensile stress was Δp = 8.3 MPa, which was 4.9 MPa lower than the value corresponding to the boundary of thermodynamic stability of the liquid phase (spinodal). The measurement results were compared to classical (homogeneous) nucleation theory (CNT) with and without neglect of the dependence of the surface tension of critical bubbles on their dimensions. In the latter case, the properties of new phase nuclei were described in terms of the Van der Waals theory of capillarity. The experimental data agree well with the CNT theory when it takes into account the “size effect.”.

  1. A study of stress reorientation of hydrides in zircaloy

    Energy Technology Data Exchange (ETDEWEB)

    Yourong, Jiang; Bangxin, Zhou [Nuclear Power Inst. of China, Chengdu, SC (China)

    1994-10-01

    Under the conditions of circumferential tensile stress from 70 to 180 MPa for Zircaloy tubes or the tensile stress from 55 to 180 MPa for Zircaloy-4 plates and temperature cycling between 150 and 400 degree C, the effects of stress and the number of temperature cycling on hydride reorientation in Zircaloy-4 tubes and plates and Zircaloy-2 tubes containing about 220 {mu}g/g hydrogen have been investigated. With the increase of stress and/or the number of temperature cycling, the level of hydride reorientation increases. When hydride reorientation takes place, there is a threshold stress concerned with the number of temperature cycling. Below the threshold stress, hydride reorientation is not obvious. When applied stress is higher than the threshold stress, the level of hydride reorientation increases with the increase of stress and the number of temperature cycling. Hydride reorientation in Zircaloy-4 tubes develops gradually from the outer surface to inner surface. It might be related to the difference of texture between outer surface and inner surface. The threshold stress is affected by both the texture and the value of B. So controlling texture could still restrict hydride reorientation under tensile stress.

  2. Nucleation in an ultra low ionization environment

    DEFF Research Database (Denmark)

    Pedersen, Jens Olaf Pepke; Enghoff, Martin Andreas Bødker; Paling, Sean

    Atmospheric ions can enhance the nucleation of aerosols, as has been established by experiments, observation, and theory. In the clean marine atmosphere ionization is mainly caused by cosmic rays which in turn are controlled by the activity of the Sun, thus providing a potential link between solar...... activity and climate. In order to understand the effect ions may have on the production of cloud condensation nuclei the overall contribution of ion induced nucleation to the global production of secondary aerosols must be determined. One issue with determining this contribution is that several mechanisms...... for nucleation exist and it can be difficult to determine the relative importance of the various mechanisms in a given nucleation event when both ion induced and electrically neutral nucleation mechanisms are at work at the same time. We have carried out nucleation experiments in the Boulby Underground...

  3. Hydrogen storage in metal hydrides and complex hydrides; Wasserstoffspeicherung in Metall- und komplexen Hydriden - Schlussbericht

    Energy Technology Data Exchange (ETDEWEB)

    Bielmann, M.; Zuettel, A.

    2007-07-01

    This final report for the Swiss Federal Office of Energy (SFOE), reports on work done in 2007 at the Swiss Federal Laboratories for Materials Science and Technology EMPA on the storage of hydrogen in metal hydrides and complex hydrides. In particular, the use of tetrahydroborates is noted. The potential of this class of materials is stressed. The structures at room-temperature were examined using neutron and X-ray diffraction methods. Thermodynamic methods helped determine the thermodynamic stability of the materials. Also, a complete energy diagram for the materials was developed. The use of silicon oxide to reduce activation energy and its catalytic effects are discussed. The challenges placed by desorption mechanisms are noted. The authors note that reversibility is basically proven.

  4. Complex metal hydrides for hydrogen, thermal and electrochemical energy storage

    DEFF Research Database (Denmark)

    Møller, Kasper T.; Sheppard, Drew; Ravnsbæk, Dorthe B.

    2017-01-01

    field. This review illustrates that complex metal hydrides may store hydrogen in the solid state, act as novel battery materials, both as electrolytes and electrode materials, or store solar heat in a more efficient manner as compared to traditional heat storage materials. Furthermore, it is highlighted...... how complex metal hydrides may act in an integrated setup with a fuel cell. This review focuses on the unique properties of light element complex metal hydrides mainly based on boron, nitrogen and aluminum, e.g., metal borohydrides and metal alanates. Our hope is that this review can provide new...

  5. Finite difference program for calculating hydride bed wall temperature profiles

    International Nuclear Information System (INIS)

    Klein, J.E.

    1992-01-01

    A QuickBASIC finite difference program was written for calculating one dimensional temperature profiles in up to two media with flat, cylindrical, or spherical geometries. The development of the program was motivated by the need to calculate maximum temperature differences across the walls of the Tritium metal hydrides beds for thermal fatigue analysis. The purpose of this report is to document the equations and the computer program used to calculate transient wall temperatures in stainless steel hydride vessels. The development of the computer code was motivated by the need to calculate maximum temperature differences across the walls of the hydrides beds in the Tritium Facility for thermal fatigue analysis

  6. Investigation process of alcoholysis of hydride aluminium-adobe

    International Nuclear Information System (INIS)

    Numanov, M.I.; Normatov, I.Sh.; Mirsaidov, U.M.

    2001-01-01

    Considering of that process of acid treatment of aluminium-adobe hydride realizes in the ethyl alcohol media it was necessary study the process of alcoholysis of AlH 3 and aluminium additives. In the end of article authors became to conclusion that deficiency of spontaneous alcoholysis of AlH 3 in adobe caused by protective action of fiber; solvate ability of LiCl and alkoxy aluminium hydride of lithium-LiCl·CO 2 H 5 OH, Li Al(OC 2 H 5 ) 4 ·nC 2 H 5 OH decreasing the expectancy of responding of alcohol with aluminium hydride

  7. Ice nucleation triggered by negative pressure.

    Science.gov (United States)

    Marcolli, Claudia

    2017-11-30

    Homogeneous ice nucleation needs supercooling of more than 35 K to become effective. When pressure is applied to water, the melting and the freezing points both decrease. Conversely, melting and freezing temperatures increase under negative pressure, i.e. when water is stretched. This study presents an extrapolation of homogeneous ice nucleation temperatures from positive to negative pressures as a basis for further exploration of ice nucleation under negative pressure. It predicts that increasing negative pressure at temperatures below about 262 K eventually results in homogeneous ice nucleation while at warmer temperature homogeneous cavitation, i. e. bubble nucleation, dominates. Negative pressure occurs locally and briefly when water is stretched due to mechanical shock, sonic waves, or fragmentation. The occurrence of such transient negative pressure should suffice to trigger homogeneous ice nucleation at large supercooling in the absence of ice-nucleating surfaces. In addition, negative pressure can act together with ice-inducing surfaces to enhance their intrinsic ice nucleation efficiency. Dynamic ice nucleation can be used to improve properties and uniformity of frozen products by applying ultrasonic fields and might also be relevant for the freezing of large drops in rainclouds.

  8. Determination of hydrogen in zirconium hydride and uranium-zirconium hydride by inert gas exraction-gravimetric method

    International Nuclear Information System (INIS)

    Hoshino, Akira; Iso, Shuichi

    1976-01-01

    An inert gas extraction-gravimetric method has been applied to the determination of hydrogen in zirconium hydride and uranium-zirconium hydride which are used as neutron moderator and fuel of nuclear safety research reactor (NSRR), respectively. The sample in a graphite-enclosed quartz crucible is heated inductively to 1200 0 C for 20 min in a helium stream. Hydrogen liberated from the sample is oxidized to water by copper(I) oxide-copper(II) oxide at 400 0 C, and the water is determined gravimetrically by absorption in anhydrone. The extraction curves of hydrogen for zirconium hydride and uranium-zirconium hydride samples are shown in Figs. 2 and 3. Hydrogen in the samples is extracted quantitatively by heating at (1000 -- 1250) 0 C for (10 -- 40) min. Recoveries of hydrogen in the case of zirconium hydride were examined as follows: a weighed zirconium rod (5 phi x 6 mm, hydrogen -5 Torr. After the chamber was filled with purified hydrogen to 200 Torr, the rod was heated to 400 0 C for 15 h, and again weighed to determine the increase in weight. Hydrogen in the rod was then determined by the proposed method. The results are in excellent agreement with the increase in weight as shown in Table 1. Analytical results of hydrogen in zirconium hydride samples and an uranium-zirconium hydride sample are shown in Table 2. (auth.)

  9. Direct measurement of free-energy barrier to nucleation of crystallites in amorphous silicon thin films

    Science.gov (United States)

    Shi, Frank G.

    1994-01-01

    A method is introduced to measure the free-energy barrier W(sup *), the activation energy, and activation entropy to nucleation of crystallites in amorphous solids, independent of the energy barrier to growth. The method allows one to determine the temperature dependence of W(sup *), and the effect of the preparation conditions of the initial amorphous phase, the dopants, and the crystallization methds on W(sup *). The method is applied to determine the free-energy barrier to nucleation of crystallites in amorphous silicon (a-Si) thin films. For thermally induced nucleation in a-Si thin films with annealing temperatures in the range of from 824 to 983 K, the free-energy barrier W(sup *) to nucleation of silicon crystals is about 2.0 - 2.1 eV regardless of the preparation conditions of the films. The observation supports the idea that a-Si transforms into an intermediate amorphous state through the structural relaxation prior to the onset of nucleation of crystallites in a-Si. The observation also indicates that the activation entropy may be an insignificant part of the free-energy barrier for the nucleation of crystallites in a-Si. Compared with the free-energy barrier to nucleation of crystallites in undoped a-Si films, a significant reduction is observed in the free-energy barrier to nucleation in Cu-doped a-Si films. For a-Si under irradiation of Xe(2+) at 10(exp 5) eV, the free-energy barrier to ion-induced nucleation of crystallites is shown to be about half of the value associated with thermal-induced nucleation of crystallites in a-Si under the otherwise same conditions, which is much more significant than previously expected. The present method has a general kinetic basis; it thus should be equally applicable to nucleation of crystallites in any amorphous elemental semiconductors and semiconductor alloys, metallic and polymeric glasses, and to nucleation of crystallites in melts and solutions.

  10. Nucleation and microstructure development in Cr-Mo-V tool steel during gas atomization

    Science.gov (United States)

    Behúlová, M.; Grgač, P.; Čička, R.

    2017-11-01

    Nucleation studies of undercooled metallic melts are of essential interest for the understanding of phase selection, growth kinetics and microstructure development during their rapid non-equilibrium solidification. The paper deals with the modelling of nucleation processes and microstructure development in the hypoeutectic tool steel Ch12MF4 with the chemical composition of 2.37% C, 12.06 % Cr, 1.2% Mo, 4.0% V and balance Fe [wt. %] in the process of nitrogen gas atomization. Based on the classical theory of homogeneous nucleation, the nucleation temperature of molten rapidly cooled spherical particles from this alloy with diameter from 40 μm to 600 μm in the gas atomization process is calculated using various estimations of parameters influencing the nucleation process - the Gibbs free energy difference between solid and liquid phases and the solid/liquid interfacial energy. Results of numerical calculations are compared with experimentally measured nucleation temperatures during levitation experiments and microstructures developed in rapidly solidified powder particles from the investigated alloy.

  11. Process for production of a metal hydride

    Science.gov (United States)

    Allen, Nathan Tait; Butterick, III, Robert; Chin, Arthur Achhing; Millar, Dean Michael; Molzahn, David Craig

    2014-08-12

    A process for production of a metal hydride compound MH.sub.x, wherein x is one or two and M is an alkali metal, Be or Mg. The process comprises combining a compound of formula (R.sup.1O).sub.xM with aluminum, hydrogen and at least one metal selected from among titanium, zirconium, hafnium, niobium, vanadium, tantalum and iron to produce a compound of formula MH.sub.x. R.sup.1 is phenyl or phenyl substituted by at least one alkyl or alkoxy group. A mole ratio of aluminum to (R.sup.1O).sub.xM is from 0.1:1 to 1:1. The catalyst is present at a level of at least 200 ppm based on weight of aluminum.

  12. Boron hydride analogues of the fullerenes

    International Nuclear Information System (INIS)

    Quong, A.A.; Pederson, M.R.; Broughton, J.Q.

    1994-01-01

    The BH moiety is isoelectronic with C. We have studied the stability of the (BH) 60 analogue of the C 60 fullerene as well as the dual-structure (BH) 32 icosahedron, both of them being putative structures, by performing local-density-functional electronic calculations. To aid in our analysis, we have also studied other homologues of these systems. We find that the latter, i.e., the dual structure, is the more stable although the former is as stable as one of the latter's lower homologues. Boron hydrides, it seems, naturally form the dual structures used in algorithmic optimization of complex fullerene systems. Fully relaxed geometries are reported as well as electron affinities and effective Hubbard U parameters. These systems form very stable anions and we conclude that a search for BH analogues of the C 60 alkali-metal supeconductors might prove very fruitful

  13. Hydrogen storage properties of metallic hydrides

    International Nuclear Information System (INIS)

    Latroche, M.; Percheron-Guegan, A.

    2005-01-01

    Nowadays, energy needs are mainly covered by fossil energies leading to pollutant emissions mostly responsible for global warming. Among the different possible solutions for greenhouse effect reduction, hydrogen has been proposed for energy transportation. Indeed, H 2 can be seen as a clean and efficient energy carrier. However, beside the difficulties related to hydrogen production, efficient high capacity storage means are still to be developed. Many metals and alloys are able to store large amounts of hydrogen. This latter solution is of interest in terms of safety, global yield and long term storage. However, to be suitable for applications, such compounds must present high capacity, good reversibility, fast reactivity and sustainability. In this paper, we will review the structural and thermodynamic properties of metallic hydrides. (authors)

  14. Mechanism of nucleation and growth of hydrogen porosity in solidifying A356 aluminum alloy: an analytical solution

    International Nuclear Information System (INIS)

    Li, K.-D.; Chang, Edward

    2004-01-01

    This study derives an analytical solution for the mechanism of nucleation and growth of hydrogen pore in the solidifying A356 aluminum alloy. A model of initial transient hydrogen redistribution in the growing dendritic grain is used to modify the lever rule for the mechanism of nucleation of pore. The model predicts the fraction of solid at nucleation, the temperature range of nucleation, the radius of hydrogen diffusion cell, and the supersaturation of hydrogen needed for nucleation. The role of solidus velocity in nucleation is explained. The parameters calculated from the model of nucleation are used for analyzing the mechanism of kinetic diffusion-controlled growth of pore, in which the mathematical transformations of variables are introduced. With the transformations, it is argued that the diffusion problem involving the liquid and solid phases during solidification could be treated as a classic problem of precipitation in the single-phase medium treated by Ham or Avrami. The analytical solution for the nucleation of pore is compared with the mechanism of macrosegregation. The predicted volume percent of porosity and radius of pore based on the mechanism of growth of pore is discussed with respect to the thermodynamic solution, the published experimental data, the numerical solutions, and the role of interdendritic fluid flow governed by Darcy's law

  15. Structuring effects in binary nucleation : Molecular dynamics simulatons and coarse-grained nucleation theory

    NARCIS (Netherlands)

    Braun, S.; Kraska, T.; Kalikmanov, V.I.

    2013-01-01

    Binary clusters formed by vapor-liquid nucleation are frequently nonhomogeneous objects in which components are not well mixed. The structure of a cluster plays an important role in nucleation and cluster growth. We demonstrate structuring effects by studying high-pressure nucleation and cluster

  16. Analytical solutions of mushy layer equations describing directional solidification in the presence of nucleation

    Science.gov (United States)

    Alexandrov, Dmitri V.; Ivanov, Alexander A.; Alexandrova, Irina V.

    2018-01-01

    The processes of particle nucleation and their evolution in a moving metastable layer of phase transition (supercooled liquid or supersaturated solution) are studied analytically. The transient integro-differential model for the density distribution function and metastability level is solved for the kinetic and diffusionally controlled regimes of crystal growth. The Weber-Volmer-Frenkel-Zel'dovich and Meirs mechanisms for nucleation kinetics are used. We demonstrate that the phase transition boundary lying between the mushy and pure liquid layers evolves with time according to the following power dynamic law: , where Z1(t)=βt7/2 and Z1(t)=βt2 in cases of kinetic and diffusionally controlled scenarios. The growth rate parameters α, β and ε are determined analytically. We show that the phase transition interface in the presence of crystal nucleation and evolution propagates slower than in the absence of their nucleation. This article is part of the theme issue `From atomistic interfaces to dendritic patterns'.

  17. New trends in the nucleation research

    Science.gov (United States)

    Anisimov, M. P.; Hopke, P. K.

