RESUMEN
The achievement of high growth rates in YBa2Cu3O7 epitaxial high-temperature superconducting films has become strategic to enable high-throughput manufacturing of long length coated conductors for energy and large magnet applications. We report on a transient liquid assisted growth process capable of achieving ultrafast growth rates (100 nm s-1) and high critical current densities (5 MA cm-2 at 77 K). This is based on the kinetic preference of Ba-Cu-O to form transient liquids prior to crystalline thermodynamic equilibrium phases, and as such is a non-equilibrium approach. The transient liquid-assisted growth process is combined with chemical solution deposition, proposing a scalable method for superconducting tapes manufacturing. Additionally, using colloidal solutions, the growth process is extended towards fabrication of nanocomposite films for enhanced superconducting properties at high magnetic fields. Fast acquisition in situ synchrotron X-ray diffraction and high resolution scanning transmission electron microscopy (STEM) become crucial measurements in disentangling key aspects of the growth process.
RESUMEN
The present paper quantifies and develops the kinetic aspects involved in the mechanism of interplay between electron and ions presented elsewhere(1) for K(h)Fe(k)[Fe(CN)(6)](l)*mH(2)O (Prussian Blue) host materials. Accordingly, there are three different electrochemical processes involved in the PB host materials: H(3)O(+), K(+), and H(+) insertion/extraction mechanisms which here were fully kinetically studied by means of the use of combined electronic and mass transfer functions as a tool to separate all the processes. The use of combined electronic and mass transfer functions was very important to validate and confirm the proposed mechanism. This mechanism allows the electrochemical and chemical processes involved in the K(h)Fe(k)[Fe(CN)(6)](l)*mH(2)O host and Prussian Blue derivatives to be understood. In addition, a formalism was also developed to consider superficial oxygen reduction. From the analysis of the kinetic processes involved in the model, it was possible to demonstrate that the processes associated with K(+) and H(+) exchanges are reversible whereas the H(3)O(+) insertion process was shown not to present a reversible pattern. This irreversible pattern is very peculiar and was shown to be related to the catalytic proton reduction reaction. Furthermore, from the model, it was possible to calculate the number density of available sites for each intercalation/deintercalation processes and infer that they are very similar for K(+) and H(+). Hence, the high prominence of the K(+) exchange observed in the voltammetric responses has a kinetic origin and is not related to the amount of sites available for intercalation/deintercalation of the ions.
RESUMEN
The K(+) reversible processes for ion exchange in K(h)Fe(k)[Fe(CN)(6)](l)*mH(2)O host compounds (Prussian Blue) were thermodynamically analyzed. A thermodynamic approach was established and developed based on the consideration of a lattice-gas model where the electronic contribution to the chemical potential is neglected and the ion-host interaction is not considered. The occupation fraction of the intercalation process was calculated from the kinetic parameters obtained through ac-electrogravimetry in a previous paper. In this way, the mass potential transfer function introduces a new way to evaluate the thermodynamic aspect of intercalation. Finally, based on the thermodynamic approach, the energy used to put each K(+) ion into the host material was calculated. The values were shown to be in good agreement with the values obtained through transient techniques, for example, cyclic voltammetry. As a result, this agreement between theory and experimental data validates the thermodynamic approach considered here, and for the first time, the thermodynamic aspects of insertion were considered for mixed valence materials.
RESUMEN
This paper develops a framework for the interpretation of ionic insertion/deinsertion reactions in an aqueous environment taking place in transition-metal hexacyanoferrates of the general formula K(h)[Fe(2+) (CN)(6)](l).mH(2)O, also called Prussian Blue. Three different processes were fully separated in the electrochemistry of these films. It was clearly identified that one of these electrochemical processes involves the insertion/deinsertion of H(3)O(+) (hydrated protons) through the channels of the K(h)[Fe(2+) (CN)(6)](l).mH(2)O structure to reach the film electroneutrality during the electron transfer between Everitt's Salt and Prussian Blue. The other electrochemical processes involve K(+) or H(+) (proton) exchange through the water crystalline structure existing in the channels of the K(h)[Fe(2+)(CN)(6)](l).mH(2)O structure.
RESUMEN
The graphical analysis of the impedance plots is used in the study of the electrodic systems that take place through two consecutive single electron transfers. The zinc anodic dissolution is studied by using this procedure. The characteristic points easily allow us to explain and to simulate the impedance behavior of this electrodic system according to the steady-state potential and the roughness of the working electrode. The direct procedure for parametrical identification from the graphical analysis allows us to reduce the time needed for an impedance experiment. This graphical analysis is suggested for studying thin coated galvanized steels.
RESUMEN
A general function for the faradaic impedance associated to a two consecutive single electron transfer mechanism followed by a irreversible first-order step has been obtained on the basis of formal kinetics. Kinetic parameters associated to this reaction mechanism can be obtained from the different kind of plots of the impedance function: Nyquist, Cole-Cole, and different Bode plots. A strategy for obtaining all parameters is suggested and analyzed on a detailed flowchart.
RESUMEN
FUNDAMENTALS: Continuous treatment with calcitonin (CT) has caused an increase of bone mineral density for the first 18 months, followed by a partial decrease of it. In order to obtain a better result in a two year follow-up, it is proposed a schedule treatment during 50% to 66% of the time in recent postmenopausal women. METHODS: Pilot, double-blind, randomised, two years follow-up study. 60 women with osteopenia less than 5 years from menopause received 40 U of intranasal elcatonin (ELC) or placebo (PL) 2 months ON, one month OFF. Compliance, safety, pain and the degree of incapacity were evaluated at baseline and every 3 months. At the start and every six months lumbar and femoral BMD were assessed with DXA. RESULTS: 41 patients completed the study (21 ELC and 20 PL). There were no basal differences. The treatment was actually used during 59% of the follow-up time in the ELC group and during 58% of the time in the PL group. Basal T-scores were -2.29 SD in the PL group and -2.42 SD in the ELC group. Bone densitometry showed an increase of BMD in the group of patients treated with ELC up to 18 months (lumbar and femoral) but a loss in those patients that received PL. CONCLUSION: 40 U of nasal elcatonin for more than 50% of the observation time prevents in the long-term (2 years) the progressive loss of bone mineral density in recent postmenopausal women.
