Chemical Engineering Commons^™

Porous Nanocomposites With Integrated Internal Domains: Application To Separation Membranes, Wenle Li, John Y. Walz

Chemical and Materials Engineering Faculty Publications

Asymmetric membranes with layered structure have made significant achievements due to their balanced properties and multi-functionalities that come from a combination of multiple layers. However, issues such as delamination and substructure resistance are generated by the intrinsic layered structure. Here, we present a strategy to integrate the traditional layered structure into an asymmetric but continuous porous network. Through infiltrations of microparticles and nanoparticles to targeted regions, active domains are created inside the porous scaffold versus having them applied externally. The fabricated internal active domains are highly adjustable in terms of its dimensions, pore size, and materials. We demonstrate that it …

Influence Of Reduction Promoters On Stability Of Cobalt/Γ-Alumina Fischer-Tropsch Synthesis Catalysts, Gary Jacobs, Wenping Ma, Burtron H. Davis

Center for Applied Energy Research Faculty and Staff Publications

This focused review article underscores how metal reduction promoters can impact deactivation phenomena associated with cobalt Fischer-Tropsch synthesis catalysts. Promoters can exacerbate sintering if the additional cobalt metal clusters, formed as a result of the promoting effect, are in close proximity at the nanoscale to other cobalt particles on the surface. Recent efforts have shown that when promoters are used to facilitate the reduction of small crystallites with the aim of increasing surface Co⁰ site densities (e.g., in research catalysts), ultra-small crystallites (e.g., < 2–4.4 nm) formed are more susceptible to oxidation at high conversion relative to larger ones. The choice of promoter is important, as certain metals (e.g., Au) that promote cobalt oxide reduction can separate from cobalt during oxidation-reduction (regeneration) cycles. Finally, some elements have been identified to promote reduction but either poison the surface of Co⁰ (e.g., Cu), or produce excessive light gas selectivity (e.g., Cu and Pd, or Au at …

Compounds And Methods For Reducing Oxidative Stress, Thomas Dziubla, J. Zach Hilt, Dipti Biswal, David B. Cochran, Paritosh Wattamwar

Chemical and Materials Engineering Faculty Patents

Antioxidant polymeric compounds are provided that comprise a plurality of monomeric portions, where each monomeric portion includes an antioxidant molecule interposed between at least two acrylate molecules, and where at least one acrylate molecule of each monomeric portion is linked by a diamine molecule to an acrylate molecule of an adjacent monomeric portion to thereby form the polymer. Methods of synthesizing polymeric compounds and methods of using the antioxidant polymeric compounds to reduce oxidative stress are also provided.

Mixed Surfactant Systems: Thermodynamics And Applications In Metal Oxide Imprinting, Suvid Joshi

Theses and Dissertations--Chemical and Materials Engineering

In this work we study mixtures of cationic surfactant (CTAB) and sugar based surfactant(s) (octyl beta-D-glucopyranoside (C8G1), dodecyl maltoside (C12G2) and octyl beta-D-xylopyranoside (C8X1)) to understand the non-ideal thermodynamic behavior of the mixtures of cationic and non-ionic surfactants in water and synthesis of imprinted materials. The thermodynamics of micellization, mixing and dilution of these systems are studied using Isothermal Titration Calorimetry (ITC) and the experimental data obtained are modeled with a pseudo-phase separation model with non-ideal mixing described by regular solution theory. It is shown that a model accounting for enthalpy of demicellization and enthalpy of dilution based on McMillan-Mayer …

Effects Of Sodium Hydroxide Pretreatment On Structural Components Of Biomass, Alicia A. Modenbach, Sue E. Nokes

Biosystems and Agricultural Engineering Faculty Publications

Pretreatment is a unit operation in the conversion of biomass to valuable products that utilizes various combinations of conditions, including chemicals, heat, pressure, and time, to reduce the recalcitrance of lignocellulose. Many such pretreatments have been developed over the years, as the operating conditions can be adapted so that lignocellulose is modified in ways unique to each pretreatment. By tailoring pretreatment conditions to achieve these modifications, the types of final products produced can be controlled. The purpose of this review is to provide a consolidated source of information for sodium hydroxide effects on lignocellulose. The structural characteristics of lignocellulose and …

