Ionically self-assembled monolayer (ISAM) films are typically an assemblage of oppositely charged polymers built layer by layer through coulombic attraction utilizing an environmentally friendly process to form ordered structures that are uniform, molecularly smooth, and physically robust. ISAM films have been shown to be capable of the noncentrosymmetric order requisite for a second-order nonlinear optical response. However, films fabricated with a nonlinear optical (NLO) polymer result in significant cancellation of the chromophore orientations. This cancellation occurs by two mechanisms: competitive orientation due to the ionic bonding of the polymer chromophore with the subsequent polycation layer, and random orientation of the chromophores within the bulk of each polyanion layer. A reduction in film thickness accompanied by an increase in net polar ordering is one possible avenue to obtain the second-order nonlinear optical susceptibility chi(2) necessary for electro-optic devices. In this thesis, we will discuss the structural characteristics of ISAM films and explore three novel approaches to obtain the desired characteristics for nonlinear optical response. One approach involves the variation of solution parameters of several different cationic polymers separately from the polyanion solution in order to reduce the competitive chromophore orientation at the layer interfaces and to reduce the thickness of the inactive polycation layer. We have found that the complexity of ISAM films does not allow large chi(2) values in polyion-based films, and that the selection of the polymer cation is vital to achieve second harmonic generation (SHG) at all. The second approach involves the incorporation of dianionic molecules into ISAM films in order to eliminate both competitive chromophore orientation and random chromophore orientation inherent with polymer chromophores. We have also studied the effects of complexing dianionic chromophores with beta-cyclodextrin in order to increase solubility and improve chromophore orientation. This approach fails because the outermost monolayer of dianionic chromophore is only tethered to the preceding polycation layer by a single ionic bond for each molecule, so each chromophore can by dissociated during the following immersion into the cation solution. Finally, we have introduced a novel approach of hybrid covalent / ionic self-assembly which overcomes these disadvantages and yields a substantial increase in chi(2) due to the chromophore being locked in place to the preceding polycation layer by a covalent bond. The films fabricated in this manner yield a chi(2) that rival any polymer-polymer films despite the very low first-order molecular hyperpolarizability beta of the incorporated monomer. This suggests that incorporation of high beta molecules may result in significant improvement of chi(2), holding high promise for the hybrid covalent / ionic self-assembly technique. / Master of Science

Nanometer thick layers of clay and polymer were formed on mica, silicon, and aluminum 2024-T3 alloy using alternating solutions of positively and negatively charged polymer and clay, respectively. Atomic force microscopy was used to observe the morphology of the composite films on mica and silicon. It was found that solution concentrations of clay above 0.02 weight percent lead to the uncontrolled deposition of clay platelets on the substrate's surface. By using solution concentrations of clay above 0.02 weight percent and ultrasonic agitation together it is possible to deposit a uniform monolayer of clay platelets on a mica substrate in £ 20 seconds. Ultrasonic agitation also produced crude patterns of montmorillonite platelets. Thin films of poly(diallydimethylammonium chloride) (PDDA) were made using concentrations ³ 2 weight percent of PDDA. It was found that the PDDA formed several unusual morphologies. Spherulites of PDDA were observed with AFM and the glass transition temperature of high molecular weight PDDA was measured using differential scanning calorimetry (DSC). Circular regions of positive charge were discovered on silicon wafers provided by three different sources. These areas of charge have never been reported in literature, but can easily be detected by placing wafers into solutions containing negatively or positively charged solutions of clay or polymer, respectively. The exact nature of these charged regions is unknown, but it is hypothesized that impurities on silicon wafers create the circular regions of positive charge. ISAM films made of a polyamide salt and a synthetic clay, Laponite RD®, demonstrated significant corrosion resistance on 2024-T3 Al alloys after 168 hours of salt spray testing. The ISAM films offered corrosion protection only if there was a significant layer of underlying surface oxide present, however. It was found that ISAM deposited films of polyarylic acid (PAA) and polyallylamine hydrochloride (PAH) may offer some corrosion resistance on 2024-T3 Al alloys, but these films' corrosion resistance is severely hampered by the presence of Cl- in the PAH solution. Funding from this project was gratefully received from the Materials Science and Engineering Department at Virginia Tech; Luna Innovations Inc; the American Chemical Society / Petroleum Research Fund #34412-G5 and the Environmental Protection Agency Contract #68-D-00-244. / Master of Science

