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Title: CONTROLLER DESIGN AND DISTRIBUTED CONTROL WITHIN MULTI-AGENT SYSTEMS
Creator: Shao, Quan Min
Date: 2013, 2013-12
Description: None
PH.D in Chemical and Biological Engineering, December 2013

Title: POLYMER ELECTROLYTE MEMBRANES FOR ELECTROCHEMICAL ENERGY CONVERSION AND STORAGE SYSTEMS: FUEL CELLS AND REDOX FLOW BATTERIES
Creator: Yun, Sukhwan
Date: 2014, 2014-12
Description: Direct methanol fuel cells (DMFCs) and redox flow batteries (RFBs) are well-known electrochemical energy conversion/storage systems that...
Show moreDirect methanol fuel cells (DMFCs) and redox flow batteries (RFBs) are well-known electrochemical energy conversion/storage systems that utilize redox reactions to convert or store electricity. Ion exchange membranes (IEMs) are used in DMFCs and RFBs as electrolyte separators. The critical requirements for IEMs in these applications are high ionic conductivity, low electrolyte permeability, high stability, and low cost. Silsesquioxane (SQO)-based sulfonated poly(etheretherketone) composite membranes were synthesized. Morphological changes in the composite membranes resulting from the introduction of SQO were studied using small-angle x-ray scattering. A sharp decrease in proton conductivity with SQO loading (> 20 wt%) was attributed to morphological changes in the membrane, including agglomeration and inhomogeneous dispersion of SQO particles within the ionic domains. Anion exchange membranes (AEMs) based on quaternized cardo-poly(etherketone) (QPEK-C) were prepared and evaluated for all-vanadium RFB (VRFB) applications. The QPEK-C AEMs with different degrees of functionalization (0.9–1.6) exhibited sulfate ion conductivities ranging between 5.6 and 15.2 mS cm-1 at 30 oC. The AEM had a lower VO2+ permeability (2.8×10-8 cm2 s-), compared to that of Nafion® 212 (2.9±0.2 ×10-7 cm2 s-1), which was attributed to the Donnan exclusion effect. The mechanical strength of QPEK-C AEM degraded by 35% after exposure to a 1.5 M VO2+ solution for 1500 hours due to the oxidation of aromatic rings. A single-cell VRFB employing the AEM separator yielded current and energy efficiencies (at 30 mA cm-2) of 97-99% and 80-82 %, respectively. Enhanced sulfate ion conductivity (8.4 ± 0.2 mS cm-1) and decreased VO2+ permeability (0.53×10-9 cm2 s-1) were achieved by incorporating 20 wt% of n-(trimethoxysilylpropyl)-n,n,n-trimethylammonium additives into QPEK-C, (the pristine QPEK-C AEM yielded corresponding values of 4.5 ± 0.5 mS cm-1 and 1.09×10-9 cm2 s-1). About 99% coulombic efficiency was achieved with the VRFBs employing the composite AEM. However, a rapid reduction of the ionic conductivity down to the value of the pristine membrane was observed when the composite AEM was immersed in 1.5 M VO2+ solution for 3 days. Vanadium-cerium RFBs (V-Ce RFBs) evaluated with QPEK-C AEM separators yielded identical energy efficiency (84%) to corresponding RFBs evaluated with Nafion® 212. However, after over 20 charge-discharge cycles, the V-Ce RFB with the AEM separator yielded unchanged efficiency and capacity, while a 50% loss of capacity was observed with the Nafion® separator. This suggested that QPEK-C AEMs are promising candidates for RFB separators when different cations are used in the two electrolyte solutions, in that they act as efficient barriers that preclude the intermixing of the cations due to the Donnan exclusion effect.
Ph.D. in Chemical Engineering, December 2014
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Title: TEMPERATURE PROFILES THROUGH THE SHELL IN EGGS HEATED BY INFRARED ENERGY
Creator: Guo, Jingxin
Date: 2012-07-30, 2012-07
Description: Infrared heating is an effective method for surface pasteurization of shell eggs. As the external temperature reaches the inactivation...
Show moreInfrared heating is an effective method for surface pasteurization of shell eggs. As the external temperature reaches the inactivation temperature, internal temperatures could become great enough to denature albumen. However, the internal temperature of albumen at the shell cannot be measured directly. The purpose of this study is to use experimental data to understand the response of the albumen temperature at the shell to infrared radiation impinging at its outer surface. Fresh eggs were obtained from a local producer and refrigerated until needed. They were prepared for each experiment by overnight equilibration with ambient conditions. Each egg was placed on a metal stage over which an infrared lamp was positioned. The stage allowed a K-type thermocouple to be inserted through a small hole in the shell opposite of the shell area facing the lamp. The thermocouple was pushed into the egg such that the tip was against the inner surface of the shell just underneath the exposed area. The external temperature of this area was measured by an infrared pyrometer. Variables for these experiments were temperature of the IR lamp (277°C, 329°C, 391°C and 452°C), distance between shell egg and IR lamp (3.13 cm – 15.83 cm), and treatment time. All experiments share the same initial lag around 30s, suggested that the initial lag did not vary with changing of lamp-egg distances and lamp temperatures. After the initial lag, internal and external temperatures were found to increase at the same rate regardless of experimental parameters, indicating and equilibrium between the infrared energy impinging on the surface and its dissipation in the interior of the egg. The difference of temperature distributes between 10°C to 20°C. However, lowering lamp temperatures or increasing distances did not change this difference significantly. Moreover, the temperature gap sustains the same temperature after initial lag. The results showed that the internal temperature could be inferred via measuring external temperature. This is valuable in processing to maximize external surface temperature while protecting heat sensitive albumen. Future work will involve modeling the heating phenomenon to determine if knowing only the lamp temperature and distance is sufficient for predicting internal temperature.
M.S. in Food Processing Engineering, July 2012
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Title: SURVIVAL OF SALMONELLA ON CHAMOMILE, PEPPERMINT AND GREEN TEA DURING STORAGE RELATED TO TEMPERATURE AND HUMIDITY
Creator: Chen, Zhengzai
Date: 2013-04-24, 2013-05
Description: Botanical/herbal teas may contain antimicrobial compounds that will affect the survival and persistence of the native as well as contaminant...
