High Temperature Behavior of Nano-Structured Ceramic Composites Studied by Mechanical Spectroscopy

Silicon nitride based ceramics (SiAlONs); tetragonal polycrystalline zirconia (3Y‐TZP); alumina and their composites reinforced with different amount of multi‐ walled carbon‐nanotubes (CNTs) have been processed by Spark Plasma Sintering (SPS). High temperature mechanical spectroscopy measurements were performed in each material between room temperature and 1600 K. In each of these materials, anelastic and viscoplastic relaxation phenomena were investigated and responsible mechanisms were explained. In particular, grain boundary (GB) sliding, which is responsible for high temperature plasticity in fine grained ceramics, gives rise to a peak or an exponential increase in the high temperature mechanical loss. Peak and exponential background depend on two forces, which control the GB sliding: a friction force due to the GB viscosity and a restoring force due to the elasticity of the surrounding grains. In the present thesis, ceramics and composites have been processed, which allow one to study the role played by these forces on the thermo‐ mechanical behavior of these refractory materials. SiAlON ceramics were chosen for studying the viscous force due to the inter‐granular glassy phase. In zirconia and alumina, it is shown how the CNT reinforcements may improve the restoring force and consequently the creep resistance. Different grades of SiAlON ceramics, processed with different sintering aids (Ca2+, Y3+, Yb3+), with oxygen rich (CaO, Y2O3 and Yb2O3) and nitrogen rich (CaH2, YN and YbN) compounds, have been studied. Mechanical spectroscopy has been used to analyze the behavior of the residual glassy phase, present after sintering, either as grain‐boundary glassy (GB) films or glass pockets located in GB triple junctions. The mechanical loss spectra show a relaxation peak, which is due to a relaxation phenomenon (the so called “α‐relaxation”) associated with the glass transition in the amorphous phase. The peak position depends on the glass viscosity and the peak height is mainly affected by the glassy phase amount and the SiAlON bimodal microstructure, namely equiaxed versus elongated grains. Moreover the peak height depends on the restoring force provided by the neighboring grains, which limit the GB sliding process. As a matter of fact, a good correlation between the mechanical loss peak and plastic deformation in a compression test has been observed. It is concluded that the elongated grains in the bimodal microstructure provide a higher restoring force, which limits the GB sliding of smaller equiaxed grains. In the case of equiaxed fine grained oxide ceramics, such as zirconia and alumina, the restoring force has been increased by CNT additions, which can reinforce the GBs. 3Y‐TZPcomposites with a homogenous distributions of CNTs, ranging within 0.5 – 5 wt%, were processed by SPS. A significant improvement in room temperature fracture toughness and shear modulus as well as creep performance at high temperature were obtained, and interpreted as due to the GB reinforcing role of the CNTs. To support this interpretation, high‐resolution electron microscopy and Raman spectroscopy have been carried out. Moreover, a remarkable enhancement of the electrical conductivity up to ten orders of magnitude due to CNT additions has been obtained with respect to the pure ceramics. The isothermal spectrum of the 3Y‐TZP composites (measured at 1600 K) is composed of a mechanical loss peak at a frequency of about 0.1 Hz, which is superimposed on an exponential increase at lower frequency. This is interpreted as primarily due to GB sliding. The absence of a well‐marked peak in monolithic 3Y‐ TZP is justified by considering that the restoring force decreases at low frequencies or high temperatures. Therefore, GB sliding is no more restricted and the mechanical loss increases exponentially, which is correlated to macroscopic creep. With CNT additions the mechanical loss decreases and the relaxation peak is better resolved with respect to the background. This is interpreted by the pinning effect of CNTs on GBs, providing addition source of restoring force, which can hinder GB sliding at high temperature, resulting in a creep resistance improvement. Similarly to 3Y‐TZP based composites, alumina specimens (3 different types of alumina powders) reinforced with different amount of CNTs were sintered by SPS. It is shown how the initial particle size of the powders may affect the dispersion of CNTs. Measurement of different properties, such as hardness, fracture toughness and mechanical loss at high temperature, have evidenced the crucial role of the CNT dispersion in the obtained mechanical properties.

