The fracture of brittle materials is of utmost importance for civil engineering and seismology applications. A different approach towards the aim of early identification of fracture and the prediction of failure before it occurs is attempted in this work. Laboratory experiments were conducted in a variety of rock and cement based material specimens of various shapes and sizes. The applied loading schemes were cyclic or increasing and the specimens were tested to compression and bending type loading of various levels. The techniques of Pressure Stimulated Current and Bending Stimulated Current were used for the detection of electric signal emissions during the various deformation stages of the specimens. The detected signals were analysed macroscopically and microscopically so as to find suitable criteria for fracture prediction and correlation between the electrical and mechanical parameters. The macroscopic proportionality of the mechanically stimulated electric signal and the strain was experimentally verified, the macroscopic trends of the PSC and BSC electric signals were modelled and the effects of material memory to the electric signals were examined. The current of a time-varying RLC electric circuit was tested against experimental data with satisfactory results and it was proposed as an electrical equivalent model. Wavelet based analysis of the signal revealed the correlation between the frequency components of the electric signal and the deformation stages of the material samples. Especially the increase of the high frequency component of the electric signal seems to be a good precursor of macrocracking initiation point. The additional electric stimulus of a dc voltage application seems to boost the frequency content of the signal and reveals better the stages of cracking process. The microscopic analysis method is scale-free and thus it can confront with the problems of size effects and material properties effects. The AC conductivity time series of fractured and pristine specimens were also analysed by means of wavelet transform and the spectral analysis was used to differentiate between the specimens. A non-destructive technique may be based on these results. Analysis has shown that the electric signal perturbation is an indicator of the forthcoming fracture, as well as of the fracture that has already occurred in specimens.

We first study noninteracting electrons moving on corner-sharing tetrahedral lattices, which represent the conduction path of LiAlyTi2−yO4. A uniform box distribution type of disorder for the on-site energies is assumed. Using the Dyson-Mehta Delta-3 statistics as a criterion for localization, we have determined the critical disorder (Wc/t = 14.5 ± 0.25) and the mobility-edge trajectories. Then we study the Anderson-Hubbard model, which includes both interactions and disorder, using a real-space self-consistent Hartree-Fock theory. We provide a partial assessment on how the Hartree-Fock theory approximates the ground states of the Anderson-Hubbard model, using small clusters which can be solved exactly. The Hartree-Fock theory works very well in reproducing the ground-state energies and local charge densities. However, it does not work as well in representing the spin-spin correlations. To find the ground state, one needs to allow maximum degree of freedom in spins. Evidence of screening of disorder by the interactions is provided. We have applied the Hartree-Fock theory to large-scale three-dimensional simple cubic lattices. For a disorder strength of W/t = 6, weak interactions (U/t ≤ 3) enhance the density of states at the Fermi level and the low-frequency conductivity. There are no local magnetic moments, and the AC conductivity is Drude-like. With stronger interactions (U/t ≥ 4), the density of states at the Fermi level and the low-frequency conductivity are both suppressed. These are accompanied by the presence of local magnetic moments, and the conductivity becomes non-Drude-like. A metal-to-insulator transition is likely to take place at a critical Uc/t ≈ 8 – 9. We find that (i) the formation of magnetic moments is essential to the suppression of the density of states at the Fermi level, and therefore essential to the metal-insulator transition; (ii) the form of magnetic moments does not matter; and (iii) these results do not depend on the type of lattice or the type of disorder. / Thesis (Ph.D, Physics, Engineering Physics and Astronomy) -- Queen's University, 2009-05-26 02:20:04.652

