This study demonstrates that a space charge layer is formed on dislocation during mechanical deformation at elevated temperature. High density of dislocation lines is generated in bulk single crystalline Y2O3 stabilized ZrO2 (YSZ) by uniaxial compression at elevated temperature. The creation of dislocation is proven with transmission electron microscopy (TEM). Then, energy-dispersive X-ray spectroscopy (EDS) and electron energy loss spectroscopy (EELS) are used to explore the changes in the composition on and away from the dislocation lines. Also, it is clarified that segregation of dopant atoms (yttrium) on the dislocation line is induced by high temperature annealing. Comparing the compositional variations with and without thermal annealing, we study the space charge layer formed on dislocation lines in a doped system.
For most applications, zirconia (ZrO2) is doped with yttria. Doping leads to the stabilization of the tetragonal or cubic phase, and increased oxygen ion conductivity. Most previous surface studies of yttria-doped zirconia were plagued by impurities, however. We have studied doping of pure, 5-monolayer ZrO2 films on Rh(111) by x-ray photoelectron spectroscopy (XPS), scanning tunneling microscopy (STM), and low-energy electron diffraction (LEED). STM and LEED show that the tetragonal phase is stabilized by unexpectedly low dopant concentrations, 0.5 mol% Y2O3, even when the films are essentiall…
Molecular dynamics (MD) is employed to investigate the plastic deformation mechanisms of single crystalline yttria-stabilized tetragonal zirconia (YSTZ) nanopillars under uniaxial compression. Simulation results show that the nanoscale plastic deformation of YSTZ is strongly dependent on the crystallographic orientation of zirconia nanopillars. For the first time, the experimental explored tetragonal to monoclinic phase transformation is reproduced by MD simulations in some particular loading directions. Three distinct mechanisms of dislocation, phase transformation, and a combination of dislo…
The electrochemical reactions of solid oxide fuel cells occur in the region where gas-phase species, electrode, and electrolyte coincide. When the electrode is an ionic insulator and the electrolyte is an electronic insulator, this `triple phase boundary' is assumed to have atomic dimensions. Here we use photoemission electron microscopy to show that the reduced surface of the electrolyte yttria-stabilized zirconia (YSZ) undergoes a metal-insulator transition near Pt negative electrodes. YSZ's electron conducting region functions as an extended triple phase boundary that can be many microns in…
The tetragonal to monoclinic (t-m) phase transformation of zirconia has been the object of extensive investigations of the last twenty years, and is now recognised as being of martensitic nature. However, martensitic transformation has only been observed by transmission electron microscopy or indirect methods. Though the benefit on the fracture toughness and crack resistance was the main interest, the transformation is now considered for its consequences on the degradation of the material. The use of AFM reported here allowed the observation of the first stages of martensite relief growth and …
The aging behavior of 3-mol%-yttria-stabilized tetragonal zirconia (3Y-TZP) ceramics sintered in air and in reducing conditions was investigated at 140°C in water vapor. It was observed by X-ray diffraction (XRD) that 3Y-TZP samples sintered in reducing conditions exhibited significantly higher tetragonal-to-monoclinic transformation than samples with similar density and average grain size values but obtained by sintering in air. This fact is explained by the increase of the oxygen vacancy concentration and by the presence at the grain boundary region of a new aggregate phase formed because of…
Stagnation of grain growth is often attributed to impurity segregation. Yttria-stabilized cubic zirconia does not evidence any segregation-induced slowdown, as its grain growth obeys the parabolic law when the grain size increases by more than one order of magnitude. However, lowering the temperature below 1300 oC triggers an abrupt slowdown, constraining the average grains to grow by less than 0.5 $μ$m in 1000 h despite a relatively large driving force imparted in the fine grains of ~0.5 $μ$m. Yet isolated pockets of abnormally large grains, along with pockets of abnormally small grains, emer…
Since the recent failure events of two particular series of zirconia femoral heads for total hip replacement prosthesis, a large decrease in the use of zirconia ceramics for orthopaedic implants has been observed. In spite of the biomedical success of this material during the last ten years, this was required for safety reasons, until the cause of the failures is known. It has been shown that these failures were related to the low temperature hydrothermal degradation (also known as ageing). Thus it is crucial to better understand the ageing behaviour, in order to be able to assess its importan…
Cubic yttria-stabilized zirconia is widely used in industrial electrochemical devices. While its fast oxygen ion diffusion is well understood, why cation diffusion is much slower-its activation energy (~5 eV) is 10 times that of anion diffusion-remains a mystery. Indeed, all previous computational studies predicted more than 5 eV is needed for forming a cation defect, and another 5 eV for moving one. In contrast, our ab initio calculations have correctly predicted the experimentally observed cation diffusivity. We found Schottky pairs are the dominant defects that provide cation vacancies, and…
We present an ab-initio based kinetic Monte Carlo model for ionic conductivity in single crystal yttria-stabilized zirconia. Ionic interactions are taken into account by combining density functional theory calculations and the cluster expansion method and are found to be essential in reproducing the effective activation energy observed in experiments. The model predicts that the effective energy barrier can be reduced by 0.15-0.25 eV by arranging the dopant ions into a super-lattice.
