Large-Scale Controlled-Condition Experiment to Evaluate Light Weight Deflectometers for Modulus Determination and Compaction Quality Assurance of Unbound Pavement Materials

Compaction control using lightweight deflectometers (LWD) is currently being evaluated in several states and countries and fully implemented for pavement construction quality assurance (QA) by a few. Broader implementation has been hampered by the lack of a widely recognized standard for interpreting the load and deflection data obtained during construction QA testing. More specifically, reliable and practical procedures are required for relating these measurements to the fundamental material property—modulus—used in pavement design. This study presents a unique set of data and analyses for three different LWDs on a large-scale controlled-condition experiment. Three 4.5x4.5 m2 test pits were designed and constructed at target moisture and density conditions simulating acceptable and unacceptable construction quality. LWD testing was performed on the constructed layers along with static plate loading testing, conventional nuclear gauge moisture-density testing, and non-nuclear gravimetric and volumetric water content measurements. Additional material was collected for routine and exploratory tests in the laboratory. These included grain size distributions, soil classification, moisture-density relations, resilient modulus testing at optimum and field conditions, and an advanced experiment of LWD testing on top of the Proctor compaction mold. This unique large-scale controlled-condition experiment provides an excellent high quality resource of data that can be used by future researchers to find a rigorous, theoretically sound, and straightforward technique for standardizing LWD determination of modulus and construction QA for unbound pavement materials.

ENERGETIC BIOCIDAL MATERIALS AND SPORE NEUTRALIZATION

The objective of this dissertation is to explore a more accurate and versatile approach to investigating the neutralization of spores suffered from ultrafast heating and biocide based stresses, and further to explore and understand novel methods to supply ultrafast heating and biocides through nanostructured energetic materials A surface heating method was developed to apply accurate (± 25 ˚C), high heating rate thermal energy (200 - 800 ˚C, ~103 - ~105 ˚C/s). Uniform attachment of bacterial spores was achieved electrophoretically onto fine wires in liquids, which could be quantitatively detached into suspension for spore enumeration. The spore inactivation increased with temperature and heating rate, and fit a sigmoid response. The neutralization mechanisms of peak temperature and heating rate were correlated to the DNA damage at ~104 ˚C/s, and to the coat rupture by ultrafast vapor pressurization inside spores at ~105 ˚C/s. Humidity was found to have a synergistic effect of rapid heating and chlorine gas to neutralization efficiency. The primary neutralization mechanism of Cl2 and rapid heat is proposed to be chlorine reacting with the spore surface. The stress-kill correlation above provides guidance to explore new biocidal thermites, and to probe mechanisms. Results show that nano-Al/K2S2O8 released more gas at a lower temperature and generated a higher maximum pressure than the other nano-Al/oxysalts. Given that this thermite formulation generates the similar amount of SO2 as O2, it can be considered as a potential candidate for use in energetic biocidal applications. The reaction mechanisms of persulfate and other oxysalts containing thermites can be divided into two groups, with the reactive thermites (e.g. Al/K2S2O8) that generate ~10× higher of pressure and ~10× shorter of burn time ignited via a solid-gas Al/O2 reaction, while the less reactive thermites (e.g. Al/K2SO4) following a condensed phase Al/O reaction mechanism. These different ignition mechanisms were further re-evaluated by investigating the roles of free and bound oxygen. A constant critical reaction rate for ignition was found which is independent to ignition temperature, heating rate and free vs. bound oxygen.

