Dimethacrylate oligomers diluted with styrene reactive diluents (so-called vinyl ester resins) are becoming increasingly important for composites in applications such as transportation vehicles, printed wiring boards and civil infrastructure. This research has focused on the generation and comparative analysis of glassy dimethacrylate networks as a function of oligomer structure, the type of reactive diluent, composition and curing conditions. A novel cycloaliphatic dimethacrylate was synthesized and its networks were compared to oligomeric structures containing dimethacrylates derived from epoxy terminated oligomers (from bisphenol-A and epichlorohydrin). Both types of dimethacrylates co-cured with methyl methacrylate exhibited increases in Mc and fracture toughness as the concentration of methyl methacrylate was increased. By contrast, networks prepared with a styrene diluent displayed reduced toughness with increasing styrene and Mc. Due to the need for long-term composite environmental durability, the effects of moisture and exposure to sunlight are important. Thus, these materials were exposed to ultraviolet light on a rotating drum for 225 days and the exposure was carefully monitored. Initial results from this study suggest that both the networks comprising the aromatic dimethacrylate/styrene structures as well as the cycloaliphatic analogues cured with methyl methacrylate undergo reductions in rubbery moduli upon aging under these conditions. X-Ray photoelectron spectroscopy shows higher levels of oxidation on the bisphenol-A vinyl ester networks cured with styrene, especially those containing dimethylaniline and cobalt naphthenate as accelerators. Scanning electron microscopy indicates a smooth surface for the cycloaliphatic networks cured with methyl methacrylate and a pitted surface for the aromatic networks cured with styrene. Water absorption is also higher for the cycloaliphatic vinyl ester; however, curing with a longer alkyl chain methacrylate (butyl methacrylate) decreases the water absorption to levels comparable to those cured with styrene. / Ph. D.

The most common use of reclaimed asphalt pavement (RAP) is in the lower layers of a pavement structure, where it has been proven as a valid substitute for virgin materials. Instead, the use of RAP in surface mixes is more limited, with a major concern being that the high RAP mixes may not perform as well as traditional mixes. To reduce risks of compromised performance, the use of RAP has commonly been controlled by specifications that limit the allowed amount of recycled material in the mixes. However, significant cost and environmental savings can be achieved if more RAP is included in the surface layer. This dissertation develops an approach that can be followed to incorporate more RAP in the surface mix while maintaining good performance. The approach is based on the results from three studies that looked at how to optimize the design of the mix, in terms of rutting and fatigue resistance, when more RAP is used. In the first study, a high RAP control mix and an optimized mix designed using different design compaction energy (65 and 50 gyrations respectively) were compared. The optimization process consisted in the definition of an alternative mix composition that supported the higher binder content allowed by the lower design compaction energy. Using Accelerated Pavement Testing and laboratory characterization it was possible to assess the potential of mix optimization with the objective of improving rutting resistance. The testing showed no indication that the optimized mixes would have rutting problems, supporting the implementation of the reduction of the design compaction energy level. The optimized mix exhibited a similar or superior rutting resistance in the full-scale setting, in the laboratory, and in the forensic investigation. The second part focused on the production of highly recycled surface mixes capable of performing well. To produce the mixes, a balanced mix design (BMD) methodology was used and a comparison with traditional mixes, prepared in accordance with the requirements of the Virginia Department of Transportation (VDOT) volumetric mix design, was performed. Through the BMD procedure, which featured the indirect tensile cracking test for evaluating the cracking resistance and the Asphalt Pavement Analyzer for evaluating rutting resistance, it was possible to optimize the selection of the optimum asphalt content. Also, it was possible to obtain a highly recycled mix (45% RAP) capable of achieving better overall performances than traditional mixes while carrying a large reduction in production cost. The final part evaluated the laboratory performance of four different highly recycled surface mixes to support their possible implementation in the state of Virginia. The mixes featured either 30% or 45% RAP, different asphalt contents, the use of a WMA additive, and a rejuvenator. To analyze the mixes' performance in great depth, a three-level (base, intermediate, and advanced) testing framework was defined. Each level was characterized by an increasing degree of complexity and included tests to characterize both the cracking resistance and the rutting resistance. The study aimed at investigating the features of the various laboratory tests. Through the review of the theoretical background, the evaluation of the test procedures, and statistical analysis of the results, it was possible to identify the strengths and weaknesses of each test and to provide guidelines to develop appropriate quality assessment criteria and mix design methodology. In summary, throughout this research, it was possible to observe that the respect of Superpave mix design requirements alone, with particular reference to gradation limits and volumetric properties, was not guarantee of satisfactory performance in terms of both cracking and rutting resistance. To