Marcio Luis Ferreira Nascimento

Does viscosity describe the kinetic barrier for crystal growth from the liquidus to the glass transition

An analysis of the kinetic coefficient of crystal growth U(kin), recently proposed by Ediger et al. [J. Chem. Phys. 128, 034709 (2008)], indicates that the Stokes-Einstein/Eyring (SE/E) equation does not describe the diffusion process controlling crystal growth rates in fragile glass-forming liquids. U(kin) was defined using the normal growth model and tested for crystal data for inorganic and organic liquids covering a viscosity range of about 10(4)-10(12) Pa  s. Here, we revisit their interesting finding considering two other models: the screw dislocation (SD) and the two-dimensional surface nucleated (2D) growth models for nine undercooled oxide liquids, in a wider temperature range, from slightly below the melting point down to the glass transition region T(g), thus covering a wider viscosity range: 10(1)-10(13) Pa  s. We then propose and use normalized kinetic coefficients (M(kin)) for the SD and 2D growth models. These new kinetic coefficients restore the ability of viscosity to describe the transport part of crystal growth rates (M(kin)∼1/η and ξ∼1) from low to moderate viscosities (η<10(6) Pa  s), and thus the SE/E equation works well in this viscosity range for all systems tested. For strong glasses, the SE/E equation works well from low to high viscosities, from the melting point down to T(g)! However, for at least three fragile liquids, diopside (kink at 1.08T(g), η=1.6×10(8) Pa  s), lead metasilicate (kink at 1.14T(g), η=4.3×10(6) Pa  s), and lithium disilicate (kink at 1.11T(g), η=1.6×10(8) Pa  s), there are clear signs of a breakdown of the SE/E equation at these higher viscosities. Our results corroborate the findings of Ediger et al. and demonstrate that viscosity data cannot be used to describe the transport part of the crystal growth (via the SE/E equation) in fragile glasses in the neighborhood of T(g).

Kinetics and mechanisms of crystal growth and diffusion in a glass-forming liquid

Extensive data on the viscosity, covering 15 orders of magnitude, and crystal growth rate, covering seven orders of magnitude, of liquid diopside (CaO.MgO.2SiO(2)) were collected in a wide range of undercoolings from 1.10T(g) to 0.99T(m) (T(g) is the glass transition temperature and T(m) the melting point). The raw growth rate data were corrected for the increased interfacial temperature produced by the heat released during crystallization. A detailed analysis confirms that growth mediated by screw dislocations reasonably explain the experimental data in these wide ranges of temperatures and growth rates. Effective diffusion coefficients were calculated from crystal growth rates and from viscosity, and were then compared with measured self-diffusion coefficients of silicon and oxygen in diopside melt. The results show that oxygen and silicon control the diffusion dynamics involved in crystal growth and viscous flow. This study not only unveils the transport mechanism in this complex liquid, but also validates the use of viscosity (through the Stokes-Einstein or the Eyring equations) to account for the kinetic term of the crystal growth expression in a wide range of temperatures.

Charge carrier concentration and mobility in alkali silicates

The respective contributions of the charge carrier concentration and mobility to the ionic conductivity in glasses remain an open question. In the present work we calculate these two parameters from conductivity data as a function of temperature below and above the glass transition temperature, T(g). The basic hypothesis assumes that ionic displacement results from the migration of cationic pairs formed by a partial dissociation, which is a temperature-activated process. Below T(g) their migration would follow a temperature-activated mechanism, while a free volume mechanism prevails above this temperature, leading to a deviation from the Arrhenius behavior. Expressions are formulated for the variation in ionic conductivity as a function of temperature in the supercooled and glassy states. Fitting the experimental data with the proposed expressions allows for the determination of characteristic parameters such as the charge carrier formation and migration enthalpies. Based on these values, it is then possible to calculate the charge carrier concentration and mobility in the entire temperature range. At room temperature, the mobility of effective charge carriers is estimated close to 10(-4) cm(2) s(-1) V(-1) for alkali disilicates glasses under study, while the ratio between the number of effective charge carriers and the total number of alkali cations is estimated to be from 10(-8) to 10(-10), comparable to the concentration of intrinsic defects in an ionic crystal or dissociated species from a weak electrolyte solution.

'Universal' curve of ionic conductivities in binary alkali silicate glasses

In the past 25 years, there has been an increasing interest in ionic-glass conductors, mainly motivated by the discovery of new glasses, attempts to produce new solid-state batteries, and the search for an ‘universal’ theory of iontransport in glassy materials. It is well-known that the ionic conductivity increases rapidly when a network glassformer is modified by the addition of an alkali metal. Despite considerable experimental and theoretical attempt, there is currently no consensus regarding the diffusion mechanism [1]. Numerous models have been proposed, and they vary from thermodynamics with principles in models for liquid electrolytes, such as the weak electrolyte model [2], to models based on solid state concepts such as the jump diffusion model [3], the strong electrolyte model [4], and the dynamic structure model [5]. Ionic conductivity σ in glass is a thermally activated process of mobile ions that overcome a potential barrier EA, of the form:

