arXiv subjects

Vincenzo Esposito

Publications and source records attributed to Vincenzo Esposito.

11 recordsLinked to original sources

arXiv2021

Electromechanical dopant defect interaction in acceptor doped ceria

Oxygen defective cerium oxides exhibits a non classical giant electromechanical response that is superior to lead based electrostrictors. In this work, we report the key role of acceptor dopants, with different size and valence Mg2+, Sc3+, Gd3+, and La3+, on polycrystalline bulk ceria. Different dopants tune the electrostrictive properties by changing the electrosteric dopant defect interactions. We find two distinct electromechanical behaviors when the interaction is weak dopant vacancy binding energy 0.3 eV, electrostriction displays high coefficient, up to 10-17 m2V-2, with strongly time dependent effects. In contrast, we observe no time dependent effects when the interaction becomes strong 0.6 eV.

cond-mat.mtrl-sci↗

arXiv2021

Atomic-scale insights into electro-steric substitutional chemistry of cerium oxide

Cerium oxide (ceria, CeO2) is one of the most promising mixed ionic and electronic conducting materials. Previous atomistic analysis has covered widely the effects of substitution on oxygen vacancy migration. However, an in-depth analysis of the role of cation substitution beyond trivalent cations has rarely been explored. Here, we investigate soluble monovalent, divalent, trivalent and tetravalent cation substituents. By combining classical simulations and quantum mechanical calculations, we provide an insight into defect association energies between substituent cations and oxygen vacancies as well as their effects on the diffusion mechanisms. Our simulations indicate that oxygen ionic diffusivity of subvalent cation-substituted systems follows the order Gd>Ca>Na. With the same charge, a larger size mismatch with Ce cation yields a lower oxygen ionic diffusivity, i.e., Na>K, Ca>Ni, Gd>Al. Based on these trends, we identify species that could tune the oxygen ionic diffusivity: we estimate that the optimum oxygen vacancy concentration for achieving fast oxygen ionic transport is 2.5% for GdxCe1-xO2-x/2, CaxCe1-xO2-x and NaxCe1-xO2-3x/2 at 800 K. Remarkably, such a concentration is not constant and shifts gradually to higher values as the temperature is increased. We find that co-substitutions can enhance the impact of the single substitutions beyond that expected by their simple addition. Furthermore, we identify preferential oxygen ion migration pathways, which illustrate the electro-steric effects of substituent cations in determining the energy barrier of oxygen ion migration. Such fundamental insights into the factors that govern the oxygen diffusion coefficient and migration energy would enable design criteria to be defined for tuning the ionic properties of the material, e.g., by co-doping.

cond-mat.mtrl-sci↗

arXiv2020

Enhanced Electromechanical Response in Defective Sm and Nd Co-doped Ceria

Highly oxygen defective cerium oxide, e.g. Gd-doped ceria is a sustainable non-classical electrostrictor with electromechanical properties that are superior to lead-based piezoelectric metal oxides. Here, we report electrostriction in co-doped ceria (Sm, Nd) with a nominally low short-range vacancy-dopant association energy. Such a strategy results in a higher electrostrictive strain coefficient at lower-frequencies, and unexpected electromechanical strain saturation and relaxation effects. These outcomes support the hypothesis that electrostriction is strongly influenced by the local environment of oxygen vacancy and by the ionic migration blocking factors built-in the microstructure.

physics.app-ph↗

arXiv2020

Effect of Cold Sintering Process (CSP) on the Electro-Chemo-Mechanical Properties of Gd-doped Ceria (GDC)

In this report, the effect of the cold sintering process (CSP) on the electro-chemo-mechanical properties of 10 mol% Gd-doped ceria (GDC) is investigated. High purity nanoscale GDC powder is sintered via a cold sintering process (CSP) in pure water followed by post-annealing at 1000 °C. The resultant CSP ceramics exhibits high relative density (~92%) with an ultrafine grain size of ~100 nm. This sample illustrates comparable electrochemical properties at intermediate/high temperatures and electromechanical properties at room temperature to the sample prepared via conventional firing, i.e. sintering in the air at 1450 °C. Moreover, a large creep constant as well as a low elastic modulus and hardness are also observed in the CSP sample.