    2017-09-01

    During the last half of century the most of efforts have been directed towards small molecule system modeling using intermolecular potentials. Summarizing the nucleation theory, it can be concluded that the nowadays theory is far from complete. The vapor-gas nucleation theory can produce values that deviate from the experimental results by several orders of magnitude currently. Experiments on the vapor-gas nucleation rate measurements using different devices show significant inconsistencies in the measured rates as well. Theoretical results generally are quite reasonable for sufficiently low vapor nucleation rates where the capillary approximation is applicable. In the present research the advantages and current problems of the vapor-gas nucleation experiments are discussed briefly and a view of the future studies is presented. Using the brake points of the first derivative for the nucleation rate surface as markers of the critical embryos phase change is fresh idea to show the gas-pressure effect for the nucleating vapor-gas systems. To test the accuracy of experimental techniques, it is important to have a standard system that can be measured over a range of nucleation conditions. Several results illustrate that high-pressure techniques are needed to study multi-channel nucleation. In practical applications, parametric theories can be used for the systems of interest. However, experimental measurements are still the best source of information on nucleation rates. Experiments are labor intensive and costly, and thus, it is useful to extend the value of limited experimental measurements to a broader range of nucleation conditions. Only limited experimental data one needs for use in normalizing the slopes of the linearized nucleation rate surfaces. The nucleation rate surface is described in terms of steady-state nucleation rates. It is supposed that several new measuring systems, such as High Pressure Flow Diffusion Chamber for pressure limit up to 150 bar will be

  18. Nucleation of recrystallization observed in situ in the bulk of a deformed metal

    International Nuclear Information System (INIS)

    Larsen, Axel W.; Poulsen, Henning F.; Margulies, Lawrence; Gundlach, Carsten; Xing Qingfeng; Huang Xiaoxu; Jensen, Dorte Juul

    2005-01-01

    Nucleation of recrystallization is studied in situ in the bulk by three-dimensional X-ray diffraction. Copper samples cold rolled 20% are investigated. The crystallographic orientations near triple junction lines are characterized before, during and after annealing. Three nuclei are identified and it is shown that two nuclei are twin related to their parent grain and one nucleus has an orientation, which is neither present in the deformed parent grains nor first order twin related to any of them. Data on the nucleation kinetics is also presented

  19. Artificial exomuscle investigations for applications-metal hydride

    International Nuclear Information System (INIS)

    Crevier, Marie-Charlotte; Richard, Martin; Rittenhouse, D Matheson; Roy, Pierre-Olivier; Bedard, Stephane

    2007-01-01

    In pursuing the development of bionic devices, Victhom identified a need for technologies that could replace current motorized systems and be better integrated into the human body motion. The actuators used to obtain large displacements are noisy, heavy, and do not adequately reproduce human muscle behavior. Subsequently, a project at Victhom was devoted to the development of active materials to obtain an artificial exomuscle actuator. An exhaustive literature review was done at Victhom to identify promising active materials for the development of artificial muscles. According to this review, metal hydrides were identified as a promising technology for artificial muscle development. Victhom's investigations focused on determining metal hydride actuator potential in the context of bionics technology. Based on metal hydride properties and artificial muscle requirements such as force, displacement and rise time, an exomuscle was built. In addition, a finite element model, including heat and mass transfer in the metal hydride, was developed and implemented in FEMLAB software. (review article)

  20. Ductile zirconium powder by hydride-dehydride process

    Energy Technology Data Exchange (ETDEWEB)

    Krishnan, T S [BHABHA ATOMIC RESEARCH CENTRE, BOMBAY (INDIA); CHAUDHARY, S [NUCLEAR FUEL COMPLEX, HYDERABAD (INDIA)

    1976-09-01

    The preparation of ductile zirconium powder by the hydride-dehydride process has been described. In this process massive zirconium obtained from Kroll reduction of ZrCl/sub 4/ is first rendered brittle by hydrogenation and the hydride crushed and ground in a ball mill to the required particle size. Hydrogen is then hot vacuum extracted to yield the metal powder. The process has been successfully employed for the production of zirconium powders with low oxygen content and having hardness values in the range of 115-130 BHN, starting from a zirconium sponge of 100-120 BHN hardness. Influence of surface characteristics of the starting metal on its hydriding behaviour has been studied and the optimum hydriding-dehydriding conditions established.

  1. Development of zirconium hydride highly effective moderator materials

    International Nuclear Information System (INIS)

    Yin Changgeng

    2005-10-01

    The zirconium hydride with highly content of hydrogen and low density is new efficient moderator material for space nuclear power reactor. Russia has researched it to use as new highly moderator and radiation protection materials. Japanese has located it between the top of pressure vessel and the main protection as a shelter, the work temperature is rach to 220 degree C. The zirconium hydride moderator blocks are main parts of space nuclear power reactor. Development of zirconium hydride moderator materials have strength research and apply value. Nuclear Power Research and Design Instituteoh China (NPIC) has sep up the hydrogenation device and inspect systems, and accumurate a large of experience about zirconium hydride, also set up a strict system of QA and QC. (authors)

  2. Planar nucleation and crystallization in the annealing process of ion implanted silicon

    International Nuclear Information System (INIS)

    Luo Yimin; Chen Zhenhua; Chen Ding

    2010-01-01

    According to thermodynamic and kinetic theory, considering the variation of bulk free energy and superficial energy after nucleation as well as the migration of atoms, we study systematically the planar nucleation and crystallization that relate to two possible transition mechanisms in the annealing process of ion implanted Si: (1) liquid/solid transition: the critical nucleation work is equal to half the increased superficial energy and inversely proportional to the supercooling ΔT. Compared with bulk nucleation, the radius of the critical nucleus decreases by half, and the nucleation rate attains its maximum at T = T m /2. (2) amorphous/crystalline transition: the atoms contained in the critical nucleus and situated on its surface, as well as critical nucleation work, are all directly proportional to the height of the nucleus, and the nucleation barrier is equal to half the superficial energy too. In addition, we take SiGe semiconductor as a specific example for calculation; a value of 0.03 eV/atom is obtained for the elastic strain energy, and a more reasonable result can be gotten after taking into account its effect on transition Finally, we reach the following conclusion as a result of the calculation: for the annealing of ion implanted Si, no matter what the transition method is-liquid or solid planar nucleation-the recrystallization process is actually carried out layer by layer on the crystal substrate, and the probability of forming a 'rod-like' nucleus is much larger than that of a 'plate-like' nucleus. (semiconductor materials)

  3. Reactions of zinc hydride and magnesium hydride with pyridine; synthesis and characterization of 1,4-dihydro-1-pyridylzinc and -magnesium complexes

    NARCIS (Netherlands)

    Koning, A.J. de; Boersma, J.; Kerk, G.J.M. van der

    1980-01-01

    The synthesis and characterization of 1,4-dihydro-1-pyridylzinc and -magnesium complexes are described. Zinc hydride and magnesium hydride dissolve in and react with pyridine, and the reaction has been studied in detail in the case of zinc hydride. Evaporation of the solvent after 1–2 hours at 0°C

  4. Electronic structure of ternary hydrides based on light elements

    Energy Technology Data Exchange (ETDEWEB)

    Orgaz, E. [Departamento de Fisica y Quimica Teorica, Facultad de Quimica, Universidad Nacional Autonoma de Mexico, CP 04510 Coyoacan, Mexico, D.F. (Mexico)]. E-mail: orgaz@eros.pquim.unam.mx; Membrillo, A. [Departamento de Fisica y Quimica Teorica, Facultad de Quimica, Universidad Nacional Autonoma de Mexico, CP 04510 Coyoacan, Mexico, D.F. (Mexico); Castaneda, R. [Departamento de Fisica y Quimica Teorica, Facultad de Quimica, Universidad Nacional Autonoma de Mexico, CP 04510 Coyoacan, Mexico, D.F. (Mexico); Aburto, A. [Departamento de Fisica, Facultad de Ciencias, Universidad Nacional Autonoma de Mexico, CP 04510 Coyoacan, Mexico, D.F. (Mexico)

    2005-12-08

    Ternary hydrides based on light elements are interesting owing to the high available energy density. In this work we focused into the electronic structure of a series of known systems having the general formula AMH{sub 4}(A=Li,Na,M=B,Al). We computed the energy bands and the total and partial density of states using the linear-augmented plane waves method. In this report, we discuss the chemical bonding in this series of complex hydrides.

  5. Spectroscopy of helium hydride and triatomic hydrogen molecules

    International Nuclear Information System (INIS)

    Ketterle, W.

    1986-07-01

    Helium hydride and triatomic hydrogen has been produced by charge exchange between fast mass selected beams of molecular ions and alkali vapor. Using this method, the first discrete spectra of helium hydride were obtained. Fine electronic transitions with resolved rotational structure were observed in the visible and near infrared. Four isotopic mixtures were studied. Furthermore the first lifetime measurement of triatomic hydrogen states were performed and compared to theoretical predictions. (orig.)

  6. Proton location in metal hydrides using electron spin resonance

    International Nuclear Information System (INIS)

    Venturini, E.L.

    1979-01-01

    Electron spin resonance (ESR) of dilute paramagnetic ions establishes the site symmetry of these ions. In the case of metal hydrides the site symmetry is determined by the number and location of neighboring protons. Typical ESR spectra for trivalent erbium in scandium and yttrium hydrides are presented and analyzed, and this technique is shown to be a versatile microscopic probe of the location, net charge and occupation probability of nearby protons

  7. The Production of Uranium Metal by Metal Hydrides Incorporated

    Energy Technology Data Exchange (ETDEWEB)

    Alexander, P. P.

    1943-01-01

    Metal Hydrides Incorporated was a pioneer in the production of uranium metal on a commercial scale and supplied it to all the laboratories interested in the original research, before other methods for its production were developed. Metal Hydrides Inc. supplied the major part of the metal for the construction of the first experimental pile which, on December 2, 1942, demonstrated the feasibility of the self-sustaining chain reaction and the release of atomic energy.

  8. Nucleation at high pressure I: Theoretical considerations.

    NARCIS (Netherlands)

    Luijten, C.C.M.; Dongen, van M.E.H.

    1999-01-01

    A theoretical approach is presented that accounts for the influence of high pressure background gases on the vapor-to-liquid nucleation process. The key idea is to treat the carrier gas pressure as a perturbation parameter that modifies the properties of the nucleating substance. Two important

  9. Simple improvements to classical bubble nucleation models.

    Science.gov (United States)

    Tanaka, Kyoko K; Tanaka, Hidekazu; Angélil, Raymond; Diemand, Jürg

    2015-08-01

    We revisit classical nucleation theory (CNT) for the homogeneous bubble nucleation rate and improve the classical formula using a correct prefactor in the nucleation rate. Most of the previous theoretical studies have used the constant prefactor determined by the bubble growth due to the evaporation process from the bubble surface. However, the growth of bubbles is also regulated by the thermal conduction, the viscosity, and the inertia of liquid motion. These effects can decrease the prefactor significantly, especially when the liquid pressure is much smaller than the equilibrium one. The deviation in the nucleation rate between the improved formula and the CNT can be as large as several orders of magnitude. Our improved, accurate prefactor and recent advances in molecular dynamics simulations and laboratory experiments for argon bubble nucleation enable us to precisely constrain the free energy barrier for bubble nucleation. Assuming the correction to the CNT free energy is of the functional form suggested by Tolman, the precise evaluations of the free energy barriers suggest the Tolman length is ≃0.3σ independently of the temperature for argon bubble nucleation, where σ is the unit length of the Lennard-Jones potential. With this Tolman correction and our prefactor one gets accurate bubble nucleation rate predictions in the parameter range probed by current experiments and molecular dynamics simulations.

  10. Nucleation in an ultra low ionisation environment

    DEFF Research Database (Denmark)

    Enghoff, Martin Andreas Bødker

    in aerosol nucleation. By exposing a controlled volume of air to varying levels of ionising radiation, and with the minimum ionisation level vastly reduced compared to normal surface laboratory conditions, we have provided both a validation of earlier studies of ion-induced nucleation and extended...

  11. Tuning Ice Nucleation with Supercharged Polypeptides

    NARCIS (Netherlands)

    Yang, Huige; Ma, Chao; Li, Kaiyong; Liu, Kai; Loznik, Mark; Teeuwen, Rosalie; van Hest, Jan C. M.; Zhou, Xin; Herrmann, Andreas; Wang, Jianjun

    2016-01-01

    Supercharged unfolded polypeptides (SUPs) are exploited for controlling ice nucleation via tuning the nature of charge and charge density of SUPs. The results show that positively charged SUPs facilitate ice nucleation, while negatively charged ones suppress it. Moreover, the charge density of the

  12. Electronic structure, bonding and chemisorption in metallic hydrides

    International Nuclear Information System (INIS)

    Ward, J.W.

    1980-01-01

    Problems that can arise during the cycling steps for a hydride storage system usually involve events at surfaces. Chemisorption and reaction processes can be affected by small amounts of contaminants that may act as catalytic poisons. The nature of the poisoning process can vary greatly for the different metals and alloys that form hydrides. A unifying concept is offered, which satisfactorily correlates many of the properties of transition-metal, rare-earth and actinide hydrides. The metallic hydrides can be differentiated on the basis of electronegativity, metallic radius (valence) and electronic structure. For those systems where there are d (transition metals) or f (early actinides) electrons near the Fermi level a broad range of chemical and catalytic behaviors are found, depending on bandwidth and energy. The more electropositive metals (rare-earths, actinides, transition metals with d > 5) dissolve hydrogen and form hydrides by an electronically somewhat different process, and as a class tend to adsorb electrophobic molecules. The net charge-transfer in either situation is subtle; however, the small differences are responsible for many of the observed structural, chemical, and catalytic properties in these hydride systems

  13. Mechanochemical synthesis of nanostructured chemical hydrides in hydrogen alloying mills

    International Nuclear Information System (INIS)

    Wronski, Z.; Varin, R.A.; Chiu, C.; Czujko, T.; Calka, A.

    2007-01-01

    Mechanical alloying of magnesium metal powders with hydrogen in specialized hydrogen ball mills can be used as a direct route for mechanochemical synthesis of emerging chemical hydrides and hydride mixtures for advanced solid-state hydrogen storage. In the 2Mg-Fe system, we have successfully synthesized the ternary complex hydride Mg 2 FeH 6 in a mixture with nanometric Fe particles. The mixture of complex magnesium-iron hydride and nano-iron released 3-4 wt.%H 2 in a thermally programmed desorption experiment at the range 285-295 o C. Milling of the Mg-2Al powder mixture revealed a strong competition between formation of the Al(Mg) solid solution and the β-MgH 2 hydride. The former decomposes upon longer milling as the Mg atoms react with hydrogen to form the hydride phase, and drive the Al out of the solid solution. The mixture of magnesium dihydride and nano-aluminum released 2.1 wt.%H 2 in the temperature range 329-340 o C in the differential scanning calorimetry experiment. The formation of MgH 2 was suppressed in the Mg-B system; instead, a hydrogenated amorphous phase (Mg,B)H x , was formed in a mixture with nanometric MgB 2 . Annealing of the hydrogen-stabilized amorphous mixture produced crystalline MgB 2

  14. The use of metal hydrides in fuel cell applications

    Directory of Open Access Journals (Sweden)

    Mykhaylo V. Lototskyy

    2017-02-01

    Full Text Available This paper reviews state-of-the-art developments in hydrogen energy systems which integrate fuel cells with metal hydride-based hydrogen storage. The 187 reference papers included in this review provide an overview of all major publications in the field, as well as recent work by several of the authors of the review. The review contains four parts. The first part gives an overview of the existing types of fuel cells and outlines the potential of using metal hydride stores as a source of hydrogen fuel. The second part of the review considers the suitability and optimisation of different metal hydrides based on their energy efficient thermal integration with fuel cells. The performances of metal hydrides are considered from the viewpoint of the reversible heat driven interaction of the metal hydrides with gaseous H2. Efficiencies of hydrogen and heat exchange in hydrogen stores to control H2 charge/discharge flow rates are the focus of the third section of the review and are considered together with metal hydride – fuel cell system integration issues and the corresponding engineering solutions. Finally, the last section of the review describes specific hydrogen-fuelled systems presented in the available reference data.

  15. Damage instability and Earthquake nucleation

    Science.gov (United States)

    Ionescu, I. R.; Gomez, Q.; Campillo, M.; Jia, X.

    2017-12-01

    Earthquake nucleation (initiation) is usually associated to the loss of the stability of the geological structure under a slip-weakening friction acting on the fault. The key parameters involved in the stability of the fault are the stress drop, the critical slip distance but also the elastic stiffness of the surrounding materials (rocks). We want to explore here how the nucleation phenomena are correlated to the material softening during damage accumulation by dynamic and/or quasi-static processes. Since damage models are describing micro-cracks growth, which is generally an unstable phenomenon, it is natural to expect some loss of stability on the associated micro-mechanics based models. If the model accurately captures the material behavior, then this can be due to the unstable nature of the brittle material itself. We obtained stability criteria at the microscopic scale, which are related to a large class of damage models. We show that for a given continuous strain history the quasi-static or dynamic problems are instable or ill-posed (multiplicity of material responses) and whatever the selection rule is adopted, shocks (time discontinuities) will occur. We show that the quasi-static equilibria chosen by the "perfect delay convention" is always stable. These stability criteria are used to analyze how NIC (Non Interacting Crack) effective elasticity associated to "self similar growth" model work in some special configurations (one family of micro-cracks in mode I, II and III and in plane strain or plain stress). In each case we determine a critical crack density parameter and critical micro-crack radius (length) which distinguish between stable and unstable behaviors. This critical crack density depends only on the chosen configuration and on the Poisson ratio.

  16. Thermal decomposition kinetics of ammonium uranyl carbonate

    International Nuclear Information System (INIS)

    Kim, E.H.; Park, J.J.; Park, J.H.; Chang, I.S.; Choi, C.S.; Kim, S.D.

    1994-01-01

    The thermal decomposition kinetics of AUC [ammonium uranyl carbonate; (NH 4 ) 4 UO 2 (CO 3 ) 3 [ in an isothermal thermogravimetric (TG) reactor under N 2 atmosphere has been determined. The kinetic data can be represented by the two-dimensional nucleation and growth model. The reaction rate increases and activation energy decreases with increasing particle size and precipitation time which appears in the particle size larger than 30 μm in the mechano-chemical phenomena. (orig.)

  17. Chemically assisted crack nucleation in zircaloy

    International Nuclear Information System (INIS)

    Williford, R.E.

    1985-01-01

    Stress corrosion cracking models (proposed to explain fuel rod failures) generally address crack propagation and cladding rupture, but frequently neglect the necessary nucleation stage for microcracks small enough to violate fracture mechanics continuum requirements. Intergranular microcrack nucleation was modeled with diffusion-controlled grain-boundary cavitation concepts, including the effects of metal embrittlement by iodine species. Computed microcrack nucleation times and strains agree with experimental observation, but the predicted grain-boundary cavities are so small that detection may be difficult. Without a protective oxide film intergranular microcracks can nucleate within 30 s at even low stresses when the embrittler concentration exceeds a threshold value. Indications were found that intergranular microcrack nucleation may be caused by combined corrosive and embrittlement phenomena. (orig.)

  18. Stochastic lag time in nucleated linear self-assembly

    Energy Technology Data Exchange (ETDEWEB)

    Tiwari, Nitin S. [Group Theory of Polymers and Soft Matter, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven (Netherlands); Schoot, Paul van der [Group Theory of Polymers and Soft Matter, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven (Netherlands); Institute for Theoretical Physics, Utrecht University, Leuvenlaan 4, 3584 CE Utrecht (Netherlands)

    2016-06-21

    Protein aggregation is of great importance in biology, e.g., in amyloid fibrillation. The aggregation processes that occur at the cellular scale must be highly stochastic in nature because of the statistical number fluctuations that arise on account of the small system size at the cellular scale. We study the nucleated reversible self-assembly of monomeric building blocks into polymer-like aggregates using the method of kinetic Monte Carlo. Kinetic Monte Carlo, being inherently stochastic, allows us to study the impact of fluctuations on the polymerization reactions. One of the most important characteristic features in this kind of problem is the existence of a lag phase before self-assembly takes off, which is what we focus attention on. We study the associated lag time as a function of system size and kinetic pathway. We find that the leading order stochastic contribution to the lag time before polymerization commences is inversely proportional to the system volume for large-enough system size for all nine reaction pathways tested. Finite-size corrections to this do depend on the kinetic pathway.