Show moreBotanical/herbal teas may contain antimicrobial compounds that will affect the survival and persistence of the native as well as contaminant microflora. Although Salmonella are known for their ability to survive in low water activity environments, their survival on dry botanical/herbal teas has not been examined. The purpose of this work is to determine the survival of Salmonella on three types of teas, chamomile peppermint, and green tea under different storage conditions. In addition, the ability of Salmonella to grow in tea brewed with contaminated product was examined. A cocktail of four Salmonella serovars was inoculated onto 1 g samples of chamomile, peppermint, and green tea to give a starting cell population of approximately 10 log cfu/g. The inoculum was allowed to dry prior to storage at 25 °C and 35 °C and at low (<30% RH) and high (> 90% RH) humidity levels. At different time intervals up to 6 months, triplicate samples at each condition were evaluated for surviving Salmonella populations. In addition, samples were used to produce a low-temperature (sun) brewed tea and inoculated. Growth was assessed after 24 hr. Under the four storage conditions tested, survival followed the order 25°C/low RH > 35°C/low RH > 25°C/high RH > 35°C/high RH. Salmonella losses at 25°C/low RH occurred primarily during drying, after which populations showed little declines over 6 months. In contrast Salmonella decreased below detection after 45 days at 35°C and high RH in all teas tested. All teas tested supported the growth of Salmonella after brewing. Storage conditions significantly impact the survival of Salmonella in dried herbal teas. If Salmonella survives after storage, it may also survive and grow after a home brewing process.
M.S. in Food Safety and Technology, May 2013
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Title: IN VITRO STUDIES OF VIRULENCE SUPPRESSION ON P. AERUGINOSA BY PHOSPHATE / POLYPHOSPHATE-LOADED NANOPARTICLES
Creator: Yin, Yushu
Date: 2015, 2015-07
Description: Critically ill patients harbor multi-drug resistant pathogens that can activate their virulence in the response to low nutrient conditions and...
Show moreCritically ill patients harbor multi-drug resistant pathogens that can activate their virulence in the response to low nutrient conditions and host stress derived factors. It was recently shown that the oversupply of inorganic phosphate to bacterial environment can profoundly suppress the virulence of pathogens. Here we hypothesized that phosphateand/ or polyphosphate-loaded nanoparticles can present a tool to deliver and slowly release phosphate in pathogen-rich niche, thereby suppressing bacterial virulence. In this work, a designed study on effect of different phosphate levels (including the phosphate released from hydrogel nanoparticles) on virulence of P. aeruginosa is addressed. In this work, we developed formulations for preparing hexametaphosphate-loaded nanoparticles on the basis of that for phosphate loaded nanoparticles. We utilized inverse miniemulsion polymerization in the synthesis of these nanoparticles. Polyethylene glycol diacrylate (PEGDA, moleculat weight of 575 Da) and N-vinyl pyrrolidone (molecular weight: 111.14 Da ) were chosen to be the initial monomers because the main crosslinker, polyethylene glycol is a kind of biocompatible material that has been approved by the U.S. Food and Drug Administration (FDA). Several parameter could be adjusted among the experiment. We selected the monomer mole fraction of PEGDA-575 as our parameter. After the synthesis, a nanoparticle size distribution between 110 nm and 150 nm was obtained. And these nanoparticles were proved to be able to release phosphate and hexametaphosphate as drug molecules. Although there were release bursts in the test of release kinetics, the crosslink density could be adjusted in following researches. The second part of this study is to test the virulence suppression effect of the nanoparticles in in vitro experiment on a kind of opportunistic pathogen, P. aeruginosa. This kind of gram-negative bacteria is one of the common intestinal microbial communities. We presented the strategy of suppressing virulence while containing rather than killing the bacteria. As a result, polyphosphate loaded nanoparticles showed to be the most effective one among several experiment groups. This result gave this study a promising future in further research in several aspects, such as in vivo test in biomedical and biomedical engineering.
M.S. in Chemical Engineering, July 2015
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Title: MATHEMATICAL MODELING OF POLY(ETHYLENE GLYCOL) DIACRYLATE HYDROGEL SYNTHESIS VIA VISIBLE LIGHT FREE-RADICAL PHOTOPOLYMERIZATION FOR TISSUE ENGINEERING APPLICATIONS
Creator: Lee, Chu-yi
Date: 2013, 2013-05
Description: Crosslinked hydrogels of poly(ethylene glycol) diacrylate (PEGDA) have been extensively used as scaffolds for applications in tissue...