increase the confidence in the RAP properties, increase the current recycling levels, and introduce more appropriate mix design specifications, BMD could be used (even with simple laboratory tests) to check performance-based criteria. / Doctor of Philosophy / Nowadays, transportation agencies are expected to perform a large number of pavement rehabilitation projects, while facing major limitations in budgetary funds. In order to have safe, efficient, and cost-effective roadways, the economic advantage of recycling is boosting an effort to increase the amount of RAP in asphalt mixtures. In addition, over the past decades, the environmental awareness of the transportation agencies and public increased significantly, pushing even more towards the use of new green technologies. The use of RAP became noticeable in the 1970s and its popularity increased significantly since that time. However, there are still many open questions which prevent larger uses of recycled materials, mainly related to the design methodology and the field performances of recycled mixtures. Therefore, today there is a large untapped potential that would grow even more the magnitude of pavement recycling and of the associated benefits. New design procedures, based on the support of laboratory tests to characterize the mixtures, and full-scale experiments are the tools that pavement engineers can use in order to enrich the knowledge of highly recycled road materials and grow the confidence of public agencies and contractors towards these new more sustainable solutions. Throughout this dissertation it was possible to evaluate new innovative ways of incorporating more RAP in the asphalt mixtures through the analysis of current state of the art and the proposition of new procedures.

The inverted-T bridge system is a rapid bridge construction technique that consists of precast inverted-T girders placed adjacent to one another and covered with a cast-in-place deck. This system was first implemented in the U.S. by the Minnesota Department of Transportation (Mn/DOT). This research focuses on improving the constructability of the Mn/DOT system while maintaining the system's structural performance characteristics. To accomplish this goal, five sub-assemblage specimens were cast and tested in the structures laboratory at Virginia Tech. These tests focused on identifying an improved precast girder geometry and transverse sub-assemblage connection for this system. From this study it was found that all of the proposed specimens behaved adequately at service load and strength. From these results, it is recommended to further evaluate a specimen with a tapered profile and no physical connection between precast girders for use in a Virginia Department of Transportation bridge near Richmond, VA. / Master of Science

The inverted T-beam bridge system is a bridge construction technique that follows accelerated bridge construction processes. The system was discovered in France and first adopted in the U.S. by the Minnesota Department of Transportation. In 2012 the system was modified and adopted by Virginia, with research being carried out at Virginia Polytechnic Institute and State University (Virginia Tech). The research focused on multiple items involving the system, but the most relevant one is that regarding the transverse bending behavior of the system for different geometries, and joint types between adjacent precast beam members. The study found that using a joint system without any mechanical connection between adjacent beams was most efficient, and gave adequate performance under monotonic loading. The study recommended cyclic load testing be carried out on this joint type, as well as a welded joint similar to those found in decked bulb-T systems. The research contained herein presents the setup and results of this testing. From the work it was found that the no-connection joint behaves adequately under cyclic loading at service loads, however surface roughening between precast and cast-in-place concrete must be adequate. The welded connection behaves well, granted the surfaces to be welded are properly prepared. From these results it is recommended to evaluate different surface roughening techniques, and repeat the cyclic testing using the best. The surface roughening technique chosen should be used to provide guidance on this aspect of construction with inverted T-beams. / Master of Science / The inverted T-beam bridge system is a new type of bridge system intended for use in short to medium length bridges. The system was discovered in France in 2004, where a similar type was being used. It was first modified slightly, and adopted in the in Minnesota. In 2012, the system was again modified to increase its strength and its construction speed, and was then adopted in Virginia. The modifications to the system in Virginia focused on the connections between the individual units making up the bridge, and the geometry of each of these units. The focus of this research was to quantify the long-term performance of two of the connection types currently used on bridges in Virginia. This was achieved by subjecting a test specimen to repeated loads in the laboratory at Virginia Tech. The loading used in the laboratory represented the conditions that a real bridge of this type would be subjected to. The research showed that the two connection types performed well under the repeated loading conditions. However, it was concluded that the concrete surfaces which are in contact with one another must be properly roughened, so that the system maintains its strength. The importance of this research is due to the fact that the large costs associated with maintaining the nation’s bridge infrastructure can be substantially reduced due to this system’s quick and simple construction. In addition to this, road users experience less disruption because of the shortened construction times.