  19. U-8 wt %Mo and 7 wt %Mo alloys powder obtained by an hydride-de hydride process

    International Nuclear Information System (INIS)

    Balart, Silvia N.; Bruzzoni, Pablo; Granovsky, Marta S.; Gribaudo, Luis M. J.; Hermida, Jorge D.; Ovejero, Jose; Rubiolo, Gerardo H.; Vicente, Eduardo E.

    2000-01-01

    Uranium-molybdenum alloys are been tested as a component in high-density LEU dispersion fuels with very good performances. These alloys need to be transformed to powder due to the manufacturing requirements of the fuels. One method to convert ductile alloys into powder is the hydride-de hydride process, which takes advantage of the ability of the U-α phase to transform to UH 3 : a brittle and relatively low-density compound. U-Mo alloys around 7 and 8 wt % Mo were melted and heat treated at different temperature ranges in order to partially convert γ -phase to α -phase. Subsequent hydriding transforms this α -phase to UH 3 . The volume change associated to the hydride formation embrittled the material which ends up in a powdered alloy. Results of the optical metallography, scanning electron microscopy, X-ray diffraction during different steps of the process are shown. (author)

  20. Role of stacking disorder in ice nucleation.

    Science.gov (United States)

    Lupi, Laura; Hudait, Arpa; Peters, Baron; Grünwald, Michael; Gotchy Mullen, Ryan; Nguyen, Andrew H; Molinero, Valeria

    2017-11-08

    The freezing of water affects the processes that determine Earth's climate. Therefore, accurate weather and climate forecasts hinge on good predictions of ice nucleation rates. Such rate predictions are based on extrapolations using classical nucleation theory, which assumes that the structure of nanometre-sized ice crystallites corresponds to that of hexagonal ice, the thermodynamically stable form of bulk ice. However, simulations with various water models find that ice nucleated and grown under atmospheric temperatures is at all sizes stacking-disordered, consisting of random sequences of cubic and hexagonal ice layers. This implies that stacking-disordered ice crystallites either are more stable than hexagonal ice crystallites or form because of non-equilibrium dynamical effects. Both scenarios challenge central tenets of classical nucleation theory. Here we use rare-event sampling and free energy calculations with the mW water model to show that the entropy of mixing cubic and hexagonal layers makes stacking-disordered ice the stable phase for crystallites up to a size of at least 100,000 molecules. We find that stacking-disordered critical crystallites at 230 kelvin are about 14 kilojoules per mole of crystallite more stable than hexagonal crystallites, making their ice nucleation rates more than three orders of magnitude higher than predicted by classical nucleation theory. This effect on nucleation rates is temperature dependent, being the most pronounced at the warmest conditions, and should affect the modelling of cloud formation and ice particle numbers, which are very sensitive to the temperature dependence of ice nucleation rates. We conclude that classical nucleation theory needs to be corrected to include the dependence of the crystallization driving force on the size of the ice crystallite when interpreting and extrapolating ice nucleation rates from experimental laboratory conditions to the temperatures that occur in clouds.

  1. Tin and tin-titanium as catalyst components for reversible hydrogen storage of sodium aluminium hydride

    Energy Technology Data Exchange (ETDEWEB)

    Qi Jia Fu; Shik Chi Tsang [University of Reading, Reading (United Kingdom). Surface and Catalysis Research Centre, School of Chemistry

    2006-10-15

    This paper is concerned with the effects of adding tin and/or titanium dopant to sodium aluminium hydride for both dehydrogenation and re-hydrogenation reactions during their reversible storage of molecular hydrogen. Temperature programmed decomposition (TPD) measurements show that the dehydrogenation kinetics of NaAlH{sub 4} are significantly enhanced upon doping the material with 2 mol% of tributyltin hydride, Sn(Bu)3H but the tin catalyst dopant is shown to be inferior than titanium. On the other hand, in this preliminary work, a significant synergetic catalytic effect is clearly revealed in material co-doped with both titanium and tin catalysts which shows the highest reversible rates of dehydrogenation and re-hydrogenation (after their hydrogen depletion). The re-hydrogenation rates of depleted Sn/Ti/NaAlH{sub 4} evaluated at both 9.5 and 140 bars hydrogen are also found to be favourable compared to the Ti/NaAlH{sub 4}, which clearly suggest the importance of the catalyst choice. Basing on these results some mechanistic insights for the catalytic reversible dehydrogenation and re-hydrogenation processes of Sn/Ti/NaAlH{sub 4} are therefore made. 31 refs., 8 figs., 2 tabs.

  2. Effect of electronegativity on the mechanical properties of metal hydrides with a fluorite structure

    International Nuclear Information System (INIS)

    Ito, Masato; Setoyama, Daigo; Matsunaga, Junji; Muta, Hiroaki; Kurosaki, Ken; Uno, Masayoshi; Yamanaka, Shinsuke

    2006-01-01

    Bulk titanium, yttrium, and zirconium hydrides, which have the same structure as that of fluorite-type fcc C 1, were produced and their mechanical properties were investigated. With an increase in the hydrogen content, the lattice parameters of titanium and zirconium hydrides increased, whereas those of yttrium hydride decreased. The elastic moduli of titanium and zirconium hydrides decreased by hydrogen addition, whereas those of yttrium hydride increased. There are linear relations between the electronegativities and hydrogen content dependence of the properties. Therefore, the mechanical properties of the metal hydrides are considered to be determined by a common rule based on the electronegativity

  3. Fullerene hydride - A potential hydrogen storage material

    International Nuclear Information System (INIS)

    Nai Xing Wang; Jun Ping Zhang; An Guang Yu; Yun Xu Yang; Wu Wei Wang; Rui long Sheng; Jia Zhao

    2005-01-01

    Hydrogen, as a clean, convenient, versatile fuel source, is considered to be an ideal energy carrier in the foreseeable future. Hydrogen storage must be solved in using of hydrogen energy. To date, much effort has been put into storage of hydrogen including physical storage via compression or liquefaction, chemical storage in hydrogen carriers, metal hydrides and gas-on-solid adsorption. But no one satisfies all of the efficiency, size, weight, cost and safety requirements for transportation or utility use. C 60 H 36 , firstly synthesized by the method of the Birch reduction, was loaded with 4.8 wt% hydrogen indicating [60]fullerene might be as a potential hydrogen storage material. If a 100% conversion of C 60 H 36 is achieved, 18 moles of H 2 gas would be liberated from each mole of fullerene hydride. Pure C 60 H 36 is very stable below 500 C under nitrogen atmosphere and it releases hydrogen accompanying by other hydrocarbons under high temperature. But C 60 H 36 can be decomposed to generate H 2 under effective catalyst. We have reported that hydrogen can be produced catalytically from C 60 H 36 by Vasks's compound (IrCl(CO)(PPh 3 ) 2 ) under mild conditions. (RhCl(CO)(PPh 3 ) 2 ) having similar structure to (IrCl(CO)(PPh 3 ) 2 ), was also examined for thermal dehydrogenation of C 60 H 36 ; but it showed low catalytic activity. To search better catalyst, palladium carbon (Pd/C) and platinum carbon (Pt/C) catalysts, which were known for catalytic hydrogenation of aromatic compounds, were tried and good results were obtained. A very big peak of hydrogen appeared at δ=5.2 ppm in 1 H NMR spectrum based on Evans'work (fig 1) at 100 C over a Pd/C catalyst for 16 hours. It is shown that hydrogen can be produced from C 60 H 36 using a catalytic amount of Pd/C. Comparing with Pd/C, Pt/C catalyst showed lower activity. The high cost and limited availability of Vaska's compounds, Pd and Pt make it advantageous to develop less expensive catalysts for our process based on

  4. Manganese Silylene Hydride Complexes: Synthesis and Reactivity with Ethylene to Afford Silene Hydride Complexes.

    Science.gov (United States)

    Price, Jeffrey S; Emslie, David J H; Britten, James F

    2017-05-22

    Reaction of the ethylene hydride complex trans-[(dmpe) 2 MnH(C 2 H 4 )] (1) with Et 2 SiH 2 at 20 °C afforded the silylene hydride [(dmpe) 2 MnH(=SiEt 2 )] (2 a) as the trans-isomer. By contrast, reaction of 1 with Ph 2 SiH 2 at 60 °C afforded [(dmpe) 2 MnH(=SiPh 2 )] (2 b) as a mixture of the cis (major) and trans (minor) isomers, featuring a Mn-H-Si interaction in the former. The reaction to form 2 b also yielded [(dmpe) 2 MnH 2 (SiHPh 2 )] (3 b); [(dmpe) 2 MnH 2 (SiHR 2 )] (R=Et (3 a) and Ph (3 b)) were accessed cleanly by reaction of 2 a and 2 b with H 2 , and the analogous reactions with D 2 afforded [(dmpe) 2 MnD 2 (SiHR 2 )] exclusively. Both 2 a and 2 b engaged in unique reactivity with ethylene, generating the silene hydride complexes cis-[(dmpe) 2 MnH(R 2 Si=CHMe)] (R=Et (4 a), Ph (4 b)). Compounds trans-2 a, cis-2 b, 3 b, and 4 b were crystallographically characterized, and bonding in 2 a, 2 b, 4 a, and 4 b was probed computationally. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Experimental investigation on lithium hydride hydrolysis

    International Nuclear Information System (INIS)

    S Charton; F Delaunay; L Saviot; F Bernard; C Maupoix

    2006-01-01

    In order to have a better understanding of LiH reaction with water, several experimental techniques were investigated and tested to determine whether they were suitable or not in a kinetic purpose. Among them, Raman spectroscopy and X-Ray photoelectrons spectroscopy (XPS) gave particularly interesting results and are extensively used in the field of our kinetic and phenomenological study of H 2 production by LiH hydrolysis. (authors)

  6. Heterogeneous nucleation of calcium oxalate on native oxide surfaces

    International Nuclear Information System (INIS)

    Song, L.; Pattillo, M.J.; Graff, G.L.; Campbell, A.A.; Bunker, B.C.

    1994-04-01

    The aqueous deposition of calcium oxalate onto colloidal oxides has been studied as a model system for understanding heterogeneous nucleation processes of importance in biomimetic synthesis of ceramic thin films. Calcium oxalate nucleation has been monitored by measuring induction times for nucleation using Constant Composition techniques and by measuring nucleation densities on extended oxide surfaces using an atomic force microscope. Results show that the dependence of calcium oxalate nucleation on solution supersaturation fits the functional form predicted by classical nucleation theories. Anionic surfaces appear to promote nucleation better than cationic surfaces, lowering the effective energy barrier to heterogeneous nucleation

  7. Reducing the stochasticity of crystal nucleation to enable subnanosecond memory writing

    Science.gov (United States)

    Rao, Feng; Ding, Keyuan; Zhou, Yuxing; Zheng, Yonghui; Xia, Mengjiao; Lv, Shilong; Song, Zhitang; Feng, Songlin; Ronneberger, Ider; Mazzarello, Riccardo; Zhang, Wei; Ma, Evan

    2017-12-01

    Operation speed is a key challenge in phase-change random-access memory (PCRAM) technology, especially for achieving subnanosecond high-speed cache memory. Commercialized PCRAM products are limited by the tens of nanoseconds writing speed, originating from the stochastic crystal nucleation during the crystallization of amorphous germanium antimony telluride (Ge2Sb2Te5). Here, we demonstrate an alloying strategy to speed up the crystallization kinetics. The scandium antimony telluride (Sc0.2Sb2Te3) compound that we designed allows a writing speed of only 700 picoseconds without preprogramming in a large conventional PCRAM device. This ultrafast crystallization stems from the reduced stochasticity of nucleation through geometrically matched and robust scandium telluride (ScTe) chemical bonds that stabilize crystal precursors in the amorphous state. Controlling nucleation through alloy design paves the way for the development of cache-type PCRAM technology to boost the working efficiency of computing systems.

  8. Anomalous Behavior of the Homogeneous Ice Nucleation Rate in “No-Man’s Land”

    Science.gov (United States)

    2015-01-01

    We present an analysis of ice nucleation kinetics from near-ambient pressure water as temperature decreases below the homogeneous limit TH by cooling micrometer-sized droplets (microdroplets) evaporatively at 103–104 K/s and probing the structure ultrafast using femtosecond pulses from the Linac Coherent Light Source (LCLS) free-electron X-ray laser. Below 232 K, we observed a slower nucleation rate increase with decreasing temperature than anticipated from previous measurements, which we suggest is due to the rapid decrease in water’s diffusivity. This is consistent with earlier findings that microdroplets do not crystallize at nucleation rate is connected with the proposed “fragile-to-strong” transition anomaly in water. PMID:26207172

  9. Nucleation of two-dimensional islands on Si (111) during high-temperature epitaxial growth

    Energy Technology Data Exchange (ETDEWEB)

    Sitnikov, S. V., E-mail: sitnikov@isp.nsc.ru; Kosolobov, S. S.; Latyshev, A. V. [Russian Academy of Sciences, Institute of Semiconductor Physics, Siberian Branch (Russian Federation)

    2017-02-15

    The process of two-dimensional island nucleation at the surface of ultra large Si (111) during hightemperature epitaxial growth is studied by in situ ultrahigh-vacuum reflection electron microscopy. The critical terrace size D{sub crit}, at which a two-dimensional island is nucleated in the center, is measured in the temperature range 900–1180°C at different silicon fluxes onto the surface. It is found that the parameter D{sub crit}{sup 2} is a power function of the frequency of island nucleation, with the exponent χ = 0.9 ± 0.05 in the entire temperature range under study. It is established that the kinetics of nucleus formation is defined by the diffusion of adsorbed silicon atoms at temperatures of up to 1180°C and the minimum critical nucleus size corresponds to 12 silicon atoms.

  10. Technical and economic evaluation of hydrogen storage systems based on light metal hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Jepsen, Julian

    2014-07-01

    Novel developments regarding materials for solid-state hydrogen storage show promising prospects. These complex hydrides exhibit high mass-related storage capacities and thus great technical potential to store hydrogen in an efficient and safe way. However, a comprehensive evaluation of economic competitiveness is still lacking, especially in the case of the LiBH4 / MgH2 storage material. In this study, an assessment with respect to the economic feasibility of implementing complex hydrides as hydrogen storage materials is presented. The cost structure of hydrogen storage systems based on NaAlH4 and LiBH4 / MgH2 is discussed and compared with the conventional high pressure (700 bar) and liquid storage systems. Furthermore, the properties of LiBH4 / MgH2, so-called Li-RHC (Reactive Hydride Composite), are scientifically compared and evaluated on the lab and pilot plant scale. To enhance the reaction rate, the addition of TiCl3 is investigated and high energy ball milling is evaluated as processing technique. The effect of the additive in combination with the processing technique is described in detail. Finally, an optimum set of processing parameters and additive content are identified and can be applied for scaled-up production of the material based on simple models considering energy input during processing. Furthermore, thermodynamic, heat transfer and kinetic properties are experimentally determined by different techniques and analysed as a basis for modelling and designing scaled-up storage systems. The results are analysed and discussed with respect to the reaction mechanisms and reversibility of the system. Heat transfer properties are assessed with respect to the scale-up for larger hydrogen storage systems. Further improvements of the heat transfer were achieved by compacting the material. In this regard, the influence of the compaction pressure on the apparent density, thermal conductivity and sorption behaviour, was investigated in detail. Finally, scaled

  11. Chemical Hydride Slurry for Hydrogen Production and Storage

    Energy Technology Data Exchange (ETDEWEB)

    McClaine, Andrew W

    2008-09-30

    The purpose of this project was to investigate and evaluate the attractiveness of using a magnesium chemical hydride slurry as a hydrogen storage, delivery, and production medium for automobiles. To fully evaluate the potential for magnesium hydride slurry to act as a carrier of hydrogen, potential slurry compositions, potential hydrogen release techniques, and the processes (and their costs) that will be used to recycle the byproducts back to a high hydrogen content slurry were evaluated. A 75% MgH2 slurry was demonstrated, which was just short of the 76% goal. This slurry is pumpable and storable for months at a time at room temperature and pressure conditions and it has the consistency of paint. Two techniques were demonstrated for reacting the slurry with water to release hydrogen. The first technique was a continuous mixing process that was tested for several hours at a time and demonstrated operation without external heat addition. Further work will be required to reduce this design to a reliable, robust system. The second technique was a semi-continuous process. It was demonstrated on a 2 kWh scale. This system operated continuously and reliably for hours at a time, including starts and stops. This process could be readily reduced to practice for commercial applications. The processes and costs associated with recycling the byproducts of the water/slurry reaction were also evaluated. This included recovering and recycling the oils of the slurry, reforming the magnesium hydroxide and magnesium oxide byproduct to magnesium metal, hydriding the magnesium metal with hydrogen to form magnesium hydride, and preparing the slurry. We found that the SOM process, under development by Boston University, offers the lowest cost alternative for producing and recycling the slurry. Using the H2A framework, a total cost of production, delivery, and distribution of $4.50/kg of hydrogen delivered or $4.50/gge was determined. Experiments performed at Boston

  12. Impact of surface nanostructure on ice nucleation.

    Science.gov (United States)

    Zhang, Xiang-Xiong; Chen, Min; Fu, Ming

    2014-09-28

    Nucleation of water on solid surface can be promoted noticeably when the lattice parameter of a surface matches well with the ice structure. However, the characteristic length of the surface lattice reported is generally less than 0.5 nm and is hardly tunable. In this paper, we show that a surface with nanoscale roughness can also remarkably promote ice nucleation if the characteristic length of the surface structure matches well with the ice crystal. A series of surfaces composed of periodic grooves with same depth but different widths are constructed in molecular dynamics simulations. Water cylinders are placed on the constructed surfaces and frozen at constant undercooling. The nucleation rates of the water cylinders are calculated in the simulation using the mean first-passage time method and then used to measure the nucleation promotion ability of the surfaces. Results suggest that the nucleation behavior of the supercooled water is significantly sensitive to the width of the groove. When the width of the groove matches well with the specific lengths of the ice crystal structure, the nucleation can be promoted remarkably. If the width does not match with the ice crystal, this kind of promotion disappears and the nucleation rate is even smaller than that on the smooth surface. Simulations also indicate that even when water molecules are adsorbed onto the surface structure in high-humidity environment, the solid surface can provide promising anti-icing ability as long as the characteristic length of the surface structure is carefully designed to avoid geometric match.

