The influence of dopant size and oxygen vacancy concentration on the room temperature elastic modulus and creep rate of ceria doped with Pr4+, Pr3+, Lu3+, and Gd3+, is investigated using a nanoindentation technique. Measurements are conducted with both fast (15 mN s−1) and slow (0.15 mN s−1) loading modes, including a load‐hold stage at 150 mN of 8 s and 30 s, respectively. Based on the data obtained using the fast loading mode, it is found that: 1) the dopant size is a primary determinant of the elastic modulus—the larger dopants (Pr3+ and Gd3+) produce lower unrelaxed moduli which are independent of the oxygen vacancy concentration. 2) The rearrangement of point defects is the major source of room temperature creep observed during load‐hold. Pr3+‐ and Gd3+‐doped ceria display the higher creep rates: due to their large size, they repel oxygen vacancies (VO), thereby promoting the formation of O7–CeCe–VO complexes that are capable of low temperature rearrangement. Lower creep rates are observed for Pr4+‐ and Lu3+‐doped ceria: the former has no vacancies and the latter, immobile vacancies. 3) Nanoindentation is a practical technique for identifying materials with labile point defects, which may indicate useful functionality such as high ionic conductivity, large electrostriction, and inelasticity.
A new model based on a linear diffusion equation is proposed to explain the current-voltage characteristics of blocking grain boundaries in Y-doped CeO2 in particular. One can also expect that the model can be applicable to the ionic conductors with blocking grain boundaries, in general. The model considers an infinitely long chain of identical grains separated by grain boundaries, which are treated as regions in which depletion layers of mobile ions are formed due to trapping of immobile charges that do not depend on the applied voltage as well as temperature. The model assumes that (1) the grain boundaries do not represent physical blocking layers, which implies that if there is a second phase at the grain boundaries, then it is too thin to impede ion diffusion and (2) the ions follow Boltzmann distribution throughout the materials. Despite its simplicity, the model successfully reproduces the "power law": current proportional to voltage power n and illustrated with the experimental example of Y-doped ceria. The model also correctly predicts that the product nT, where T is the temperature in K, is constant and is proportional to the grain boundary potential as long as the charge at the grain boundaries remains trapped. The latter allows its direct determination from the current-voltage characteristics and promises considerable simplification in the analysis of the electrical characteristics of the grain boundaries with respect to the models currently in use.
2D transition metal carbides and nitrides, namely MXenes, are normally synthesized in acidic solutions and are delaminated in basic solutions. This results in versatile materials with unique physical/chemical properties suitable for various practical applications. However, solution‐based chemical treatments can affect the chemical structures of MXenes, which accelerates the oxidation reactions and degrades their intrinsic properties. Here, long‐term stable Ti3C2Tx dispersion in deep eutectic solvents (DESs) that resisted oxidation degradation for up to 28 weeks is demonstrated. As an anti‐oxidative dispersion medium, DESs helped prevent oxidation of Ti3C2Tx layers due to hydrogen bond accepting and donating molecules passivated surface of the Ti3C2Tx. In addition, DES molecules in bulk solution can also be hydrated in the presence of water, which stabilizes reactive oxygen by forming stable DES‐water cluster. Therefore, the use of DESs enhanced the delamination of the Ti3C2Tx nanosheets, while preventing oxidation of the nanosheets in solution and even in their dried state. As a result, thick and thin films of Ti3C2Tx fabricated using DESs exhibited stable sheet resistance in comparison with pristine‐Ti3C2Tx. In addition, Ti3C2Tx dispersed in DESs can be applied as electrodes for electrochemical capacitors, in which they showed higher chemical stability and better performance than pristine Ti3C2Tx.
The validity and limitations of two quantitative approaches for estimating the height of the potential barrier at grain boundaries, Ψgb, in polycrystalline ionic conductors are examined both theoretically and experimentally. The linear diffusion model recently proposed by Kim and Lubomirsky determines Ψgb from the value of the power exponent of the current (Igb)-voltage (Ugb) relationship at the grain boundary, dln(Igb)/dln(Ugb), while the conventional approach calculates Ψgb from the ratio of the grain boundary resistivity to the grain core resistivity. The results of our theoretical analysis demonstrate that both approaches should yield consistent values for Ψgb if the ionic current through the grain boundary is limited exclusively by space charge. While the value of Ψgb obtained by the power law procedure is relatively insensitive to other causes of current obstruction, e.g. current constriction and/or local structural disorder, the resistivity ratio method, if not explicitly corrected for these additional limitations, results in a considerable overestimate of the grain boundary potential barrier. Hence, it is possible to distinguish between grain boundary resistance due to the presence of space charge and that due to additional sources by comparing the values of Ψgb determined using each of the two methods. Our theoretical analysis is confirmed experimentally with 3 mol% Gd-doped ceria with and without an additional source of current constriction across the grain boundary.
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