Show moreCrosslinked hydrogels of poly(ethylene glycol) diacrylate (PEGDA) have been extensively used as scaffolds for applications in tissue engineering. In this thesis, PEGDA hydrogels are synthesized using visible light free-radical photopolymeriza- tion (λ = 514 nm) in the presence of the visible light photosensitive dye, EosinY, the co-initiator, triethanolamine (TEA), a comonomer, N-vinyl pyrrolidone (NVP), a crosslinking agent, PEGDA, and an optional PEG monoacrylate monomer that contains the cell adhesive ligand YRGDS. The incorporation level of the YRGDS lig- and as well as the physical and mechanical properties of these hydrogels dictate cell behavior and tissue regeneration. These hydrogel properties may be tuned through variations in polymerization conditions. The goal of this thesis was to develop a math- ematical model for PEGDA hydrogel formation which predicts the incorporation level of YRGDS and the crosslink density of hydrogel as a variety of polymerization con- ditions. This model provides insight into the process of hydrogel crosslinking and in effectively guiding the experimental design of these scaffolds for tissue engineering applications. To accomplish this task two major components comprised the studies of this thesis. The first component involved an investigation of the visible light photo- initiation mechanism of EosinY and TEA, and the second component involved the develop of a hydrogel synthesis model and its validation. Experiments and modeling were used to determine an expression for the rate of initiation of the EosinY/TEA initiation system and to propose a photoinitiation mechanism. In Chapter 2, exper- imental data and parameter fitting were utilized to obtain an empirical expression for the rate of initiation. However, this empirical expression did not consider the ef- fect of inhomogeneous light distribution which is present in this experimental system. The dynamics of light absorption during polymerization were measured under differ- xiv ent conditions in order to gain insight into the kinetic photoinitiation mechanism as well as the rate of initiation. In Chapter 3, a mechanism for this photo-initiation was proposed. Using this mechanism the light absorption dynamics accounting for inhomogeneous light distribution were simulated which were found to be in an agree- ment with the light absorption measurements shown in Chapter 2. Further validation of this proposed mechanism was achieved from polyNVP conversion measurements. This photo-initiation mechanism was implemented in the hydrogel model. In Chapter 4, the hydrogel synthesis model was developed based on the kinetic approach of the method of moments combined with the Numerical Fractionation technique. The model was used to predict the dynamics of hydrogel properties such as gel fraction, crosslink density, and RGD incorporation under various polymerization conditions. Model predictions were compared with experimental data. Three sets of experiments were conducted. In the first set of experiments where hydrogels were formed in the absence of Acryl-PEG-RGD, the total double bond concentration was kept constant while varying the compositions of NVP and PEGDA. The model and the experiments showed a maximum crosslink density for an acrylate to double bond ratio of 0.5 to 0.6. This is related to the synergistic cross-propagation between NVP and PEGDA, which results in an increase in the rate of polymerization leading to higher crosslink density. In the second set of experiments, hydrogels were formed in the presence of Acryl-PEG-RGD to investigate its incorporation as well as the hydrogel crosslink density. The model showed reasonable agreement with the experimental data and in some cases the predicted RGD deviated from the experimental measurements due to changes in volume upon swelling. The effect of swelling was not considered by the model. The calculated crosslink densities were compared with the inverse swelling ratios from the experiments. The reduction of free volume due to the space occupied xv by the unreacted pendant double bonds was not considered by the model. This reduc- tion of free volume affected the apparent swelling ratio obtained from experiments thus resulting in the observed mismatch between the experimental trends and the predicted crosslink density by the model. In the third set of experiments, additional crosslink density measurements were conducted using a PEGDA macromer of lower molecular weight (MW = 575 Da.). The experiments were performed in the absence of Acryl-PEG-RGD. Few cases were not accurately predicted since the model did not consider the reduction in the concentration of available pendant double bonds when gelation occurs. Among the three set of experiments, the hydrogel synthesis model offers reasonable predictions for most of the experimental cases. This model can be used as a guide for experimen- tally designing PEGDA hydrogels with the desired properties for tissue engineering applications.
PH.D in Chemical and Biological Engineering, May 2013
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Title: DETECTION OF SUPEROXIDE ANION RADICALS IN ANION EXCHANGE MEMBRANE FUEL CELLS USING IN-SITU FLUORESCENCE SPECTROSCOPY
Creator: Zhang, Yunzhu
Date: 2016, 2016-07
Description: Anion exchange membrane (AEM) stability is a long-standing challenge that has limited the widespread development and adoption of AEM fuel...
Show moreAnion exchange membrane (AEM) stability is a long-standing challenge that has limited the widespread development and adoption of AEM fuel cells. It is essential to understand the mechanism of AEM degradation during fuel cell operation. There are multiple modes of AEM degradation, broadly classified as chemical, mechanical and thermal degradation. Chemical degradation is among the most destructive modes, and can be further sub-divided into nucleophilic degradation (induced by the hydroxide ion), and oxidative degradation (induced by reactive oxygen species). While the former has been extensively studied, there is minimal work on oxidative AEM degradation. The reactive oxygen chemical species produced during the operation of an AEM fuel cell have hitherto not been detected during operation. Given the high pH, it is postulated that superoxide anion radicals (𝑂2∙−), as opposed to hydroxyl radicals, are primarily involved in the degradation progress. The objective of this study was to confirm the 𝑂2∙− formation during AEM fuel cell operation and to monitor in real-time the rate of 𝑂2∙− generation in an operating fuel cell using in-situ fluorescence spectroscopy. 1,3-diphenlisobenzofuran (DPBF) was chosen as the fluorescence probe, the sensitivity of which towards 𝑂2∙− was evaluated by performing ex-situ experiments in a semi-batch reactor. We demonstrate that the fluorescence intensity of this dye selectively decreased upon exposing 𝑂2∙−. DPBF was then incorporated into an AEM (membrane was solution cast after mixing the dye with the casting solution), which was assembled into a fuel cell. 𝑂2∙− generation in an operating AEM fuel cell was then monitored via in-situ fluorescence spectroscopy using a bifurcated optical probe, when the cell was operated in H2/O2 mode. To confirm the impact of 𝑂2∙− on AEM degradation, independent experiments (without dye) were performed under identical conditions, under both H2/O2 and N2/N2 modes, and the ionic conductivity and ion exchange capacity were monitored to estimate degradation extent. From our in-situ fluorescence studies, we were able to estimate the rate constants and activation energy for oxidative AEM degradation in an operating AEM fuel cell.
M.S. in Chemical Engineering, July 2016
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Title: CORROSION-RESISTANT ELECTRO-CATALYSTS AND SUPPORTS FOR ELECTROCHEMICAL ENERGY CONVERSION
Creator: Wang, Guanxiong
Date: 2016, 2016-12
Description: Polymer electrolyte fuel cells (PEFCs) convert chemical energy of fuels (eg. Hydrogen) directly to electrical energy with excellent power...