  13. Nonclassical nucleation pathways in protein crystallization.

    Science.gov (United States)

    Zhang, Fajun

    2017-11-08

    Classical nucleation theory (CNT), which was established about 90 years ago, has been very successful in many research fields, and continues to be the most commonly used theory in describing the nucleation process. For a fluid-to-solid phase transition, CNT states that the solute molecules in a supersaturated solution reversibly form small clusters. Once the cluster size reaches a critical value, it becomes thermodynamically stable and favored for further growth. One of the most important assumptions of CNT is that the nucleation process is described by one reaction coordinate and all order parameters proceed simultaneously. Recent studies in experiments, computer simulations and theory have revealed nonclassical features in the early stage of nucleation. In particular, the decoupling of order parameters involved during a fluid-to-solid transition leads to the so-called two-step nucleation mechanism, in which a metastable intermediate phase (MIP) exists between the initial supersaturated solution and the final crystals. Depending on the exact free energy landscapes, the MIPs can be a high density liquid phase, mesoscopic clusters, or a pre-ordered state. In this review, we focus on the studies of nonclassical pathways in protein crystallization and discuss the applications of the various scenarios of two-step nucleation theory. In particular, we focus on protein solutions in the presence of multivalent salts, which serve as a model protein system to study the nucleation pathways. We wish to point out the unique features of proteins as model systems for further studies.

  14. Heat transfer enhancement on nucleate boiling

    International Nuclear Information System (INIS)

    Zhuang, M.; Guibai, L.

    1990-01-01

    This paper reports on enhancement of nucleate boiling heat transfer with additives that was investigated experimentally. More than fifteen kinds of additives were chosen and tested. Eight kinds of effective additives which can enhance nucleate boiling heat transfer were selected. Experimental results showed that boiling heat transfer coefficient of water was increased by 1 to 5 times and that of R-113 was increased by 1 to 4 times when trace amount additives were put in the two boiling liquids. There exist optimum concentrations for the additives, respectively, which can enhance nucleate boiling heat transfer rate best. In order to analyze the mechanism of the enhancement of boiling heat transfer with additives, the surface tension and the bubble departure diameter were measured. The nucleation sites were investigated by use of high-speed photograph. Experimental results showed that nucleation sites increase with additive amount increasing and get maximum. Increasing nucleation sites is one of the most important reason why nucleate boiling heat transfer can be enhanced with additives

  15. Nonclassical nucleation pathways in protein crystallization

    Science.gov (United States)

    Zhang, Fajun

    2017-11-01

    Classical nucleation theory (CNT), which was established about 90 years ago, has been very successful in many research fields, and continues to be the most commonly used theory in describing the nucleation process. For a fluid-to-solid phase transition, CNT states that the solute molecules in a supersaturated solution reversibly form small clusters. Once the cluster size reaches a critical value, it becomes thermodynamically stable and favored for further growth. One of the most important assumptions of CNT is that the nucleation process is described by one reaction coordinate and all order parameters proceed simultaneously. Recent studies in experiments, computer simulations and theory have revealed nonclassical features in the early stage of nucleation. In particular, the decoupling of order parameters involved during a fluid-to-solid transition leads to the so-called two-step nucleation mechanism, in which a metastable intermediate phase (MIP) exists between the initial supersaturated solution and the final crystals. Depending on the exact free energy landscapes, the MIPs can be a high density liquid phase, mesoscopic clusters, or a pre-ordered state. In this review, we focus on the studies of nonclassical pathways in protein crystallization and discuss the applications of the various scenarios of two-step nucleation theory. In particular, we focus on protein solutions in the presence of multivalent salts, which serve as a model protein system to study the nucleation pathways. We wish to point out the unique features of proteins as model systems for further studies.

  16. Solubility of hydrogen isotopes in stressed hydride-forming metals

    International Nuclear Information System (INIS)

    Coleman, C.E.; Ambler, J.F.R.

    1983-01-01

    Components made from hydride-forming metals can be brittle when particles of hydride are present. The solid solubility limit of hydrogen in these metals needs to be known so that fracture resistance can be properly assessed. Stress affects the solubility of hydrogen in metals. As hydrogen dissolves the metal volume increases, an applied hydrostatic tensile stress supplies work to increase the solubility. Precipitation of hydrides increases the volume further. A hydrostatic tensile stress promotes the formation of hydrides and tends to reduce the terminal solubility. For materials containing hydrogen in solution in equilibrium with hydrides, the effect of stress on the terminal solubility is given. Hydrogen migrates up tensile stress gradients because of the effect of stress on the solubility and solubility limit. Consequently, hydrogen concentrates at flaws. When hydrides are present in the metal matrix, those remote from the flaw tip will preferentially dissolve in favor of those precipitated at the flaw. If the stress is large enough, at some critical condition the hydrides at the flaw will crack. This is delayed hydrogen cracking. Notched and fatigue-cracked cantilever beam specimens (6) (38 x 4 x 3 mm) were machined from the circumferential direction of several cold-worked Zr-2.5 at. % Nb pressure tubes. The chemical compositions had the ranges (in atomic %) Nb - 2.5 to 2.7; O - 0.58 to 0.71; H - 0.018 to 0.18. The effect of test temperature is for a specimen containing 0.13 at. % protium and 0.29 at .% deuterium. Between 505 K and 530 K was less than 1 hr, between 530 K and 537 K it increased to 25.8 h, while at 538 K no cracking was observed up to the 54 h

  17. Influence of uranium hydride oxidation on uranium metal behaviour

    International Nuclear Information System (INIS)

    Patel, N.; Hambley, D.; Clarke, S.A.; Simpson, K.

    2013-01-01

    This work addresses concerns that the rapid, exothermic oxidation of active uranium hydride in air could stimulate an exothermic reaction (burning) involving any adjacent uranium metal, so as to increase the potential hazard arising from a hydride reaction. The effect of the thermal reaction of active uranium hydride, especially in contact with uranium metal, does not increase in proportion with hydride mass, particularly when considering large quantities of hydride. Whether uranium metal continues to burn in the long term is a function of the uranium metal and its surroundings. The source of the initial heat input to the uranium, if sufficient to cause ignition, is not important. Sustained burning of uranium requires the rate of heat generation to be sufficient to offset the total rate of heat loss so as to maintain an elevated temperature. For dense uranium, this is very difficult to achieve in naturally occurring circumstances. Areas of the uranium surface can lose heat but not generate heat. Heat can be lost by conduction, through contact with other materials, and by convection and radiation, e.g. from areas where the uranium surface is covered with a layer of oxidised material, such as burned-out hydride or from fuel cladding. These rates of heat loss are highly significant in relation to the rate of heat generation by sustained oxidation of uranium in air. Finite volume modelling has been used to examine the behaviour of a magnesium-clad uranium metal fuel element within a bottle surrounded by other un-bottled fuel elements. In the event that the bottle is breached, suddenly, in air, it can be concluded that the bulk uranium metal oxidation reaction will not reach a self-sustaining level and the mass of uranium oxidised will likely to be small in relation to mass of uranium hydride oxidised. (authors)

  18. Influence of uranium hydride oxidation on uranium metal behaviour

    Energy Technology Data Exchange (ETDEWEB)

    Patel, N.; Hambley, D. [National Nuclear Laboratory (United Kingdom); Clarke, S.A. [Sellafield Ltd (United Kingdom); Simpson, K.

    2013-07-01

    This work addresses concerns that the rapid, exothermic oxidation of active uranium hydride in air could stimulate an exothermic reaction (burning) involving any adjacent uranium metal, so as to increase the potential hazard arising from a hydride reaction. The effect of the thermal reaction of active uranium hydride, especially in contact with uranium metal, does not increase in proportion with hydride mass, particularly when considering large quantities of hydride. Whether uranium metal continues to burn in the long term is a function of the uranium metal and its surroundings. The source of the initial heat input to the uranium, if sufficient to cause ignition, is not important. Sustained burning of uranium requires the rate of heat generation to be sufficient to offset the total rate of heat loss so as to maintain an elevated temperature. For dense uranium, this is very difficult to achieve in naturally occurring circumstances. Areas of the uranium surface can lose heat but not generate heat. Heat can be lost by conduction, through contact with other materials, and by convection and radiation, e.g. from areas where the uranium surface is covered with a layer of oxidised material, such as burned-out hydride or from fuel cladding. These rates of heat loss are highly significant in relation to the rate of heat generation by sustained oxidation of uranium in air. Finite volume modelling has been used to examine the behaviour of a magnesium-clad uranium metal fuel element within a bottle surrounded by other un-bottled fuel elements. In the event that the bottle is breached, suddenly, in air, it can be concluded that the bulk uranium metal oxidation reaction will not reach a self-sustaining level and the mass of uranium oxidised will likely to be small in relation to mass of uranium hydride oxidised. (authors)

  19. Developments in delayed hydride cracking in zirconium alloys

    International Nuclear Information System (INIS)

    Puls, Manfred P.

    2008-01-01

    Delayed hydride cracking (DHC) is a process of diffusion assisted localized hydride embrittlement at flaws or regions of high stress. Models of DHC propagation and initiation have been developed that capture the essential elements of this phenomenon in terms of parameters describing processes occurring at the micro-scale. The models and their predictions of experimental results applied to Zr alloys are assessed. The propagation model allows rationalization of the effect of direction of approach to temperature and of the effect of the state and morphology of the beta phase in Zr-2.5Nb on DHC velocity. The K I dependence of the DHC velocity can only be approximately rationalized by the propagation models. This is thought to be because these models approximate the DHC velocity by a constant and shape-invariant rate of growth of the hydride at the flaw and have not incorporated a coupling between the applied stress field due to the flaw alone and the precipitated hydrides that would result in a variation of the shape and density of the hydrided region with K I . Separately, models have been developed for DHC initiation at cracks and blunt flaws. Expressions are obtained for the threshold stress intensity factor, K IH , for DHC initiation at a crack. A model for K IH has been used to rationalize the experimental result that DHC initiation is not possible above a certain temperature, even when hydrides can form at the crack tip. For blunt flaws with root radii in the μm range, and engineering process zone procedure has been derived to determine the initiation conditions requiring that both a critical stress and a critical flaw tip displacement must be achieved for hydride fracture. The engineering process zone procedure takes account of the dependence of DHC initiation on the flaw's root radius. Although all of the foregoing models are capable of describing the essential features of DHC, they are highly idealized and in need of further refinement. (author)

  20. Multidimensional simulations of hydrides during fuel rod lifecycle

    International Nuclear Information System (INIS)

    Stafford, D.S.

    2015-01-01

    In light water reactor fuel rods, waterside corrosion of zirconium-alloy cladding introduces hydrogen into the cladding, where it is slightly soluble. When the solubility limit is reached, the hydrogen precipitates into crystals of zirconium hydride which decrease the ductility of the cladding and may lead to cladding failure during dry storage or transportation events. The distribution of the hydride phase and the orientation of the crystals depend on the history of the spatial temperature and stress profiles in the cladding. In this work, we have expanded the existing hydride modeling capability in the BISON fuel performance code with the goal of predicting both global and local effects on the radial, azimuthal and axial distribution of the hydride phase. We compare results from 1D simulations to published experimental data. We demonstrate the new capability by simulating in 2D a fuel rod throughout a lifecycle that includes irradiation, short-term storage in the spent fuel pool, drying, and interim storage in a dry cask. Using the 2D simulations, we present qualitative predictions of the effects of the inter-pellet gap and the drying conditions on the growth of a hydride rim. - Highlights: • We extend BISON fuel performance code to simulate lifecycle of fuel rods. • We model hydrogen evolution in cladding from reactor through dry storage. • We validate 1D simulations of hydrogen evolution against experiments. • We show results of 2D axisymmetric simulations predicting hydride formation. • We show how our model predicts formation of a hydride rim in the cladding.

  1. Damage nucleation in Si during ion irradiation

    International Nuclear Information System (INIS)

    Holland, O.W.; Fathy, D.; Narayan, J.

    1984-01-01

    Damage nucleation in single crystals of silicon during ion irradiation is investigated. Experimental results and mechanisms for damage nucleation during both room and liquid nitrogen temperature irradiation with different mass ions are discussed. It is shown that the accumulation of damage during room temperature irradiation depends on the rate of implantation. These dose rate effects are found to decrease in magnitude as the mass of the ions is increased. The significance of dose rate effects and their mass dependence on nucleation mechanisms is discussed

  2. Controlled nucleation and crystallization of fluorozirconate glasses

    International Nuclear Information System (INIS)

    Frischat, G.H.

    1993-01-01

    Pt, Se, and Ag, respectively, were used as nucleating agents for a ZrF 4 -BaF 4 -YF 3 -AlF 3 glass. Nucleation and crystal growth rates were determined as a function of experimental conditions. In all cases the bulk crystals mainly consist of β-BaZrF6, leading to a relatively coarse-grained microstructure. However, in the case of Ag used as a nucleating agent, the microstructure is bimodal with an additional fine-grained crystal phase. In the cases of Se and Ag the relative crystal fraction could be developed in a controlled way between 0 and 100%

  3. Viscosity of interfacial water regulates ice nucleation

    International Nuclear Information System (INIS)

    Li, Kaiyong; Chen, Jing; Zhang, Qiaolan; Zhang, Yifan; Xu, Shun; Zhou, Xin; Cui, Dapeng; Wang, Jianjun; Song, Yanlin

    2014-01-01

    Ice formation on solid surfaces is an important phenomenon in many fields, such as cloud formation and atmospheric icing, and a key factor for applications in preventing freezing. Here, we report temperature-dependent nucleation rates of ice for hydrophilic and hydrophobic surfaces. The results show that hydrophilic surface presents a lower ice nucleation rate. We develop a strategy to extract the thermodynamic parameters, J 0 and Γ, in the context of classical nucleation theory. From the extracted J 0 and Γ, we reveal the dominant role played by interfacial water. The results provide an insight into freezing mechanism on solid surfaces

  4. Nanowires and nanoneedles nucleation on vicinal substrate

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Xu, E-mail: zhangxubetter@gmail.com [Henan Key Laboratory of Laser and Opto-electric Information Technology, School of Information Engineering, Zhengzhou University, Zhengzhou 450052 (China); Xie, Dan; Huang, Genling [Zhengzhou Railway Vocational and Technical College, Zhengzhou 450052 (China); Sun, Xiao-Hong [Henan Key Laboratory of Laser and Opto-electric Information Technology, School of Information Engineering, Zhengzhou University, Zhengzhou 450052 (China)

    2015-01-01

    An analytic stress-driven nucleation model of nanowires (NWs) and nanoneedles (NNs) growing on a mismatched vicinal substrate is proposed. It is demonstrated that the formation enthalpy of NWs and NNs is a function of three independent variables, the base radius, aspect ratio and miscut angle of the vicinal surface. Theoretical analysis shows that the minimum nucleation barrier of an island decreases with increment of substrate misorientation, which means the nucleation of islands on a vicinal substrate is more favorable than that on a flat substrate.

  5. Permeation rates for RTF metal hydride vessels

    International Nuclear Information System (INIS)

    Klein, J.E.

    1992-01-01

    Contamination rates have been estimated for the RTF nitrogen heating and cooling system (NH and CS) due to tritium permeation through the walls of metal hydride vessels. Tritium contamination of the NH and CS will be seen shortly after start-up of the RTF with the majority of it coming from the TCAP units. Contamination rates of the NH and CS are estimated to exceed 400 Ci/year after three years of operation and will elevate tritium concentrations in the NH and CS above 6 x 10 -3 μCi/cc. To reduce tritium activity in the NH and CS, a stripper or ''getter'' bed may need to be installed in the NH and CS. Increasing the purge rate of nitrogen from the NH and CS is shown to be an impractical method for reducing tritium activity due to the high purge rates required. Stripping of the NH and CS nitrogen in the glove box stripper system will give a temporary lowering of tritium activity in the NH and CS, but tritium activity will return to its previous level in approximately two weeks

  6. Hydriding and neutron irradiation in zircaloy-4

    International Nuclear Information System (INIS)

    Ramos, Ruben Fortunato; Martin, Juan Ezequiel; Orellano, Pablo; Dorao, Carlos; Analia Soldati; Ghilarducci, Ada Albertina; Corso, Hugo Luis; Peretti, Hernan Americo; Bolcich, Juan Carlos

    2003-01-01

    The composition of Zircaloy-4 for nuclear applications is specified by the ASTM B350 Standard, that fixes the amount of alloying elements (Sn, Fe, Cr) and impurities (Ni, Hf, O, N, C, among others) to optimize good corrosion and mechanical behavior.The recycling of zircaloy-4 scrap and chips resulting from cladding tube fabrication is an interesting issue.However, changes in the final composition of the recycled material may occur due to contamination with tool pieces, stainless steel chips, turnings, etc. while scrap is stored and handled. Since the main components of the possible contaminants are Fe, Cr and Ni, it arises the interest in studying up to what limit the Fe, Ni and Cr contents could be exceeded beyond the standard specification without affecting significantly the alloy properties.Zircaloy-4 alloys elaborated with Fe, Cr and Ni additions and others of standard composition in use in nuclear plants are studied by tensile tests, SEM observations and EDS microanalysis.Some samples are tested in the initial condition and others after hydriding treatments and neutron irradiation in the RA6

  7. Optical and photoemission studies of lanthanum hydrides

    International Nuclear Information System (INIS)

    Peterman, D.J.; Peterson, D.T.; Weaver, J.H.