Multilayered heterostructures of Ce0.85Sm0.15O2-delta and Y0.16Zr0.92O2-delta of a high crystallographic quality were fabricated on (001) - oriented MgO single crystal substrates. Keeping the total thickness of the heterostructures constant, the number of ceria-zirconia bilayers was increased while reducing the thickness of each layer. At each interface Ce was found primarily in the reduced, 3+ oxidation state in a layer extending about 2 nm from the interface. Concurrently, the conductivity decreased as the thickness of the layers was reduced suggesting a progressive confinement of the charge…
Additive manufacturing represents a revolution due to its unique capabilities for freeform fabrication of near net shapes with strong reduction of waste material and capital cost. These unfair advantages are especially relevant for expensive and energy-demanding manufacturing processes of advanced ceramics such as Yttria-stabilized Zirconia, the state-of-the-art electrolyte in Solid Oxide Fuel Cell applications. In this study, self-supported electrolytes of yttria-stabilized zirconia have been printed by using a stereolithography three-dimensional printer. Printed electrolytes and complete cel…
First-principles calculation and anharmonic dynamical theory were used in sequence to explain a large excess heat capacity observed in yttria-stabilized zirconia in comparison with the additive rule value. It is found that the excessive shape of heat capacity decays gradually with the Y$_{2}$O$_{3}$ doping when the number of environmentally different O sites falls to its zero value at 33 mol % Y$_{2}$O$_{3}$-ZrO$_2$ due to the Y atoms adjacent. The model and results presented in this work provide a key insight into the complex behaviour and characterization of fast-ion conductors.
The tetragonal to monoclinic phase transformation of zirconia has been the subject of extensive studies over the last 20 years [1-4]. The main features of the transformation have been identified and its martensitic nature is now widely recognised [5-8]. More specifically, the relevance of a nucleation and growth model to describe the transformation is widely accepted. Recent fracture episodes [9] of zirconia hip joint heads were reported, failures related to the t-m transformation degradation. Among the materials solutions considered for decreasing the sensitivity to t-m phase transformation, …
Yttria-stabilized zirconia (YSZ), a ZrO2-Y2O3 solid solution that contains a large population of oxygen vacancies, is widely used in energy and industrial applications. Past computational studies correctly predicted the anion diffusivity but not the cation diffusivity, which is important for material processing and stability. One of the challenges lies in identifying a plausible configuration akin to the ground state in a glassy landscape. This is unlikely to come from random sampling of even a very large sample space, but the odds are much improved by incorporating packing preferences reveale…
Interdiffusion between the yttria stabilized zirconia (YSZ) electrolyte and the gadolinia doped ceria (CGO) barrier layer is one of the major causes to the degradation of solid oxide fuel cells (SOFCs). We present in this work experimental investigations on CGO-YSZ bi-layer electrolyte sintered at 1250 C or 1315 C and element transport as a function of sintering temperature and dwelling time. In order to quantitatively simulate the experimental observations, the CALPHAD-type thermodynamic assessment of the CGO-YSZ system is performed by simplifying the system to a CeO2-ZrO2 quasi-binary system…
The isothermal tetragonal-to-monoclinic transformation of 3Y-TZP ceramics sintered at two different temperatures (1450°C and 1550°C) and duration (2 and 5 h) is investigated at 134°C in steam. Particular attention is paid to the presence of a cubic phase and its effect on isothermal aging. Sintering at 1550°C can result in a significant amount of large cubic grains in the specimens, that have a detrimental impact on aging resistance, especially for the first stage of the aging process. Cubic grains appear to be enriched in yttrium, which in turn leads to a depletion of yttrium in the neighbori…
Specimen- and grain-size effects on nanoscale plastic deformation mechanisms and mechanical properties of polycrystalline yttria-stabilized tetragonal zirconia (YSTZ) nanopillars are studied by molecular dynamics simulations. Through uniaxial compression of YSTZ columnar nanopillars, intergranular and transgranular deformation mechanisms are investigated. Cooperative intergranular deformations including grain boundary sliding and migration, grain rotation, and amorphous phase formation at grain boundaries are revealed. Results also reveal formation of partial dislocations, which act as splitte…
We have used electron paramagnetic resonance to study the thermal annealing of colour centres induced in cubic yttria-stabilized zirconia by swift electron and heavy ion-irradiations. Single crystals were irradiated with 1 or 2-MeV electrons, and 200-MeV 127I, or 200-MeV 197Au ions. Electron and ion beams produce the same colour centres: namely i) an F+-like centre, ii) the so-called T-centre (Zr3+ in a trigonal oxygen local environment), and iii) a hole center. Isochronal annealing was performed up to 973 K. Isothermal annealing was performed at various temperatures on samples irradiated with…
We have succeeded in growing epitaxial and highly stoichiometric films of EuO on yttria-stabilized cubic zirconia (YSZ) (001). The use of the Eu-distillation process during the molecular beam epitaxy assisted growth enables the consistent achievement of stoichiometry. We have also succeeded in growing the films in a layer-by-layer fashion by fine tuning the Eu vs. oxygen deposition rates. The initial stages of growth involve the limited supply of oxygen from the YSZ substrate, but the EuO stoichiometry can still be well maintained. The films grown were sufficiently smooth so that the capping w…