Development Of Cementitious Materials For Adhesion Type Applications Comprising Calcium Sulfoaluminate (Csa) Cement And Latex Polymer, Joshua V. Brien

Theses and Dissertations--Civil Engineering

The objective of this research was to develop high performing polymer modified calcium sulfoaluminate (CSA) cement materials for use in applications requiring superior adhesion characteristics. Little information is available describing interactions of CSA cement containing minor phase tri-calcium aluminate (C₃A) with commonly used admixtures. Given the scarcity of information, a basic approach for developing cementitious materials was followed. The basic approach consisted of four tasks: cement design, admixture design, polymer design and testing developed materials. The iterative, time consuming process is necessary for understanding the influence of specific constituent components on overall system behavior. Results from the cement …

Quantification Of Factors Governing Drug Release Kinetics From Nanoparticles: A Combined Experimental And Mechanistic Modeling Approach, Kyle Daniel Fugit

Theses and Dissertations--Pharmacy

Advancements in nanoparticle drug delivery of anticancer agents require mathematical models capable of predicting in vivo formulation performance from in vitro characterization studies. Such models must identify and incorporate the physicochemical properties of the therapeutic agent and nanoparticle driving in vivo drug release. This work identifies these factors for two nanoparticle formulations of anticancer agents using an approach which develops mechanistic mathematical models in conjunction with experimental studies.

A non-sink ultrafiltration method was developed to monitor liposomal release kinetics of the anticancer agent topotecan. Mathematical modeling allowed simultaneous determination of drug permeability and interfacial binding to the bilayer from release …

Nanofiltration Membranes From Oriented Mesoporous Silica Thin Films, Mary K. Wooten

Theses and Dissertations--Chemical and Materials Engineering

The synthesis of mesoporous silica thin films using surfactant templating typically leads to an inaccessible pore orientation, making these films not suitable for membrane applications. Recent advances in thin film synthesis provide for the alignment of hexagonal pores in a direction orthogonal to the surface when templated on chemically neutral surfaces. In this work, orthogonal thin film silica membranes are synthesized on alumina supports using block copolymer poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) (P123) as the template. The orthogonal pore structure is achieved by sandwiching membranes between two chemically neutral surfaces, resulting in 90 nm thick films. Solvent flux of ethanol through …

Quartz Crystal Microbalance Investigation Of Cellulosome Activity From Clostridium Thermocellum On Model Cellulose Films, Shanshan Zhou

Theses and Dissertations--Chemical and Materials Engineering

The cost of deconstructing cellulose into soluble sugars is a key impediment to the commercial production of lignocellulosic biofuels. The use of the quartz crystal microbalance (QCM) to investigate reaction variables critical to enzymatic cellulose hydrolysis is investigated here, extending previous studies of fungal cellulase activity for the first time to whole cell cellulases. Specifically, the activity of the cellulases of Clostridium thermocellum, which are in the form of cellulosomes, was investigated. To clearly differentiate the activity of free cellulosome and cell-bound cellulosome, the distribution of free cellulosome and cell-bound cellulosome in crude cell broth at different growth stages …

Functionalized Membranes For Environmental Remediation And Selective Separation, Li Xiao

Theses and Dissertations--Chemical and Materials Engineering

Membrane process including microfiltration (MF), ultrafiltration (UF), nanofiltration (NF) and reverse osmosis (RO) have provided numerous successful applications ranging from drinking water purification, wastewater treatment, to material recovery. The addition of functional moiety in the membranes pores allows such membranes to be used in challenging areas including tunable separations, toxic metal capture, and catalysis. In this work, polyvinylidene fluoride (PVDF) MF membrane was functionalized with temperature responsive (poly(N-isopropylacrylamide), PNIPAAm) and pH responsive (polyacrylic acid, PAA) polymers. It’s revealed that the permeation of various molecules (water, salt and dextran) through the membrane can be thermally or pH controlled. The introduction of …

Nanometer-Scale Membrane Electrode Systems For Active Protein Separation, Enzyme Immobilization And Cellular Electroporation, Zhiqiang Chen