Show morePolymer electrolyte fuel cells (PEFCs) convert chemical energy of fuels (eg. Hydrogen) directly to electrical energy with excellent power density, high efficiency, and zero emissions. Several challenges have delayed the commercialization of fuel cells with one being the high cost and durability of the carbon-supported-platinum-based (Pt/C) electrocatalysts. The lifetime/durability issue is critical as insufficient durability/reliability of the catalysts affects the lifetime and economical viability of these devices. Carbon support corrosion is a major durability issue since the corrosion reaction is thermodynamically favorable but kinetically sluggish under normal operating conditions. The potential transients that occur during start and stop in automotive applications can lead to electrode potential excursions of up to 1.5 V and contribute to carbon corrosion. The best way to mitigate support corrosion in PEFCs is to replace the carbon supports with alternatives having high electronic conductivity, surface area and porosity. This dissertation investigates the following carbon alternatives: (i) tin doped indium oxide (ITO) and (ii) 1:1 mixed oxides of ruthenia and silica (RSO). Microstructure characterization and electrochemical evaluations, including accelerated stress tests (start-up/shut-down and load cycling protocols) were performed to evaluate ORR activity, fuel cell performance, and electrochemical stability under PEFC operating conditions. The ITO support and 40%Pt/ITO catalysts demonstrated exceptional electrochemical stability (and reasonable ORR activity) in rotating disk electrode (RDE) experiments under accelerated potential cycling that mimicked automotive drive cycles. However, Pt/ITO exhibited poor performance and stability during MEA evaluation in a PEFC. X-ray photoelectron spectroscopy (XPS) was employed to reveal the degradation modes of Pt/ITO during PEFC operation and it was found that the increase in the surface hydroxide concentration generates a passivating In(OH)3 layer that increases electrode resistance and undermines PEFC performance. The influence of the catalyst support on PEM degradation during PEFC operation was also studied. Rotating ring-disk electrode (RRDE) experiments were employed to estimate the fraction of H2O2 generated during the ORR on the supports (C and RSO) and catalysts (benchmark Pt/C and Pt/RSO). The percentage of H2O2 generated on C and Pt/C was 50% higher than that on RSO and Pt/RSO thus explaining the observed oxidative degradation resistance of the PEM with the latter supports/catalysts.
Ph.D. in Chemical Engineering, December 2016
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Title: OIL RECOVERY IN SINGLE CAPILLARIES AND POROUS MEDIA USING WETTING NANOFLUIDS
Creator: Zhang, Hua
Date: 2016, 2016-05
Description: Recent experiments and modeling conducted in our laboratory have demonstrated that the spreading of nanofluids, liquid suspensions of...
Show moreRecent experiments and modeling conducted in our laboratory have demonstrated that the spreading of nanofluids, liquid suspensions of nanosized particles, on solids are enhanced due to self-structuring of nanoparticles in the confined three-phase oil-nanofluid-solid contact region. Nanofluids have recently been proposed as agents for enhanced oil recovery (EOR). Despite recently widely conducted research using nanofluids for EOR, the underlying operating mechanism is not well understood. In this thesis, we attempt to understand the mechanism of nanofluid based EOR and evaluate its performance from reservoir core samples and model systems (glass capillary and sintered bead-pack). To visualize how oil displacement in the rock pores by nanofluid, we conducted model study using hexadecane and single glass capillary and showed the oil film dynamics in air and nanofluid after oil was displaced in the capillary. Based on the understanding of the role of nanofluid on oil displacement in capillaries, we conducted imbibition tests using Berea sandstones and flooding experiments in sintered glass-beads. X-ray microtomography was used to visualize and analyze fluid distribution and to see the effect of nanofluid in EOR. We finally considered fractured media by fabricating such structures. The dynamics of a cylindrical hexadecane layer deposited inside glass capillaries after the oil/air displacement was studied experimentally and by modeling. The oil layer subject to surface perturbation becomes unstable forming uniform, regularly-spaced double concave menisci across the capillary that are bridged with dimples (collars). In order to reveal the phenomena of the film thinning and stability between the double concave meniscus and the dimple, we monitored an air bubble approaching a flat glass surface in hexadecane. We found that the oil film thinning in a cylindrical glass capillary and on a flat glass substrate were similar; We adapted the model proposed by Gauglitz and Radke for our system (oil-air displacement) and solved it numerically. The numerical result shows a stable film between the liquid bridge and the dimple, which is consistent with our experimental observations. We also estimated the meniscus-film-dimple thickness profile and found it was in fair agreement with the model prediction. The dynamics of cylindrical hexadecane film after displacement by a nanofluid in a glass capillary was studied. We found the thick hexadecane film is unstable, and over time it breaks and forms a thin film. Once the thick film ruptures, it retracts and forms an annular rim (liquid ridge) that collects liquid. As the volume of the annular rim increases over time, it forms a double concave meniscus across the capillary and dewetting stops. The thin film on the right side of the double concave meniscus then breaks and the contact angle increases. The process repeats until droplets build along the capillary wall. Finally, the droplets are displaced from the capillary wall by the nanofluid and spherical droplets appear inside the capillary. This is a novel phenomenon not observed during dewetting by a solution without nanoparticles. The theoretical model based on the lubrication approximation using the capillary pressure gradient was developed to estimate the annular rim dewetting velocity. The predicted dewetting velocity is found to be in fair agreement with the experimental value. We conducted imbibition tests using a reservoir crude oil and a reservoir brine solution with a high salinity and a suitable nanofluid that displaces crude oil from Berea sandstone and single glass capillaries. We present visual evidence of the underlying mechanism based on the structural disjoining pressure for the crude oil displacement using a polymeric nanofluid (our definition of such a fluid means a suspension of polymeric particles in an aqueous substrate) in high salinity brine. The polymeric nanofluid is specially formulated to survive in a high salinity environment and is found to result in an increased efficiency of 50% for Berea sandstone compared to 17% using the brine alone at a reservoir temperature of 55 oC. These results aid our understanding of the role of the nanofluid in displacing crude oil from the rock especially in a high salinity environment containing Ca++ and Mg++ ions. Results are also reported using Berea sandstone and a nanofluid containing silica nanoparticles. We conducted a series of flooding experiments at different capillary numbers to quantify the performance of a polymeric nanofluid compared to brine using the sintered glass-beads. A high resolution X-ray microtomography (microCT) was used to visualize oil and brine distribution in a sintered bead-pack before and after nanofluid flooding. The results of flooding experiments showed that an additional oil recovery of approximately 15% is possible with nanofluids compared to brine at low capillary numbers, and is as effective as high capillary number brine flooding. Nanofluid induced additional oil recovery decreases as we increase the capillary number and the total oil recovered shows a marginal decrease. At first glance, these results are opposite of what one expects in the conventional EOR, where oil recovery is known to increase progressively with increasing capillary number. These results cannot be explained based on mobilization theories due to the reduced capillarity. Our results however are consistent with the mechanism of wettability alteration caused by structural disjoining pressure leading to the formation of the wetting nanofluid film between oil and substrate.We presented experimental studies of nanofluid flooding in fractured porous media formed with sintered glass-beads. The nanofluid injection is conducted at a rate where structural disjoining pressure driven recovery is operational. We found an additional 23.8% oil can be displaced using nanofluid after brine injection with an overall displacement efficiency of 90.4% provided the matrix was in its native wettability state. In summary, nanofluids are excellent EOR agents and their economic viability needs to be examined.