<div>Sensing of mechanical state is critical in diverse fields including biomedical implants, intelligent robotics, consumer technology interfaces, and integrated structural health monitoring among many others. Recently, materials that are self-sensing via the piezoresistive effect (i.e. having deformation-dependent electrical conductivity) have received much attention due to their potential to enable intrinsic, material-level strain sensing with lesser dependence on external/ad hoc sensor arrays. In order to effectively use piezoresistive materials for strain-sensing, however, it is necessary to understand the deformation-resistivity change relationship. To that end, many studies have been conducted to model the piezoresistive effect, particularly in nanocomposites which have been modified with high aspect-ratio carbonaceous fillers such as carbon nanotubes or carbon nanofibers. However, prevailing piezoresistivity models have important limitations such as being limited to microscales and therefore being computationally prohibitive for macroscale analyses, considering only simple deformations, and having limited accuracy. These are important issues because small errors or delays due to these challenges can substantially mitigate the effectiveness of strain-sensing via piezoresistivity. Therefore, the first objective of this thesis is to develop a conceptual framework for a piezoresistive tensorial relation that is amenable to arbitrary deformation, macroscale analyses, and a wide range of piezoresistive material systems. This was achieved by postulating a general higher-order resistivity-strain relation and fitting the general model to experimental data for carbon nanofiber-modified epoxy (as a representative piezoresistive material with non-linear resistivity-strain relations) through the determination of piezoresistive constants. Lastly, the proposed relation was validated experimentally against discrete resistance changes collected over a complex shape and spatially distributed resistivity changes imaged via electrical impedance tomography (EIT) with very good correspondence. Because of the generality of the proposed higher-order tensorial relation, it can be applied to a wide variety of material systems (e.g. piezoresistive polymers, cementitious, and ceramic composites) thereby lending significant potential for broader impacts to this work. </div><div><br></div><div>Despite the expansive body of work on direct current (DC) transport, DC-based methods have important limitations which can be overcome via alternating current (AC)-based self-sensing. Unfortunately, comparatively little work has been done on AC transport-deformation modeling in self-sensing materials. Therefore, the second objective of this thesis is to establish a conceptual framework for the macroscale modeling of AC conductivity-strain coupling in piezoresistive materials. For this, the universal dielectric response (UDR) as described by Joncsher's power law for AC conductivity was fit to AC conductivity versus strain data for CNF/epoxy (again serving as a representative self-sensing material). It was found that this power law does indeed accurately describe deformation-dependent AC conductivity and power-law fitting constants are non-linear in both normal and shear strain. Curiously, a piezoresistive switching behavior was also observed during this testing. That is, positive piezoresistivity (i.e. decreasing AC conductivity with increasing tensile strain) was observed at low frequencies and negative piezoresistivity (i.e. increasing AC conductivity with increasing tensile strain) was observed at high frequencies. Consequently, there exists a point of zero piezoresistivity (i.e. frequency at which AC conductivity does not change with deformation) between these behaviors. Via microscale computational modeling, it was discovered that changing inter-filler tunneling resistance acting in parallel with inter-filler capacitance is the physical mechanism of this switching behavior.</div>

Measurements of higher harmonics of the ac voltage response in YBCO thin film strips under low amplitude and low frequency harmonic excitation, as a function of temperature, show a non linear response of the conductivity in the superconducting transition interval. The third and fifth harmonics of the local voltage as a function of T exhibit a peak near Tc and their amplitudes seem to be closely related to the T-derivative of the first harmonic. The peaks are linearly dependent on the current amplitude and do not depend on frequency. The observed data are partially interpreted in terms of ac current induced thermal modulation of the sample temperature added to strong thermally activated fluctuations in the transition region. The fit of the model to the data gives information of some sample properties such as zero temperature critical current, zero onset resistance and thermal boundary conductance.

The work in this thesis relates to the preparation and structural and electrical characterisation of calcium and strontium hydrides, imides and nitride hydrides. Conventional solid state methods in controlled atmospheres were used to synthesise these materials. High temperature neutron diffraction, thermal analysis and conductivity studies performed on calcium and strontium hydride suggest an order – disorder transition in these materials at 350 – 450°C. Disordering is believed to involve rapid exchange of hydride ions across two crystallographic sites. This manifests itself in a lowering of the activation energy for bulk hydride ion conduction. The hydride ion conduction is good in these undoped materials: σ[total]subscript = 0.01 S/cm for CaH₂ at 1000K; for SrH₂, σ[total]subscript = 0.01 S/cm at 830K. Doping of SrH₂ with NaH causes a significant increase in the low temperature conductivity, due to presence of extrinsic defects. The high temperature conductivity is negatively affected by NaH doping. Calcium nitride hydride (Ca₂NH) was obtained as a single phase material by reacting either calcium metal or calcium hydride (CaH₂) in an argon atmosphere containing 5 – 7% H₂ and 1 – 7% N₂. Imide ions substituting for hydride and nitride ions constitute a major chemical defect in this material. Long range ordering of the nitride and hydride ions occurs, giving rise to a double cubic crystal symmetry. This order breaks down at 600 – 650°C. Applying the same reaction conditions to strontium metal results in a mixed phase of strontium nitride hydride and imide. No long range order in the nitride hydride phase could be observed. Doping Ca₂NH with lithium hydride (LiH) causes the appearance of a second calcium imide phase, whereas doping with sodium hydride (NaH) increases the amount of imide ions as a defect in the nitride hydride structure, thereby decreasing the long range ordering of nitride and hydride ions.

State of the art conductivity equipment has been used to measure deuterium isotope effects on the molar conductivity of strong electrolytes in the temperature range of 298 K to 598 K as a means of exploring solvation effects under hydrothermal conditions. Individual ionic contributions were determined by extrapolation of published transference number data to elevated temperature. The temperature dependence of the Walden product ratio indicates that there is little difference in the transport of ions between light and heavy water . Excess conductivity observed in hydrogen and deuterium compounds arising from proton hopping in hydrogen-bonded networks has been determined in the temperature range of 318 K to 598 K for the first time