    1980-01-01

    The results of optical absorptivity and photoemission measurements on lanthanum hydrides, LaH/sub x/ (1.98 less than or equal to x less than or equal to 2.89) are reported. The low energy (hν less than or equal to 0.5 eV) optical features in LaH/sub x/ are attributed to the filling of octahedral sites. Higher energy interband absorption involves states within the d-band complex, analogous to other dihydrides. As x increases above 2.0, the optical features change rapidly due to the increase in the number of occupied octahedral sites. Various band structure studies suggest that LaH 3 might be a semiconductor. Photoemission results show that as x increases, the d-derived states at E/sub F/ are drawn down and that for LaH 2 89 only very weak valence band emission is observed. The hydrogen-derived bonding bands are shown centered approx. 5 eV below E/sub F/. Observed chemical shifts in the La 5p/sub 1/2 3/2/ cores are discussed for 1.98 less than or equal to x less than or equal to 2.89

  8. Towards establishing a combined rate law of nucleation and crystal growth - The case study of gypsum precipitation

    Science.gov (United States)

    Rendel, Pedro M.; Gavrieli, Ittai; Wolff-Boenisch, Domenik; Ganor, Jiwchar

    2018-03-01

    The main obstacle in the formulation of a quantitative rate-model for mineral precipitation is the absence of a rigorous method for coupling nucleation and growth processes. In order to link both processes, we conducted a series of batch experiments in which gypsum nucleation was followed by crystal growth. Experiments were carried out using various stirring methods in several batch vessels made of different materials. In the experiments, the initial degree of supersaturation of the solution with respect to gypsum (Ωgyp) was set between 1.58 and 1.82. Under these conditions, heterogeneous nucleation is the dominant nucleation mode. Based on changes in SO42- concentration with time, the induction time of gypsum nucleation and the following rate of crystal growth were calculated for each experiment. The induction time (6-104 h) was found to be a function of the vessel material, while the rates of crystal growth, which varied over three orders of magnitude, were strongly affected by the stirring speed and its mode (i.e. rocking, shaking, magnetic stirrer, and magnetic impeller). The SO42- concentration data were then used to formulate a forward model that couples the simple rate laws for nucleation and crystal growth of gypsum into a single kinetic model. Accordingly, the obtained rate law is based on classical nucleation theory and heterogeneous crystal growth.

  9. Dynamic observations of vesiculation reveal the role of silicate crystals in bubble nucleation and growth in andesitic magmas

    Energy Technology Data Exchange (ETDEWEB)

    Pleše, P.; Higgins, M. D.; Mancini, L.; Lanzafame, G.; Brun, F.; Fife, J. L.; Casselman, J.; Baker, D. R.

    2018-01-01

    Bubble nucleation and growth control the explosivity of volcanic eruptions, and the kinetics of these processes are generally determined from examinations of natural samples and quenched experimental run products. These samples, however, only provide a view of the final state, from which the initial conditions of a time-evolving magmatic system are then inferred. The interpretations that follow are inexact due to the inability of determining the exact conditions of nucleation and the potential detachment of bubbles from their nucleation sites, an uncertainty that can obscure their nucleation location – either homogeneously within the melt or heterogeneously at the interface between crystals and melts. We present results of a series of dynamic, real-time 4D X-ray tomographic microscopy experiments where we observed the development of bubbles in crystal bearing silicate magmas. Experimentally synthesized andesitic glasses with 0.25–0.5 wt% H2O and seed silicate crystals were heated at 1 atm to induce bubble nucleation and track bubble growth and movement. In contrast to previous studies on natural and experimentally produced samples, we found that bubbles readily nucleated on plagioclase and clinopyroxene crystals, that their contact angle changes during growth and that they can grow to sizes many times that of the silicate on whose surface they originated. The rapid heterogeneous nucleation of bubbles at low degrees of supersaturation in the presence of silicate crystals demonstrates that silicates can affect when vesiculation ensues, influencing subsequent permeability development and effusive vs. explosive transition in volcanic eruptions.

  10. Dynamic observations of vesiculation reveal the role of silicate crystals in bubble nucleation and growth in andesitic magmas

    Science.gov (United States)

    Pleše, P.; Higgins, M. D.; Mancini, L.; Lanzafame, G.; Brun, F.; Fife, J. L.; Casselman, J.; Baker, D. R.

    2018-01-01

    Bubble nucleation and growth control the explosivity of volcanic eruptions, and the kinetics of these processes are generally determined from examinations of natural samples and quenched experimental run products. These samples, however, only provide a view of the final state, from which the initial conditions of a time-evolving magmatic system are then inferred. The interpretations that follow are inexact due to the inability of determining the exact conditions of nucleation and the potential detachment of bubbles from their nucleation sites, an uncertainty that can obscure their nucleation location - either homogeneously within the melt or heterogeneously at the interface between crystals and melts. We present results of a series of dynamic, real-time 4D X-ray tomographic microscopy experiments where we observed the development of bubbles in crystal bearing silicate magmas. Experimentally synthesized andesitic glasses with 0.25-0.5 wt% H2O and seed silicate crystals were heated at 1 atm to induce bubble nucleation and track bubble growth and movement. In contrast to previous studies on natural and experimentally produced samples, we found that bubbles readily nucleated on plagioclase and clinopyroxene crystals, that their contact angle changes during growth and that they can grow to sizes many times that of the silicate on whose surface they originated. The rapid heterogeneous nucleation of bubbles at low degrees of supersaturation in the presence of silicate crystals demonstrates that silicates can affect when vesiculation ensues, influencing subsequent permeability development and effusive vs. explosive transition in volcanic eruptions.

  11. Effect of amorphous Mg{sub 50}Ni{sub 50} on hydriding and dehydriding behavior of Mg{sub 2}Ni alloy

    Energy Technology Data Exchange (ETDEWEB)

    Guzman, D., E-mail: danny.guzman@uda.cl [Departamento de Ingenieria en Metalurgia, Facultad de Ingenieria, Universidad de Atacama y Centro Regional de Investigacion y Desarrollo Sustentable de Atacama (CRIDESAT), Av. Copayapu 485, Copiapo (Chile); Ordonez, S. [Departamento de Ingenieria Metalurgica, Facultad de Ingenieria, Universidad de Santiago de Chile, Av. Lib. Bernardo O' Higgins 3363, Santiago (Chile); Fernandez, J.F.; Sanchez, C. [Departamento de Fisica de Materiales, Facultad de Ciencias, Universidad Autonoma de Madrid, Cantoblanco 28049, Madrid (Spain); Serafini, D. [Departamento de Fisica, Facultad de Ciencias, Universidad de Santiago de Chile and Center for Interdisciplinary Research in Materials, CIMAT, Av. Lib. Bernardo O' Higgins 3363, Santiago (Chile); Rojas, P.A. [Escuela de Ingenieria Mecanica, Facultad de Ingenieria, Av. Los Carrera 01567, Quilpue, Pontificia Universidad Catolica de Valparaiso, PUCV (Chile); Aguilar, C. [Departamento de Ingenieria Metalurgica y Materiales, Universidad Tecnica Federico Santa Maria, Av. Espana 1680, Valparaiso (Chile); Tapia, P. [Departamento de Ingenieria en Metalurgia, Facultad de Ingenieria, Universidad de Atacama, Av. Copayapu 485, Copiapo (Chile)

    2011-04-15

    Composite Mg{sub 2}Ni (25 wt.%) amorphous Mg{sub 50}Ni{sub 50} was prepared by mechanical milling starting with nanocrystalline Mg{sub 2}Ni and amorphous Mg{sub 50}Ni{sub 50} powders, by using a SPEX 8000 D mill. The morphological and microstructural characterization of the powders was performed via scanning electron microscopy and X-ray diffraction. The hydriding characterization of the composite was performed via a solid gas reaction method in a Sievert's-type apparatus at 363 K under an initial hydrogen pressure of 2 MPa. The dehydriding behavior was studied by differential thermogravimetry. On the basis of the results, it is possible to conclude that amorphous Mg{sub 50}Ni{sub 50} improved the hydriding and dehydriding kinetics of Mg{sub 2}Ni alloy upon cycling. A tentative rationalization of experimental observations is proposed. - Research Highlights: {yields} First study of the hydriding behavior of composite Mg{sub 2}Ni (25 wt.%) amorphous Mg{sub 50}Ni{sub 50}. {yields} Microstructural characterization of composite material using XRD and SEM was obtained. {yields} An improved effect of Mg{sub 50}Ni{sub 50} on the Mg{sub 2}Ni hydriding behavior was verified. {yields} The apparent activation energy for the hydrogen desorption of composite was obtained.

  12. Nucleation of dislocation loops during irradiation in binary FCC alloys with different alloy compositions

    International Nuclear Information System (INIS)

    Hashimoto, T.; Shigenaka, N.; Fuse, M.

    1992-01-01

    Dislocation loop nucleation is analyzed using a rate theory based model for face-centered cubic (fcc) binary alloys containing A- and B-atoms. In order to calculate the nucleation process in concentrated alloys, the model considers three types of interstitial dumbbells composed of A- and B-atoms, AA-, BB-, and AB-type dumbbells. Conversions between these interstitial dumbbells are newly introduced in the formulation in consideration of dumbbell configurations and movements. The model also includes reactions, such as point defect production by irradiation, mutual recombination of an interstitial and a vacancy, and dislocation loop nucleation and growth. Parameter values are chosen based on the atom size of the alloy component elements, and dislocation loop nucleation kinetics are investigated while varying alloy compositions. Two different types of kinetics are obtained in accordance with the dominant loop nucleus type. The migration energy difference of AA- and BB-type interstitial dumbbells is important in the determination of the dominant loop nucleus type. The present model predicts that the dislocation loop concentration decrease with increasing under sized atoms content, but defect production rate and temperature dependences of loop concentration are insensitive to alloy compositions. (author)

  13. Nucleation mechanisms of refined alpha microstructure in beta titanium alloys

    Science.gov (United States)

    Zheng, Yufeng

    . Therefore, the nucleation mechanisms proposed could successfully explain the features of refined and super-refined precipitates microstructure in Ti-5553, validated by thermodynamic calculations and phase field modeling simulation. In addition to the study of microstructure evolution in beta titanium alloys upon various heat treatment conditions, another effort made in the current study is to apply various phase transformation analysis tools on titanium alloys in order to capture the initial stage of precipitation and investigate the kinetics of precipitation. Especially Electro-Thermo-Mechanical Tester (ETMT) is used to in-situ measure the physical properties change of Ti-5553 during heat treatment and therefore analyze the kinetics of phase transformation. This part of work can be treated as complementary work of the study of microstructure evolution in beta titanium alloys. In summary, refined and super-refined precipitates microstructure in Ti-5553 are studied using both modern characterization techniques and computational simulation. Nucleation mechanisms are proposed to explain all the features of two specific microstructures and critical heat treatment conditions are figured out. Therefore, this insightful study is not only beneficial to understanding the details of phase transformation in the scientific aspect but also complement to selection of heat treatment conditions in industry area.

  14. Dynamics of protein aggregation and oligomer formation governed by secondary nucleation

    Energy Technology Data Exchange (ETDEWEB)

    Michaels, Thomas C. T., E-mail: tctm3@cam.ac.uk; Lazell, Hamish W.; Arosio, Paolo; Knowles, Tuomas P. J., E-mail: tpjk2@cam.ac.uk [Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW (United Kingdom)

    2015-08-07

    The formation of aggregates in many protein systems can be significantly accelerated by secondary nucleation, a process where existing assemblies catalyse the nucleation of new species. In particular, secondary nucleation has emerged as a central process controlling the proliferation of many filamentous protein structures, including molecular species related to diseases such as sickle cell anemia and a range of neurodegenerative conditions. Increasing evidence suggests that the physical size of protein filaments plays a key role in determining their potential for deleterious interactions with living cells, with smaller aggregates of misfolded proteins, oligomers, being particularly toxic. It is thus crucial to progress towards an understanding of the factors that control the sizes of protein aggregates. However, the influence of secondary nucleation on the time evolution of aggregate size distributions has been challenging to quantify. This difficulty originates in large part from the fact that secondary nucleation couples the dynamics of species distant in size space. Here, we approach this problem by presenting an analytical treatment of the master equation describing the growth kinetics of linear protein structures proliferating through secondary nucleation and provide closed-form expressions for the temporal evolution of the resulting aggregate size distribution. We show how the availability of analytical solutions for the full filament distribution allows us to identify the key physical parameters that control the sizes of growing protein filaments. Furthermore, we use these results to probe the dynamics of the populations of small oligomeric species as they are formed through secondary nucleation and discuss the implications of our work for understanding the factors that promote or curtail the production of these species with a potentially high deleterious biological activity.

  15. Hydrogen storage as a hydride. Citations from the International Aerospace Abstracts data base

    Science.gov (United States)

    Zollars, G. F.

    1980-01-01

    These citations from the international literature concern the storage of hydrogen in various metal hydrides. Binary and intermetallic hydrides are considered. Specific alloys discussed are iron titanium, lanthanium nickel, magnesium copper and magnesium nickel among others.

  16. Sodium-based hydrides for thermal energy applications

    Science.gov (United States)

    Sheppard, D. A.; Humphries, T. D.; Buckley, C. E.

    2016-04-01

    Concentrating solar-thermal power (CSP) with thermal energy storage (TES) represents an attractive alternative to conventional fossil fuels for base-load power generation. Sodium alanate (NaAlH4) is a well-known sodium-based complex metal hydride but, more recently, high-temperature sodium-based complex metal hydrides have been considered for TES. This review considers the current state of the art for NaH, NaMgH3- x F x , Na-based transition metal hydrides, NaBH4 and Na3AlH6 for TES and heat pumping applications. These metal hydrides have a number of advantages over other classes of heat storage materials such as high thermal energy storage capacity, low volume, relatively low cost and a wide range of operating temperatures (100 °C to more than 650 °C). Potential safety issues associated with the use of high-temperature sodium-based hydrides are also addressed.

  17. Energetics of dislocation nucleation under a nanoindenter

    International Nuclear Information System (INIS)

    Zhang Chuanli; Xu Guanshui

    2005-01-01

    We present an analysis of dislocation nucleation under an idealized nanoindenter based on the variational boundary integral formulation of the Peierls-Nabarro dislocation model. By solving the embryonic dislocation profiles, corresponding to the relative displacements between the two adjacent atomic layers along the slip plane, we have determined the critical conditions for athermal dislocation nucleation as well as the activation energies required to thermally activate embryonic dislocations from their stable to unstable saddle point configurations. The effect of the size of the indenter on the energetics of dislocation nucleation is quantitatively characterized. The result is compared with a simplified analysis based on the application of the Rice model for dislocation nucleation at a crack tip

  18. Energetics of dislocation nucleation under a nanoindenter

    Energy Technology Data Exchange (ETDEWEB)

    Zhang Chuanli [College of Mechanical Engineering, Yangtze University, Jingzhou, Hubei 434023 (China); Department of Mechanical Engineering, University of California, Riverside, CA 92521 (United States); Xu Guanshui [Department of Mechanical Engineering, University of California, Riverside, CA 92521 (United States)]. E-mail: guanshui.xu@ucr.edu

    2005-07-25

    We present an analysis of dislocation nucleation under an idealized nanoindenter based on the variational boundary integral formulation of the Peierls-Nabarro dislocation model. By solving the embryonic dislocation profiles, corresponding to the relative displacements between the two adjacent atomic layers along the slip plane, we have determined the critical conditions for athermal dislocation nucleation as well as the activation energies required to thermally activate embryonic dislocations from their stable to unstable saddle point configurations. The effect of the size of the indenter on the energetics of dislocation nucleation is quantitatively characterized. The result is compared with a simplified analysis based on the application of the Rice model for dislocation nucleation at a crack tip.

  19. Theories of nucleation and growth of bubbles and voids

    International Nuclear Information System (INIS)

    Speight, M.V.

    1977-01-01

    The application of classical nucleation theory to the formation of voids from a supersaturated concentration of vacancies is reviewed. The effect of a dissolved concentration of barley soluble gas on the nucleation rate of voids is emphasized. Exposure to a damaging flux of irradiation is the most effective way of introducing a vacancy supersaturation, but interstitials are produced at an equal rate. The concentration of interstitials inhibits the nucleation of voids which can occur only in the presence of dislocations since they preferentially absorb interstitials. It is well known that a definite value of internal gas pressure is necessary to stabilize a bubble so that it shows no tendencies to either shrink or grow. The arguments are reviewed which conclude that this pressure is determined by the specific surface free energy of the solid rather than the surface tension. While the former property refers to the energy necessary to create new surface, the latter is a measure of the work done in elastically stretching a a given surface. The presence of an equilibrium gas bubble leaves the stresses in the surrounding solid unperturbed only when surface energy and surface tension are numerically equal. A bubble with internal pressure greater than the restraint offered by surface energy tends to grow to relieve the excess pressure. The mechanism of growth can involve the migration of vacancies from remote sources to the bubble surface or the plastic straining of the solid surrounding the bubble. The kinetics of both mechanisms are developed and compared. The theory of growth of grain-boundary voids by vacancy condensation under an applied stress is also considered. (author)

  20. Nucleation of metastable aragonite CaCO3 in seawater.

    Science.gov (United States)

    Sun, Wenhao; Jayaraman, Saivenkataraman; Chen, Wei; Persson, Kristin A; Ceder, Gerbrand

    2015-03-17

    Predicting the conditions in which a compound adopts a metastable structure when it crystallizes out of solution is an unsolved and fundamental problem in materials synthesis, and one which, if understood and harnessed, could enable the rational design of synthesis pathways toward or away from metastable structures. Crystallization of metastable phases is particularly accessible via low-temperature solution-based routes, such as chimie douce and hydrothermal synthesis, but although the chemistry of the solution plays a crucial role in governing which polymorph forms, how it does so is poorly understood. Here, we demonstrate an ab initio technique to quantify thermodynamic parameters of surfaces and bulks in equilibrium with an aqueous environment, enabling the calculation of nucleation barriers of competing polymorphs as a function of solution chemistry, thereby predicting the solution conditions governing polymorph selection. We apply this approach to resolve the long-standing "calcite-aragonite problem"--the observation that calcium carbonate precipitates as the metastable aragonite polymorph in marine environments, rather than the stable phase calcite--which is of tremendous relevance to biomineralization, carbon sequestration, paleogeochemistry, and the vulnerability of marine life to ocean acidification. We identify a direct relationship between the calcite surface energy and solution Mg:Ca [corrected] ion concentrations, showing that the calcite nucleation barrier surpasses that of metastable aragonite in solutions with Mg:Ca ratios consistent with modern seawater, allowing aragonite to dominate the kinetics of nucleation. Our ability to quantify how solution parameters distinguish between polymorphs marks an important step toward the ab initio prediction of materials synthesis pathways in solution.