Theses and Dissertations--Chemical and Materials Engineering

Automated and continuous processes are the future trends in downstream protein purification. A functionalized nanometer-scale membrane electrode system, mimicking the function of cell wall transporters, can selectively capture genetically modified proteins and subsequently pump them through the system under programmed voltage pulses. Numerical study of the two-step pulse pumping cycles coupled with experimental His-GFP releasing study reveals the optimal 14s/1s pumping/repel pulse pumping condition at 10 mM bulk imidazole concentration in the permeate side. A separation factor for GFP: BSA of 9.7 was achieved with observed GFP electrophoretic mobility of 3.1×10^-6 cm² s^-1 V^-1 at 10 …

Iron And Iron Oxide Functionalized Membranes With Applications To Selected Chloro-Organic And Metal Removal From Water, Minghui Gui

Theses and Dissertations--Chemical and Materials Engineering

The development of functionalized membranes with tunable pores and catalytic properties provides us an opportunity to manipulate the membrane pore structure, selectivity and reactivity. By introducing the functional groups into membrane pores, dissolved metal ions and reactive particles can be effectively immobilized within the polymer matrix for toxic chloro-organic and heavy metal remediation in water.

A polyelectrolyte functionalized membrane platform with tunable pore size and ion exchange capacity has been developed for iron/iron oxide nano-catalyst synthesis and chlorinated organic compound (trichloroethylene, TCE and polychlorinated biphenyls, PCBs) degradation. Highly robust polyvinylidene fluoride (PVDF) microfiltration membranes are used as the support with …

Layer-By-Layer Assemblies For Membrane-Based Enzymatic Catalysis, Andrew R. Tomaino

Theses and Dissertations--Chemical and Materials Engineering

While considerable progress has been made towards understanding the effect that membrane-based layer-by-layer (LbL) immobilizations have on the activity and stability of enzymatic catalysis, detailed work is required in order to fundamentally quantify and optimize the functionalization and operating conditions that define these properties. This work aims to probe deeper into the nature of transport mechanisms by use of pressure-induced, flow-driven enzymatic catalysis of LbL-functionalized hydrophilized poly(vinyldiene) (PVDF)-poly(acrylic acid) (PAA)-poly(allylamine hydrochloride) (PAH)-glucose oxidase (GOx) membranes. These membranes were coupled in a sealed series following cellulose acetate (CA) membranes for the elimination of product accumulation within the feed-side solution during operation. …

Generation Of Multicomponent Polymer Blend Microparticles Using Droplet Evaporation Technique And Modeling Evaporation Of Binary Droplet Containing Non-Volatile Solute, Venkat N. Rajagopalan

Theses and Dissertations--Chemical and Materials Engineering

Recently, considerable attention has been focused on the generation of nano- and micrometer scale multicomponent polymer particles with specifically tailored mechanical, electrical and optical properties. As only a few polymer-polymer pairs are miscible, the set of multicomponent polymer systems achievable by conventional methods, such as melt blending, is severely limited in property ranges. Therefore, researchers have been evaluating synthesis methods that can arbitrarily blend immiscible solvent pairs, thus expanding the range of properties that are practical. The generation of blended microparticles by evaporating a co-solvent from aerosol droplets containing two dissolved immiscible polymers in solution seems likely to exhibit a …

A Multidisciplinary Techno-Economic Decision Support Tool For Validating Long-Term Economic Viability Of Biorefining Processes, Sumesh Sukumara

Theses and Dissertations--Chemical and Materials Engineering

Increasing demand for energy and transportation fuel has motivated researchers all around the world to explore alternatives for a long-term sustainable source of energy. Biomass is one such renewable resource that can be converted into various marketable products by the process of biorefining. Currently, research is taking strides in developing conversion techniques for producing biofuels from multiple bio-based feedstocks. However, the greatest concern with emerging processes is the long-term viability as a sustainable source of energy. Hence, a framework is required that can incorporate novel and existing processes to validate their economic, environmental and social potential in satisfying present energy …

Thermo-Chemical Conversion Of Coal-Biomass Blends: Kinetics Modeling Of Pyrolysis, Moving Bed Gasification And Stable Carbon Isotope Analysis, Abhijit Bhagavatula