Polarizable interaction potentials, parametrized using ab initio electronic structure calculations, have been used in molecular dynamics simulations to study the conduction mechanism in Y2 O3 - and Sc2 O3 -doped zirconias. The influence of vacancy-vacancy and vacancy-cation interactions on the conductivity of these materials has been characterised. While the latter can be avoided by using dopant cations with radii which match those of Zr4+ (as is the case of Sc3+), the former is an intrinsic characteristic of the fluorite lattice which cannot be avoided and which is shown to be responsible for…
Voltage control of interfacial magnetism has been greatly highlighted in spintronics research for many years, as it might enable ultra-low power technologies. Among few suggested approaches, magneto-ionic control of magnetism has demonstrated large modulation of magnetic anisotropy. Moreover, the recent demonstration of magneto-ionic devices using hydrogen ions presented relatively fast magnetization toggle switching, tsw ~ 100 ms, at room temperature. However, the operation speed may need to be significantly improved to be used for modern electronic devices. Here, we demonstrate that the spee…
Changes in crystalline phases resulting from low-temperature ageing of different yttria doped and non-doped zirconia-toughened alumina composites and nanocomposites were investigated under controlled humidity and temperature conditions in autoclave. A classical powder mixing processing route and a new modified colloidal processing route were used to process the composites. Different compositions ranging from 2.5 wt.% zirconia in a matrix of alumina to pure zirconia (3Y-TZP) were studied. It was observed that Al2O3+yttria stabilised ZrO2 composites exhibited significant ageing. However, ageing …
The stability of a metal thin films on a dielectric substrate is conditioned by the magnitude of the interactive forces at the interface. In the case of a non-reactive interface and weak adhesion, the minimization of free surface energy gives rise to an instability of the thin film. In order to study these effects, Pt thin films with a thickness of 50 nm were deposited via ion-beam sputtering on yttria stabilized zirconia single crystals. All Pt films were subjected to heat treatments up to 973 K for 2 h. The morphological evolution of Pt thin films has been investigated by means of scanning e…
Three dimensional difference pair distribution functions from X-ray and neutron diffraction experiments are reported for yttria stabilized zirconia (Zr$_{0.82}$Y$_{0.18}$O$_{1.91}$). We use a quantitative analysis of the signatures in the 3D-$Δ$PDFs to establish that oxygen ions neighbouring a vacancy shift by 0.515(5)~Å along $\langle 1,0,0 \rangle$ towards the vacancy while metal ions neighbouring a vacancy shift by 0.269(2)~Å along $\langle 1,1,1 \rangle$ away from the vacancy. The neutron 3D-$Δ$PDF shows a tendency for vacancies to cluster along $\langle \frac{1}{2},\frac{1}{2},\frac{1}{2}…
Ionic conductivity blocking at grain boundaries in polycrystalline electrolytes is one of the main obstacles that need to be overcome in order to improve the performance of solid state fuel cells and batteries. To this aim, harnessing the physical properties of grain boundaries in ionic conducting materials such as yttria stabilized zirconia (YSZ) down to the atomic scale arises as a greatly important task. Here we present a structural and compositional analysis of a single grain boundary in a 9 mol% yttria content YSZ bicrystal by means of aberration corrected scanning transmission electron m…
Highly porous Pt/Al thin film electrodes on yttria stabilized zirconia electrolytes were prepared by dealloying of co-sputtered Pt/Al films. The oxygen reduction capability of the resulting electrodes was analyzed in a solid oxide fuel cell setup at elevated temperatures. During initial heating to 523 K exceptionally high performances compared to conventional Pt thin film electrodes were measured. This results from the high internal surface area and large three phase boundary length obtained by the dealloying process. Exposure to elevated temperatures of 673 K or 873 K gave rise to degradation…
Dimension reduction procedure is the recipe to represent defects in two dimensional dislocation dynamics according to the changes in the geometrical properties of the defects triggered by different conditions such as radiation, high temperature, or pressure. In the present study, this procedure is extended to incorporate further features related to the presence of defects with a special focus on face-centered cubic/body-centered cubic alloys used for diverse engineering purposes. In order to reflect the microstructural state of the alloy on the computational cell of two dimensional dislocation…
Homogeneous highly epitaxial LaSrMnO3 (LSMO) thin films have been grown on Yttria-stabilized-Zirconia (YsZ) / CeO2 buffer layers on technological relevant 4" silicon wafers using a Twente Solid State Technology B.V. (TSST) developed large area Pulsed Laser Deposition (PLD) setup. We study and show the results of the effect of an additional SrRuO3 buffer layer on the growth temperature dependent structural and magnetic properties of LSMO films. With the introduction of a thin SrRuO3 layer on top of the buffer stack, LSMO films show ferromagnetic behaviour for growth temperatures as low as 250C.…