  1. Heterogeneous nucleation of entrained eutectic Si in high purity melt spun Al-Si alloys investigated by entrained droplet technique and DSC

    International Nuclear Information System (INIS)

    Li, J H; Schumacher, P; Albu, M; Hofer, F; Ludwig, T H; Arnberg, L

    2016-01-01

    Entrained droplet technique and DSC analyses were employed to investigate the influence of trace elements of Sr, Eu and P on the heterogeneous nucleation of entrained eutectic Si in high purity melt spun Al-5wt.% Si alloys. Sr and Eu addition was found to exert negative effects on the nucleation process, while an increased undercooling was observed. This can be attributed to the formation of phosphide compounds having a lower free energy and hence may preferentially form compared to AlP. Only a trace P addition was found to have a profound effect on the nucleation process. The nucleation kinetics is discussed on the basis of the classical nucleation theory and the free growth model, respectively. The estimated AlP patch size was found to be sufficient for the free growth of Si to occur within the droplets, which strongly indicates that the nucleation of Si on an AlP patch or AlP particle is a limiting step for free growth. The maximum nucleation site density within one droplet is directly related to the size distribution of AlP particles or AlP patches for Si nucleation, but is independent of the cooling rates. Although the nucleation conditions were optimized in entrained droplet experiments, the observed mechanisms are also valid at moderate cooling conditions, such as in shape casting. (paper)

  2. Grain nucleation and growth during phase transformations

    DEFF Research Database (Denmark)

    Offerman, S.E.; Dijk, N.H. van; Sietsma, J.

    2002-01-01

    of individual grains. Our measurements show that the activation energy for grain nucleation is at least two orders of magnitude smaller than that predicted by thermodynamic models. The observed growth curves of the newly formed grains confirm the parabolic growth model but also show three fundamentally...... different types of growth. Insight into the grain nucleation and growth mechanisms during phase transformations contributes to the development of materials with optimal mechanical properties....

  3. Experimental study on thermophysical and kinetic properties of the LaNi5-H2 system

    International Nuclear Information System (INIS)

    Yoshida, A.; Naka, A.; Ohkita, T.

    1991-01-01

    This paper reports on thermophysical and kinetic properties of the LaNi 5 -H 2 system that were investigated for the practical utilization of hydriding alloys. Measurements of the thermophysical properties were carried out by a transient hot-wire method along the P-C isotherms. The effective thermal conductivities of the system increase not only with an increase of hydrogen gas pressure but also in the plateau region with an increase of composition of metal hydride. The specific heats of the metal hydride increase with an increase in composition. The kinetic properties were measured under both isobaric and isothermal conditions. The derived intrinsic chemical reaction rates indicate a difference in the reaction mechanism between the absorption and the desorption processes

  4. A classical view on nonclassical nucleation.

    Science.gov (United States)

    Smeets, Paul J M; Finney, Aaron R; Habraken, Wouter J E M; Nudelman, Fabio; Friedrich, Heiner; Laven, Jozua; De Yoreo, James J; Rodger, P Mark; Sommerdijk, Nico A J M

    2017-09-19

    Understanding and controlling nucleation is important for many crystallization applications. Calcium carbonate (CaCO 3 ) is often used as a model system to investigate nucleation mechanisms. Despite its great importance in geology, biology, and many industrial applications, CaCO 3 nucleation is still a topic of intense discussion, with new pathways for its growth from ions in solution proposed in recent years. These new pathways include the so-called nonclassical nucleation mechanism via the assembly of thermodynamically stable prenucleation clusters, as well as the formation of a dense liquid precursor phase via liquid-liquid phase separation. Here, we present results from a combined experimental and computational investigation on the precipitation of CaCO 3 in dilute aqueous solutions. We propose that a dense liquid phase (containing 4-7 H 2 O per CaCO 3 unit) forms in supersaturated solutions through the association of ions and ion pairs without significant participation of larger ion clusters. This liquid acts as the precursor for the formation of solid CaCO 3 in the form of vaterite, which grows via a net transfer of ions from solution according to z Ca 2+ + z CO 3 2- → z CaCO 3 The results show that all steps in this process can be explained according to classical concepts of crystal nucleation and growth, and that long-standing physical concepts of nucleation can describe multistep, multiphase growth mechanisms.

  5. Nucleation and growth of oxides on metals with special reference to mild steel and zirconium

    Energy Technology Data Exchange (ETDEWEB)

    Gadiyar, H S [Bhabha Atomic Research Centre, Bombay (India). Metallurgy Div.

    1977-01-01

    The oxidation of metals is a complex phenomenon of metal-gas interface for the understanding of which a multidisciplinary approach is necessary. Some aspects of this phenomena are discussed with reference to oxygen or steam as the oxidant. As a case study, the nucleation of oxide through microstructural characterisation, the kinetics and mechanism involved in the case of oxidation of Zr and its alloys have been examined.

  6. Simultaneous determination of hydride and non-hydride forming elements by inductively coupled plasma optical emission spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Benzo, Z. [Instituto Venezolano de Investigaciones Cientificas, IVIC, Altos de Pipe, Caracas (Venezuela, Bolivarian Republic of); Matos-Reyes, M.N.; Cervera, M.L.; Guardia, M. de la, E-mail: m.luisa.cervera@uv.es [Department of Analytical Chemistry, University of Valencia, Valencia (Spain)

    2011-09-15

    The operating characteristics of a dual nebulization system were studied including instrumental and chemical conditions for the hydride generation and analytical figures of merit for both, hydride and non hydride forming elements. Analytical performance of the nebulization system was characterized by detection limits from 0.002 to 0.0026 {mu}g mL{sup -1} for the hydride forming elements and between 0.0034 and 0.0121 {mu}g mL{sup -1} for the non-hydride forming elements, relative standard deviation for 10 replicate measurements at 0.25 mg L{sup -1} level and recovery percentages between 97 and 103%. The feasibility of the system was demonstrated in the simultaneous determination of Ca, Cd, Co, Cr, Cu, Fe, Mg, Mn, Mo, Ni, Zn, As, Bi, Sb, Se, and Te in the NIST 1549 (non-fat milk powder), NIST 1570a (spinach leaves), DORM-2 (dogfish muscle) and TORT-2 (lobster hepatopancreas) certified samples for trace elements. Results found were in good agreement with the certified ones. (author)

  7. Infrared diode laser spectroscopy of lithium hydride

    International Nuclear Information System (INIS)

    Yamada, C.; Hirota, E.

    1988-01-01

    The fundamental and hot bands of the vibration--rotation transitions of 6 LiH, 7 LiH, 6 LiD, and 7 LiD were observed by infrared diode laser spectroscopy at Doppler-limited resolution. Lithium hydride molecules were produced by the reaction of the Li vapor with hydrogen at elevated temperatures. Some 40 transitions were observed and, after combined with submillimeter-wave spectra reported by G. M. Plummer et al. [J. Chem. Phys. 81, 4893 (1984)], were analyzed to yield Dunham-type constants with accuracies more than an order of magnitude higher than those published in the literature. It was clearly demonstrated that the Born--Oppenheimer approximation did not hold, and some parameters representing the breakdown were evaluated. The Born--Oppenheimer internuclear distance r/sup BO//sub e/ was derived to be 1.594 914 26 (59) A, where a new value of Planck's constant recommended by CODATA was employed. The relative intensity of absorption lines was measured to determine the ratio of the permanent dipole moment to its first derivative with respect to the internuclear distance: μ/sub e/ [(partialμpartialr)/sub e/ r/sub e/ ] = 1.743(86). The pressure broadening parameter Δν/sub p/ P was determined to be 6.40 (22) MHzTorr by measuring the linewidth dependence on the pressure of hydrogen, which was about four times larger than the value for the dipole--quadrupole interaction estimated by Kiefer and Bushkovitch's theory

  8. A fractographic distinction between hydride cracking and stress corrosion cracking in zircaloys

    International Nuclear Information System (INIS)

    Cox, B.

    1978-06-01

    The fractographic details of SCC and delayed hydride failures are compared by scanning and replica electron microscopy. It is shown that there are distinct features ascribable to the fracture of hydride platelets which are absent from SCC fractures and which distinguish them from fractures produced by delayed hydride cracking. (author)

  9. A computer model for hydride blister growth in zirconium alloys

    International Nuclear Information System (INIS)

    White, A.J.; Sawatzky, A.; Woo, C.H.

    1985-06-01

    The failure of a Zircaloy-2 pressure tube in the Pickering unit 2 reactor started at a series of zirconium hydride blisters on the outside of the pressure tube. These blisters resulted from the thermal diffusion of hydrogen to the cooler regions of the pressure tube. In this report the physics of thermal diffusion of hydrogen in zirconium is reviewed and a computer model for blister growth in two-dimensional Cartesian geometry is described. The model is used to show that the blister-growth rate in a two-phase zirconium/zirconium-hydride region does not depend on the initial hydrogen concentration nor on the hydrogen pick-up rate, and that for a fixed far-field temperature there is an optimum pressure-type/calandria-tube contact temperature for growing blisters. The model described here can also be used to study large-scale effects, such as hydrogen-depletion zones around hydride blisters

  10. Hydrides and deuterides of lithium and sodium. Pt. 1

    International Nuclear Information System (INIS)

    Haque, E.

    1990-01-01

    An interionic potential model is developed for lighter and heavier alkali hydrides and deuterides. The method uses a combination of theoretical techniques, empirical fit, and a few plausible assumptions. An assessment of the derived potentials is made by calculating the lattice statics and dynamics of the crystals and by comparing both with experiment (where available) and with other calculations. The potentials are found to describe the elastic and dielectric properties reasonably well. The phonon dispersion curves of hydride and deuteride of sodium are compared with the calculations of Dyck and Jex based on force constant model approach and the results are discussed. The need for further experiments on heavier hydrides and deuterides is stressed. (author)

  11. Research in Nickel/Metal Hydride Batteries 2017

    Directory of Open Access Journals (Sweden)

    Kwo-Hsiung Young

    2018-02-01

    Full Text Available Continuing from a special issue in Batteries in 2016, nineteen new papers focusing on recent research activities in the field of nickel/metal hydride (Ni/MH batteries have been selected for the 2017 Special Issue of Ni/MH Batteries. These papers summarize the international joint-efforts in Ni/MH battery research from BASF, Wayne State University, Michigan State University, FDK Corp. (Japan, Institute for Energy Technology (Norway, Central South University (China, University of Science and Technology Beijing (China, Zhengzhou University of Light Industry (China, Inner Mongolia University of Science and Technology (China, Shenzhen Highpower (China, and University of the Witwatersrand (South Africa from 2016–2017 through reviews of AB2 metal hydride alloys, Chinese and EU Patent Applications, as well as descriptions of research results in metal hydride alloys, nickel hydroxide, electrolyte, and new cell type, comparison work, and projections of future works.

  12. New ternary hydride formation in U-Ti-H system

    International Nuclear Information System (INIS)

    Yamamoto, Takuya; Kayano, Hideo; Yamawaki, Michio.

    1991-01-01

    Hydrogen absorption properties of two titanium-rich uranium alloys, UTi 2 and UTi 4 , were studied in order to prepare and identify the recently found ternary hydride. They slowly reacted with hydrogen of the initial pressure of 10 5 Pa at 873K to form the ternary hydride. The hydrogenated specimen mainly consisted of the pursued ternary hydride but contained also U(or UO 2 ), TiH x , and some transient phases. X-ray powder diffraction and Electron Probe Micro Analysis proved that it was the UTi 2 H x with the expected MgCu 2 structure, though all the X-ray peaks were broad probably because of inhomogeneity. This compound had extremely high resistance to powdering on its formation, which showed high potential utilities for a non-powdering tritium storage system or for other purposes. (author)

  13. Devitrification kinetics of Sb2O3-PbI2 glasses

    Czech Academy of Sciences Publication Activity Database

    Legouera, M.; Rahal, F.; Kostka, Petr; Poulain, M.

    2009-01-01

    Roč. 34, č. 4 (2009), s. 249-266 ISSN 0151-9107 Institutional research plan: CEZ:AV0Z40320502 Keywords : crystallization kinetics * nucleation Subject RIV: CA - Inorganic Chemistry Impact factor: 0.250, year: 2009

  14. Competition between Primary Nucleation and Autocatalysis in Amyloid Fibril Self-Assembly

    Science.gov (United States)

    Eden, Kym; Morris, Ryan; Gillam, Jay; MacPhee, Cait E.; Allen, Rosalind J.

    2015-01-01

    Kinetic measurements of the self-assembly of proteins into amyloid fibrils are often used to make inferences about molecular mechanisms. In particular, the lag time—the quiescent period before aggregates are detected—is often found to scale with the protein concentration as a power law, whose exponent has been used to infer the presence or absence of autocatalytic growth processes such as fibril fragmentation. Here we show that experimental data for lag time versus protein concentration can show signs of kinks: clear changes in scaling exponent, indicating changes in the dominant molecular mechanism determining the lag time. Classical models for the kinetics of fibril assembly suggest that at least two mechanisms are at play during the lag time: primary nucleation and autocatalytic growth. Using computer simulations and theoretical calculations, we investigate whether the competition between these two processes can account for the kinks which we observe in our and others’ experimental data. We derive theoretical conditions for the crossover between nucleation-dominated and growth-dominated regimes, and analyze their dependence on system volume and autocatalysis mechanism. Comparing these predictions to the data, we find that the experimentally observed kinks cannot be explained by a simple crossover between nucleation-dominated and autocatalytic growth regimes. Our results show that existing kinetic models fail to explain detailed features of lag time versus concentration curves, suggesting that new mechanistic understanding is needed. More broadly, our work demonstrates that care is needed in interpreting lag-time scaling exponents from protein assembly data. PMID:25650930

  15. Electrochemical and metallurgical characterization of ZrCr{sub 1-x}NiMo{sub x} AB{sub 2} metal hydride alloys

    Energy Technology Data Exchange (ETDEWEB)

    Erika, Teliz [Universidad de la República, Facultad de Ciencias, Laboratorio de Electroquímica Fundamental, Núcleo Interdisciplinario Ingeniería Electroquímica, Igua 4225, CP 11400 Montevideo (Uruguay); Ricardo, Faccio [Universidad de la República, Crystallography, Solid State and Materials Laboratory (Cryssmat-Lab), DETEMA, Centro NanoMat, Polo Tecnológico de Pando, Espacio Interdisciplinario, Facultad de Química, Montevideo (Uruguay); Fabricio, Ruiz [Consejo Nacional de Investigaciones Científicas y Técnicas , CONICET, Av. Rivadavia 1917, C1033AAJ Ciudad de Buenos Aires (Argentina); Centro Atómico Bariloche , Comisión Nacional de Energía Atómica (CAB-CNEA), Av. Bustillo 9500, CP 8400 S.C. de Bariloche, RN (Argentina); Fernando, Zinola [Universidad de la República, Facultad de Ciencias, Laboratorio de Electroquímica Fundamental, Núcleo Interdisciplinario Ingeniería Electroquímica, Igua 4225, CP 11400 Montevideo (Uruguay); and others

    2015-11-15

    The effects of partial replacement of chromium by molybdenum was studied on the structure and electrochemical kinetic properties of ZrCr{sub 1-x}NiMo{sub x}(x = 0.0, 0.3 and 0.6) metal hydride alloys. The arc-melting prepared alloys were metallurgically characterized by X-ray diffraction and energy dispersive spectroscopy microanalysis, which showed AB{sub 2} (with hexagonal C14 structure) and Zr{sub x}Ni{sub y} (Zr{sub 7}Ni{sub 10}, Zr{sub 9}Ni{sub 11}) phases. After a partial substitution of chromium by molybdenum, secondary phases monotonically increase with the C14 unit cell volume indicating that most of molybdenum atoms locate in the B-site. The alloys were electrochemically characterized using charge/discharge cycling, electrochemical impedance spectroscopy and rate capability experiments that allowed the determination of hydriding reaction kinetic parameters. The presence of molybdenum produces a positive effect for hydrogen diffusion in the alloy lattice, and ZrCr{sub 0.7}NiMo{sub 0.3} alloy depicts the better kinetics associated with a fast activation, lower charge transfer resistance and the best high rate discharge behavior. This fact would be related to a lower diffusion time constant and a bigger value of the product between exchange density current and surface active area. There is a trade-off in the amounts of secondary phase and Laves phases in order to improve the kinetic performance. - Highlights: • Metallurgical characterization evidences the presence of Zr{sub x}Ni{sub y} and C14 phases. • The partial replacement of Cr by Mo promotes the segregation of Zr{sub x}Ni{sub y} phase. • The incorporation of molybdenum improves the kinetics for the hydriding process. • Mo produces a decrease in the diffusion time constant.

  16. Complex Metal Hydrides for Hydrogen, Thermal and Electrochemical Energy Storage

    DEFF Research Database (Denmark)

    Moller, Kasper T.; Sheppard, Drew; Ravnsbaek, Dorthe B.

    2017-01-01

    Hydrogen has a very diverse chemistry and reacts with most other elements to form compounds, which have fascinating structures, compositions and properties. Complex metal hydrides are a rapidly expanding class of materials, approaching multi-functionality, in particular within the energy storage...... inspiration to solve the great challenge of our time: efficient conversion and large-scale storage of renewable energy....... field. This review illustrates that complex metal hydrides may store hydrogen in the solid state, act as novel battery materials, both as electrolytes and electrode materials, or store solar heat in a more efficient manner as compared to traditional heat storage materials. Furthermore, it is highlighted...

  17. Hydriding and dehydriding properties of CaSi

    International Nuclear Information System (INIS)

    Aoki, Masakazu; Ohba, Nobuko; Noritake, Tatsuo; Towata, Shin-ichi

    2005-01-01

    The hydriding and dehydriding properties of CaSi were investigated both theoretically and experimentally. First-principles calculations suggested that CaSiH n is thermodynamically stable. Experimentally, the p -c isotherms clearly demonstrated plateau pressures in a temperature range of 473-573 K and the maximum hydrogen content was 1.9 weight % (wt.%) under a hydrogen pressure of 9 MPa at 473 K. The structure of CaSiH n is different from those of ZrNi hydrides, although CaSi has the CrB-type structure as well as ZrNi

  18. Thermophysical properties of solid lithium hydride and its isotopic modifications

    International Nuclear Information System (INIS)

    Mel'nikova, T.N.