Ph.D. in Chemical Engineering, May 2016
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Title: ECONOMIC BASED CONTROL SYSTEM DESIGN
Creator: Omell, Benjamin Peter
Date: 2013, 2013-12
Description: EMPC differs from traditional MPC by directly utilizing a profit based function as the objective as opposed to a quadratic function that...
Show moreEMPC differs from traditional MPC by directly utilizing a profit based function as the objective as opposed to a quadratic function that minimizes the distance from a set point that is predetermined. However, implementation of EMPC can result in unexpected and at times pathological closed-loop behavior, including inventory creep, bang-bang actuation and instability. To address these issues, an infinite-horizon version of EMPC is developed and shown to avoid many of the performance issues observed in the finite-horizon version. First, modifications to the EMPC problem will be used for the conceptual development of the Economic Linear Optimal Controller (ELOC), which is a statistically constrained linear feedback controller. Then, pointwise- in-time constraints can be reintroduced using one of two methods; Constrained ELOC or Infinite-Horizon EMPC (IH-EMPC). We also investigate the impact of problem formulation modifications on the ELOC. The first issue is that of disturbance modeling and the second is the impact of controller sample-time. The third topic concerns incorporation of computational delay in the feedback-loop, using both full and partial state information structures. Finally an illustration of the impact of plant-model mismatch is presented. The Constrained ELOC formulation is further modified to allow for market responsive smart grid applications. In particular an Integrated Gasification Combined Cycle (IGCC) process with hydrogen storage will be used to demonstrate the Constrained ELOC for such applications. The ELOC will be used as a vehicle to exploit dispatch capabilities by pursuing directly the objective of maximizing revenue. The idea being that process modifications to enable dispatch capabilities will allow for a time-shift of power production away from periods of low energy value to periods of high value. An in depth discussion is provided on how energy value forecasts are incorporated into the design of the constrained ELOC. Finally, an extension of the ix ELOC to the controller embedded equipment design is provided. The work concludes with a discussion of the computational aspects of solving the ELOC problem. In particular, the impact of reverse-convex constraints inherent to the ELOC problem are discussed along with existing solution methods. The main contribution of this final chapter is a novel application of the Generalized Bender’s Decomposition (GBD) algorithm to the ELOC problem. This new approach is shown to retain global optimality, reduce computational effort (by orders of magnitude) and expand the class of problems one can solve.
PH.D in Chemical Engineering, December 2013
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Title: SUSTAINABLE NEW CITY MENTOUGOU, CHINA
Creator: Yin, Lu
Date: 2013-04-30, 2013-05
Description: This thesis will demonstrate one of the first urban models for the future of China’s growth. The Urban Operating System and GPS make the smart...
Show moreThis thesis will demonstrate one of the first urban models for the future of China’s growth. The Urban Operating System and GPS make the smart city smarter by linking up networks of billions of distributed sensors, systems, and intelligence across urban environments via city-scale operating systems. Personal Rapid Transit system runs everywhere and it is accessed and ordered by smart phone. Green belt is the medium that links all the natural area and parks in the city which become the core element in the city because it plays the most important role. Two types of transportation system including the Meglev for 10 minute access to Beijing and the PRT system for all internal urban mobility. The population of the new city is 80000. 80% of the people live here and work here, 20% of the people live here but work in Beijing. 30% of the people will use PRT system everyday. All the city blocks are mixed-use blocks. There are several types of residential buildings including mid-rise, high-rise and Beijing traditional courtyard house. This sustainable new city provides quality of lift to all the people live in the city.
M.S. in Architecture, May 2013
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Title: STRUCTURAL CHARACTERIZATION OF THE FLIGHT MUSCLE OF MANDUCA SEXTA
Creator: Cheng, Yu-shu
Date: 2013-04-22, 2013-05
Description: There are several properties of the flight muscle Manduca sexta that are interesting. In its physiological characteristics, like mammalian...
Show moreThere are several properties of the flight muscle Manduca sexta that are interesting. In its physiological characteristics, like mammalian skeletal and cardiac striated muscle, it is a synchronous muscle. However, it is much more similar structurally to the more widely known asynchronous insect flight muscles of Drosophila and Lethocerus. The goal of the thesis is to study the structural characteristics and perform mechanical studies of dorsal and ventral muscle of Manduca flight muscle. In pursuit of this goal, a secondary purpose was to develop better storage conditions for skinned insect muscle which can maintain muscle structure and function. Maximum active force as a function of time in storage was compared for storing at 4℃ without glycerol and storing at -80℃ with 75% glycerol. The maximum force values were almost the same during days 0-4. However, the muscle stored at -80℃ with 75% glycerol gave higher active force in high calcium (pCa 4.5) solution over a longer time in storage than muscle stored at 4℃. Both ventral and dorsal muscles can deliver 40-50% of original active force for up to 21 days in storage. X-ray diffraction experiments were done to compare the response of chemically skinned Manduca flight muscle to temperature and to the induction of rigor. The lattice spacing (d10) decreased and intensity ratio I20/I10 increased when the temperature of the relaxing solution bathing the solution increased from 10℃ to 40℃. Lattice spacing (d10) decreased, but the I20/I10 intensity ratio increased slightly while concentration of dextran increased from 1% to 6%. Six percent dextran was insufficient to restore the in vivo lattice spacing.
M.S. in Molecular Biochemistry and Biophysics, May 2013
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Title: INVESTIGATION OF ANION EXCHANGE MEMBRANES FOR ELECTROCHEMICAL ENERGY CONVERSION AND STORAGE SYSTEMS
Creator: Wang, Lihui
Date: 2017, 2017-05
Description: The alkaline stability of poly (arylene ether) backbones in anion exchange membranes (AEMs) derivatized with quaternary benzyl N, N-...
