<p>Producing bio-based commodity chemicals, such as polymers and fuels, is of significant interest as petroleum reserves continue to decline. A major roadblock to bio-based production is high processing costs. These costs are associated with the need for highly-specialized catalysts to produce bio-based commodity chemicals from agricultural products and wastes. This prevents bioprocessing facilities from fully taking advantage of commodities of scale, where purchasing materials in greater quantities reduces the material cost. Discovering catalysts capable of being used in multiple production pathways could reduce the per unit processing of a biorefinery. <br> Recent works have shown that maleic acid can be used for multiple conversion reactions of plant material to valuable products: xylose to furfural, glucose to hydroxymethylfurfural (HMF), and the pretreatment of lignocellulosic material for second generation biofuel production. This work evaluates the use of maleic acid as a catalyst for producing HMF from corn starch, with a specific focus on reducing operating costs. Additionally, the use of maleic acid as a liquefaction catalyst for producing corn stover slurries is tested. </p> <p>To evaluate HMF production from starch, a combined computational and experimental approach is used. Through modelling and experimental validation, molar HMF yields of ~30% are reached by incorporating dilute dimethylsulfoxide and acetonitrile into the reaction mixture. However, HMF yield was limited by low stability in the reaction media. The addition of activated carbon to the reactor overcomes challenges with second order side reactions, resulting in HMF selling prices that are competitive with similar petroleum-derived chemicals. The key technical roadblocks to commercialization of HMF production are identified as solvent recycling and HMF separation efficiency in a sensitivity analysis. During liquefaction of corn stover, maleic acid was found to reduce the yield stress required to begin slurry flow through a pipe. However, a reduction in the free water content of the reactor through binding of water in the matrix of biomass limited liquefaction, resulting in solids concentrations not financially feasible at scale. To overcome this, maleic acid treatment was performed at solids contents of 25%, followed by a water removal step and enzymatic liquefaction at 30% solids. Yield stress was reduced from >6000 Pa for untreated samples to ~50 Pa for samples treated with maleic acid and enzymes sequentially. Such treatment reduces the challenges associated with feeding solid biomass into a pretreatment reactor. Additionally, reduced slurry yield stress results in lower capital costs, since smaller pumps can be used in the production facility. </p> This work provides a step forward in transitioning away from a petroleum-based economy to a bio-based economy without significant disruptions in product pricing and availability.

<p>The primary research question of this dissertation is, \textit{How do contestants make sequential design decisions under the influence of competition?} To address this question, I study the influence of three factors, that can be controlled by the contest organizers, on the contestants' sequential information acquisition and decision-making behaviors. These factors are (i) a contestant's domain knowledge, (ii) framing of a design problem, and (iii) information about historical contests. The \textit{central hypothesis} is that by conducting controlled behavioral experiments we can acquire data of contestant behaviors that can be used to calibrate computational models of contestants' sequential decision-making behaviors, thereby, enabling predictions about the design outcomes. The behavioral results suggest that (i) contestants better understand problem constraints and generate more feasible design solutions when a design problem is framed in a domain-specific context as compared to a domain-independent context, (ii) contestants' efforts to acquire information about a design artifact to make design improvements are significantly affected by the information provided to them about their opponent who is competing to achieve the same objectives, and (iii) contestants make information acquisition decisions such as when to stop acquiring information, based on various criteria such as the number of resources, the target objective value, and the observed amount of improvement in their design quality. Moreover, the threshold values of such criteria are influenced by the information the contestants have about their opponent. The results imply that (i) by understanding the influence of an individual's domain knowledge and framing of a problem we can provide decision-support tools to the contestants in engineering design contexts to better acquire problem-specific information (ii) we can enable contest designers to decide what information to share to improve the quality of the design outcomes of design contest, and (iii) from an educational standpoint, we can enable instructors to provide students with accurate assessments of their domain knowledge by understanding students' information acquisition and decision making behaviors in their design projects. The \textit{primary contribution} of this dissertation is the computational models of an individual's sequential decision-making process that incorporate the behavioral results discussed above in competitive design scenarios. Moreover, a framework to conduct factorial investigations of human decision making through a combination of theory and behavioral experimentation is illustrated. <br></p>

