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 (V-(O) over dot ) in the lattice. In this work, we investigate for the first time the role of oxygen defects 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-delta, delta = 0.05. Nanometric starting powders of ca. similar to 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 plays a key role in ceria electrostriction, overcoming the expected contributions from grain size and dopant concentration. (C) 2019 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Conductivity, dielectric and piezoelectric properties of SrBi4Ti4O15

Strontium Bismuth Titanate is a very promising material for high temperature piezoelectric applications, its elevated ferroelectric phase transition (530°C), linear piezoelectric properties under low field and relatively low room temperature conductivity (compared to others Bismuth Titanates) make it very attractive for precision sensors. However, under severe conditions (low frequency, high field, high temperature or low oxygen partial pressure) some of those advantages disappear. Piezoelectric response is dominated by charge drift in general becomes unstable. Above all, at high temperature and low oxygen partial pressure, a large conductivity increase reduces the piezoelectric efficiency of the material, in this work, electrical conductivity, piezoelectric properties and dielectric permittivity of SrBIT ceramic have been investigated in conditions of high temperature, low oxygen partial pressure, low to moderate driving field and frequency. As a result of this research, a better understanding of SrBIT properties was achieved. Thanks to a careful study of SrBIT processing as a bulk ceramic, a reproducible route was established. Many basic mechanisms leading to both SrBIT crystallization and sintering have been identified. It was demonstrated that a detailed knowledge of the exact processing conditions is required in order to achieve high quality material. DC conductivity measurements were carried out as a function of temperature, oxygen partial pressure and dopant concentration. It was found that the apparent activation energy for conduction for undoped SrBIT was 1 eV between 140 and 220°C and 1.5 eV between 450 and 700°C. Decrease of the activation energy in the lower temperature range has been discussed considering grain boundary conductivity, as a transition from electronic to ionic conduction or as consequence of small polarons conduction. It was shown that lower activation energy resulted from Manganese doping (0.5 eV), this was interpreted as either growing influence of grain boundary conductivity as dopant concentration increases or as shallow hole trap formation. DC conductivity measurements and acceptor/donor doping experiments demonstrated p-type conductivity in the low temperature range (up to 220°C) as donor doping decreases conductivity, while oxygen partial pressure controlled measurements indicated n-type conductivity at higher temperature (above 700°C). An electrical impedance analysis was performed with several equivalent circuits. The aim of these models was to simulate the impedance of SrBIT. The best approximation was found with a distributed element of Havriliak-Negami type. However, as the physical justification for this circuit was not clear, the investigation of the grain, grain boundary and electrode impedances was performed with multiple discrete parallel RC elements. With temperature, grain size and oxygen activity variations, the identification of three separate contributions as grain, grain boundary and electrode was realized. The anisotropy of conductivity and permittivity was demonstrated with textured material and both DC and AC analysis. With the master curves built for the electrical modulus, it was found that the impedance probably related to Bismuth oxide layers produces an additional high frequency are. From this finding and by comparing characteristic relaxation frequencies of undoped, 2 mol.% Mn and 4 mol.% Nb SrBIT, it was determined that conductivity is higher in the ab plane direction than in the c direction within both perovskite units and Bismuth oxide layers. With conductivity measurements under controlled oxygen partial pressure, it was found that an acceptor-based (intrinsic or extrinsic) model could be used to describe the electrical conductivity under controlled oxygen partial pressure of both undoped and 2 mol.% Mn doped SrBIT. However, as neither a pO2-1/6 region (intrinsic oxygen vacancies compensated by electrons) for undoped SrBIT nor a pO2-1/4 region (oxygen vacancies compensated by singly ionized acceptors) for Mn doped SrBIT were seen, it was concluded that the acceptorcontrolled model is not sufficient for a complete description of SrBIT. For this reason and in order to include the low oxygen partial pressure behavior of undoped SrBIT, a donor-based (intrinsic) model was also considered. The source of intrinsic donors would be in that case Bi3+ cations sitting on Sr2+ sites in the perovskite sublattice. Considering Bismuth vacancies as the negative compensating species, both pO2-1/4 and pO2-independent regions could be predicted with the model. However, even if the donor-controlled model seems to better match conductivity measurements in the full PO2) range, rejecting the acceptor-based model would be an error. It is actually not demonstrated that in SrBIT the concentration of exchanged Bismuth cations is always (all temperature, pressure) larger than the natural acceptor impurity concentration. It is very likely that the cation exchange is dependent of the oxygen partial pressure. It is also not proved as suggested in the literature that direct compensation between exchanged Strontium and Bismuth exists, reducing the net donor-excess. With the acceptor-controlled model, the mass-action constants for reduction and for ionization of intrinsic carriers across the band gap were determined. The band gap of SrBIT was estimated to be 3.5 eV. The ionic conductivity of SrBIT was determined at high temperature with measurements under controlled oxygen partial pressure. It was found that the electrical conductivity of SrBIT is probably mixed (electronic and ionic) as the estimation of the transference number provided quite large values (t=0.8 at 800°C). From electronic and ionic conductivity data, mixed conduction can actually be predicted in a large temperature range (above room temperature). The piezoelectric measurements using direct effect demonstrated that it is actually possible to unlock piezoelectrically active ferroelectric domain walls and create non-linear piezoelectric properties in undoped SrBIT. This occurs above a threshold elastic field, which is thermally activated. With a piezoelectric composite, it was demonstrated that the electromechanical coupling between two different phases creates a piezoelectric relaxation. This one could be positive or negative depending on the respective properties of each composite's component. It was shown experimentally that a small temperature change is sufficient to transform a positive relaxation into a negative one. While these experiments did not provide a detailed microstructural explanation for the piezoelectric relaxation observed in 2 mol.% Mn doped SrBIT, they gave a first insight into an original phenomenological approach. Microstructure and piezoelectric properties were related with the calculation of a piezoelectric relaxation composite made of two textured samples. This demonstrated that a piezoelectric relaxation may occur just because of anisotropy. Microstructural reproduction of this coupling is actually an important feature of Aurivillius phases.