TEACHERS’ ATTITUDES TOWARD INCLUSION OF CHILDREN WITH DISABILITIES IN RURAL EL SALVADOR

The attitude of school teachers toward inclusion of children with disabilities is an important factor in the successful implementation of a national inclusion program. With the universal pressure to provide education for all and international recognition of the importance of meeting the needs of diverse populations, inclusive education has become important to governments around the world. El Salvador’s Ministry of Education seeks to establish inclusion as an integral part of their struggle to meet the needs of children across the country, but this is a difficult process, especially for a country with limited resources which still struggles to meet international expectations of educational access and quality. Teacher attitude is an important factor in the success of inclusion programs and can be investigated in relation to various factors which may affect teachers’ classroom practice. While these factors have been investigated in multiple countries, there is a need for more knowledge of the present situation in developing countries and especially in schools across the rural areas of El Salvador to meet the needs of the diverse learners in that country. My research was a mixed methods case study of the rural schools of one municipality, using a published survey and interviews with teachers to investigate their attitudes regarding inclusion. This research was the first investigation of teachers’ attitudes toward inclusion in rural El Salvador and explored the needs and challenges which exist in creating inclusive schools across this country. The findings of this study revealed the following important themes. Some children with disabilities are not in school and those with mild disabilities are not always getting needed services. Teachers agreed with the philosophy of inclusion, but believed that some children with disabilities would receive a better education in special schools. They were not concerned about classroom management. Teachers desired more training on disability and inclusion. They believed that a lack of resources, including materials and personnel, was a major barrier to inclusion. Teachers’ attitudes were consistent regardless of family and professional experience with disability or amount of inclusion training. They were concerned about the role of family support for children with disabilities.

A Generalized Methodology to Characterize Composite Materials for Pyrolysis Models

The predictive capabilities of computational fire models have improved in recent years such that models have become an integral part of many research efforts. Models improve the understanding of the fire risk of materials and may decrease the number of expensive experiments required to assess the fire hazard of a specific material or designed space. A critical component of a predictive fire model is the pyrolysis sub-model that provides a mathematical representation of the rate of gaseous fuel production from condensed phase fuels given a heat flux incident to the material surface. The modern, comprehensive pyrolysis sub-models that are common today require the definition of many model parameters to accurately represent the physical description of materials that are ubiquitous in the built environment. Coupled with the increase in the number of parameters required to accurately represent the pyrolysis of materials is the increasing prevalence in the built environment of engineered composite materials that have never been measured or modeled. The motivation behind this project is to develop a systematic, generalized methodology to determine the requisite parameters to generate pyrolysis models with predictive capabilities for layered composite materials that are common in industrial and commercial applications. This methodology has been applied to four common composites in this work that exhibit a range of material structures and component materials. The methodology utilizes a multi-scale experimental approach in which each test is designed to isolate and determine a specific subset of the parameters required to define a material in the model. Data collected in simultaneous thermogravimetry and differential scanning calorimetry experiments were analyzed to determine the reaction kinetics, thermodynamic properties, and energetics of decomposition for each component of the composite. Data collected in microscale combustion calorimetry experiments were analyzed to determine the heats of complete combustion of the volatiles produced in each reaction. Inverse analyses were conducted on sample temperature data collected in bench-scale tests to determine the thermal transport parameters of each component through degradation. Simulations of quasi-one-dimensional bench-scale gasification tests generated from the resultant models using the ThermaKin modeling environment were compared to experimental data to independently validate the models.

Nonlinear Optics and Carrier Dynamics in Nanostructured and Two-Dimensional Materials