Diffusion coefficients for crystal nucleation and growth in deeply undercooled glass-forming liquids

We calculate, employing the classical theory of nucleation and growth, the effective diffusion coefficients controlling crystal nucleation of nanosize clusters and the subsequent growth of micron-size crystals at very deep undercoolings, below and above Tg, using experimental nucleation and growth data obtained for stoichiometric Li2O.2SiO2 and Na2O.2CaO.3SiO2 glasses. The results show significant differences in the magnitude and temperature dependence of these kinetic coefficients. We explain this difference showing that the composition and/or structure of the nucleating critical clusters deviate from those of the stable crystalline phase. These results for diffusion coefficients corroborate our previous conclusion for the same glasses, based on different experiments, and support the view that, even for the so-called case of stoichiometric (polymorphic) crystallization, the nucleating phase may have a different composition and/or structure as compared to the parent glass and the evolving macroscopic crystalline phase. This finding gives a key to explain the discrepancies between calculated (by classical nucleation theory) and experimentally observed nucleation rates in these systems, in particular, and in deeply undercooled glass-forming liquids, in general.

Charge carrier mobility and concentration as a function of composition in AgPO3-AgI glasses

Conductivity data of the xAgI(1 - x)AgPO(3) system (0 ≤ x ≤ 0.5) were collected in the liquid and glassy states. The difference in the dependence of ionic conductivity on temperature below and above their glass transition temperatures (T(g)) is interpreted by a discontinuity in the charge carriers mobility mechanisms. Charge carrier displacement occurs through an activated mechanism below T(g) and through a Vogel-Fulcher-Tammann-Hesse mechanism above this temperature. Fitting conductivity data with the proposed model allows one to determine separately the enthalpies of charge carrier formation and migration. For the five investigated compositions, the enthalpy of charge carrier formation is found to decrease, with x, from 0.86 to 0.2 eV, while the migration enthalpy remains constant at ≈0.14 eV. Based on these values, the charge carrier mobility and concentration in the glassy state can then be calculated. Mobility values at room temperature (≈10(-4) cm(2) V(-1) s(-1)) do not vary significantly with the AgI content and are in good agreement with those previously measured by the Hall-effect technique. The observed increase in ionic conductivity with x would thus only be due to an increase in the effective charge carrier concentration. Considering AgI as a weak electrolyte, the change in the effective charge carrier concentration is justified and is correlated to the partial free energy of silver iodide forming a regular solution with AgPO(3).

Carbon Nanotube@MnO2@Polypyrrole composites: chemical synthesis, characterization and application in supercapacitors

Core/shell structures of carbon-based materials/ metal oxide have been considered as potential candidates for electrochemical devices due to their improved pseudocapacitance/electrical double layer capacitance and high conductivity/ superior surface area. The development of multiple core-shell structures of MWCNT@MnO2@PPy was analyzed as a standard procedure for mass production of supercapacitor electrodes. The relative concentration of carbon nanotubes in the composite was varied to optimize the double layer capacitance contribution in overall response of device. Resulting structures presented capacitance in order of 272.7 Fg-1 and reasonable cycling performance.

Electrospinning of polymeric fibres: an unconventional view on the influence of surface tension on fibre diameter

The production of regular and bead-free electrospun polymeric fibres requires an adequate combination of different parameters applied in the experimental setup viz. voltage for electrodeposition, viscosity of the solution, density of the polymeric support, the distance between electrodes and the geometry of the spinneret. Determination of the physical balance of forces on the droplet during fibre production was explored and provides relevant theo retical information about the surface tension and radius of polymeric fibres. Based on these predictions, we prepared polymeric electropun fibres of poly (vinyl alcohol), poly (vinyl pyrrolidone) and Eudragit® L100 in order to analyse non-conventional physical properties of experimental systems such as droplet stiffness and their influence on the diameter of resulting fibres.

STAPHYLOCOCCUS AUREUS BIOFILM FORMATION ON POLYPYRROLE: AN ELECTRICAL OVERVIEW

The development of organic devices based on conducting polymers for biofilm detection requires the combination of superior electrical response and high surface area for biofilm incorporation. Polypyrrole is a potential candidate for application in biofilm detection and control due to its characteristic superior electrical response and strong interaction with bacteria, which enables the use of the bioelectric effect in resulting devices. In this study, chemically synthesized polypyrrole was applied as a support for biofilm growth of S. aureus. Modifications in the electrical response of the polymeric template were explored to identify general mechanisms established during the deposition of the biofilm.

Electrospun Fibers of Enteric Polymer for Controlled Drug Delivery

The production of electrospun fibers of enteric polymer for controlled delivery of drugs represents a simple and low cost procedure with promising advantages relative to the longer therapeutic window provided by cylindrical geometry in association with intrinsic properties of pH-dependent drug carriers. In this work, we have explored the incorporation of additives (block copolymers of poly(ethylene)-b-poly(ethylene oxide)) into matrix of Eudragit L-100 and the effective action of hybrid composites on delivery of nifedipine, providing improvement in the overall process of controlled release of loaded drug.