Pavement macrotexture has been shown to influence a range of safety and comfort issues including wet weather friction, splash and spray, ambient and in-vehicle noise, tire wear, and rolling resistance. While devices and general guidance exist to measure macrotexture, the wide-scale collection and use of macrotexture is neither mandated nor is it typically employed in the United States. This work seeks to improve upon the methods used to calibrate, collect, pre-process, and distill macrotexture data into useful information that can be utilized by pavement managers. This is accomplished by 1. developing a methodology to evaluate and compare candidate data collection devices; 2. plans and procedures to evaluate the accuracy of high-speed network data collection devices with reference surfaces and measurements; 3. the development of a method to remove erroneous data from emerging 3-D macrotexture sensors; 4. development of a model to describe the change in macrotexture as a function of traffic; 5.finally, distillation of the final collected pavement surface profiles into parameters for the prediction of important pavement surface properties aforementioned. Various high-speed macrotexture measurement devices were shown to have good repeatability (between 0.06 to 0.09mm MPD) and interchangeability of single-spot laser dfevices was demonstrated via a limits of agreement analysis. The operational factors of speed and acceleration were shown to affect the resulting MPD of several devices and guidelines are given for vehicle speed and sensor exposure settings. Devices with single spot and line lasers were shown to reproduce reference waveforms on manufactured surfaces within predefined tolerances. A model was developed that predicts future macrotexture levels (as measured by RMS) for pavements prone to bleeding due to rich asphalt content. Finally, several previously published macrotexture parameters along with a suite of novel parameters were evaluated for their effectiveness in the prediction of wet weather friction and certain types of road noise. Many of the parameters evaluated outperformed the current metrics of MPD and RMS. / Doctor of Philosophy

Understanding the lifetime behavior of their products is crucial to the success of any company in the manufacturing and engineering industries. Statistical methods for lifetime data are a key component to achieving this level of understanding. Sometimes a statistical procedure must be updated to be adequate for modeling specific data as is discussed in Chapter 2. However, there are cases in which the methods used in industrial standards are themselves inadequate. This is distressing as more appropriate statistical methods are available but remain unused. The research in Chapter 4 deals with such a situation. The research in Chapter 3 serves as a combination of both scenarios and represents how both statisticians and engineers from the industry can join together to yield beautiful results. After introducing basic concepts and notation in Chapter 1, Chapter 2 focuses on lifetime prediction for a product consisting of multiple components. During the production period, some components may be upgraded or replaced, resulting in a new ``generation" of component. Incorporating this information into a competing risks model can greatly improve the accuracy of lifetime prediction. A generalized competing risks model is proposed and simulation is used to assess its performance. In Chapter 3, optimal and compromise test plans are proposed for constant amplitude fatigue testing. These test plans are based on a nonlinear physical model from the fatigue literature that is able to better capture the nonlinear behavior of fatigue life and account for effects from the testing environment. Sensitivity to the design parameters and modeling assumptions are investigated and suggestions for planning strategies are proposed. Chapter 4 considers the analysis of ADDT data for the purposes of estimating a thermal index. The current industry standards use a two-step procedure involving least squares regression in each step. The methodology preferred in the statistical literature is the maximum likelihood procedure. A comparison of the procedures is performed and two published datasets are used as motivating examples. The maximum likelihood procedure is presented as a more viable alternative to the two-step procedure due to its ability to quantify uncertainty in data inference and modeling flexibility. / Ph. D.