Understanding and measuring the interaction of light with sub-wavelength structures and atomically thin materials is of critical importance for the development of next generation photonic devices.  One approach to achieve the desired optical properties in a material is to manipulate its mesoscopic structure or its composition in order to affect the properties of the light-matter interaction.  There has been tremendous recent interest in so called two-dimensional materials, consisting of only a single to a few layers of atoms arranged in a planar sheet.  These materials have demonstrated great promise as a platform for studying unique phenomena arising from the low-dimensionality of the material and for developing new types of devices based on these effects.  A thorough investigation of the optical and electronic properties of these new materials is essential to realizing their potential.  In this work we present studies that explore the nonlinear optical properties and carrier dynamics in nanoporous silicon waveguides, two-dimensional graphite (graphene), and atomically thin black phosphorus. We first present an investigation of the nonlinear response of nanoporous silicon optical waveguides using a novel pump-probe method. A two-frequency heterodyne technique is developed in order to measure the pump-induced transient change in phase and intensity in a single measurement. The experimental data reveal a characteristic material response time and temporally resolved intensity and phase behavior matching a physical model dominated by free-carrier effects that are significantly stronger and faster than those observed in traditional silicon-based waveguides.  These results shed light on the large optical nonlinearity observed in nanoporous silicon and demonstrate a new measurement technique for heterodyne pump-probe spectroscopy. Next we explore the optical properties of low-doped graphene in the terahertz spectral regime, where both intraband and interband effects play a significant role. Probing the graphene at intermediate photon energies enables the investigation of the nonlinear optical properties in the graphene as its electron system is heated by the intense pump pulse. By simultaneously measuring the reflected and transmitted terahertz light, a precise determination of the pump-induced change in absorption can be made. We observe that as the intensity of the terahertz radiation is increased, the optical properties of the graphene change from interband, semiconductor-like absorption, to a more metallic behavior with increased intraband processes. This transition reveals itself in our measurements as an increase in the terahertz transmission through the graphene at low fluence, followed by a decrease in transmission and the onset of a large, photo-induced reflection as fluence is increased.  A hybrid optical-thermodynamic model successfully describes our observations and predicts this transition will persist across mid- and far-infrared frequencies.  This study further demonstrates the important role that reflection plays since the absorption saturation intensity (an important figure of merit for graphene-based saturable absorbers) can be underestimated if only the transmitted light is considered. These findings are expected to contribute to the development of new optoelectronic devices designed to operate in the mid- and far-infrared frequency range.  Lastly we discuss recent work with black phosphorus, a two-dimensional material that has recently attracted interest due to its high mobility and direct, configurable band gap (300 meV to 2eV), depending on the number of atomic layers comprising the sample. In this work we examine the pump-induced change in optical transmission of mechanically exfoliated black phosphorus flakes using a two-color optical pump-probe measurement. The time-resolved data reveal a fast pump-induced transparency accompanied by a slower absorption that we attribute to Pauli blocking and free-carrier absorption, respectively. Polarization studies show that these effects are also highly anisotropic - underscoring the importance of crystal orientation in the design of optical devices based on this material. We conclude our discussion of black phosphorus with a study that employs this material as the active element in a photoconductive detector capable of gigahertz class detection at room temperature for mid-infrared frequencies.

Ceramic Materials Development for Intermediate Temperature Solid Oxide Fuel Cell (IT-SOFC)

Solid oxide fuel cell (SOFC) is an electrochemical device that converts chemical energy into electric power with high efficiency. Traditional SOFC has its disadvantages, such as redox cycling instability and carbon deposition while using hydrocarbon fuels. It is because traditional SOFC uses Ni-cermet as anode. In order to solve these problems, ceramic anode is a good candidate to replace Ni. However, the conductivity of most ceramic anode materials are much lower than Ni metal, and it introduces high ohmic resistance. How to increase the conductivity is a hot topic in this research field. Based on our proposed mechanism, several types of ceramic materials have been developed. Vanadium doped perovskite, Sr1-x/2VxTi1-xO3 (SVT) and Sr0.2Na0.8Nb1-xVxO3 (SNNV), achieved the conductivity as high as 300 S*cm-1 in hydrogen, without any high temperature reduction. GDC electrolyte supported cell was fabricated with Sr0.2Na0.8Nb0.9V0.1O3 and the performance was measured in hydrogen and methane respectively. Due to vanadium’s intrinsic problems, the anode supported cell is not easy. Fe doped double perovskite Sr2CoMoO6 (SFCM) was also developed. By carefully doping Fe, the conductivity was improved over one magnitude, without any vigorous reducing conditions. SFCM anode supported cell was successfully fabricated with GDC as the electrolyte. By impregnating Ni-GDC nano particles into the anode, the cell can be operated at lower temperatures while having higher performance than the traditional Ni-cermet cells. Meanwhile, this SFCM anode supported SOFC has long term stability in the reformate containing methane. During the anode development, cathode improvement caused by a thin Co-GDC layer was observed. By adding this Co-GDC layer between the electrolyte and the cathode, the interfacial resistance decreases due to fast oxygen ion transport. This mechanism was confirmed via isotope exchange. This Co-GDC layer works with multiple kinds of cathodes and the modified cell’s performance is 3 times as the traditional Ni-GDC cell. With this new method, lowering the SOFC operation temperature is feasible.