Theses and Dissertations--Chemical and Materials Engineering

The past few years have seen an upsurge in the use of renewable biomass as a source of energy due to growing concerns over greenhouse gas emissions caused by the combustion of fossil fuels and the need for energy independence due to depleting fossil fuel resources. Although coal will continue to be a major source of energy for many years, there is still great interest in replacing part of the coal used in energy generation with renewable biomass. Combustion converts inherent chemical energy of carbonaceous feedstock to only thermal energy. On the other hand, partial oxidation processes like gasification convert …

Binding, Transcytosis And Biodistribution Of Anti-Pecam-1 Iron Oxide Nanoparticles For Brain-Targeted Delivery, Mo Dan, David B. Cochran, Robert A. Yokel, Thomas D. Dziubla

Pharmaceutical Sciences Faculty Publications

OBJECTIVE: Characterize the flux of platelet-endothelial cell adhesion molecule (PECAM-1) antibody-coated superparamagnetic iron oxide nanoparticles (IONPs) across the blood-brain barrier (BBB) and its biodistribution in vitro and in vivo.

METHODS: Anti-PECAM-1 IONPs and IgG IONPs were prepared and characterized in house. The binding affinity of these nanoparticles was investigated using human cortical microvascular endothelial cells (hCMEC/D3). Flux assays were performed using a hCMEC/D3 BBB model. To test their immunospecificity index and biodistribution, nanoparticles were given to Sprague Dawley rats by intra-carotid infusion. The capillary depletion method was used to elucidate their distribution between the BBB and brain parenchyma.

RESULTS: Anti-PECAM-1 …

Compounds And Methods For Reducing The Occurrence Of Post-Surgical Adhesions, Thomas Dziubla, Eugene Kaplan, John Mark Medley Jr.

Chemical and Materials Engineering Faculty Patents

Compounds and methods for reducing the occurrence of a post-surgical adhesion are provided. The compounds can include acrylic acid groups and ethylene glycol groups, and can be directed to an area of damaged tissue by the incorporation of a fibrin targeting peptide. The compounds can further include a brush-like portion, capable of creating a steric barrier between a damaged tissue or organ and adjacent tissues or organs, and a targeting portion, capable of directing the compounds to a damaged tissue or organ. Methods of detecting damaged tissue and kits are also provided.

A Tensile Deformation Model For In-Situ Dendrite/Metallic Glass Matrix Composites, J. W. Qiao, T. Zhang, Fuqian Yang, P. K. Liaw, S. Pauly, B. S. Xu

Chemical and Materials Engineering Faculty Publications

In-situ dendrite/metallic glass matrix composites (MGMCs) with a composition of Ti₄₆Zr₂₀V₁₂Cu₅Be₁₇ exhibit ultimate tensile strength of 1510 MPa and fracture strain of about 7.6%. A tensile deformation model is established, based on the five-stage classification: (1) elastic-elastic, (2) elastic-plastic, (3) plastic-plastic (yield platform), (4) plastic-plastic (work hardening), and (5) plastic-plastic (softening) stages, analogous to the tensile behavior of common carbon steels. The constitutive relations strongly elucidate the tensile deformation mechanism. In parallel, the simulation results by a finite-element method (FEM) are in good agreement with the experimental findings and theoretical calculations. The present study gives a mathematical model to clarify …

Metal-Based Nanoparticle Interactions With The Nervous System: The Challenge Of Brain Entry And The Risk Of Retention In The Organism, Robert A. Yokel, Eric A. Grulke, Robert C. Macphail

Pharmaceutical Sciences Faculty Publications

This review of metal-based nanoparticles focuses on factors influencing their distribution into the nervous system, evidence they enter brain parenchyma, and nervous system responses. Gold is emphasized as a model metal-based nanoparticle and for risk assessment in the companion review. The anatomy and physiology of the nervous system, basics of colloid chemistry, and environmental factors that influence what cells see are reviewed to provide background on the biological, physical–chemical, and internal milieu factors that influence nervous system nanoparticle uptake. The results of literature searches reveal little nanoparticle research included the nervous system, which about equally involved in vitro and in …

