519 research outputs found
Non-mean-field theory of anomalously large double-layer capacitance
Mean-field theories claim that the capacitance of the double-layer formed at
a metal/ionic conductor interface cannot be larger than that of the Helmholtz
capacitor, whose width is equal to the radius of an ion. However, in some
experiments the apparent width of the double-layer capacitor is substantially
smaller. We propose an alternate, non-mean-field theory of the ionic
double-layer to explain such large capacitance values. Our theory allows for
the binding of discrete ions to their image charges in the metal, which results
in the formation of interface dipoles. We focus primarily on the case where
only small cations are mobile and other ions form an oppositely-charged
background. In this case, at small temperature and zero applied voltage dipoles
form a correlated liquid on both contacts. We show that at small voltages the
capacitance of the double-layer is determined by the transfer of dipoles from
one electrode to the other and is therefore limited only by the weak
dipole-dipole repulsion between bound ions, so that the capacitance is very
large. At large voltages the depletion of bound ions from one of the capacitor
electrodes triggers a collapse of the capacitance to the much smaller
mean-field value, as seen in experimental data. We test our analytical
predictions with a Monte Carlo simulation and find good agreement. We further
argue that our ``one-component plasma" model should work well for strongly
asymmetric ion liquids. We believe that this work also suggests an improved
theory of pseudo-capacitance.Comment: 19 pages, 14 figures; some Monte Carlo results and a section about
aqueous solutions adde
Measurements of the Casimir-Lifshitz force in fluids: the effect of electrostatic forces and Debye screening
In this work, we present detailed measurements of the Casimir-Lifshitz force
between two gold surfaces (a sphere and a plate) immersed in ethanol and study
the effect of residual electrostatic forces, which are dominated by static
fields within the apparatus and can be reduced with proper shielding.
Electrostatic forces are further reduced by Debye screening through the
addition of salt ions to the liquid. Additionally, the salt leads to a
reduction of the Casimir-Lifshitz force by screening the zero-frequency
contribution to the force; however, the effect is small between gold surfaces
at the measured separations and within experimental error. An improved
calibration procedure is described and compared to previous methods. Finally,
the experimental results are compared to Lifshitz's theory and found to be
consistent for the materials used in the experiment.Comment: 11 figures. PRA in pres
Compressibility of titanosilicate melts
The effect of composition on the relaxed adiabatic bulk modulus (K0) of a range of alkali- and alkaline earth-titanosilicate [X 2 n/n+ TiSiO5 (X=Li, Na, K, Rb, Cs, Ca, Sr, Ba)] melts has been investigated. The relaxed bulk moduli of these melts have been measured using ultrasonic interferometric methods at frequencies of 3, 5 and 7 MHz in the temperature range of 950 to 1600°C (0.02 Pa s < s < 5 Pa s). The bulk moduli of these melts decrease with increasing cation size from Li to Cs and Ca to Ba, and with increasing temperature. The bulk moduli of the Li-, Na-, Ca- and Ba-bearing metasilicate melts decrease with the addition of both TiO2 and SiO2 whereas those of the K-, Rb- and Cs-bearing melts increase. Linear fits to the bulk modulus versus volume fraction of TiO2 do not converge to a common compressibility of the TiO2 component, indicating that the structural role of TiO2 in these melts is dependent on the identity of the cation. This proposition is supported by a number of other property data for these and related melt compositions including heat capacity and density, as well as structural inferences from X-ray absorption spectroscopy (XANES). The compositional dependence of the compressibility of the TiO2 component in these melts explains the difficulty incurred in previous attempts to incorporate TiO2 in calculation schemes for melt compressibility. The empirical relationship KV-4/3 for isostructural materials has been used to evaluate the compressibility-related structural changes occurring in these melts. The alkali metasilicate and disilicate melts are isostructural, independent of the cation. The addition of Ti to the metasilicate composition (i.e. X2TiSiO5), however, results in a series of melts which are not isostructural. The alkaline-earth metasilicate and disilicate compositions are not isostructural, but the addition of Ti to the metasilicate compositions (i.e. XTiSiO5) would appear, on the basis of modulus-volume systematics, to result in the melts becoming isostructural with respect to compressibility
Collective dynamics in crystalline polymorphs of ZnCl: potential modelling and inelastic neutron scattering study
We report a phonon density of states measurement of -ZnCl using
the coherent inelastic neutron scattering technique and a lattice dynamical
calculation in four crystalline phases of ZnCl using a transferable
interatomic potential. The model calculations agree reasonably well with the
available experimental data on the structures, specific heat, Raman frequencies
and their pressure variation in various crystalline phases. The calculated
results have been able to provide a fair description of the vibrational as well
as the thermodynamic properties of ZnCl in all its four phases.Comment: Accepted in J. Phys.: Condens. Matte
Control parameters on the fabrication of ZnO hollow nanocolumns
[EN] The present work reports on the fabrication of hollow ZnO nanocolumns by a sequential combination of electrochemical deposition, chemical attack and regeneration. Initially, ZnO nanocolumns were deposited in two different substrates, namely Fluor Tin Oxide and Indium Tin Oxide. In a further step, a statistical analysis on the most influencing control parameters in the dissolution stage to produce the hollow ZnO nanowires on the FTO substrates was carried out. The control variables considered were electrolyte concentration, dissolution time and temperature, whereas the output variable was the percentage of the hollow nanocolumns obtained. The statistical analysis consisted of a two-level factorial design of experiments on three variables, therefore involving a series of 8 experiments. An analysis of variance (ANOVA) on the results was also carried out. The results showed that all the control variables were significant, the most important being the dissolution time.This work was supported by the Spanish Government through MCINN Grant MAT2009-14625-C03-03, Generalitat Valenciana programme PROMETEO/2009/063 and European Commission through NanoCIS project FP7-PEOPLE-2010-IRSES (ref. 269279). Technical support given to the authors by the Servei de Microscopia at the Universitat Politecnica de Valencia (Spain) is greatly acknowledged.Cembrero Cil, J.; Busquets Mataix, DJ.; Rayón Encinas, E.; Pascual Guillamón, M.; Pérez Puig, MA.; Marí Soucase, B. (2013). Control parameters on the fabrication of ZnO hollow nanocolumns. Materials Science in Semiconductor Processing. 16:211-216. https://doi.org/10.1016/j.mssp.2012.04.014S2112161
Interfacial Tensions near Critical Endpoints: Experimental Checks of EdGF Theory
Predictions of the extended de Gennes-Fisher local-functional theory for the
universal scaling functions of interfacial tensions near critical endpoints are
compared with experimental data. Various observations of the binary mixture
isobutyric acid water are correlated to facilitate an analysis of the
experiments of Nagarajan, Webb and Widom who observed the vapor-liquid
interfacial tension as a function of {\it both} temperature and density.