Contactless Spectral-Dependent Measurement of Bulk Lifetime and Surface Recombination Velocity in Silicon Photovoltaic Materials

Charge carrier lifetime measurements in bulk or unfinished photovoltaic (PV) materials allow for a more accurate estimate of power conversion efficiency in completed solar cells. In this work, carrier lifetimes in PV- grade silicon wafers are obtained by way of quasi-steady state photoconductance measurements. These measurements use a contactless RF system coupled with varying narrow spectrum input LEDs, ranging in wavelength from 460 nm to 1030 nm. Spectral dependent lifetime measurements allow for determination of bulk and surface properties of the material, including the intrinsic bulk lifetime and the surface recombination velocity. The effective lifetimes are fit to an analytical physics-based model to determine the desired parameters. Passivated and non-passivated samples are both studied and are shown to have good agreement with the theoretical model.

Assessment and Life-Cycle Analysis of Recycled Materials for Sustainable Highway

Recycled materials replacing part of virgin materials in highway applications has shown great benefits to the society and environment. Beneficial use of recycled materials can save landfill places, sparse natural resources, and energy consumed in milling and hauling virgin materials. Low price of recycled materials is favorable to cost-saving in pavement projects. Considering the availability of recycled materials in the State of Maryland (MD), four abundant recycled materials, recycled concrete aggregate (RCA), recycled asphalt pavement (RAP), foundry sand (FS), and dredged materials (DM), were studied. A survey was conducted to collect the information of current usage of the four recycled materials in States’ Department of Transportation (DOTs). Based on literature review, mechanical and environmental properties, recommendations, and suggested test standards were investigated separately for the four recycled materials in different applications. Constrains in using these materials were further studied in order to provide recommendations for the development of related MD specifications. To measure social and environmental benefits from using recycled materials, life-cycle assessment was carried out with life-cycle analysis (LCA) program, PaLATE, and green highway rating system, BEST-in-Highway. The survey results indicated the wide use of RAP and RCA in hot mix asphalt (HMA) and graded aggregate base (GAB) respectively, while FS and DM are less used in field. Environmental concerns are less, but the possibly low quality and some adverse mechanical characteristics may hinder the widely use of these recycled materials. Technical documents and current specifications provided by State DOTs are good references to the usage of these materials in MD. Literature review showed consistent results with the survey. Studies from experimental research or site tests showed satisfactory performance of these materials in highway applications, when the substitution rate, gradation, temperature, moisture, or usage of additives, etc. meet some requirements. The results from LCA revealed significant cost savings in using recycled materials. Energy and water consumption, gas emission, and hazardous waste generation generally showed reductions to some degree. Use of new recycled technologies will contribute to more sustainable highways.

EXPLORING THE EFFECTS OF THE RELATIONSHIP BETWEEN SCHOOL CHARACTERISTICS, TEACHER CHARACTERISTICS, ADMINISTRATIVE SUPPORT, AND SCHOOL CLIMATE ON VOLUNTARY INTRA-DISTRICT TEACHER MIGRATION

This quantitative research study utilized a binary logistic regression in a block design to investigate exogenous and endogenous factors influencing a teacher’s decision to make an intra-district move. The research focused on the following exogenous factors: classroom characteristics (size of class, percent minority, percent of students with an individualized education plan, and percent of students that are English language learners) and teacher characteristics (experience and gender). The following endogenous factors were examined: direct administrative influence (administrative support, rules enforced, school vision, teacher recognition, and job security) and indirect administrative influence (school climate, student misbehavior, parental support, materials, staff collaboration). The research was conducted by using information available from the National Center for Educational Statistics, the SASS from 2011-2012 and TFS from 2012-2013. The 2012-2013 Teacher Follow-up Survey identified 60 teachers who made a voluntary intra-district move. Results illustrate there is a statistically significant relationship between percentage of English Language Learners and overall job satisfaction and teachers choosing to make an intra-district move.