    1981-01-01

    The theory of the anharmonic lattice is used to calculate the thermophysical properties (thermal expansivity, lattice constant, compressibility, and elastic moduli) of all the isotopic modifications of solid lithium hydride sup(6,7)Li(H,D,T) at temperatures up to the melting point. A general analysis of isotopic effects is carried out; in particular the reverse isotopic effect in the lattice constant is explained and the isotopic effect in melting is discussed. The results of the calculations agree with available experimental data and can be used for those isotopic modifications of lithium hydride for which there exist no experimental results. (author)

  19. Observations on Hydride Structures at the Tip of Arrested Cracks Grown under Conditions of Delayed Hydride Cracking

    International Nuclear Information System (INIS)

    Pettersson, Kjell; Oskarsson, Magnus; Bergqvist, Hans

    2003-04-01

    One sample of Zr2.5%Nb and one sample of cold worked and stress relieved Zircaloy-4 which have been tested for hydrogen induced crack growth have been examined in the crack tip region with the aim of determining the mechanism behind the growth of cracks. The proposed mechanisms are brittle failure of a crack tip hydride and hydrogen enhanced localized shear. The examinations were done by TEM and SEM. However attempts to produce a TEM specimen with a thinned region at the tip of the crack were unsuccessful in both samples. One feature observed in the Zr2.5%Nb material may however be an indication of intense shear deformation at the tip of the crack. On the other hand all observations on the Zircaloy-4 sample indicate precipitation of hydrides ahead of the crack tip and the presence of hydrides on the crack flanks

  20. Numerical study to represent non-isothermal melt-crystallization kinetics at laser-powder cladding

    CSIR Research Space (South Africa)

    Niziev, VG

    2013-04-01

    Full Text Available for volume fraction of new phase with the known nucleation and growth rates. This approximate approach is convenient when associated heat and phase transition kinetics equations are solved together. Earlier, this approach was used, for example, for phase... Copyright © 2013 SciRes. MNSMS V. G. NIZIEV ET AL. 64 evolution. Phase change is taken as kinetic process which is associated with nucleation and growth of nuclei of liquid...

  1. A comparison of the smeared-dislocation and super-dislocation description of a hydrided region in the context of modelling delayed hydride cracking initiation

    International Nuclear Information System (INIS)

    Smith, E.

    1994-01-01

    In quantifying the stress distribution within a hydrided region in the context of modelling delayed hydride cracking (DHC) initiation in zirconium alloys, this paper highlights the desirability of accounting for image effects, i.e. the interaction between the hydrided region and any free surface, for example a sharp crack, blunt notch or planar surface. The super-dislocation representation of a finite thickness hydrided region is ideal for accounting for image effects. It also adequately accounts for the finite thickness, t, of a hydrided region provided, as is the case in practice, we are concerned with the stress value within the hydride at distances ≥ 0.25 t from an end of the region. (Author)

  2. Using rheometry for determining nucleation density in colored system containing a nucleation agent

    NARCIS (Netherlands)

    Ma, Z.; Steenbakkers, R.J.A.; Giboz, J.; Peters, G.W.M.

    2011-01-01

    A new suspension-based rheological method was applied to study experimentally the crystallization of a nucleating agent (NA) filled isotactic polypropylene. This method allows for determination of point-nucleation densities where other methods fail. For example, optical microscopy can fail because

  3. Cytoplasmic Nucleation and Atypical Branching Nucleation Generate Endoplasmic Microtubules in Physcomitrella patens[OPEN

    Science.gov (United States)

    Nakaoka, Yuki; Kimura, Akatsuki; Tani, Tomomi; Goshima, Gohta

    2015-01-01

    The mechanism underlying microtubule (MT) generation in plants has been primarily studied using the cortical MT array, in which fixed-angled branching nucleation and katanin-dependent MT severing predominate. However, little is known about MT generation in the endoplasm. Here, we explored the mechanism of endoplasmic MT generation in protonemal cells of Physcomitrella patens. We developed an assay that utilizes flow cell and oblique illumination fluorescence microscopy, which allowed visualization and quantification of individual MT dynamics. MT severing was infrequently observed, and disruption of katanin did not severely affect MT generation. Branching nucleation was observed, but it showed markedly variable branch angles and was occasionally accompanied by the transport of nucleated MTs. Cytoplasmic nucleation at seemingly random locations was most frequently observed and predominated when depolymerized MTs were regrown. The MT nucleator γ-tubulin was detected at the majority of the nucleation sites, at which a single MT was generated in random directions. When γ-tubulin was knocked down, MT generation was significantly delayed in the regrowth assay. However, nucleation occurred at a normal frequency in steady state, suggesting the presence of a γ-tubulin-independent backup mechanism. Thus, endoplasmic MTs in this cell type are generated in a less ordered manner, showing a broader spectrum of nucleation mechanisms in plants. PMID:25616870

  4. Kinetic Typography

    DEFF Research Database (Denmark)

    van Leeuwen, Theo; Djonov, Emilia

    2014-01-01

    After discussing broad cultural drivers behind the development of kinetic typography, the chapter outlines an approach to analysing kinetic typography which is based on Halliday's theory of transitivity, as applied by Kress and Van Leeuwen to visual images.......After discussing broad cultural drivers behind the development of kinetic typography, the chapter outlines an approach to analysing kinetic typography which is based on Halliday's theory of transitivity, as applied by Kress and Van Leeuwen to visual images....

  5. Microtubule nucleation and organization in dendrites

    Science.gov (United States)

    Delandre, Caroline; Amikura, Reiko; Moore, Adrian W.

    2016-01-01

    ABSTRACT Dendrite branching is an essential process for building complex nervous systems. It determines the number, distribution and integration of inputs into a neuron, and is regulated to create the diverse dendrite arbor branching patterns characteristic of different neuron types. The microtubule cytoskeleton is critical to provide structure and exert force during dendrite branching. It also supports the functional requirements of dendrites, reflected by differential microtubule architectural organization between neuron types, illustrated here for sensory neurons. Both anterograde and retrograde microtubule polymerization occur within growing dendrites, and recent studies indicate that branching is enhanced by anterograde microtubule polymerization events in nascent branches. The polarities of microtubule polymerization events are regulated by the position and orientation of microtubule nucleation events in the dendrite arbor. Golgi outposts are a primary microtubule nucleation center in dendrites and share common nucleation machinery with the centrosome. In addition, pre-existing dendrite microtubules may act as nucleation sites. We discuss how balancing the activities of distinct nucleation machineries within the growing dendrite can alter microtubule polymerization polarity and dendrite branching, and how regulating this balance can generate neuron type-specific morphologies. PMID:27097122

  6. Modelling the stochastic behaviour of primary nucleation.

    Science.gov (United States)

    Maggioni, Giovanni Maria; Mazzotti, Marco

    2015-01-01

    We study the stochastic nature of primary nucleation and how it manifests itself in a crystallisation process at different scales and under different operating conditions. Such characteristics of nucleation are evident in many experiments where detection times of crystals are not identical, despite identical experimental conditions, but instead are distributed around an average value. While abundant experimental evidence has been reported in the literature, a clear theoretical understanding and an appropriate modelling of this feature is still missing. In this contribution, we present two models describing a batch cooling crystallisation, where the interplay between stochastic nucleation and deterministic crystal growth is described differently in each. The nucleation and growth rates of the two models are estimated by a comprehensive set of measurements of paracetamol crystallisation from aqueous solution in a 1 mL vessel [Kadam et al., Chemical Engineering Science, 2012, 72, 10-19]. Both models are applied to the cooling crystallisation process above under different operating conditions, i.e. different volumes, initial concentrations, cooling rates. The advantages and disadvantages of the two approaches are illustrated and discussed, with particular reference to their use across scales of nucleation rate measured in very small crystallisers.

  7. Ice nucleation rates near ˜225 K

    Science.gov (United States)

    Amaya, Andrew J.; Wyslouzil, Barbara E.

    2018-02-01

    We have measured the ice nucleation rates, Jice, in supercooled nano-droplets with radii ranging from 6.6 nm to 10 nm and droplet temperatures, Td, ranging from 225 K to 204 K. The initial temperature of the 10 nm water droplets is ˜250 K, i.e., well above the homogeneous nucleation temperature for micron sized water droplets, TH ˜235 K. The nucleation rates increase systematically from ˜1021 cm-3 s-1 to ˜1022 cm-3 s-1 in this temperature range, overlap with the nucleation rates of Manka et al. [Phys. Chem. Chem. Phys. 14, 4505 (2012)], and suggest that experiments with larger droplets would extrapolate smoothly the rates of Hagen et al. [J. Atmos. Sci. 38, 1236 (1981)]. The sharp corner in the rate data as temperature drops is, however, difficult to match with available theory even if we correct classical nucleation theory and the physical properties of water for the high internal pressure of the nanodroplets.

  8. Characteristics of hydride precipitation and reorientation in spent-fuel cladding

    International Nuclear Information System (INIS)

    Chung, H.M.; Daum, R.S.; Hiller, J.M.; Billone, M.C.

    2002-01-01

    Transmission electron microscopy (TEM) was used to examine Zircaloy fuel cladding, either discharged from several PWRs and a BWR after irradiation to fluence levels of 3.3 to 8.6 X 10 21 n cm -2 (E > 1 MeV) or hydrogen-charged and heat-treated under stress to produce radial hydrides; the goal was to determine the microstructural and crystallographic characteristics of hydride precipitation. Morphologies, distributions, and habit planes of various types of hydrides were determined by stereo-TEM. In addition to the normal macroscopic hydrides commonly observed by optical microscopy, small 'microscopic' hydrides are present in spent-fuel cladding in number densities at least a few orders of magnitude greater than that of macroscopic hydrides. The microscopic hydrides, observed to be stable at least up to 333 deg C, precipitate in association with -type dislocations. While the habit plane of macroscopic tangential hydrides in the spent-fuel cladding is essentially the same as that of unirradiated unstressed Zircaloys, i.e., the [107] Zr plane, the habit plane of tangential hydrides that precipitate under high tangential stress is the [104] Zr plane. The habit plane of radial hydrides that precipitate under tangential stress is the [011] Zr pyramidal plane, a naturally preferred plane for a cladding that has 30 basal-pole texture. Effects of texture on the habit plane and the threshold stress for hydride reorientation are also discussed. (authors)

  9. In situ synchrotron X-ray diffraction study of hydrides in Zircaloy-4 during thermomechanical cycling

    Energy Technology Data Exchange (ETDEWEB)

    Cinbiz, Mahmut N., E-mail: cinbizmn@ornl.gov [Department of Mechanical and Nuclear Engineering, Pennsylvania State University, University Park, PA, 16802 (United States); Koss, Donald A., E-mail: koss@ems.psu.edu [Department of Materials Science and Engineering, Pennsylvania State University, University Park, PA, 16802 (United States); Motta, Arthur T., E-mail: atm2@psu.edu [Department of Mechanical and Nuclear Engineering, Pennsylvania State University, University Park, PA, 16802 (United States); Department of Materials Science and Engineering, Pennsylvania State University, University Park, PA, 16802 (United States); Park, Jun-Sang, E-mail: parkjs@aps.anl.gov [Advanced Photon Source, Argonne National Laboratory, Argonne, IL, 60439 (United States); Almer, Jonathan D., E-mail: almer@aps.anl.gov [Advanced Photon Source, Argonne National Laboratory, Argonne, IL, 60439 (United States)

    2017-04-15

    The d-spacing evolution of both in-plane and out-of-plane hydrides has been studied using in situ synchrotron radiation X-ray diffraction during thermo-mechanical cycling of cold-worked stress-relieved Zircaloy-4. The structure of the hydride precipitates is such that the δ{111} d-spacing of the planes aligned with the hydride platelet face is greater than the d-spacing of the 111 planes aligned with the platelet edges. Upon heating from room temperature, the δ{111} planes aligned with hydride plate edges exhibit bi-linear thermally-induced expansion. In contrast, the d-spacing of the (111) plane aligned with the hydride plate face initially contracts upon heating. These experimental results can be understood in terms of a reversal of stress state associated with precipitating or dissolving hydride platelets within the α-zirconium matrix. - Highlights: •The δ{111} d-spacings aligned with the hydride plate edges exhibit a bi-linear thermal expansion. •Stress state reversal is predicted with the onset of hydride dissolution. •During dissolution, the δ{111} planes oriented parallel to the hydride plate face initially contract upon heating. •Hydride d-spacings indicate that both in-plane (circumferential) and out-of-plane (radial) hydrides are in the same strain-state and likely in the same stress state as well.

  10. The influence of hydride on fracture toughness of recrystallized Zircaloy-4 cladding

    Energy Technology Data Exchange (ETDEWEB)

    Hsu, Hsiao-Hung, E-mail: 175877@mail.csc.com.tw [Institute of Nuclear Energy Research (INER), Lungtan Township, Taoyuan County 32546, Taiwan, ROC (China); China Steel Corporation, Hsiao Kang District, Kaohsiung 81233, Taiwan, ROC (China); Chiang, Ming-Feng [China Steel Corporation, Hsiao Kang District, Kaohsiung 81233, Taiwan, ROC (China); Chen, Yen-Chen [Institute of Nuclear Energy Research (INER), Lungtan Township, Taoyuan County 32546, Taiwan, ROC (China)

    2014-04-01

    In this work, RXA cladding tubes were hydrogen-charged to target hydrogen content levels between 150 and 800 wppm (part per million by weight). The strings of zirconium hydrides observed in the cross sections are mostly oriented in the circumferential direction. The fracture toughness of hydrided RXA Zircaloy-4 cladding was measured to evaluate its hydride embrittlement susceptibility. With increasing hydrogen content, the fracture toughness of hydrided RXA cladding decreases at both 25 °C and 300 °C. Moreover, highly localized hydrides (forming a hydride rim) aggravate the degradation of the fracture properties of RXA Zircaloy-4 cladding at both 25 °C and 300 °C. Brittle features in the form of quasi-cleavages and secondary cracks were observed on the fracture surface of the hydride rim, even for RXA cladding tested at 300 °C.

  11. Internal friction study of hydrides in zirconium at low hydrogen contents

    International Nuclear Information System (INIS)

    Peretti, H.A.; Corso, H.L.; Gonzalez, O.A.; Fernandez, L.; Ghilarducci, A.A.; Salva, H.R.

    1999-01-01

    Full text: Internal friction and shear modulus measurements were carried out on crystal bar zirconium in the as received and hydride conditions using an inverted forced pendulum. Hydriding was achieved in two ways: inside and out of the pendulum. The final hydrogen content determined by fusion analysis in the 'in situ' hydride sample was of 36 ppm. Another sample was hydride by the cathodic charge method with 25 ppm. The thermal solid solubility (TSS) phase boundary presents hysteresis between the precipitation (TSSP) and the dissolution (TSSD) temperatures for the zirconium hydrides. During the first thermal cycling the anelastic effects could be attributed to the δ, ε and metastable γ zirconium hydrides. After 'in situ' annealing at 490 K, these peaks completely disappear in the electrolytically charged sample, while in the 'in situ' hydride, the peaks remain with decreasing intensity. This effect can be understood in terms of the different surface conditions of the samples. (author)

  12. Applicability of the Fokker-Planck equation to the description of diffusion effects on nucleation

    Science.gov (United States)

    Sorokin, M. V.; Dubinko, V. I.; Borodin, V. A.

    2017-01-01

    The nucleation of islands in a supersaturated solution of surface adatoms is considered taking into account the possibility of diffusion profile formation in the island vicinity. It is shown that the treatment of diffusion-controlled cluster growth in terms of the Fokker-Planck equation is justified only provided certain restrictions are satisfied. First of all, the standard requirement that diffusion profiles of adatoms quickly adjust themselves to the actual island sizes (adiabatic principle) can be realized only for sufficiently high island concentration. The adiabatic principle is essential for the probabilities of adatom attachment to and detachment from island edges to be independent of the adatom diffusion profile establishment kinetics, justifying the island nucleation treatment as the Markovian stochastic process. Second, it is shown that the commonly used definition of the "diffusion" coefficient in the Fokker-Planck equation in terms of adatom attachment and detachment rates is justified only provided the attachment and detachment are statistically independent, which is generally not the case for the diffusion-limited growth of islands. We suggest a particular way to define the attachment and detachment rates that allows us to satisfy this requirement as well. When applied to the problem of surface island nucleation, our treatment predicts the steady-state nucleation barrier, which coincides with the conventional thermodynamic expression, even though no thermodynamic equilibrium is assumed and the adatom diffusion is treated explicitly. The effect of adatom diffusional profiles on the nucleation rate preexponential factor is also discussed. Monte Carlo simulation is employed to analyze the applicability domain of the Fokker-Planck equation and the diffusion effect beyond it. It is demonstrated that a diffusional cloud is slowing down the nucleation process for a given monomer interaction with the nucleus edge.

  13. A system of hydrogen powered vehicles with liquid organic hydrides

    International Nuclear Information System (INIS)

    Taube, M.

    1981-07-01

    A motor car system based on the hydrogen produced by nuclear power stations during the night in the summer, and coupled with organic liquid hydride seems to be a feasible system in the near future. Such a system is discussed and the cost is compared with gasoline. (Auth.)

  14. Process of forming a sol-gel/metal hydride composite

    Science.gov (United States)

    Congdon, James W [Aiken, SC

    2009-03-17

    An external gelation process is described which produces granules of metal hydride particles contained within a sol-gel matrix. The resulting granules are dimensionally stable and are useful for applications such as hydrogen separation and hydrogen purification. An additional coating technique for strengthening the granules is also provided.

  15. Hydrogen storage alloys for nickel/metal hydride battery

    Energy Technology Data Exchange (ETDEWEB)

    Kuriyama, Nobuhiro; Sakai, Tetsuo; Myamura, Hiroshi; Tanaka, Hideaki; Ishikawa, Hiroshi; Uehara, Itsuki [Osaka National Research Inst. (Japan)

    1996-06-01

    Efforts to improve performance of metal hydride electrodes such as substitution of alloy components, heat treatment, and surface treatment intended to change surface and bulk structure of hydrogen storage alloys, mainly LaNi{sub 5} based alloys, are reviewed. The importance of control of morphology is emphasized. (author)

  16. Cascades for hydrogen isotope separation using metal hydrides

    International Nuclear Information System (INIS)

    Hill, F.B.; Grzetic, V.