Oxidative processes are linked to a number of major disease states as well as the breakdown of many materials. Of particular importance are reactive oxygen species (ROS), as they are known to be endogenously produced in biological systems as well as exogenously produced through a variety of different means. In hopes of better understanding what controls the behavior of ROS, researchers have studied radical chemistry on a fundamental level. Fundamental knowledge of what contributes to oxidative processes can be extrapolated to more complex biological or macromolecular systems. Fundamental concepts and applied data (i.e. interaction of ROS with polymers, biomolecules, etc.) are critical to understanding the reactivity of ROS. A detailed review of the literature, focusing primarily on the hydroxyl radical (HO•) and hydrogen atom (H•) abstraction reactions, is presented in Chapter 1. Also reviewed herein is the literature concerning high density polyethylene (HDPE) degradation. Exposure to treated water systems is known to greatly reduce the lifetime of HDPE pipe. While there is no consensus on what leads to HDPE breakdown, evidence suggests oxidative processes are at play. The research which follows in Chapter 2 focuses on the reactivity of the hydroxyl radical and how it is controlled by its environment. The HO• has been thought to react instantaneously, approaching the diffusion controlled rate and showing little to no selectivity. Both experimental and calculational evidence suggest that some of the previous assumptions regarding hydroxyl radical reactivity are wrong and that it is decidedly less reactive in an aprotic polar solvent than in aqueous solution. These findings are explained on the basis of a polarized transition state that can be stabilized via the hydrogen bonding afforded by water. Experimental and calculational evidence also suggest that the degree of polarization in the transition state will determine the magnitude of this solvent effect. Chapter 3 discusses the results of HDPE degradation studies. While HDPE is an extremely stable polymer, exposure to chlorinated aqueous conditions severely reduces the lifetime of HDPE pipes. While much research exists detailing the mechanical breakdown and failure of these pipes under said conditions, a gap still exists in defining the species responsible or mechanism for this degradation. Experimental evidence put forth in this dissertation suggests that this is due to an auto-oxidative process initiated by free radicals in the chlorinated aqueous solution and propagated through singlet oxygen from the environment. A mechanism for HDPE degradation is proposed and discussed. Additionally two small molecules, 2,3-dichloro-2-methylbutane and 3-chloro-1,1-di-methylpropanol, have been suggested as HDPE byproducts. While the mechanism of formation for these products is still elusive, evidence concerning their identification and production in HDPE and PE oligomers is discussed. Finally, Chapter 4 deals with concluding remarks of the aforementioned work. Future work needed to enhance and further the results published herein is also addressed. / Ph. D.

Accelerated Bridge Construction, also known as ABC, is a methodology that seeks to improve project development of bridges by reducing the overall project schedule and the impact on the traveling public by implementing innovative technologies and strategies in any phase of project development. However, ABC may incur additional direct costs for the project and some risks are associated because of the accelerated constraints implied in this methodology. On the positive side, the opportunity costs and reductions of traffic disruptions costs may overcome the additional costs associated with ABC. Decision-making methodologies for assessment of ABC as an alternative to traditional construction are of great interest for project developers. The topics of research about ABC are diverse but focus mainly on the means and methods, technical aspects, applications, innovations, and decision-making of ABC. Decision-making is of great concern for project developers, especially government organizations, to sustain project goals of serviceability and to validate the additional expenditures in a project. In addition, project developers improve their decisions and project outcomes by reviewing success and failure cases for completed projects in the past. This study seeks to improve the decision-making processes in ABC by finding a more direct correlation of projects to compare by means of a categorization of these ABC projects. Smaller groups in this categorization will help narrow the scope of the characteristics of the projects to consider and to find more relevant lessons learned from the smaller groups of the categorization. To develop the categorization in this study, the data source used is the completed ABC projects database from the Federal Highway Administration (FHWA). The statistical categorization methodology for this study is the Agglomerate Hierarchy Clustering which developed a determined number of cluster based on the closeness among data parameters with "n" number of dimensions of analysis. The number of dimensions for the analysis in this study was established as 13 parameters collected from the database and these were considered critical decision-making parameters and consequential parameters to reflect project decisions and consequences of those decisions. The results of this study rendered 3 categories, and into these categories, 5 sub-categories were distributed according to the same analysis developed. The sub-categories show similarities between the projects