High temperature mechanical spectroscopy of fine-grained zirconia and alumina containing nano-sized reinforcements

Claudia Ionascu

Polycrystalline zirconia (3Y-TZP grade) unreinforced and reinforced with multiwalled carbon nanotubes (CNTs) or silicon carbide whiskers (SiCw) or silicon carbide particles (SiCp) have been processed and studied by mechanical spectroscopy with complementary observations of electron microscopy and creep tests. Moreover, for comparison with zirconia, polycrystalline alumina specimens, unreinforced and reinforced with silicon carbide nanoparticles, have also been studied. The high-temperature mechanical loss spectrum of pure zirconia presents an exponential background (exponential increase with temperature) accompanied by a decrease of the dynamic shear modulus above 1200 K. A dissipation peak, which transforms into an exponential increase, appears in the spectra obtained as a function of frequency (isothermal spectrum). The peak does not depend on the amplitude of the applied stress, whereas the exponential increase is stress dependent above a certain threshold. This result has been linked to the interface reaction, which plays an important role in deformation accommodation during creep. The high-temperature mechanical loss is grain size dependent. Smaller the grain size, higher the mechanical loss. The presence of the impurities in the starting powder of zirconia leads to a shift of the entire mechanical- loss spectrum towards lower temperatures. Doping zirconia with different amounts of CNTs results in a decrease of the isothermal-mechanical loss level with respect to pure zirconia. A dissipation peak that transforms into an exponential increase is present for a higher amount of CNTs in the mechanical-loss spectrum as a function of temperature. Zirconia doped with CNTs exhibits a lower creep strain than pure zirconia when submitted to a compressive stress at high temperature. Also, addition of different amounts of SiCw to zirconia leads to a decrease of the mechanical-loss level. A high-temperature dissipation peak is presents in the isochronal spectrum. The peak is better resolved for a higher amount of SiCw. The creep-strain curve is lower in SiCw-doped zirconia than in pure zirconia at high temperature. Addition of SiCp to zirconia may shift or not the mechanical-loss spectrum towards lower temperatures. Doping zirconia with different amounts of SiCp results in the appearance of a peak or peaks in the high temperature isochronal and isothermal spectrum. The height of the peaks depends on the amount of SiCp to zirconia. Similar to zirconia, the high-temperature mechanical loss spectrum of alumina consists of an exponential increase of the mechanical loss and a decrease in the dynamic shear modulus above 1200 K. Additions of SiCp lower the high-temperature mechanical loss with respect to the one in pure alumina. High-temperature plastic deformation of pure zirconia and alumina is interpreted in terms of a theoretical model of GB sliding. When GB sliding is not limited by obstacles like multiple junctions, GB asperities or other defects, creep occur and an exponential background is observed in the mechanical-loss spectrum. Addition of nano-sized reinforcements on the GBs results in a decrease of the exponential background. This means that the GB sliding is more difficult and as a consequence a better creep resistance is observed. The activation parameters obtained from the Arrhenius plots were apparent. Two methods are used to correct the apparent values. However, even if the corrected values seem more reasonable than the values obtained from the Arrhenius plots, they do not bring useful information. It is proposed that apparent too high values of the activation enthalpy account for the evolution of the GB microstructure with temperature. Thermal evolution of the GB microstructure is believed to offer short circuit paths for GB diffusion, which allows the pinning nano-sized reinforcements to be overcome. Then pinning effect is less efficient.

EPFL2008

High Temperature Mechanical Spectroscopy Study of 3 mol% Yttria Stabilized Tetragonal Zirconia Reinforced with Carbon Nanotubes

Gilbert Fantozzi, Daniele Mari, Mehdi Mazaheri, Robert Schaller

Composites containing 3 mol% yttria stabilized tetragonal zirconia (3Y-TZP) reinforced with multiwalled carbon nanotubes (CNTs) with various amounts of CNTs (3Y-TZP / X wt% CNT, X= 0, 0.5, 1.5, 3 and 5) were processed by spark plasma sintering. Microscopic analysis proves that CNTs were well dispersed and embedded in grain boundaries of the sintered body. High temperature mechanical properties have been investigated using mechanical spectroscopy and low stress (6 MPa) creep. The isothermal spectrum (measured at 1600 K) consists of a mechanical loss peak at a frequency of about 0.1 Hz, which is superimposed on an exponential increase at low frequency. The absence of a well-marked peak in monolithic 3Y-TZP is justified considering that restoring force decreases at low frequencies or high temperatures due to the elasticity of neighboring grains. Therefore, strain is no more restricted and the mechanical loss increases exponentially, which is correlated to macroscopic creep. However, with CNT additions the mechanical loss decreases and a better resolved peak was observed. In parallel, the results have shown that the creep rate drastically decreases with CNT additions. These results can be interpreted by the pinning effect of CNTs which can hinder grain boundary sliding at high temperatures, resulting in a creep resistance improvement.

Trans Tech Publications Ltd, Laublsrutistr 24, Ch-8717 Stafa-Zurich, Switzerland2012

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

High temperature mechanical spectroscopy of fine-grained zirconia and alumina containing nano-sized reinforcements

Claudia Ionascu

EPFL2008

Conductivity, dielectric and piezoelectric properties of SrBi4Ti4O15

EPFL2000