Yes / In order to improve the frequency-dependent dielectric properties of the immiscible polymeric blends which were melt-compounded by composing poly (vinylidene fluoride) (PVDF) and low density polyethylene (LDPE), the layer multiplication and the solid phase orientation technologies were respectively adopted as two effective strategies to optimize the dispersion state and the orientation of internal microstructure, aiming at reducing physical porosity and improving the barrier performance as well as crystal phase of the polymer extrudates. Results comparison showed the dielectric properties were greatly dependent on the crystal type and the physical porosity density which were also emphasized as the interfacial effect in the previous work [ref. 29: Lin X et al, J Appl Polym Sci 2015; 132(36), 42507]. It was found that the multilayer-structure manipulation could substantially improve the dispersion state between the two immiscible components, enhance the mechanical performance and reduce the internal defects and increase the dielectric constant while keeping the dielectric loss stable. By uniaxial stretching the sample sheets at a rubber state temperature of ca. 10-20˚C below the melting point, crystal transformation was induced by increasing molecular chains orientation degree which was also contributed to the enhancement of the dielectric properties. These techniques implied the potential as a promising way for inducing functional structures of polymeric blends.

Structure evolution of silica aerogel was studied in microwave- and conventionally processed samples over the temperature range from 25 to 1200â °C. The samples were produced using sol-gel processing and dried under carbon dioxide supercritical conditions. After drying, the monolithic samples received a thermal treatment at different programmed temperatures in two different ovens, conventional and microwave. The microwave process was performed using a single mode microwave oven at 2.45GHz. Dielectric properties were measured using the cavity perturbation method, and structural characterization was carried out using a variety of techniques, including absorption surface analysis, Helium pycnometry, Archimedes principle, Fourier transform infrared spectroscopy, X-ray diffraction, and high resolution microscopy. The data obtained revealed that structural differences do exist between microwave- and conventionally processed samples. Three different regions were identified from the structural characterization of the samples. Regions I exhibited a structure densification at temperatures between 25 and 850â °C. Region II was characterized by a bulk densification in the temperature range from 850 to 1200â °C. Region III was represented by the onset of crystallization above 1200â °C. Explanation and possible causes behind the structural differences observed in each region are provided. In general, the structure evolution observed in microwave- and conventionally processed samples followed the same order, but occurred at lower temperature for the microwave process. / Ph. D.

Electro-active polymers (EAPs) have emerged as a new class of active materials, which produce large deformations in response to an electric stimulus. EAPs have attractive characteristics of being lightweight, inexpensive, stretchable, and flexible. Additionally, EAPs are conformable, and their properties can be tailored to satisfy a broad range of requirements. These advantages have enabled many target applications in actuation and sensing. A general constitutive formulation for isotropic and anisotropic electro-active materials is developed using continuum mechanics framework and invariant theory. Based on the constitutive law, electromechanical stability of the electro-elastic materials is investigated using convexity and polyconvexity conditions. Implementation of the electro-active material model into a commercial finite element software (ABAQUS 6.9.1, PAWTUCKET, RI, USA) is presented. Several boundary and initial value problems are solved to investigate the actuation and sensing response of isotropic and anisotropic dielectric elastomers (DEs) subject to combined mechanical and electrical loads. The numerical response is compared with experimental results to validate the theoretical model. For the constitutive formulation of the electro-elastic materials, invariants for the coupling between two families of electro-active fibers (or particles) and the applied electric field are introduced. The effect of the orientation of the electro-active fibers and the electric field on the electromechanical coupling is investigated under equibiaxial extension. Advantage of the constitutive formulation derived in this research is that the electromechanical coupling can be illustrated easily by choosing invariants for the deformation gradient tensor, the electro-active fibers, and the electric field. For the electromechanical stability, it is shown that the stability can be controlled by tuning the material properties and the orientation of the electro-active fibers. The electromechanical stability condition is useful to build a stable free energy function and prevent the instabilities (wrinkling and electric breakdown) for the electro-elastic materials. The invariant-based constitutive formulation for the electro-elastic materials including the isotropic and anisotropic DEs is implemented into a user subroutine (UMAT in ABAQUS: user defined material) by using multiplicative decomposition of the deformation gradient and the applicability of the UMAT is shown by simulating a complicated electromechanical coupling problem in ABAQUS/CAE. Additionally, the static and dynamic sensing and actuation response of tubular DE transducers (silicone and polyacrylate materials) with respect to combined electrical and mechanical stimuli is obtained experimentally. It is shown that the silicone samples have better dynamic and static sensing characteristics than the polyacrylate. The theoretical modeling accords well with the experimental results. / Ph. D.