EPFL2000

Broadband Dielectric Response in Hard and Soft PZT

Li Jin

Lead zirconate titanate (Pb(Zr1-xTix)O3 or PZT) ferroelectric ceramics have been widely used in transducers, actuators, and sensors, since they posses high dielectric and piezoelectric properties with a relatively high temperature of operation. Commercially used PZT ceramics are always modified by different dopants and are divided into the "soft" (donor doped) and "hard" (acceptor doped) groups. Compared with the undoped composition, hard PZT often shows lower but more stable properties after ageing. In contrast, soft PZT shows higher properties and insensitivity to ageing. The difference in properties between the soft and hard PZT ceramics is rather large, even though the doping level is limited to a very low value (on the order of 1 mole %). The large difference of the physical properties between them mainly originates from the contributions from domain wall motion rather than properties of the crystal lattice. However, the mechanisms of hardening and softening are not well understood. In order to understand better the hardening and softening mechanisms, in this thesis the different contributions to the dielectric properties of soft and hard PZT ceramics are studied by means of a broadband dielectric spectroscopy from 10 mHz to 20 GHz. Properties at THz and infrared frequencies where only crystalline lattice contributes to the dielectric response were also investigated in collaboration with another group. In the frequency range below 20 GHz, the different contributions to the permittivity by domain wall motion were revealed in hard and soft materials. In order to correlate the properties to the microscopic structure of hard and soft PZT ceramics, the domain structures were also investigated by transmission electron microscopy. Piezoelectric spectroscopy was employed to help separating different contributions at frequencies below 100 Hz. The main results of this work are: The microwave dielectric dispersion of all PZT ceramics (including undoped, soft and hard PZT ceramics), which is characterized by a rapid decrease of the permittivity and a loss peak in the GHz frequency range, is contributed by both domain wall motion and piezoelectric grain resonances. These two mechanisms are separated by gradual poling of samples. The dispersion related to the domain wall motion appears at a higher frequency than the one related to grain resonance and constitutes the main contribution to the microwave dielectric properties of unpoled samples. Above the GHz frequency range, the dielectric properties of hard and soft PZT ceramics are rather close and approach the upper limit value of their intrinsic properties, which are identified by dielectric properties determined by THz dielectric spectrum. The contributions by domain wall motion make up more than 50% of the quasistatic dielectric properties (measured at 100 kHz) in all studied samples. Below GHz frequency range, another dielectric dispersion due to the domain wall creep, which manifests itself by a logarithmic decrease of permittivity with increasing frequency, is indentified in both soft and hard PZT ceramics in a relatively broad frequency region over at least eight decades. The difference of the dielectric properties between the hard and soft PZT mainly results from this logarithmic dispersion, since soft PZTs exhibit stronger logarithmic dispersion than hard PZTs. By controlling the doping kind and crystalline symmetry, the slope of the logarithmic function can be adjusted. Large values are observed in the system with disordered distribution of defect dipoles (soft, donor doped materials) while nearly zero slope could be observed in hard, acceptor doped materials with tetragonal structure with defect dipoles well aligned with polarization within domains. Rapid increase of both permittivity and loss below 1 Hz, which cannot be described by the logarithmic function, is observed in hard PZT ceramics. To interpret this behavior, results of dielectric spectroscopy were complemented by piezoelectric measurements in the frequency range from 10 mHz to 100 Hz. The absence of the strong dispersion in the piezoelectric properties and presence in the dielectric response strongly indicates that its origin is in charge transport (such as hopping conductivity) rather than in motion of domain walls. Nanodomains, observed in Fe3+-doped hard PZT with composition at morphotropic phase boundary do not lead to the high dielectric and piezoelectric properties, as would be expected from some theoretical models. Acceptor doping rapidly decreases the domain size in PZT ceramics with compositions in rhombohedral, tetragonal and MPB regions. This effect could not be interpreted by the decrease of the grain size according to the commonly assumed parabolic relationship between the domain size and grain size. The small domain size is rather related to the presence of oxygen vacancies which break continuity of polarization.