On Electric Conduction Of Amorphous Silicon Carbonitride Derived From A Polymeric Precursor, Yaohan Chen, Fuqian Yang, Linan An

Chemical and Materials Engineering Faculty Publications

A long-existing problem that the conductivity of amorphous silicon carbonitrides derived from polymeric precursor increases significantly with pyrolysis temperature is investigated. We show that the conductivity exhibited an Arrhenius dependence on pyrolysis temperature, with the activation energy of ∼3.41 eV. Structural analysis using Raman spectroscopy reveals that the free carbon within the material undergoes a sp³-to-sp² transition as pyrolysis temperature increases, with the activation energy of ∼3.6 eV. We conclude that the pyrolysis-temperature induced increase in the conductivity is mainly due to the increase in the conductivity of the free carbon. A simple model is proposed to …

Modeling Of Biorefinery Supply Chain Economic Performance With Discrete Event Simulation, Joseph S. Amundson

Theses and Dissertations--Manufacturing Systems Engineering

As competition for fossil fuels accelerates, alternative sources of chemicals, fuels, and energy production become more appealing to researchers and the layman. Among the candidates to fill this growing niche is lignocellulosic biomass. Many researchers have examined supply chain design and optimization for biofuel and bioenergy production throughout the years. However, these models often fail to capture the variability and uncertainty inherent to the biomass supply chain. Multiple factors with high degrees of stochasticity can have major impacts on the performance of a biorefinery: weather, biomass quality, feedstock availability, and market demand for products are just a few. To begin …

Froth Flotation Performance Enhancement By Feed Cavitation And Magnetic Plastic Particle Addition, Mehmet Saracoglu

Theses and Dissertations--Mining Engineering

Froth flotation is the most commonly used process to recover and upgrade the portion of the coal preparation plant feed that has a particle size smaller than 150 microns. Problems that occur when employing froth flotation in the coal industry include i) coal surfaces that are weakly-to-moderately hydrophobic, and ii) flotation systems that are overloaded and limited by insufficient retention time.

Research was performed to evaluate techniques that could be implemented to improve flotation performance under the aforementioned scenarios. Pre-aeration of flotation feed using a cavitation system was extensively evaluated in laboratory and full-scale test programs. The benefits of adding …

The Critical Role Of Mechanism-Based Models For Understanding And Predicting Liposomal Drug Loading, Binding And Release Kinetics, Sweta Modi

Theses and Dissertations--Pharmacy

Liposomal delivery systems hold considerable promise for improvement of cancer therapy provided that critical formulation design criteria can be met. The main objective of the current project was to enable quality by design in the formulation of liposomal delivery systems by developing comprehensive, mechanism-based mathematical models of drug loading, binding and release kinetics that take into account not only the therapeutic requirement but the physicochemical properties of the drug, the bilayer membrane, and the intraliposomal microenvironment.

Membrane binding of the drug affects both drug loading and release from liposomes. The influence of bilayer composition and phase structure on the partitioning …

Engineering Novel Terpene Production Platforms In The Yeast Saccharomyces Cerevisiae, Xun Zhuang

Theses and Dissertations--Plant and Soil Sciences

The chemical diversity and biological activities of terpene and terpenoids have served in the development of new flavors, fragrances, medicines and pesticides. While terpenes are made predominantly by plants and microbes in small amounts and as components of complex mixtures, chemical synthesis of terpenes remains technically challenging, costly and inefficient. In this dissertation, methods to create new yeast lines possessing a dispensable mevalonate biosynthetic pathway wherein carbon flux can be diverted to build any chemical class of terpene product are described. The ability of this line to generate diterpenes was next investigated. Using a 5.5 L fed bath fermentation system, …

Applications Of Antioxidant And Anti-Inflammatory Polymers To Inhibit Injury And Disease, David B. Cochran