Ground penetrating radar (GPR) technology has been used for the past 20 years for a variety of applications to assess transportation infrastructure. However, the main issue after all these years remains: "How well does GPR work and under what conditions?" Results show that GPR works well for some situations, but is not an appropriate tool for other situations. It is not used currently on a routine basis by the US Departments of Transportation (DOTs) due mainly to difficulties encountered with data interpretation. Data interpretation difficulties are mainly attributed to the fact that images obtained from the reflected signals are not photographs of the features that are beneath the surface being investigated. The images show the amplitude of the radar-reflected signals from the interfaces with different dielectric properties. Therefore, a considerable amount of experience and operator skill may be required to correctly interpret sub-surface radar results. To better understand reflected GPR signals, this research was conducted with the following objectives: to determine the dielectric properties of concrete over the used GPR frequency range; to synthesize the reflected air-coupled radar signals and compare them with measured waveforms; to model and study the effects of simulated defects in concrete on the reflected air-coupled and ground-coupled radar signals; and to validate the research results in the field by predicting layer thicknesses of flexible pavements and detecting moisture in flexible pavement systems. Several concrete slabs, 1.5x1.5 m, were constructed with known thicknesses, simulated defects, and different reinforcement configurations. The concrete mixes included four different bridge deck mixes and one concrete pavement mix used in the State of Virginia. Results have shown that the dielectric constant of concrete is frequency and mix dependent. However, modeling the reflected signals using an average complex dielectric constant over the entire radar frequency range led to modeled waveforms comparable to the measured waveforms. Although air- and water-filled voids did distort the reflected waveforms, a model was developed to predict the reflected waveforms from the simulated defects. Reinforcement was found to affect the reflected waveforms only when it was oriented in a direction perpendicular to the GPR antennas. A model was also developed to predict the GPR waveforms obtained from flexible pavements. This model could be used in a procedure to measure layer thicknesses more accurately by including losses that occur inside the pavement materials. Two different case studies, where a ground-coupled GPR system was used to locate moisture at different layers, have led to the conclusion that the ground-coupled GPR is a feasible tool to detect moisture inside pavements. / Ph. D.

With the recent resurgence of interest in double negative (DNG) materials and the reported construction of a metamaterial with DNG characteristics, applications of these materials become feasible and examination of the behavior of systems and devices a potentially fruitful topic. The most promising area of research, upon inquiry into past work related to DNG materials, proves to be dielectric waveguides. The present investigation, then, focuses on the inclusion of DNG materials in various planar dielectric waveguide configurations. These waveguides involve a core region surrounded by various numbers of symmetrically-placed cladding layers. The present investigation involves the review of the electromagnetic properties of DNG materials by a thorough analysis based on Maxwell's equations. The use of a negative index of refraction for these materials is justified. These results are then used to perform a frequency domain analysis of an N-layer formulation for dielectric waveguides which is general for any combination of DNG and double positive (DPS) materials. This N-layer formulation allows for the derivation of the characteristic equation, which relates the operating frequency and the propagation constant solutions, along with the cutoff conditions and field distributions. A causal material model which obeys the Kramers-Kronig relations and which is based on measurements of a realized metamaterial is studied and used in the investigation in order to produce realistic results. The N-layer formulation is then applied to the three-layer (slab) waveguide and known results are reviewed. A new interpretation of intramodal degeneracy is given, whereby degenerate modes are split into two separate modes, one with positive phase velocity and one with negative phase velocity but both with a causal positive group (energy) velocity. Next, the formulation is applied to the five-layer waveguide. New behaviors are observed in this case which are not seen for the three-layer waveguide, including the return of the fundamental mode in some cases, whereas it is never present for the three-layer guide, the absence of certain higher-order modes in some situations and the appearance of new modes. Additionally, for some configurations the order of the even and odd modes in the DNG frequency range is found to be reversed from that of conventional waveguides. The photonic crystal waveguide, which involves an infinite number of periodically placed cladding layers, is next studied using ray analysis, and a slight variation of the N-layer formulation is used to compare these results with those of the pseudo-photonic crystal waveguide. The pseudo-photonic crystal waveguide is identical to the photonic crystal waveguide with the exception that it has only large but finite number of layers. It is seen that the results of these two cases are similar for conventional modes, but the photonic crystal waveguide allows for new modes called photonic crystal modes which are inaccessible through conventional waveguides. Interesting phenomena such as mode crossings among the photonic crystal modes are observed and discussed. Using the results from the frequency domain analysis of the five-layer waveguide, a Fourier transform technique is used to study pulse propagation in a waveguide containing DNG materials. A Gaussian pulse is launched in the waveguide over the frequency range covering a portion of the positive- and negative-phase-velocity fundamental transverse electric (TE) modes. Splitting of the input pulse into two separate pulses is observed, where both of these new pulses have a causal, positive energy velocity. The interpretation of intramodal degeneracy given in previous discussions is buttressed with evidence from this portion of the investigation, thus completing the analysis and bringing the present study to its conclusion. / Ph. D.