Engineering designers commonly make sequential information acquisition decisions such as selecting designs for performance evaluation, selecting information sources, deciding whom to communicate with in design teams, and deciding when to stop design exploration. There is significant literature on normative decision making for engineering design, however, there is a lack of descriptive modeling of how designers actually make information acquisition decisions. Such descriptive modeling is important for accurately modeling design decisions, identifying sources of inefficiencies, and improving the design process. To that end, the research objective of the dissertation is to understand how designers make sequential information acquisition decisions and identify models that provide the best description of a designer’s decisions strategies. For gaining this understanding, the research approach consists of a synthesis of descriptive theories from psychological and cognitive sciences, along with empirical evidence from behavioral experiments under different design situations. Statistical Bayesian inference is used to determine how well alternate descriptive decision models describe the experimental data. This approach quantifies a designer's decision strategies through posterior parameter estimation and Bayesian model comparison. <br><br>Two research studies, presented in this dissertation, focus on assessing the effects of monetary incentives, fixed budget, type of design space exploration, and the availability of system-wide information on information acquisition decisions. The first study presented in this dissertation investigates information acquisition by an individual designer when multiple information sources are available and the total budget is limited. The results suggest that the student subjects' decisions are better represented by the heuristic-based models than the expected utility(EU)-based models. <br>While the EU-based models result in better net payoff, the heuristic models used by the subjects generate better design performance. The results also indicate the potential for nudging designers' decisions towards maximizing the net payoff by setting the fixed budget at low values and providing monetary incentives proportional to the saved budget.<br><br>The second study investigates information acquisition through communication. The focus is on designers’ decisions about whom to communicate with, and how much to communicate when there is interdependence between subsystems being designed. This study analyzes team communication of NASA engineers at a mission design laboratory (MDL) as well as of engineering students designing a simplified automotive engine in an undergraduate classroom environment. The results indicate that the rate of interactions increases in response to the reduce in system-level design performance in both settings. Additionally, the following factors seem to positively influence communication decisions: the pairwise design interdependence, node-wise popularity (significant with NASA MDL engineers due to large team size), and pairwise reciprocity.<br><br>The dissertation work increases the knowledge about engineering design decision making in following aspects. First, individuals make information acquisition decisions using simple heuristics based on in-situ information such as available budget amount and present system performance.<br>The proposed multi-discipline approach proves helpful for describing heuristics analytically and inferring context-specific decision strategies using statistical Bayesian inference. This work has potential application in developing decision support tools for engineering design. Second, the comparison of communication patterns between student design teams and NASA MDL teams reveals that the engine experiment preserves some but not all of the communication patterns of interest. We find that the representativeness depends not on matching subjects, tasks, and context separately, but rather on the behavior that results from the interactions of these three dimensions. This work provides lessons for designing representative experiments in the future.

<p>Cadmium (Cd) is a highly mobile and toxic heavy metal that negatively affects plants, soil biota, animals and humans, even in very low concentrations. Currently, Cd contamination of cocoa produced in Latin American countries is a significant problem, as concentrations can exceed acceptable levels set by the European Union (0.5 mg/kg), sometimes by more than 10 times allowable levels. In South America, <i>Theobroma cacao</i> is an essential component of the basic market basket. This crop contributes to the Latin-American trade balance, as these countries export cacao and chocolate-based products to major consumer countries such as the United States and Europe. Some soil amendments can alter the bioavailability and uptake of Cd into edible plant tissues, though cacao plants can accumulate Cd without displaying any visible symptoms of phytotoxicity, which makes it difficult to determine if potential remediation strategies are successful. Currently, the only effective way to quantify Cd accumulation in plant tissues is via destructive post-harvest practices that are time-consuming and expensive. New hyperspectral imaging (HSI) technologies developed for use in high-throughput plant phenotyping are powerful tools for monitoring environmental stress and predicting the nutritional status in plants. Consequently, the experiments described in this thesis were conducted to determine if HSI technologies could be adapted for monitoring plant stress caused by Cd, and estimating its concentration in vegetative plant tissues. Two leafy green crops were used in these experiments, basil (<i>Ocimum basilicum L.</i> var. Genovese) and kale (<i>Brassica oleracea L</i>. var. Lacinato), because they are fast growing, and therefore, could serve as indicator crops on cacao farms. In addition, we expected these two leafy green crops would differ in their morphological responses to Cd stress. Specifically, we predicted that stress responses would be visible in basil, but not kale, which is known to be a hyperaccumulator. The plants were subject to four levels of soil Cd (0, 5, 10 and 15 ppm), and half of the pots were amended with biochar at a rate of 3% (v/v), as this amendment has previously been demonstrated to improve plant health and reduce Cd uptake. The experiments were conducted at Purdue’s new Controlled Environment Phenotyping Center (CEPF). The plants were imaged weekly and manual measurements of plant growth and development were collected at the same times, and concentrations of Cd as well as many other elements were determined after harvest. Fourteen vegetation indices generated using HSI images collected from the side and top view of plants were evaluated for their potential to identify subtle signs of plant stress due soil Cd and the biochar amendment. In addition, three mathematical models were evaluated for their potential to estimate Cd concentrations in the plant biomass and determine if they exceed safe standards (0.28 mg/kg) set by the Food and Agriculture Organization (FAO) for leafy greens. Results of these studies confirm that like many plants, these leafy green crops can accumulate Cd levels that are well above safety thresholds for human health, but exhibit few visible symptoms of stress. The normalized difference vegetation index (NDVI) and the chlorophyll index at the red edge (CI_RE) were the best indices for detecting Cd stress in these crops, and the plant senescence and reflectance index (PSRI) and anthocyanin reflectance index (ARI) were the best at detecting subtle changes in plant physiology due to the biochar amendment. The heavy metal stress index (HMSSI), developed exclusively for detecting heavy metal stress, was only able to detect Cd stress in basil when images were taken from the top view. Results of the mathematical models indicated that principal components analysis (PCA) and partial least squares (PLS) models overfit despite efforts to transform the data, indicating that they are not capable of predicting Cd concentrations in these crops at these levels. However, the artificial neural networks (ANN) was able to predict whether leafy greens had levels of Cd that were above or below critical thresholds suggested by the FAO, indicating that HSI could be further developed to predict Cd concentrations in plant tissues. Further research conducted in the field and in the presence of other environmental stress factors are needed to confirm the utility of these tools, and determine whether they can be adapted to monitor Cd uptake in cacao plants.</p>