EPFL2011

Grain Boundary Relaxation in 18-carat Gold Alloys

Ann-Kathrin Audren

Grain boundaries (GBs) play an important role for the mechanical properties of metals. In addition to dislocation motion inside the grains, some metal alloys deform along the GBs at high temperatures. GBs can also be the cause of a brittle behaviour of some metallic alloys, where crack propagation along the GBs is observed. This thesis aims to understand the role of GBs on the thermo-mechanical behaviour of metals and especially to define the microscopic mechanism, which leads to a deformation at the GBs. In this thesis, polycrystals, single crystals and bi-crystals of a yellow gold alloy are studied in detail, primarily by mechanical spectroscopy. The analysis and interpretation of the experimental data identifies different anelastic relaxations (internal energy dissipation processes), that produce peaks in the mechanical loss spectrum. The mechanical loss spectrum of polycrystals shows a relaxation peak P2 at about 780K, which is absent in single crystals made from the same alloy. Stepwise deformation of a single crystal causes an increase of the high temperature mechanical loss background and the appearance of a high temperature peak (P3). Above a critical deformation, P3 disappears and the peak P2, which is normally observed in polycrystals, appears. The increase of the exponential background is interpreted as due to the introduction of new dislocations whereas the peak P3 is attributed to a dislocation relaxation mechanism in the sub-grain boundaries. The peak P2 located at intermediate temperatures depends on the grain size: with grain growth, the peak position shifts to higher temperatures. It is shown that the relaxation time is proportional to the grain size d. Such a grains size dependence is in agreement with the Zener model based on geometrical considerations of an assembly of elastic grains, which can slide against each other. The investigations on bi-crystals containing a single GB with a specific misorientation between crystal lattices and a specific boundary plane orientation show that the relaxation peak P2 is closely related to a mechanism taking place at the boundary. The peak height is proportional to the GB density in a bi-crystal, whereas a single crystalline part cut from a bi-crystal does not show a relaxation peak. Molecular dynamics simulations are performed in order to illustrate the potential microscopic mechanisms responsible for the stress relaxation peak P2 in polycrystals. A Sigma5 grain boundary is submitted to a shear deformation parallel to the boundary plane. The grain boundary shows a migration perpendicular to the boundary plane coupled to shear for temperatures below 700K. Above 1000K, only grain boundary sliding is observed. Two models are developed that provide expressions for the relaxation strength and the relaxation time that are compared to experimental measurements performed on polycrystals. The observed grain size dependence favours the sliding model over the migration model. Measurements as a function of stress allow a refinement of the sliding model. The stress amplitude dependence of the peak P2 indicates a depinning mechanism, which is interpreted as due to GB dislocations between zones where sliding of different amount occurred. Obstacles to the sliding movement like steps or extended coincidence sites in the GB plane act as pinning points. The pinning points can be overcome at high temperatures close to the melting point, which results in the onset of local microscopic creep.

EPFL2014