The Educational Imaginary in Radical Reconstruction: Congressional Public Policy Rhetoric and American Federalism, 1862-1872

Facing the exigencies of Emancipation, a South in ruins, and ongoing violence, between 1862 and 1872 the United States Congress debated the role education would play in the postbellum polity. Positing schooling as a panacea for the nation’s problems, a determiner of individual worth, and a way of ameliorating state and federal tensions, congressional leaders envisioned education as a way of reshaping American political life. In pursuit of this vision, many policymakers advocated national school agencies and assertive interventions into state educational systems. Interrogating the meaning of “education” for congressional leaders, this study examines the role of this ambiguous concept in negotiating the contradictions of federal and state identity, projecting visions of social change, evaluating civic preparedness, and enabling broader debates over the nation’s future. Examining legislative debates over the Reconstruction Acts, Freedmen’s Bureau, Bureau of Education, and two bills for national education reform in the early 1870s, this project examines how disparate educational visions of Republicans and Democrats collided and mutated amid the vicissitudes of public policy argument. Engaging rhetorical concepts of temporality, disposition, and political judgment, it examines the allure and limitations of education policy rhetoric, and how this rhetoric shifted amid the difficult process of coming to policy agreements in a tumultuous era. In a broader historical sense, this project considers the role of Reconstruction Era congressional rhetoric in shaping the long-term development of contemporary Americans’ “educational imaginary,” the tacit, often unarticulated assumptions about schooling that inflect how contemporary Americans engage in political life, civic judgment, and social reform. Treating the analysis of public policy debate as a way to gain insights into transitions in American political life, the study considers how Reconstruction Era debate converged upon certain common agreements, and obfuscated significant fault lines, that persist in contemporary arguments.

Who Governs Educational Change? The Paradoxes of State Power and the Pursuit of Educational Reform in Post-Neoliberal Ecuador (2007-2015)

This study identifies and compares competing policy stories of key actors involved in the Ecuadorian education reform under President Rafael Correa from 2007-2015. By revealing these competing policy stories the study generates insights into the political and technical aspects of education reform in a context where state capacity has been eroded by decades of neoliberal policies. Since the elections in 2007, President Correa has focused much of his political effort and capital on reconstituting the state’s authority and capacity to not only formulate but also implement public policies. The concentration of power combined with a capacity building agenda allowed the Correa government to advance an ambitious comprehensive education reform with substantive results in equity and quality. At the same time the concentration of power has undermined a more inclusive and participatory approach which are essential for deepening and sustaining the reform. This study underscores both the limits and importance of state control over education; the inevitable conflicts and complexities associated with education reforms that focus on quality; and the limits and importance of participation in reform. Finally, it examines the analytical benefits of understanding governance, participation and quality as socially constructed concepts that are tied to normative and ideological interests.

Advanced Analytical Microscopy at the Nanoscale: Applications in Wide Bandgap and Solid Oxide Fuel Cell Materials

The atomic-level structure and chemistry of materials ultimately dictate their observed macroscopic properties and behavior. As such, an intimate understanding of these characteristics allows for better materials engineering and improvements in the resulting devices. In our work, two material systems were investigated using advanced electron and ion microscopy techniques, relating the measured nanoscale traits to overall device performance. First, transmission electron microscopy and electron energy loss spectroscopy (TEM-EELS) were used to analyze interfacial states at the semiconductor/oxide interface in wide bandgap SiC microelectronics. This interface contains defects that significantly diminish SiC device performance, and their fundamental nature remains generally unresolved. The impacts of various microfabrication techniques were explored, examining both current commercial and next-generation processing strategies. In further investigations, machine learning techniques were applied to the EELS data, revealing previously hidden Si, C, and O bonding states at the interface, which help explain the origins of mobility enhancement in SiC devices. Finally, the impacts of SiC bias temperature stressing on the interfacial region were explored. In the second system, focused ion beam/scanning electron microscopy (FIB/SEM) was used to reconstruct 3D models of solid oxide fuel cell (SOFC) cathodes. Since the specific degradation mechanisms of SOFC cathodes are poorly understood, FIB/SEM and TEM were used to analyze and quantify changes in the microstructure during performance degradation. Novel strategies for microstructure calculation from FIB-nanotomography data were developed and applied to LSM-YSZ and LSCF-GDC composite cathodes, aged with environmental contaminants to promote degradation. In LSM-YSZ, migration of both La and Mn cations to the grain boundaries of YSZ was observed using TEM-EELS. Few substantial changes however, were observed in the overall microstructure of the cells, correlating with a lack of performance degradation induced by the H2O. Using similar strategies, a series of LSCF-GDC cathodes were analyzed, aged in H2O, CO2, and Cr-vapor environments. FIB/SEM observation revealed considerable formation of secondary phases within these cathodes, and quantifiable modifications of the microstructure. In particular, Cr-poisoning was observed to cause substantial byproduct formation, which was correlated with drastic reductions in cell performance.