Three main objectives have been set for this research. The first is to develop an accurate method for measuring the dielectric constant of PCC using a capacitor probe (C-Probe) that has been recently developed at Virginia Tech and validate it for field application to detect internal PCC flaws such as delamination. The C-Probe consists of two flexible conducting plates, connected to a Network Analyzer, with a specific separation between them. The second is to optimize the C-Probe design configuration for different PCC slab thicknesses. The third objective is to develop a predictive model that correlates the bulk dielectric constant of PCC with its critical parameters (cement, aggregate, and air content). Five calibration methods have been developed and evaluated for the C-Probe to measure the dielectric properties of PCC. This evaluation has demonstrated that open, short, Teflon material (OSM) calibration method is the most appropriate one for the C-Probe. The selected calibration method was used to validate the C-Probe fixture for field application by measuring 1.5 x 1.5 m PCC slabs prepared with different mix properties, thicknesses, and induced deterioration. The C-Probe has been proved to detect induced voids in the PCC slabs. In addition, the effect of steel reinforcement on measurements can be mastered by controlling the penetration of electromagnetic (EM) field in the PCC slabs. The effective penetration depth of the EM field for different C-Probe design configuration was optimized by computer simulation. The results have been used to develop a predictive model that correlates the effective penetration depth with the plates' size, separation between them, and the dielectric constant of the PCC under test. Thus, an optimum design for different desired penetration depth was achieved. Two experimental designs were developed to identify the critical parameters that affect the bulk dielectric constant of PCC. A computer simulation was used to identify the significance of each parameter. A predictive model has been developed to correlate the PCC bulk dielectric constant to the critical parameters. The estimated dielectric constant of PCC using the predictive model was correlated to that obtained by other theoretical mixture models; the predictive model has found to correlate well with Looyenga theoretical mixture model. / Ph. D.

All entirely new method had previously been perfected (1) for the determination of molecular weight of cellulose acetate in solution. The applicability of the dielectric dispersion method to other cellulosics was the next step in the development of this new procedure. Ethyl celluloee fractions were refractionated by a fractional precipitation procedure in order to obtain fractions that were homogeneous with respect to chain length. Ethyl acetate and acetone were used in the ratio of three to one (3:1) as solvents, and water acetone in the ratio of ninety-five to five (9515) was employed as a precipitating agent. The homogeneous ethyl cellulose fractions were investigated in a number of solvents – dioxane, benzene, toluene, carbon tetrachloride and n-butyl acetate. This was done in order that the applicability of different solvents could be observed as well as the relation between the viscosity and the critical frequency. The critical frequency is defined as the frequency at which the dispersion is fifty percent completed. 1. Havkine, M. C., Master of Science Thesis, Virginia Polytechnic Institute, 1956. / Ph. D.