    1982-01-01

    Designs are presented for continuous countercurrent hydrogen isotope separation cascades based on the use of metal hydrides. The cascades are made up of pressure swing adsorption (PSA) or temperature swing adsorption (TSA) stages. The designs were evolved from consideration of previously conducted studies of the separation performance of four types of PSA and TSA processes

  17. Deiodination reactions using tributyltin hydride for potential labelling experiments

    International Nuclear Information System (INIS)

    Zippi, E.M.; Plourde, G.W. II; Satyamurthy, N.

    1995-01-01

    2,6-Dinitro-1-iodobenzene and 2,4-dinitro-1-iodobenzene were deiodinated with tributylin hydride at different temperatures using various addition modes. The product ratios of 1,3-dinitrobenzene and the corresponding tributylstannyldinitrobenzene compounds were determined by NMR in order to evaluate the optimum conditions for impending tritiation experiments. (Author)

  18. Metal Hydride assited contamination on Ru/Si surfaces

    NARCIS (Netherlands)

    Pachecka, Malgorzata; Lee, Christopher James; Sturm, Jacobus Marinus; Bijkerk, Frederik

    2013-01-01

    In extreme ultraviolet lithography (EUVL) residual tin, in the form of particles, ions, and atoms, can be deposited on nearby EUV optics. During the EUV pulse, a reactive hydrogen plasma is formed, which may be able to react with metal contaminants, creating volatile and unstable metal hydrides that

  19. Design and integration of a hydrogen storage on metallic hydrides

    International Nuclear Information System (INIS)

    Botzung, M.

    2008-01-01

    This work presents a hydrogen storage system using metal hydrides for a Combined Heat and Power (CHP) system. Hydride storage technology has been chosen due to project specifications: high volumetric capacity, low pressures (≤ 3.5 bar) and low temperatures (≤ 75 C: fuel cell temperature). During absorption, heat from hydride generation is dissipated by fluid circulation. An integrated plate-fin type heat exchanger has been designed to obtain good compactness and to reach high absorption/desorption rates. At first, the storage system has been tested in accordance with project specifications (absorption 3.5 bar, desorption 1.5 bar). Then, the hydrogen charge/discharge times have been decreased to reach system limits. System design has been used to simulate thermal and mass comportment of the storage tank. The model is based on the software Fluent. We take in consideration heat and mass transfers in the porous media during absorption/desorption. The hydride thermal and mass behaviour has been integrated in the software. The heat and mass transfers experimentally obtained have been compared to results calculated by the model. The influence of experimental and numerical parameters on the model behaviour has also been explored. (author) [fr

  20. Diastereoselectivity in the reduction of bicyclic enones with hindered hydrides

    OpenAIRE

    Camozzato, Andreza C.; Tenius, Beatriz S. M.; Oliveira, Eduardo R. de; Viegas Jr., Cláudio; Victor, Maurício M.; Silveira, Leandro G. da

    2008-01-01

    Reduction of five substituted octalones employing lithium tri-sec-butylborohydride (L-selectride®) in THF and ethyl ether led to allylic alcohols with moderate diastereoselectivity. The stereoselectivity of addition of bulky hydrides showed to be different from most examples in the literature and was strongly influenced by substitution on the octalone ring.

  1. Diastereoselectivity in the reduction of bicyclic enones with hindered hydrides

    International Nuclear Information System (INIS)

    Camozzato, Andreza C.; Tenius, Beatriz S. M.; Oliveira, Eduardo R. de; Viegas Junior, Claudio; Victor, Mauricio M.; Silveira, Leandro G. da

    2008-01-01

    Reduction of five substituted octalones employing lithium tri-sec-butylborohydride (L-selectride R ) in THF and ethyl ether led to allylic alcohols with moderate diastereoselectivity. The stereoselectivity of addition of bulky hydrides showed to be different from most examples in the literature and was strongly influenced by substitution on the octalone ring. (author)

  2. Fractal analysis of electrolytically-deposited palladium hydride dendrites

    International Nuclear Information System (INIS)

    Bursill, L.A.; Julin, Peng; Xudong, Fan.

    1990-01-01

    The fractal scaling characteristics of the surface profile of electrolytically-deposited palladium hydride dendritic structures have been obtained using conventional and high resolution transmission electron microscopy. The results are in remarkable agreement with the modified diffusion-limited aggregation model. 19 refs., 3 tabs., 13 figs

  3. Development of transmutation technologies of radioactive waste by actinoid hydride

    International Nuclear Information System (INIS)

    Konashi, Kenji; Matsui, Hideki; Yamawaki, Michio

    2001-01-01

    Two waste treatment methods, geological disposal and transmutation, have been studied. The transmutation method changes long-lived radioactive nuclides to short-lived one or stabilizes them by nuclear transformation. The transmutation by actinoid hydride is exactly alike that transformation method from actinoid disposal waste to Pu fuel. For this object, OMEGA project is processing now. The transmutation is difficult by two causes such as large amount of long-lived radioactive nuclides and not enough development of control technologies of nuclear reaction except atomic reactor. The transmutation using actinoid hydride has merits that the amount of actinoid charged in the target increases and the effect of thermal neutrons on fuel decreases depending on homogeneous transmutation velocity in the target. Development of stable actinoid hydride under the conditions of reactor temperature and irradiation environment is important. The experimental results of U-ZrH 1.6 are shown in this paper. The irradiation experiment using Th hydride has been proceeding. (S.Y.)

  4. Hydrogen and dihydrogen bonding of transition metal hydrides

    International Nuclear Information System (INIS)

    Jacobsen, Heiko

    2008-01-01

    Intermolecular interactions between a prototypical transition metal hydride WH(CO) 2 NO(PH 3 ) 2 and a small proton donor H 2 O have been studied using DFT methodology. The hydride, nitrosyl and carbonyl ligand have been considered as site of protonation. Further, DFT-D calculations in which empirical corrections for the dispersion energy are included, have been carried out. A variety of pure and hybrid density functionals (BP86, PW91, PBE, BLYP, OLYP, B3LYP, B1PW91, PBE0, X3LYP) have been considered, and our calculations indicate the PBE functional and its hybrid variation are well suited for the calculation of transition metal hydride hydrogen and dihydrogen bonding. Dispersive interactions make up for a sizeable portion of the intermolecular interaction, and amount to 20-30% of the bond energy and to 30-40% of the bond enthalpy. An energy decomposition analysis reveals that the H...H bond of transition metal hydrides contains both covalent and electrostatic contributions

  5. Hydrogen and dihydrogen bonding of transition metal hydrides

    Science.gov (United States)

    Jacobsen, Heiko

    2008-04-01

    Intermolecular interactions between a prototypical transition metal hydride WH(CO) 2NO(PH 3) 2 and a small proton donor H 2O have been studied using DFT methodology. The hydride, nitrosyl and carbonyl ligand have been considered as site of protonation. Further, DFT-D calculations in which empirical corrections for the dispersion energy are included, have been carried out. A variety of pure and hybrid density functionals (BP86, PW91, PBE, BLYP, OLYP, B3LYP, B1PW91, PBE0, X3LYP) have been considered, and our calculations indicate the PBE functional and its hybrid variation are well suited for the calculation of transition metal hydride hydrogen and dihydrogen bonding. Dispersive interactions make up for a sizeable portion of the intermolecular interaction, and amount to 20-30% of the bond energy and to 30-40% of the bond enthalpy. An energy decomposition analysis reveals that the H⋯H bond of transition metal hydrides contains both covalent and electrostatic contributions.

  6. Hydrogen and dihydrogen bonding of transition metal hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Jacobsen, Heiko [KemKom, Libellenweg 2, 25917 Leck, Nordfriesland (Germany)], E-mail: jacobsen@kemkom.com

    2008-04-03

    Intermolecular interactions between a prototypical transition metal hydride WH(CO){sub 2}NO(PH{sub 3}){sub 2} and a small proton donor H{sub 2}O have been studied using DFT methodology. The hydride, nitrosyl and carbonyl ligand have been considered as site of protonation. Further, DFT-D calculations in which empirical corrections for the dispersion energy are included, have been carried out. A variety of pure and hybrid density functionals (BP86, PW91, PBE, BLYP, OLYP, B3LYP, B1PW91, PBE0, X3LYP) have been considered, and our calculations indicate the PBE functional and its hybrid variation are well suited for the calculation of transition metal hydride hydrogen and dihydrogen bonding. Dispersive interactions make up for a sizeable portion of the intermolecular interaction, and amount to 20-30% of the bond energy and to 30-40% of the bond enthalpy. An energy decomposition analysis reveals that the H...H bond of transition metal hydrides contains both covalent and electrostatic contributions.

  7. Cascades for hydrogen isotope separation using metal hydrides

    Energy Technology Data Exchange (ETDEWEB)

    Hill, F B; Grzetic, V [Brookhaven National Lab., Upton, NY (USA)

    1983-02-01

    Designs are presented for continuous countercurrent hydrogen isotope separation cascades based on the use of metal hydrides. The cascades are made up of pressure swing adsorption (PSA) or temperature swing adsorption (TSA) stages. The designs were evolved from consideration of previously conducted studies of the separation performance of four types of PSA and TSA processes.

  8. Diffusion model of delayed hydride cracking in zirconium alloys

    NARCIS (Netherlands)

    Shmakov, AA; Kalin, BA; Matvienko, YG; Singh, RN; De, PK

    2004-01-01

    We develop a method for the evaluation of the rate of delayed hydride cracking in zirconium alloys. The model is based on the stationary solution of the phenomenological diffusion equation and the detailed analysis of the distribution of hydrostatic stresses in the plane of a sharp tensile crack.

  9. Hydrogen Storage in Porous Materials and Magnesium Hydrides

    NARCIS (Netherlands)

    Grzech, A.

    2013-01-01

    In this thesis representatives of two different types of materials for potential hydrogen storage application are presented. Usage of either nanoporous materials or metal hydrides has both operational advantages and disadvantages. A main objective of this thesis is to characterize the hydrogen

  10. The Properties of Some Simple Covalent Hydrides: An Ab Initio ...

    African Journals Online (AJOL)

    Some properties of the monomeric binary hydrides of the elements of the first two rows of the periodic table have been determined using ab initio molecular orbital theory. The properties in question are the energetic, structural, electronic, topological and vibrational characteristics. In general, a gradual convergence towards ...

  11. Synthesis, properties, and assimilation methods of aluminium hydride

    International Nuclear Information System (INIS)

    Mirsaidov, U.M.

    2013-01-01

    We have discovered a new source of aluminium hydride-conversion of tetrahydrofurane under influence of halogenous alkyls. We have proposed the chlorbenzene method of synthesis of AlH 3 , which excludes adhesion and ensure high quality of the product with respect to its purity, thermal stability, habits of crystals (round shape), and granulometric composition. We determined capability of benzyl chloride to fix AlH 4 -groups by the way of complexes formation. This allows increasing efficient concentration of AlH 3 solutions and their productivity. We have carried out 'direct' crystallization of aluminium hydride in one stage using interaction of binary metal hydride with aluminium chloride in the medium of ether-toluene at 60-100 d ig C a nd using solvent distillation. In the reaction of Li H with AlCl 3 , we achieved output of pure crystal AlH 3 of hexagonal modification, which was close to quantitative. We have discovered the assimilation methods of aluminium hydride in carrying out of solid-phase chemical reactions. (author)

  12. Crystallization Kinetics within a Generic Modeling Framework

    DEFF Research Database (Denmark)

    Meisler, Kresten Troelstrup; von Solms, Nicolas; Gernaey, Krist V.

    2014-01-01

    of employing a well-structured model library for storage, use/reuse, and analysis of the kinetic models are highlighted. Examples illustrating the application of the modeling framework for kinetic model discrimination related to simulation of specific crystallization scenarios and for kinetic model parameter......A new and extended version of a generic modeling framework for analysis and design of crystallization operations is presented. The new features of this framework are described, with focus on development, implementation, identification, and analysis of crystallization kinetic models. Issues related...... to the modeling of various kinetic phenomena like nucleation, growth, agglomeration, and breakage are discussed in terms of model forms, model parameters, their availability and/or estimation, and their selection and application for specific crystallization operational scenarios under study. The advantages...

  13. ON THE PRECISION OF THE NUCLEATOR

    Directory of Open Access Journals (Sweden)

    Javier González-Villa

    2017-06-01

    Full Text Available The nucleator is a design unbiased method of local stereology for estimating the volume of a bounded object. The only information required lies in the intersection of the object with an isotropic random ray emanating from a fixed point (called the pivotal point associated with the object. For instance, the volume of a neuron can be estimated from a random ray emanating from its nucleolus. The nucleator is extensively used in biosciences because it is efficient and easy to apply. The estimator variance can be reduced by increasing the number of rays. In an earlier paper a systematic sampling design was proposed, and theoretical variance predictors were derived, for the corresponding volume estimator. Being the only variance predictors hitherto available for the nucleator, our basic goal was to check their statistical performance by means of Monte Carlo resampling on computer reconstructions of real objects. As a plus, the empirical distribution of the volume estimator revealed statistical properties of practical relevance.

  14. Trapping crystal nucleation of cholesterol monohydrate

    DEFF Research Database (Denmark)

    Solomonov, I.; Weygand, M.J.; Kjær, K.

    2005-01-01

    Crystalline nucleation of cholesterol at the air-water interface has been studied via grazing incidence x-ray diffraction using synchrotron radiation. The various stages of cholesterol molecular assembly from monolayer to three bilayers incorporating interleaving hydrogen-bonded water layers......, at least initially, an intralayer cholesterol rearrangement in a single-crystal-to-single-crystal transition. The preferred nucleation of the monoclinic phase of cholesterol . H2O followed by transformation to the stable monohydrate phase may be associated with an energetically more stable cholesterol...... bilayer arrangement of the former and a more favorable hydrogen-bonding arrangement of the latter. The relevance of this nucleation process of cholesterol monohydrate to pathological crystallization of cholesterol from cell biomembranes is discussed....

  15. Effect of Air Injection on Nucleation Rates

    DEFF Research Database (Denmark)

    Capellades Mendez, Gerard; Kiil, Søren; Dam-Johansen, Kim

    2017-01-01

    From disruption of the supersaturated solution to improved mass transfer in the crystallizing suspension, the introduction of a moving gas phase in a crystallizer could lead to improved rates of nucleation and crystal growth. In this work, saturated air has been injected to batch crystallizers...... to study the effects on formation of the first crystal and subsequent turbidity buildup. To account for the typically large sample-to-sample variation, nucleation rates were evaluated for a large number of replicates using probability distributions of induction times. The slope and the intercept...... was reduced from 69 to 13 min, and the mean induction time decreased from 128 to 36 min. The effect on aqueous solutions of l-arginine was less apparent, with a detection delay reduction from 15 to 3 min, and no significant changes on the rate of primary nucleation. These results demonstrate the potential...

  16. A variational approach to nucleation simulation.

    Science.gov (United States)

    Piaggi, Pablo M; Valsson, Omar; Parrinello, Michele

    2016-12-22

    We study by computer simulation the nucleation of a supersaturated Lennard-Jones vapor into the liquid phase. The large free energy barriers to transition make the time scale of this process impossible to study by ordinary molecular dynamics simulations. Therefore we use a recently developed enhanced sampling method [Valsson and Parrinello, Phys. Rev. Lett.113, 090601 (2014)] based on the variational determination of a bias potential. We differ from previous applications of this method in that the bias is constructed on the basis of the physical model provided by the classical theory of nucleation. We examine the technical problems associated with this approach. Our results are very satisfactory and will pave the way for calculating the nucleation rates in many systems.

  17. A parameterization of cloud droplet nucleation

    International Nuclear Information System (INIS)

    Ghan, S.J.; Chuang, C.; Penner, J.E.

    1993-01-01

    Droplet nucleation is a fundamental cloud process. The number of aerosols activated to form cloud droplets influences not only the number of aerosols scavenged by clouds but also the size of the cloud droplets. Cloud droplet size influences the cloud albedo and the conversion of cloud water to precipitation. Global aerosol models are presently being developed with the intention of coupling with global atmospheric circulation models to evaluate the influence of aerosols and aerosol-cloud interactions on climate. If these and other coupled models are to address issues of aerosol-cloud interactions, the droplet nucleation process must be adequately represented. Here we introduce a droplet nucleation parametrization that offers certain advantages over the popular Twomey (1959) parameterization

  18. Heterogeneous nucleation of ice in the atmosphere

    International Nuclear Information System (INIS)

    Nicosia, A; Piazza, M; Santachiara, G; Belosi, F

    2017-01-01

    The occurrence of ice-nucleating aerosols in the atmosphere has a profound impact on the properties of clouds, and in turn, influences our understanding on weather and climate. Research on this topic has grown constantly over the last decades, driven by advances in online and offline instruments capable of measuring the characteristics of these cloud-modifying aerosol particles. This article presents different aspects to the understanding of how aerosol particles can trigger the nucleation of ice in clouds. In addition, we present some experimental results obtained with the Dynamic Filter Processing Chamber, an off-line instrument that has been applied extensively in the last years and that circumvents some of the problems related to the measurement of Ice Nucleating Particles properties. (paper)

  19. Investigation of the kinetics of the reactions of oxidation, nitration, and hydrogenation of uranium

    International Nuclear Information System (INIS)

    Adda, Y.

    1955-06-01

    Various physico-chemical methods have been used to investigate the kinetics of the oxidation hydridation and nitridation of uranium. The experimental results show that the kinetics of these reactions are influenced by many factors also the Pilling and Bedworth rule is valid only under very limited conditions. The disagreement between this rule and the experimental results could be explained by the existence of numerous mechanical faults in the compounds obtained by the dry corrosion of the metal. (author) [fr

  20. Kinetics and mechanism of nitrobenzene hydrogenation to phenylhydroxylamine in rhenium thiocomplexes solutions

    International Nuclear Information System (INIS)

    Korenyako, G.I.; Belousov, V.M.

    1985-01-01

    A study was made on kinetics of nitrobenzene hydrogenation to phenylhydroxylamine in dimethylformamide solutions of rhenium thiocomplexes. The mechanism of hydrogenation was suggested. Formation of hydride catalyst complex represents the first stage of the process. Kinetic equation derived on the basis of suggested mechanism corresponds satisfactorily with experimental results. Thermodynamic parameters of separate process stages calculated on the basis of equilibrium constant values testify as well to the benefit of suggested mechanism