Show moreThe alkaline stability of poly (arylene ether) backbones in anion exchange membranes (AEMs) derivatized with quaternary benzyl N, N- dimethylhexylammmonium (DMH+) and trimethylammonium (TMA+) cation groups were investigated in poly (2,6- dimethyl 1,4-phenylene) oxide (PPO) and Udel® polysulfone (PSF) polymers. Previous studies have demonstrated that quaternary ammonium and phosphonium groups trigger backbone degradation in commercially available poly (arylene ether)-based AEMs, despite the base polymers’ resilience to alkaline solutions. Herein, I demonstrate that the electron withdrawing or donating character in the poly (arylene ether) backbone ultimately dictates whether the prepared AEMs will become brittle in alkaline media due to cation-triggered backbone degradation (Arges, Parrondo, Johnson, Nadhan, & Ramani, 2012a; Christopher G. Arges, Lihui Wang, Javier Parrondo, & Vijay Ramani, 2013). Mitigation of cation-triggered backbone degradation was only achieved when electron withdrawing substituents (not including the cation), such as sulfone or bromine, were eliminated from the polymer backbone (or, alternately, when electron donating groups were present). Hence, PPO AEMs prepared through chloromethylation, rather than free radical bromination, were resistant to backbone hydrolysis in alkaline media because each cation-functionalized repeat unit had two electron-donating methyl groups rather than a single methyl group. This study presents some design rules for preparing mechanically stable poly (arylene ether) AEMs from low cost, commercially available polymers for alkaline electrochemical devices.
Ph.D. in Chemical Engineering, May 2017
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Title: MODELING OF A DCFC ANODE IN CONNECTION WITH THE EXPERIMENTAL RESEARCH ON THE WETTING BEHAVIOR OF A GRAPHIC ROD IN MOLTEN CARBONATE
Creator: Li, Yue
Date: 2013, 2013-12
Description: Not available
M.S. in Civil Engineering, July 2013

Title: TOWARDS THE EXACT CALCULATIONS OF THE FREE ENERGY FOR ENTANGLED SEMIFLEXIBLE POLYMER CHAIN
Creator: Pilyugina, Ekaterina
Date: 2015, 2015-05
Description: This work consists of two separate projects unified by the idea to extend the Discrete Slip-Link Model, which has been being successfully...
Show moreThis work consists of two separate projects unified by the idea to extend the Discrete Slip-Link Model, which has been being successfully developed in this group to predict rheological behavior of entangled flexible polymers, to new applications. The first project was dedicated to application of the Discrete Slip-Link Model to dielectric relaxation in order to simultaneously predict linear rheology and dielectric relaxation experiments of entangled polyisoprenes. Linear monodisperse, linear bidisperse and star-branched monodisperse systems were studied. It was found that all circumstances save one are well described. Namely, dilute long chains in a sea of short chains can be predicted rheologically, but dielectric relaxation data show a reduction in the relaxation time of long chains greater than that predicted by either the DSM or the expected Rouse motion. The second project was focused on the derivation of the exact free energy expression for semiflexible chains in the presence of entanglements in order to implement the DSM for semiflexible polymers. The special cases of chains with one, two and three strands are examined. An additional implementation of obtained results for one and two strands to buckling instability was performed. It is believed that in two dimensional case the critical buckling force is increased by thermal fluctuations in comparison to classical Euler buckling. However, how the critical buckling force is influenced by thermal fluctuations in three dimensions remains unclear. Some research groups calculate the critical buckling force approximately and conclude that, in opposite to 2D case, in 3D the force is decreased by thermal fluctuations. In this work the critical buckling force for semiflexible chain under compression was calculated exactly. It was shown that thermal fluctuations significantly increase the critical force over classical Euler buckling force in both two and three dimensions.
Ph.D. in Chemical Engineering, May 2015
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Title: CO2 CAPTURE AND HYDROGEN PRODUCTION IN SORBENT ENHANCED WATER-GAS SHIFT (SEWGS) PROCESS WITH REGENERABLE SOLID SORBENT
Creator: Zarghami Khanehsar, Shahin
Date: 2015, 2015-07
Description: Carbon dioxide emission from fossil fuel combustion and its impact on global warming is one of the most critical environmental issues nowadays...
Show moreCarbon dioxide emission from fossil fuel combustion and its impact on global warming is one of the most critical environmental issues nowadays. Coal as a main source of produce energy is the most CO2-intensive fossil fuel. Advanced power generation processes that use gasification technology, such as Integrated Gasification Combined Cycle (IGCC), which offer higher efficiency, are among the leading contenders for power generation in the 21st century. In an IGCC process, because of high pressure, carbon dioxide in the fuel gas is at higher concentration, which can be captured and sequestered at lower costs. Utilization of regenerable MgO-based sorbents has been shown to be an effective method for capturing CO2 from gasification-based processes at elevated temperatures and pressures (i.e. p > 20 atm and 330° < T < 450°C). Low cost MgO based sorbent can be prepared through modification of natural dolomite. The reactivity of the sorbent in carbonation/regeneration cycles has a significant impact on the economics of the proposed regenerable process. Although the sorbent can be regenerated in successive cycles, the sorbent reactivity and capacity gradually decline during the cyclic process. Therefore, it is crucial to develop a better understanding on the role of the key parameters affecting the reactivity of the sorbent going through the cyclic carbonation/regeneration process. In this work, a systematic study on the sorbent preparation parameters (i.e., calcination temperature, calcination duration, calcination temperature ramp, potassium concentration, impregnation duration, drying temperature, re-calcination temperature, and re-calcination duration) was conducted to understand the effect of each parameter on the overall capacity and reactivity of the sorbent. The concentration of potassium additive (as carbonation reaction promoter) has the most significant effect on the reactivity of the sorbent and the optimum K/Mg molar ratio appears to be in the range of 0.1-0.16. The reactivity of the sorbent toward carbon dioxide at various operating conditions (i.e. temperature, CO2 concentration and steam concentration) was experimentally evaluated. The presence of steam significantly improves the reactivity of the sorbent which is attributed to formation of more favorable pore structure as well as the existence of a parallel carbonation reaction pathway involving the formation of a transient MgO.H2O* compound. The optimum carbonation reaction temperature in the presence of steam is around 380˚C. The effect of cycling on CO2 capture capacity of MgO-based sorbent was also experimentally investigated in this work. Series of carbonation/regeneration cycles (up to 25) have been carried out in a dispersed bed reactor to determine the effect of various variables on long term durability of the sorbent. The gradual loss of CO2 sorption capacity appears to be mainly due to loss potassium (a carbonation reaction promoter) in the cyclic process. Durability of the sorbents improves in the presence of steam, which is likely due to the favorable changes in the pore structure of the sorbents. A kinetic model was developed to fit the reactivity curves obtained from the dispersed bed tests at different operating conditions which was needed to predict the sorbent/catalyst performance in the regenerative process. Model parameters were defined and discussed for each of the operating conditions, as well as dispersed bed cyclic tests. Furthermore, the thermal behavior and the kinetics of partial decomposition of dolomite were studied in a dispersed-bed reactor to improve the reactivity of the sorbent. The microstructure and the nature of the solid products were found to be strongly dependent on the CO2 partial pressure near the reacting interface and on the decomposition temperature. A significant increase in the rate of the dolomite decomposition reaction was found in the presence of steam. Steam improves the kinetics of decomposition, modifies the radial distribution of the pores; and improves the connectivity of the pores inside the dolomite particles, which decreases the diffusion resistance of produced carbon dioxide inside the particle. A shrinking core model with variable product layer diffusivity was used to fit the experimental data and determine the kinetic parameters of the dolomite decomposition reaction. The results indicate that transport of CO2 across the reacting interface in the porous particle was the main limiting factor in the decomposition reaction at the experimental conditions investigated. A lab-scaled high-pressure/high-temperature packed-bed reactor was utilized to evaluate the performance of the sorbent in simultaneous water-gas shift reaction and sorbent carbonation environment. It was shown that the CO2 in the coal gas can be removed by regenerable MgO-based sorbents at temperatures around 350°C, and the CO2 removal can shift WGS reaction to enhance hydrogen production. Therefore, Sorbent Enhanced Water-Gas-Shift (SEWGS) can result in much higher hydrogen production without lowering the temperature, leading to higher overall process efficiency.