Theses and Dissertations--Chemical and Materials Engineering

There is an undeniable link between oxidative stress, inflammation, and disease. Currently, approaches using antioxidant therapies have been largely unsuccessful due to poor delivery and bioavailability. Responding to these limitations, we have developed classes of polymer and delivery systems that can overcome the challenges of antioxidant and anti-inflammatory therapy. In our initial studies, nanoparticles of poly(trolox), a polymeric form of trolox, were surface-modified with antibodies. This modification allows for specific targeting to endothelial cells, affording controllable and localized protection against oxidative stress. We have shown these targeted nanoparticles bind, internalize, and provide protection against oxidative stress generation and cytotoxicity from …

The Effects Of Ceria Addition On Aging And Sulfation Of Lean Nox Traps For Stand Alone And Lnt-Scr Applications, Vencon G. Easterling

Theses and Dissertations--Chemical and Materials Engineering

THE EFFECTS OF CERIA ADDITION ON AGING AND SULFATION OF LEAN NO_x TRAPS FOR STAND ALONE AND LNT-SCR APPLICATIONS

Model powder and fully formulated monolithic lean NO_x trap (LNT) catalysts were used to investigate the effect of ceria on desulfation behavior. Temperature-programmed reduction (TPR) experiments (model catalysts) showed each of the oxide phases present is able to store sulfur and possesses distinct behavior (temperature at which desulfation occurs). La-CeO₂ or CeO₂-ZrO₂-containing samples (monoliths) showed a greater resistance to deactivation during sulfation and required lower temperatures to restore the NO_x storage efficiency to …

Characterization Of And Controlling Morphology Of Ultra-Thin Nanocomposites, Guy C. Laine

Theses and Dissertations--Chemical and Materials Engineering

Ultrathin film nanocomposites are becoming increasingly important for specialized performance of commercial coatings. Critical challenges for ultrathin film nanocomposites include their synthesis and characterization as well as their performance properties, including surface roughness, optical properties (haze, refractive index as examples), and mechanical properties. The objective of this work is to control the surface roughness of ultrathin film nanocomposites by changing the average particle size and the particle volume fraction (loading) of monomodal particle size distributions. This work evaluated one-layer and two-layer films for their surface properties. Monodispersed colloidal silica nanoparticles were incorporated into an acrylate-based monomer system as the model …

Incorporation Of Catalytic Dehydrogenation Into Fischer-Tropsch Synthesis To Significantly Reduce Carbon Dioxide Emissions, Gerald P. Huffman

Chemical and Materials Engineering Faculty Patents

A new method of producing liquid transportation fuels from coal and other hydrocarbons that significantly reduces carbon dioxide emissions by combining Fischer-Tropsch synthesis with catalytic dehydrogenation is claimed. Catalytic dehydrogenation (CDH) of the gaseous products (C1-C4) of Fischer-Tropsch synthesis (FTS) can produce large quantities of hydrogen while converting the carbon to multi-walled carbon nanotubes (MWCNT). Incorporation of CDH into a FTS-CDH plant converting coal to liquid fuels can eliminate all or most of the CO₂ emissions from the water-gas shift (WGS) reaction that is currently used to elevate the H₂ level of coal-derived syngas for FTS. Additionally, the …

Rat Brain Pro-Oxidant Effects Of Peripherally Administered 5 Nm Ceria 30 Days After Exposure, Sarita S. Hardas, Rukhsana Sultana, Govind Warrier, Mo Dan, Rebecca L. Florence, Peng Wu, Eric A. Grulke, Michael T. Tseng, Jason M. Unrine, Uschi M. Graham, Robert A. Yokel, D. Allan Butterfield

Chemistry Faculty Publications

The objective of this study was to determine the residual pro-or anti-oxidant effects in rat brain 30 days after systemic administration of a 5 nm citrate-stabilized ceria dispersion. A ∼4% aqueous ceria dispersion was iv-infused (0 or 85 mg/kg) into rats which were terminated 30 days later. Ceria concentration, localization, and chemical speciation in the brain was assessed by inductively coupled plasma mass spectrometry (ICP-MS), light and electron microscopy (EM), and electron energy loss spectroscopy (EELS), respectively. Pro- or anti-oxidant effects were evaluated by measuring levels of protein carbonyls (PC), 3-nitrotyrosine (3NT), and protein-bound-4-hydroxy-2-trans-nonenal (HNE) in the hippocampus, cortex, and …