according to the parameters established, so the sub-categories help narrow the scope of projects for project developers. As a complement to the categorization, a project matching tool for external projects was also developed to help decision-makers to test their projects according to the analysis in this study and also help developers narrow their review of cases in search for lessons learned. Uses of this study include the prediction of information of parameters according to the variables and ranges in this categorization, and the narrowing of study cases to review. Stakeholders interested can be government organizations seeking to establish the viability of an ABC project, or to improve their project outcomes at any stage of development. Other stakeholders can be designers and contractors that also need to improve their projects at any stage of development. / Master of Science / Accelerated Bridge Construction (ABC) reduces construction time and diminishes traffic disruption by applying strategies and innovations to the way bridges are designed and constructed. However, it implies additional initial costs that need to be justified. Project developers need to evaluate their projects to make decisions to assure the best execution and outcomes. The review of lessons learned from previous bridge projects has been one of the sources that developers have found to find strategies and tips to implement best practices or to avoid mistakes during planning and construction of new bridge projects. This study relies on the lessons learned compiled on the completed ABC project database from the federal transportation authority, the Federal Highway Administration (FHWA), in order to help developers, narrow the scope of projects to be reviewed and find more relevant cases to compare their projects. This scope includes the development of a categorization or a structured hierarchy of completed ABC projects with the FHWA database by applying a statistical analysis and a validation procedure. The results of this study rendered a categorization with 3 categories and 5 subcategories, each with its definition of parameters, which highlight the similarities among projects in the same groups and the differences among different categories. In addition, a framework was developed to match external projects with the categorization in this study to help project developers narrow the projects to review, or even predict missing information according to the parameters in this study. These results may help decision-makers better inform their decisions and support the research in the field of study.

This thesis investigates the impact of interface surface treatment methods for use in the Virginia Inverted T-Beam bridge system. The specific system consists of precast beams with thin bottom flanges placed next to one another, with a cast-in-place slab on top. Previous research has shown that the strength of this system after cyclic loading is highly dependent upon the shear strength of the interface between the precast and cast-in-place sections, especially for the adhesion-based connection configuration. The approval of this bridge system for use in bridges with high daily traffic volumes hinges on the verification of its strength and durability for a 50-year lifespan. The shear strength of ten different surface textures was tested using push-off tests to determine which interface roughening methods would prove adequate for use in the bridge system. The strength was found to depend on both the amplitude and the geometry of the undulations on the beam-to-slab interface. Using this information, a texture was selected for a new trial of the adhesion-based connection configuration, and a test specimen was constructed. After completing cyclic loading to simulate the design life of the bridge, it was found that the system achieved a strength similar to previous monotonically loaded specimens. It was concluded that the bridge is safe for use in high daily traffic areas provided that a surface roughening with adequate shear strength is used. / Master of Science / The Virginia Inverted T-Beam bridge system was initially designed to be more durable and economical than other types of bridges. The bridge is constructed by arranging prefabricated beams side-by-side across the span before placing fresh concrete overtop. In the most economical version of the system, the only connection between the beams is the newly placed concrete. For the beams and topping to act together, the bond between them must be strong. Roughening the surface of the prefabricated beams increases the strength of the bond, although different roughening patterns achieve different levels of strength. Past tests of the bridge system have utilized inadequate roughing patterns which lead to low bridge failure loads after many loading cycles. This low-cost configuration is currently only approved for use in low daily traffic areas. The goal of this research was to determine a roughening pattern that would result in a high bridge failure load which would allow the low-cost configuration to be approved for high daily traffic areas. Several roughening patterns were investigated and the patterns producing the highest shear strengths were determined. The best pattern was chosen to be used for the bridge configuration and a sub-section of the bridge was constructed. This specimen was subjected to a loading protocol that simulated the traffic that an actual bridge would be subjected to over its life span. The failure load was then measured and found to be high enough to warrant the use of the specific system in high daily traffic areas.