Ph.D. in Chemical Engineering, July 2015
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Title: INVESTIGATION OF THE EFFICACY OF REACTIVE OXYGEN SPECIES GENERATED BY BOVINE AORTIC ENDOTHELIAL CELLS FOR INITIATING FREE-RADICAL POLYMERIZATION
Creator: Lu, Chenlin
Date: 2013, 2013-12
Description: Reactive oxygen species are reported to be generated by bovine aortic endothelial cells during ischemia followed by reperfusion. This...
Show moreReactive oxygen species are reported to be generated by bovine aortic endothelial cells during ischemia followed by reperfusion. This biological response, believed to be the cause of post-ischemic reperfusion injury, inspired us to investigate the possibility of coupling it with the initiation of free-radical polymerization to produce polymer hydrogels for cell encapsulation. In this work, the generation of reactive oxygen species during ischemia and reperfusion was examined by fluorescence detection and the feasibility of initiating free-radical polymerization by generated reactive oxygen species was investigated in two sets of experiments. The generation of reactive oxygen species by bovine aortic endothelial cells when subjected to anoxia followed by reoxygenation was investigated in both attached and suspended cells. Both intracellular and extracellular generations of ROS appeared to occur in the experiments of attached cells. Cell viability experiments demonstrated that the generation of ROS was sufficient to cause cell damage and death. The feasibility of initiating free-radical polymerization by reactive oxygen species generated by bovine aortic endothelial cells subjected to anoxia followed by reoxygenation was investigated in two sets of experiments. One set involved the linear polymerization of NVP which allowed us to quantify the extent of polymerization and characterization of the weight conversion of PVP polymer. The other set involved the formation of PEGDA hydrogels which were characterized by imaging and staining methods. To our knowledge this is the first evidence of cell induced polymerization initiated by reactive oxygen species and gelation which can be used for a variety of biomedical applications.
M.S. in Chemical and Biological Engineering, December 2013
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Title: EVALUATION OF COXIELLA BURNETII NINE MILE PHASE II INACTIVATION IN WHOLE MILK AFTER THERMAL TREATMENT BY INTEGRATED CELL CULTURE-PCR ASSAY
Creator: Ma, Songchuan
Date: 2013-04-30, 2013-05
Description: Coxiella burnetii, the etiologic agent of Q fever, is a Gram-negative, obligate intracellular coccobacillus, which has been used as the...
Show moreCoxiella burnetii, the etiologic agent of Q fever, is a Gram-negative, obligate intracellular coccobacillus, which has been used as the reference organism for defining milk pasteurization conditions. A developed Integrated Cell Culture-PCR (ICC-PCR) assay may be helpful for evaluating C. burnetii inactivation by thermal process in whole milk products. The purpose of this research was to characterize and optimize an ICCPCR assay in whole milk and evaluate this assay by thermal process. Coxiella burnetii was diluted into whole milk from FDA stock and treated by thermal process. Samples were sealed in glass vials and placed in ice-water to obtain a consistent starting temperature. Cooled vials were heated in a shaking waterbath at 60 °C, 62 °C and 64 °C in for various times. Thermally treated samples were diluted by RPMI+1% FBS and inoculated on Vero cell culture monolayers with PBS, incubated for 48 hours to infect the Vero cells, and then incubated for another 9 days to allow propagation. The propagated C. burnetii mix was subjected to freeze-thaw followed by DNA extraction with Autogen DNA Tissue Kit by using Quickgene Mini80. Extracted DNA was amplified by using TaqMan-MGB based qPCR targeting published primers for the IS1111a transposase gene to verify C. burnetii growth. For detection limit determination, serial dilutions of C. burnetii were mixed independently in whole milk and 1% FBS+RPMI. The mix was overlaid on confluent Vero cells for 2 days and 11 days. The DNA extractions were followed using DNA tissue kit by Quickgene Mini80 and PCR. At least duplicate trials using 3 replicates per trial were completed for each time/temperature condition.
M.S. in Food Safety and Technology, May 2013
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Title: MODEL-BASED EXPLORATION OF THE FEASIBILITY OF CREATING MULTIPLE PROPERTY GRADIENT IN CROSSLINKED POLYMER FILMS IN CONTROLLED LIVING POLYMERIZATION
Creator: Qin, Zikai
Date: 2014, 2014-05
Description: The functional gradient materials have been widely used in chemical engineering, biomedical engineering and tissue engineering since they have...