This research focuses on the Crash Analysis Methodology for Segments (CAMS) which provides a way for engineers at the Utah Department of Transportation (UDOT) to prioritize safety improvements on state-owned roadways. Unlike the Utah crash analysis methodologies that come before it, the CAMS focuses exclusively on segment-related crashes. The benefits of such an analysis can be found in identifying locations that have safety concerns unbiased from intersections and their related crashes. The CAMS uses UDOT data to create a spreadsheet of roadway segments and their associated crashes. Each segment is homogeneous with respect to five variables: Annual Average Daily Traffic (AADT), functional class, number of lanes, speed limit, and urban code. In the statistical analyses performed on the data, four years of crash data (2014-2017) are used to predict distributions of crashes for the most recent year of data (2018). Observed crash counts are compared to the predicted distributions and assigned a percentile value within the distributions, and segments are subsequently ranked in order of safety concern according to those percentiles. Two-page technical reports are created for segments that rank high in the state or UDOT Region. These reports consist of concise tables of roadway data and crash trends pertaining to each segment. Research analysts also add observations made in virtual site visits to the reports. In the end, the results and the reports are sent to UDOT where UDOT Region engineers may review and study identified segments in further detail. This research also includes modifications made to the Intersection Safety Analysis Methodology (ISAM) which focuses exclusively on intersection-related crashes. The modifications made to the ISAM mirror the abilities of the CAMS, thus allowing the pair of methodologies to analyze the entire state route network without overlapping any crash data.

Organic materials exhibiting second-order non-linear optical (NLO) properties are a key to the development of advanced electro-optic (EO) modulators used in fiber-optic communications system. This work addresses the fabrication and characterization of organic materials with NLO properties using a self-assembly approach by alternately dipping a charged substrate into positively and negatively charged polymers to build up layer-by-layer (LbL) films. The effect of solution pH on the formation of LbL films fabricated using the polycation poly(allylamine hydrochloride) (PAH) and the polyanion poly{1-[p-(3–-carboxy-4–-hydroxyphenylazo)benzenesulfonamido]-1,2-ethandiyl} (PCBS) was studied using a quartz crystal microbalance with dissipation (QCM-D) monitoring, ellipsometry, absorbance, and second harmonic generation (SHG) measurements. PCBS has an azo-benzene chromophore side group that, when sufficiently oriented, results in measurable SHG. Films of PAH/PCBS fabricated at neutral pH where both PAH and PCBS are highly charged led to thin bilayers, ~1 nm, with a 1:1 molar ratio of PCBS:PAH. This molar ratio was found to be important for long-range polar ordering of PCBS in these films. Increasing the rate of convection was found to reduce the time required for complete adsorption of the polyion. This can have a significant impact on fabrication of films with high bilayer numbers. A variation of the above technique, which involves adsorbing one of the constituents electrostatically and another covalently, was studied using PAH and a reactive dye, Procion Brown (PB), which has a significantly higher hyperpolarizability than PCBS. It was found that a high pH, ~10.5, was important for achieving covalent attachment of the PB to the underlying PAH films. This resulted in much higher SHG intensities compared to when PB was deposited pH at 8.5-9.5 where the attachment of PB was due to a combination of electrostatic and covalent interactions. QCM-D results for PAH/PB films revealed the presence of a high percentage of unreacted amine groups in the underlying PAH film. A rate constant value for PB attachment step to the underlying PAH was also calculated. To enhance the SHG intensity of these films, silver nanoprisms were synthesized and deposited onto films using physisorption. An enhancement in the SHG intensity was observed for both PAH/PCBS and PAH/PB films. / Ph. D.