Lap splices are used in reinforced concrete structures to transfer tension forces across discontinuous reinforcing bars to allow for continuity of load path in structural elements. Lap splices of straight reinforcing bars present a number of disadvantages when used in connections of large precast concrete elements typical of bridge substructure. Most importantly, lap splices of large (e.g., No. 11) straight bars are substantially long. Since the closure joint connecting two precast elements must be at least long enough to fit the lap splice, traditional lap splices result in impractically large closure joints, offsetting the benefits of using precast concrete elements. To address this problem, bridge designers are using hooked bars in noncontact lap splices to connect precast elements, presuming that hooked bars will allow for shorter required splice lengths. However, there exists neither substantial design guidance nor studies of the behavior of hooked bar lap splices in large precast elements justifying this design philosophy. To develop design guidance permitting the use of noncontact hooked bar lap splices and address the knowledge gap regarding the behavior of such splices, an extensive experimental and computational research program was conducted which is described in this dissertation. Fifty-eight large-scale beam-splice specimens containing hooked bar lap splices were tested to physically study the behavior of hooked bar lap splices and develop a dataset to justify design guidance permitting the use of such splices in practice. Bond variables were parametrically varied among the test specimens to produce guidance applicable over the wide range of geometric configurations and material properties expected in bridge design. The specimens were subjected to monotonic, four-point loading and were designed to fail in a mode related to anchorage to study splice behavior. Nonlinear finite element analyses were conducted to examine the mechanism of force transfer in hooked bar lap splices and numerically assess splice configurations not experimentally studied. A simple approach to modelling hooked reinforcing bars in solid concrete elements which accounts for conditions of imperfect bond was developed and validated using the experimental results. Test results from the 58 specimens were used to assess the appropriateness of using existing guidance for hooked bar anchorages to design hooked bar lap splices. Because the existing guidance was found to be deficient for this application, descriptive and design equations characterizing hooked bar lap splices were developed using power regression analyses. The results demonstrated that all else being equal, a bottom-cast hooked bar lap splice can develop approximately 40% greater stress than contact lap splices of straight bars. Accordingly, hooked bars can be used to splice bars over a substantially shorter length than straight bars. Noncontact hooked bar lap splices without secondary reinforcement (e.g., ties) can fail due to a mode termed "hook side bulging", resulting from eccentricity between the lapped bars. Splices with secondary reinforcement typically fail due to more typical modes observed in the literature, such as side-face blowout and concrete crushing. Unlike as suggested by code authorities and some researchers for noncontact lap splices of straight bars, noncontact hooked bar lap splices were found to exhibit weaker splice strengths than contact splices as the splice spacing increased. The use of steel fibers and increases in lap length, concrete compressive strength, cover depth, amount of secondary reinforcement, or the number of lap splices allowed for greater stress on average to be developed in spliced bars. All else being equal, an increase in either bar size or the number of spliced reinforcement layers decreased the stress that could be developed in the spliced bars. A descriptive equation characterizing splice strength with an average test-to-calculation ratio and coefficient of variation of 6% was developed. The descriptive equation was adapted to develop a design equation for the minimum required lap length of hooked bars which uniformly characterizes the influence of the bond variables over the ranges explored in this study. Design examples and code language facilitating technology transfer of the design equation into immediate practice were developed. / Doctor of Philosophy / Precast concrete is widely used in highway bridges to enable more rapid and economical construction than could be achieved using cast-in-place concrete. However, the connection of two or more precast, prefabricated bridge elements introduces several difficulties which may inhibit construction, thereby reducing overall economy. One of the most significant difficulties is that connections of substructure elements supporting the superstructures are impractically long using a common, code-approved detail―lap splices of straight reinforcing bars. Such splices are quite long (e.g., 5 ft in length) since large bars are typically used in substructure elements, requiring long splice lengths to transfer the large forces in each bar across the connection. Details which would shorten the required splice length would consequently reduce the required connection length, thereby reducing the amount of cast-in-place concrete construction required in the field. Consequently, the speed of construction, economy, and worker safety would increase. This dissertation thus summarizes an extensive experimental and numerical study aimed at validating the use of noncontact hooked bar lap splices to shorten the required splice length of large precast elements. In support of this objective, the anchorage behavior of noncontact hooked bar lap splices was studied through static load testing of 58 large-scale beam-splice specimens and nonlinear finite element models accounting for bond-slip behavior. These efforts revealed that hooked bar lap splices can develop on average approximately 40% more stress over the same lap length than contact splices of straight bars. Existing design provisions which might presently be used to design hooked bar lap splices were evaluated against the experimental results and were found to be deficient in characterizing splice strength. Thus, a design equation was developed for the splice length of hooked bars which accurately characterizes anchorage behavior and allows for significantly shorter splices lengths than what could be achieved with straight bars.