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.

BEHAVIOR OF FIBER REINFORCED POLYMER COMPOSITE PILES WITH ELLIPTICAL CROSS SECTIONS IN INTEGRAL ABUTMENT BRIDGE FOUNDATIONS

Every year in the US and other cold-climate countries considerable amount of money is spent to restore structural damages in conventional bridges resulting from (or “caused by”) salt corrosion in bridge expansion joints. Frequent usage of deicing salt in conventional bridges with expansion joints results in corrosion and other damages to the expansion joints, steel girders, stiffeners, concrete rebar, and any structural steel members in the abutments. The best way to prevent these damages is to eliminate the expansion joints at the abutment and elsewhere and make the entire bridge abutment and deck a continuous monolithic structural system. This type of bridge is called Integral Abutment Bridge which is now widely used in the US and other cold-climate countries. In order to provide lateral flexibility, the entire abutment is constructed on piles. Piles used in integral abutments should have enough capacity in the perpendicular direction to support the vertical forces. In addition, piles should be able to withstand corrosive environments near the surface of the ground and maintain their performance during the lifespan of the bridge. Fiber Reinforced Polymer (FRP) piles are a new type of pile that can not only accommodate large displacements, but can also resist corrosion significantly better than traditional steel or concrete piles. The use of FRP piles extends the life of the pile which in turn extends the life of the bridge. This dissertation studies FRP piles with elliptical shapes. The elliptical shapes can simultaneously provide flexibility and stiffness in two perpendicular axes. The elliptical shapes can be made using the filament winding method which is a less expensive method of manufacturing compared to the pultrusion or other manufacturing methods. In this dissertation a new way is introduced to construct the desired elliptical shapes with the filament winding method. Pile specifications such as dimensions, number of layers, fiber orientation angles, material, and soil stiffness are defined as parameters and the effects of each parameter on the pile stresses and pile failure have been studied. The ANSYS software has been used to model the composite materials. More than 14,000 nonlinear finite element pile models have been created, each slightly different from the others. The outputs of analyses have been used to draw curves. Optimum values of the parameters have been defined using generated curves. The best approaches to find optimum shape, angle of fibers and types of composite material have been discussed.

Prediction of Upward Flame Spread over Polymers

In this work, the existing understanding of flame spread dynamics is enhanced through an extensive study of the heat transfer from flames spreading vertically upwards across 5 cm wide, 20 cm tall samples of extruded Poly (Methyl Methacrylate) (PMMA). These experiments have provided highly spatially resolved measurements of flame to surface heat flux and material burning rate at the critical length scale of interest, with a level of accuracy and detail unmatched by previous empirical or computational studies. Using these measurements, a wall flame model was developed that describes a flame’s heat feedback profile (both in the continuous flame region and the thermal plume above) solely as a function of material burning rate. Additional experiments were conducted to measure flame heat flux and sample mass loss rate as flames spread vertically upwards over the surface of seven other commonly used polymers, two of which are glass reinforced composite materials. Using these measurements, our wall flame model has been generalized such that it can predict heat feedback from flames supported by a wide range of materials. For the seven materials tested here – which present a varied range of burning behaviors including dripping, polymer melt flow, sample burnout, and heavy soot formation – model-predicted flame heat flux has been shown to match experimental measurements (taken across the full length of the flame) with an average accuracy of 3.9 kW m-2 (approximately 10 – 15 % of peak measured flame heat flux). This flame model has since been coupled with a powerful solid phase pyrolysis solver, ThermaKin2D, which computes the transient rate of gaseous fuel production of constituents of a pyrolyzing solid in response to an external heat flux, based on fundamental physical and chemical properties. Together, this unified model captures the two fundamental controlling mechanisms of upward flame spread – gas phase flame heat transfer and solid phase material degradation. This has enabled simulations of flame spread dynamics with a reasonable computational cost and accuracy beyond that of current models. This unified model of material degradation provides the framework to quantitatively study material burning behavior in response to a wide range of common fire scenarios.

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.