cond-mat.mtrl-sci↗

arXiv2020

Electro-Chemo-Mechanical Properties in Nanostructured Ca-doped Ceria (CDC) by Field Assisted Sintering

Recent investigations have shown that highly oxygen defective cerium oxides generate non-classical electrostriction that is superior to lead-based ferroelectrics. In this work, we report the effect of field-assisted spark plasma sintering (SPS) on electro-chemo-mechanical properties on Ca-doped ceria (CDC). Nanometric powders of ca. 10 nm are rapidly consolidated to form polycrystalline nanostructures with a high degree of crystalline disorder. Remarkably, the resultant material demonstrates a large electromechanical strain without a frequency-related relaxation effect. We conclude that electromechanical activity in CDC materials strictly depends on the Ca-VO interaction, while disorder at the crystalline boundaries has a minor effect.

cond-mat.mtrl-sci↗

arXiv2020

The Role of Oxygen Defects on the Electro-Chemo-Mechanical Properties of Highly Defective Gadolinium Doped Ceria

In light of the recent discovery of giant electrostriction in defective fluorites, here we investigate the interplay between mechanical, electrochemical and electromechanical properties of oxygen defective ceria compositions as the effect of Gd-doping at low temperatures. Highly dense polycrystalline ceramics are prepared as micron-size grains with a minimized grain boundary extent. Electrochemical ionic migration reveals that doping controls the configuration of oxygen vacancies in the samples. Unexpectedly, we observe that electromechanical activity depends on oxygen vacancy configuration rather than on its nominal concentration. The primary creep at room temperature indicates a declining viscoelastic trend with increasing oxygen defects.

physics.app-ph↗

arXiv2019

Impact of cation redox chemistry on continuous hydrothermal synthesis of 2D-Ni(Co/Fe) hydroxides

Continuous hydrothermal flow synthesis (CHFS) is a facile, upscalable and cost-efficient synthetic method enabling the nanostructuring of advanced functional materials in steady conditions, i.e. not in batch synthesis. In this paper, we use CHFS to crystallize NiCo- and NiFe-hydroxides in water solution with 2D nanofeatures. By tuning the synthetic parameters, we disclose the key role of the cation redox chemistry in the transition between two competitive phases: from 2D-nanoplatelets of brucite to layered double hydroxides (LDH). For controlling the precipitation of different Ni, Fe, Co-hydroxide phases, we propose the combined use of an oxidizing (H2O2) and a complexing (NH3) agent. At temperatures as low as 80 °C, the presence of H2O2 and a low concentration of NH3 favour the Ni2+/Co3+ over Ni2+/Co2+ oxidation states, shifting the product structure from brucite phase (temperatures > 80 °C) to LDH. Conversely, for the NiFe-hydroxides the transition from LDH (temperatures < 80 °C) to brucite phase (temperatures > 80 °C) is controlled by the reaction temperature only. Due to the high stability of Fe3+, the synthesis of NiFe products by CHFS does not require oxidizing and complexing agents, resulting in a robust process for large-scale production.

cond-mat.mtrl-sci↗

arXiv2019

Effect of Oxygen Defects Blocking Barriers on Gadolinium Doped Ceria (GDC) Electro-Chemo-Mechanical Properties

Some oxygen defective metal oxides, such as cerium and bismuth oxides, have recently shown exceptional electrostrictive properties that are even superior to the best performing lead-based electrostrictors, e.g. lead-magnesium-niobates (PMN). Compared to piezoelectric ceramics, electromechanical mechanisms of such materials do not depend on crystalline symmetry, but on the concentration of oxygen vacancy in the lattice. In this work, we investigate for the first time the role of oxygen defect configuration on the electro-chemo-mechanical properties. This is achieved by tuning the oxygen defects blocking barrier density in polycrystalline gadolinium doped ceria with known oxygen vacancy concentration, Ce0.9Gd0.1O2-x,x= 0.05. Nanometric starting powders of ca. 12 nm are sintered in different conditions, including field assisted spark plasma sintering (SPS), fast firing and conventional method at high temperatures. These approaches allow controlling grain size and Gd-dopant diffusion, i.e. via thermally driven solute drag mechanism. By correlating the electro-chemo-mechanical properties, we show that oxygen vacancy distribution in the materials play a key role in ceria electrostriction, overcoming the expected contributions from grain size and dopant concentration.