Studying dynamics of proteins in their biological milieu such as water is interesting because of their strong absorption in the terahertz range that contain information on their global and sub-global collective vibrational modes (conformational dynamics) and global dynamical correlations among solvent water molecules and proteins. In addition, water molecules dynamics within protein solvation layers play a major role in enzyme activity. However, due to the strong absorption of water in the gigahertz-to-terahertz frequencies, it is challenging to study the properties of the solvent dynamics as well as the conformational changes of protein in water. In response, we have developed a highly sensitive megahertz-to-terahertz dielectric spectroscopy system to probe the hydration shells as well as large-scale dynamics of these biomolecules. Thereby, we have deduced the conformation flexibility of proteins and compare the hydration dynamics around proteins to understand the effects of surface-mediated solvent dynamics, relationships among different measures of interfacial solvent dynamics, and protein-mediated solvent dynamics based on the complex dielectric response from 50 MHz up to 2 THz by using the system we developed. Comparing these assets of various proteins in different classes helps us shed light on the macromolecular dynamics in a biologically relevant water environment. / Doctor of Philosophy / Proteins are complicated biomolecules that exist in all living creatures and they are, mostly, involved in building up structures and cell functions in various biological systems. Not only their existence but also their complex movements and dynamics are vital to cell functions in living beings. Until recently, their chemical functions and dynamics have been extremely challenging to investigate and track in their native environments. Thanks to various efforts by researchers all over the world to learn more about their convoluted behavior, new techniques have arisen to study these properties. We, as a part of this community, have been able to develop highly sensitive megahertz-to-terahertz dielectric spectroscopy system to probe proteins and other biomolecules dynamics in picosecond to microsecond range. Using our benchmark system, we have been able to map the detailed dynamical properties of biomolecules as well as their exclusive hydration shell characterizations. In this work, we gathered details about three well-known proteins and biomolecules by studying their dielectric responses. Thus, we have been able to discuss the movements, relaxation processes and hydration shell properties of these molecules in liquid water as their basic native environment.

A transmission electron microscopy study involving direct and replicating techniques is directed to a definition of the microstructure of radio frequency-sputtered, thin lead-dielectric cermet films. Once defined, this microstructure is used to obtain theoretical film refractive indices. The Maxwell Garnet theory provides a basis for the theoretical results. Measurements of film transmission and reflectivity are used to obtain rough experimental values for film refractive indices by the Tekucheva method. More exact values are obtained via ellipsometry. The rough Tekucheva values are used to determine the range over which computer calculations interpreting the ellipsometric results must be made. This technique yields accurate values for the film refractive indices. The films are radio-frequency-sputtered from lead glass targets with varying amounts of lead attached to their faces. Three different targets are used, resulting in three sets of films, each containing a different percentage of lead. The lead content of the films is measured by microprobe analysis as well as visual inspection of micrographs. The lower content lead films are seen to consist of tiny balls of lead embedded in the dielectric, as are the intermediate lead content films; but the higher lead content films form metallic networks throughout the dielectric. The lower and intermediate lead content films have indices which agree with the predictions of the Maxwell Garnett theory; but the higher lead content films, whose structure fails to conform to the Maxwell Garnett configuration, have indices whose values diverge from the Maxwell Garnett predictions. It is thus shown that the theory of Maxwell Garnett is valid for thin cermet films whose structure consists of tiny metal balls embedded in a dielectric medium. / Ph. D.

There is emerging concern about the potential for elevated lead in water after water utilities conduct EPA mandated (or voluntary) partial replacements of existing lead service lines. Connections between dissimilar metals results in the accelerated corrosion of the less noble metal via galvanic attack, increasing metal concentrations in water and posing potential public health risks. Many practical problems associated with stopping galvanic attack between copper:galvanized iron and copper:lead via use of dielectrics have also been raised. Galvanic corrosion can be effectively stopped by isolating the dissimilar metals; however, completely eliminating electrical continuity may not always be practical or allowed by code. Instead, increasing separation distance between the two metals was hypothesized to considerably reduce galvanic corrosion. Galvanic corrosion and lead leaching were evaluated for lead:copper connections with varying separation distances while maintaining electrical continuity. Increased distance between lead and copper pipe dramatically reduced the galvanic current and the magnitude of lead release. Galvanized iron and copper connections were also investigated using various commercial fittings, and results verified that a controlling factor was separation distance between the two dissimilar metals. When considering the long-term behavior of partially replaced lead service lines, detrimental effects from galvanic corrosion worsened with time. Even when water was sampled consistently at moderate flow rate, the condition representing traditional partial service line replacement was 40% worse than a full lead service line. At elevated flowrates, lead concentrations and variability increased for partly replaced lead pipe versus full lead pipe due to reservoirs of lead rust formed via galvanic corrosion. At low flowrates, these negative impacts were not observed. Finally, crevices formed by the use of commercial couplings increased lead release. Overall, the results enhance practical understanding of galvanic corrosion impacts and use of dielectrics in water service lines and premise plumbing. / Master of Science