Optical sensor systems that integrate Long-Period-Gratings (LPG) as the detection arm have been proven to be highly sensitive and reliable in many applications. With increasing public recognition of threats from bacteria-induced diseases and their potential outbreak among densely populated communities, an intrinsic, low-cost biosensor device that can perform quick and precise identification of the infection type is in high demand to respond to such challenging situations and control the damage those diseases could possibly cause. This dissertation describes the development of a biosensor platform that utilizes polymer thin films, known as ionic self-assembled multilayer (ISAM) films, to be the sensitivity- enhancing medium between an LPG fiber and specific, recognition layer. With the aid of cross- linking reactions, monoclonal antibodies (IgG) or DNA probes are immobilized onto the surface of the ISAM-coated fiber, which form the core component of the biosensor. By immersing such biosensor fiber into a sample suspension, the immobilized antibody molecules will bind the specific antigen and capture the target cells or cell fragments onto the surface of the fiber sensor, resulting in increasing the average thickness of the fiber cladding and changing the refractive index of the cladding. This change occurring at the surface of the fiber results in a decrease of optical power emerging from the LPG section of the fiber. By comparing the transmitted optical power before and after applying the sample suspension, we are able to determine whether or not certain bacterial species have attached to the surface of the fiber, and as a consequence, we are able to determine whether or not the solution contains the targeted bacteria. This platform has the potential for detection of a wide range of bacteria types. In our study, we have primarily investigated the sensitivity and specificity of the biosensor to methicillin- resistant Staphlococcus aureus (MRSA). The data we obtained have shown a sensitive threshold at as low as 102 cfu/ml with pure culture samples. A typical MRSA antibody-based biosensor assay with MRSA sample at this concentration has shown optical power reduction of 21.78%. In a detailed study involving twenty-six bacterial strains possessing the PBP2a protein that enables antibiotic resistance and sixteen strains that do not, the biosensor system was able to correctly identify every sample in pure culture samples at concentration of 104 cfu/ml. Further studies have also been conducted on infected mouse tissues and clinical swab samples from human ears, noses, and skin, and in each case, the system was in full agreement with the results of standard culture tests. However, the system is not yet able to correctly distinguish MRSA and non-MRSA infections in clinical swab samples taken from infected patient wounds. It is proposed that nonspecific binding due to insufficient blocking methods is the key issue. Other bacterial strains, such as Brucella and Francisella tularensis have also been studied using a similar biosensor platform with DNA probes and antibodies, respectively, and the outcomes are also promising. The Brucella DNA biosensor is able to reflect the existence of 3 Brucella strains at 100 cfu/ml with an average of 12.2% signal reduction, while negative control samples at 106cfu/ml generate an average signal reduction of -2.1%. Similarly, the F. tularensis antibodies biosensor has shown a 25.6% signal reduction to LVS strain samples at 100 cfu/ml, while for negative control samples at the same concentration, it only produces a signal reduction of 0.05%. In general, this biosensor platform has demonstrated the potential of detecting a wide range of bacteria in a rapid and relatively inexpensive manner. / Ph. D.

The ability to position yourself and map the surroundings is an important aspect for both civilian and military applications. Global navigation satellite systems are very popular and are widely used for positioning. This kind of system is however quite easy to disturb and therefore lacks robustness. The introduction of autonomous vehicles has accelerated the development of local positioning systems. This thesis work is done in collaboration with FOI in Linköping, using a positioning system with LIDAR and IMU sensors in a EKF-SLAM system using the GTSAM framework. The goal was to evaluate the system in different conditions and also investigate the possibility of using the road surface for positioning. Data available at FOI was used for evaluation. These data sets have a known sensor setup and matches the intended hardware. The data sets used have been gathered on three different occasions in a residential area, a country road and a forest road in sunny spring weather on two occasions and one occasion in winter conditions. To evaluate the performance several different measures were used, common ones such as looking at positioning error and RMSE, but also the number of found landmarks, the estimated distance between landmarks and the drift of the vehicle. All results pointed towards the forest road providing the best positioning, the country road the worst and the residential area in between. When comparing different weather conditions the data set from winter conditions performed the best. The difference between the two spring data sets was quite different which indicates that there may be other factors at play than just weather. A road edge detector was implemented to improve mapping and positioning. Vectors, denoted road vectors, with position and orientation were adapted to the edge points and the change between these road vectors were used in the system using GTSAM in areas with few landmarks. The clearest improvements to the drift in the vehicle direction was in the longer country area where the error was lowered with 6.4 % with increase in the error sideways and in orientation as side effects. The implemented method has a significant impact on the computational cost of the system as well as requiring precise adjustment of uncertainty to have a noticeable improvement and not worsen the overall results.