cond-mat.mtrl-sci↗

arXiv2019

Gd0.2Ce0.8O1.9/Y0.16Zr0.84O1.92 nanocomposite thin films for low temperature ionic conductivity

Gd0.2Ce0.8O1.9/Y0.16Zr0.84O1.92 (GDC/YSZ) nanocomposite is synthesized by a novel hybrid chemical route, where colloidal crystalline GDC nanoparticles from continuous hydrothermal synthesis are dispersed into a metalorganic YSZ matrix precursor. The result is a mixture of metal oxides in which GDC nanoparticles are finely distributed in a continuous metalorganic polymeric matrix to be crystallized after calcination. The GDC nanoparticles reduce the temperature necessary to obtain crystalline YSZ, which is already formed at 400 °C. The nanocomposite reveals structural stability up to 800 °C when treated in both air and reducing atmosphere, showing the onset of diffusion below 1000 °C. The diffusional processes are largely dependent on the nanometric grain size, with Zr4+ diffusing abruptly towards GDC in air at 1000 °C and GDC/YSZ interdiffusion being hindered in reducing environment despite the onset temperature of 900 °C. The nanocomposite precursor is an inkjet-printable reactive water-based material, suitable for the deposition of thin films with a thickness below 100 nm after calcination at 750 °C. The crystal structure of the film reveals no interaction between GDC and YSZ but a microstrain (0.3% tensile strain for YSZ). The thin film microstructure shows a compact layer with 94% density. The nanocomposite shows high oxygen ionic conductivity at low temperatures (> 5 * 10-3 S cm-1 at 500 °C), low activation energy (0.55 eV), and dominant oxygen ionic conductivity even in reducing conditions (pO2 < 10-25 atm). We show that these properties arise from the large interface between the components of the composite, due to the embedding of the GDC nanoparticles in the YSZ matrix, while ZrO-CeO intermixing can be avoided and no n-type conductivity is observed even at low oxygen activities and high temperatures.

cond-mat.mtrl-sci↗

arXiv2019

Continuous hydrothermal flow synthesis of Gd-doped CeO2 (GDC) nanoparticles for inkjet printing of SOFC electrolytes

GdxCe1-xO2-d (GDC) nanoparticles were synthesized, using continuous hydrothermal flow synthesis. By varying the synthesis conditions, particle size and morphology could be tailored. Here, particle sizes between 6 and 40 nm with polyhedral or octahedral shape could be obtained. Gd0.2Ce0.8O2-d nanoparticles were further processed into inks for inkjet printing. Despite the small particle size/large surface area, inks with excellent printing behavior were formulated. For proof-of-concept, thin GDC layers were printed on a) green NiO-GDC substrates, and on b) presintered NiO-YSZ substrates. While no dense layers could be obtained on the green NiO-GDC substrates, GDC nanoparticles printed on NiO-YSZ substrates formed a dense continuous layer after firing.

cond-mat.mtrl-sci↗

arXiv2019

Stabilization of binary NiO-YSZ nanocolloids for direct inkjet deposition

Water-based inks, containing nanometric NiO and YSZ particles in 66/34 vol. % ratio, are produced by colloidal stabilization of a binary dispersion obtained via continuous hydrothermal synthesis at supercritical conditions, i.e. 280 bar and 400 C. The method yields single-crystal particles with diameter < 10 nm for both phases in a single-step process, achieving a highly mixed composite. Two different approaches are applied to formulate inks printable with piezoelectric printheads, i.e. an electrostatic and an electrosteric stabilization path. The use of the electrosteric dispersant results in colloids with superior stability > 200 days, more uniform thin films and finely nanostructured porous cermet films with thickness below 500 nm, after reducing NiO to Ni. Particles coarsening to 50-150 nm is obtained at 1000 C, accompanied by a shrinkage of ca. 43 % in thickness without the formation of cracks or delamination of the zirconia substrates.

physics.app-ph↗