MANIPULATION OF IONS, ELECTRONS, AND PHOTONS IN 2D MATERIALS BY ION INTERCALATION

2D materials have attracted tremendous attention due to their unique physical and chemical properties since the discovery of graphene. Despite these intrinsic properties, various modification methods have been applied to 2D materials that yield even more exciting results. Among all modification methods, the intercalation of 2D materials provides the highest possible doping and/or phase change to the pristine 2D materials. This doping effect highly modifies 2D materials, with extraordinary electrical transport as well as optical, thermal, magnetic, and catalytic properties, which are advantageous for optoelectronics, superconductors, thermoelectronics, catalysis and energy storage applications. To study the property changes of 2D materials, we designed and built a planar nanobattery that allows electrochemical ion intercalation in 2D materials. More importantly, this planar nanobattery enables characterization of electrical, optical and structural properties of 2D materials in situ and real time upon ion intercalation. With this device, we successfully intercalated Li-ions into few layer graphene (FLG) and ultrathin graphite, heavily dopes the graphene to 0.6 x 10^15 /cm2, which simultaneously increased its conductivity and transmittance in the visible range. The intercalated LiC6 single crystallite achieved extraordinary optoelectronic properties, in which an eight-layered Li intercalated FLG achieved transmittance of 91.7% (at 550 nm) and sheet resistance of 3 ohm/sq. We extend the research to obtain scalable, printable graphene based transparent conductors with ion intercalation. Surfactant free, printed reduced graphene oxide transparent conductor thin film with Na-ion intercalation is obtained with transmittance of 79% and sheet resistance of 300 ohm/sq (at 550 nm). The figure of merit is calculated as the best pure rGO based transparent conductors. We further improved the tunability of the reduced graphene oxide film by using two layers of CNT films to sandwich it. The tunable range of rGO film is demonstrated from 0.9 um to 10 um in wavelength. Other ions such as K-ion is also studied of its intercalation chemistry and optical properties in graphitic materials. We also used the in situ characterization tools to understand the fundamental properties and improve the performance of battery electrode materials. We investigated the Na-ion interaction with rGO by in situ Transmission electron microscopy (TEM). For the first time, we observed reversible Na metal cluster (with diameter larger than 10 nm) deposition on rGO surface, which we evidenced with atom-resolved HRTEM image of Na metal and electron diffraction pattern. This discovery leads to a porous reduced graphene oxide sodium ion battery anode with record high reversible specific capacity around 450 mAh/g at 25mA/g, a high rate performance of 200 mAh/g at 250 mA/g, and stable cycling performance up to 750 cycles. In addition, direct observation of irreversible formation of Na2O on rGO unveils the origin of commonly observed low 1st Columbic Efficiency of rGO containing electrodes. Another example for in situ characterization for battery electrode is using the planar nanobattery for 2D MoS2 crystallite. Planar nanobattery allows the intrinsic electrical conductivity measurement with single crystalline 2D battery electrode upon ion intercalation and deintercalation process, which is lacking in conventional battery characterization techniques. We discovered that with a “rapid-charging” process at the first cycle, the lithiated MoS2 undergoes a drastic resistance decrease, which in a regular lithiation process, the resistance always increases after lithiation at its final stage. This discovery leads to a 2- fold increase in specific capacity with with rapid first lithiated MoS2 composite electrode material, compare with the regular first lithiated MoS2 composite electrode material, at current density of 250 mA/g.