Antonow's rule is confirmed and, with the aid of previously studied {\it
universal amplitude ratios}, the crucial analytic ``background'' contribution
to the surface tension near the endpoint is estimated. The residual singular
behavior thus uncovered is consistent with the theoretical scaling predictions
and confirms the expected lack of symmetry in . A searching test of
theory, however, demands more precise and extensive experiments; furthermore,
the analysis highlights, a previously noted but surprising, three-fold
discrepancy in the magnitude of the surface tension of isobutyric acid
water relative to other systems.Comment: 6 figure
Size-dependent spinodal and miscibility gaps for intercalation in nano-particles
Using a recently-proposed mathematical model for intercalation dynamics in
phase-separating materials [Singh, Ceder, Bazant, Electrochimica Acta 53, 7599
(2008)], we show that the spinodal and miscibility gaps generally shrink as the
host particle size decreases to the nano-scale. Our work is motivated by recent
experiments on the high-rate Li-ion battery material LiFePO4; this serves as
the basis for our examples, but our analysis and conclusions apply to any
intercalation material. We describe two general mechanisms for the suppression
of phase separation in nano-particles: (i) a classical bulk effect, predicted
by the Cahn-Hilliard equation, in which the diffuse phase boundary becomes
confined by the particle geometry; and (ii) a novel surface effect, predicted
by chemical-potential-dependent reaction kinetics, in which
insertion/extraction reactions stabilize composition gradients near surfaces in
equilibrium with the local environment. Composition-dependent surface energy
and (especially) elastic strain can contribute to these effects but are not
required to predict decreased spinodal and miscibility gaps at the nano-scale
Diffuse-Charge Dynamics in Electrochemical Systems
The response of a model micro-electrochemical system to a time-dependent
applied voltage is analyzed. The article begins with a fresh historical review
including electrochemistry, colloidal science, and microfluidics. The model
problem consists of a symmetric binary electrolyte between parallel-plate,
blocking electrodes which suddenly apply a voltage. Compact Stern layers on the
electrodes are also taken into account. The Nernst-Planck-Poisson equations are
first linearized and solved by Laplace transforms for small voltages, and
numerical solutions are obtained for large voltages. The ``weakly nonlinear''
limit of thin double layers is then analyzed by matched asymptotic expansions
in the small parameter , where is the
screening length and the electrode separation. At leading order, the system
initially behaves like an RC circuit with a response time of
(not ), where is the ionic diffusivity, but nonlinearity
violates this common picture and introduce multiple time scales. The charging
process slows down, and neutral-salt adsorption by the diffuse part of the
double layer couples to bulk diffusion at the time scale, . In the
``strongly nonlinear'' regime (controlled by a dimensionless parameter
resembling the Dukhin number), this effect produces bulk concentration
gradients, and, at very large voltages, transient space charge. The article
concludes with an overview of more general situations involving surface
conduction, multi-component electrolytes, and Faradaic processes.Comment: 10 figs, 26 pages (double-column), 141 reference
Critical Review of Theoretical Models for Anomalous Effects (Cold Fusion) in Deuterated Metals
We briefly summarize the reported anomalous effects in deuterated metals at
ambient temperature, commonly known as "Cold Fusion" (CF), with an emphasis on
important experiments as well as the theoretical basis for the opposition to
interpreting them as cold fusion. Then we critically examine more than 25
theoretical models for CF, including unusual nuclear and exotic chemical
hypotheses. We conclude that they do not explain the data.Comment: 51 pages, 4 Figure
Suppression of Phase Separation in LiFePO4 Nanoparticles During Battery Discharge
Using a novel electrochemical phase-field model, we question the common
belief that LixFePO4 nanoparticles separate into Li-rich and Li-poor phases
during battery discharge. For small currents, spinodal decomposition or
nucleation leads to moving phase boundaries. Above a critical current density
(in the Tafel regime), the spinodal disappears, and particles fill
homogeneously, which may explain the superior rate capability and long cycle
life of nano-LiFePO4 cathodes.Comment: 27 pages, 8 figure
- …