Show moreThe functional gradient materials have been widely used in chemical engineering, biomedical engineering and tissue engineering since they have been reported because of their admirable mechanical, physical and chemical properties. Several traditional methods of synthesis gradient materials are known to all. Here we introduced a new mathematical model of designing and producing crosslinked polymeric films with target multiple gradients. We derive our model from batch reactor system and explore how each condition of the system affects the gradient of the polymer film. Then we extend to semi-batch reactor to control the gradient in crosslink density and set up different strategies to make the target multiple gradient crosslink density accomplish. With any given target gradient crosslinked polymer film, we can make an exact similar film in our model.
M.S. in Chemical Engineering, May 2014
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Title: PEGYLATION OF FIBRONECTIN AND ITS FUNCTIONAL DOMAINS: EFFECT ON STABILITY AND BIOLOGICAL ACTIVITY
Creator: Zhang, Chen
Date: 2013, 2013-07
Description: Delayed wound healing in many chronic wounds has been linked to the lack of extracellular matrix (ECM) support and the degradation of...
Show moreDelayed wound healing in many chronic wounds has been linked to the lack of extracellular matrix (ECM) support and the degradation of fibronectin (FN) by an abnormally high protease level. The ECM is important in wound healing because it provides physical and chemical cues that direct tissue growth and development. FN is a key ECM protein that attracts and binds different molecules and cells and thereby supports biological responses associated with wound healing. The goal of my study is two fold: (1) To create an ECM analogue based on a composite of polyethylene glycol (PEG) hydrogels and FN binding domains and (2) To stabilize FN against proteolytic degradation by conjugating it to PEG. To address the first goal, I used Michael addition chemistry to covalently link the cell-binding domain of FN, III9−10, to PEG diacrylate and cross-linked the conjugate to PEG hydrogels. The conjugation of PEG to III9−10 was through cysteines in the affinity tag Glutathione S Transferase (GST). The conjugate of GST-III9−10 and PEG was characterized by: (i) Circular dichroism studies to determine secondary structure, (ii) Sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE) to determine molecular weight, and (iii) Ellmans reagent to determine the efficiency of PEG conjugation to GST-III9−10. The conjugate of PEG and GST-III9−10 had comparable secondary structure to GST-III9−10. SDS-PAGE studies showed that up to three PEG molecules were attached to one GST-III9−10 molecule. The efficiency of PEG conjugation was greater than 90% and occurred within 30 minutes after PEG diacrylate addition. Adhesion assays were used as a metric of biological activity. These assays demonstrated that on a molar basis cell adhesion and spreading were significantly higher on PEG hydrogels with GST-III9−10 than those with the commonly used arginine-glycine-aspartic acid (RGD) peptide. Scaffold rigidity is an important biological cues that influence xi cell responses. However, a comparative study of rigidity on GST-III9−10 and RGD functionalized PEG hydrogels demonstrated that differences in rigidity could not account for differences in cell adhesion and spreading between RGD and GST-III9−10 functionalized PEG hydrogels. Thus as ECM analogues, GST-III9−10 functionalized hydrogels provide more robust biochemical cues than RGD functionalized hydrogels. Studies of PEG hydrogel composites with mixtures of III9−10 and a fibronectin binding domain demonstrated that biological responses of adhesion and spreading and extracellular matrix assembly could be controlled by varying the ratio of these two domains and the rigidity of the PEG hydrogels. FN was stabilized against proteolytic degradation by covalent attaching it to PEG or by PEGylating it. FN was first isolated from human plasma by gelatin affinity chromatography and then PEGylated using two methods. The first method is to PEGylate human plasma fibronectin (HPFN) at cysteine residues with 3.4 kDa PEG diacrylate. The second method is to PEGylate HPFN at lysine residues on the surface with 2-10 kDa PEG Succinimidyl carboxy methyl esters. Cysteine PEGylation of HPFN was first carried out because cysteines are concentrated in the amino- terminus of HPFN which leaves two-thirds of the molecule, including the cell-binding domain, unperturbed. PEGylation of HPFN on cysteines resulted in a molecule that supported cell adhesion, spreading, focal adhesion formation and cell migration in a comparable manner to native HPFN. Moreover, PEGylated HPFN was incorporated into the ECM in a similar manner to native HPFN when present in the culture media but not when coated on a surface indicating that PEGylation on cysteines modified some biological activity of HPFN. Additionally, HPFN PEGylated by this manner could not bind denatured collagen or gelatin. The gelatin-binding domain is at the site of cysteine PEGylation. The second approach for PEGylation of HPFN was through lysine residues xii on the surface of the protein. This approach was used because it targeted different amino acid residues in FN. The length of PEG and extent of PEGylation have been reported to influence biological activity of proteins. In the second approach, both PEG length and extent were varied. HPFN completely PEGylated on lysines residues was significantly more proteolytically stable than native HPFN but had reduced cell attachment and spreading. Furthermore, cell spreading and attachment on surfaces conjugated with this lysine PEGylated HPFN decreased with increasing PEG length. Partially PEGylated HPFN was synthesized by masking the cell and gelatin binding domains during PEGylation. The partially PEGylated HPFN supported cell adhesion and spreading in a similar manner to native HPFN and was more proteolytically stable. For the partially PEGylated HPFN, the size of PEG poly had no significant influence on the attachment and spreading of cells. These studies are the first attempt by any laboratory to stabilize FN against proteolytic degradation while retaining activity and show the feasibility of this approach as a potential therapeutic approach. The work presented here shows a two-prong approach by which the problem of ECM degradation and deficiency chronic wound healing can be addressed. The first approach for addressing ECM deficiency is through a scaffold design methodology. The novelty of the scaffold approach is that it uses the cell-binding domains of FN instead of the often-used RGD peptide. I demonstrate that a PEG hydrogel with the cell-binding domain produces a more robust biological response in cells than a PEG hydrogel with the RGD peptide. I also demonstrate that varying different functional domains of fibronectin can be used to controllably stimulate multiple biological responses. The second approach demonstrates a method by which FN, a key ECM protein, is stabilized against proteolytic degradation without perturbing its activity. These studies of creating PEG-FN conjugates are the first of their kind. Collectively, the data that I present in this thesis will lead to novel therapeutic methods for treating chronic wounds.
PH.D in Chemical Engineering, December 2012
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