Chemical Engineering Commons^™

Kinetic Analysis Of Thiol Oxidation To Study The Effects Of Fluorinated Groups On Metal Phthalocyanine Catalysts, Nellone Eze Reid

Dissertations

The oxidation of thiol (RSH) to disulfide (RSSR) is important biologically and industrially. Corrosive and malodorous thiols exist as contaminants in wastewater discharge from mining facilities, pulp and paper mills, tanneries, and oil refineries. The elimination of thiols from petroleum products is necessary for even cleaner fuels. Thiols in gas products can also inhibit catalyst activity for some downstream processes.

Experiments and mechanistic kinetic studies were conducted for the aerobic oxidation of 2-mercaptoethanol (2-ME) and 4-fluorobenzenethiol (4-FBT) catalyzed by cobalt phthalocyanines: H₁₆PcCo, F₁₆PcCo, and F₆₄PcCo, each exhibiting a metal center subject to increasing Lewis …

Discrete Element Method Based Scale-Up Model For Material Synthesis Using Ball Milling, Priya Radhi Santhanam

Dissertations

Mechanical milling is a widely used technique for powder processing in various areas. In this work, a scale-up model for describing this ball milling process is developed. The thesis is a combination of experimental and modeling efforts.

Initially, Discrete Element Model (DEM) is used to describe energy transfer from milling tools to the milled powder for shaker, planetary, and attritor mills. The rolling and static friction coefficients are determined experimentally. Computations predict a quasi- steady rate of energy dissipation, Ed, for each experimental configuration. It is proposed that the milling dose defined as a product of Ed and milling …

Investigation Of Recycled Paper Deinking Mechanisms, Veronika Husovska

Dissertations

The use of water-based inks is on the rise. Sub-micron pigment particles are used for flexographic and inkjet water-based inks. Conventional deinking eliminates larger particles than those from these new ink systems. Therefore, water-based inks represent recycling difficulty.

Deinking experiments of water-based inks are carried out. The deinking strategy initially investigated elimination of pressure sensitive adhesive due to similar acrylic polymer chemistry used in water based inks. The impact of pH on stickies and ink agglomeration during deinking is studied. Experiments in acidic regions show growth of acrylic inks and stickies agglomerates, simplifying elimination.

Pre-recycling of water-based inks is explored. …

Batch And Continuous Production Of Stable Dense Suspensions Of Drug Nanoparticles In A Wet Stirred Media Mill, Afolawemi Afolabi

Dissertations

One way to improve the bioavailability of poorly water-soluble drugs is to reduce particle size of drug crystals down to nanoscale via wet stirred media milling. An increase in total surface area per mass loading of the drug and specific surface area as well as reduced external mass transfer resistance allow a faster dissolution of the poorly-water soluble drug from nanocrystals. To prevent aggregation of nanoparticles, polymers and surfactants are dissolved in water acting as stabilizers via adsorption onto the drug crystals.

In the last two decades, ample experimental data were generated in the area of wet stirred media milling …

Pressure Swing Membrane Absorption Process For Separation Of Low Temperature Post-Shift Reactor Syngas, John Chau

Dissertations

This thesis is concerned with a cyclic pressure swing membrane absorption process (PSMAB) for separation of the feed gas mixture containing —40% CO₂-He balance using pure ionic liquid, 1-butyl-3-methylimidazolium dicyanamide ([bmim][DCA]), and its solution containing poly(amidoamine) (PAMAM) dendrimer Gen 0 primarily with a dry feed gas. An advanced pressure swing membrane absorption process is developed to produce purified He as a surrogate for H₂ at a high pressure from simulated low- temperature shifted syngas for different membrane modules. The PSMAB process also simultaneously produces a highly purified CO₂ stream containing bulk of the CO₂ in …

New Approaches On Deinking Evaluations, Roland Gong

Dissertations

Paper recycling in the U.S. is the most successful program of environmental sustainability. Approximately two thirds of consumed paper products were recycled, according to the EPA and AF&PA. However, domestic mills only applied one third of recycled fibers into new products, which is much lower than reported in China (67%). The domestic recycle mills claimed that outdated facilities, poor recycled fiber quality and high manufacturing cost are the major issues. They also said that these recycle mills have been put in a “no-win” position, which threatens the whole recycling loop eventually. A case study about Chinese recycle mills has been …

The Effect Of Nanoclays On The Properties Of Aspirin Modified Enteric Polymer Prepared By Hot-Melt Mixing, Nonjaros Chomcharn

Dissertations

Melt mixing in batch equipment or continuous extruders is a technique that recently gained the attention of the pharmaceutical industry. This dissertation investigates two controlled-release drug delivery systems. The first system, namely the enteric matrix, contains an active pharmaceutical ingredient (API) and plasticizer in an enteric polymer while in the second system a nanoclay is added to the enteric matrix, to produce a polymer nanocomposite. The first system employs hot-melt mixing to prepare a modified enteric matrix, as a delayed-release dosage form. Different concentrations of aspirin (ASP) ranging from 10 – 30% w/w are melt-mixed with a plasticized Eudragit® …

Reaction Mechanisms Of Hydrocarbon And Mercury Systems In The Atmosphere And In Combustion: A Theoretical Study Of Thermochemical And Kinetic Properties, Itsaso Auzmendi Murua

Dissertations

The continuing increase in the world population and the rapidly changing lifestyle and education of this population projects significant increases in energy requirements. Global warming is a worldwide major concern with a very serious potential stress on our climate threatening major changes to the environment. It is, without question, of major importance to improve the efficiency and optimize the current available combustion processes and fuel sources, to develop alternative fuels and to reduce the emissions of toxic pollutants.

The objective of this dissertation is to present thermochemical, kinetic and modeling results on two reference fuels (the land vehicle fuel isooctane …

Metal Based Reactive Nanocomposites Prepared By Cryomilling, Shasha Zhang

Dissertations

Aluminum is one of the most commonly used metal fuel additives for propellants, explosives, and pyrotechnics. Recent interest has been focused on replacements for aluminum as fuel additives to achieve higher combustion temperatures and stronger pressure pulses for applications in advanced munitions systems. Two applications are addressed in this work. In the applications for explosives designed to defeat stockpiles of chemical and biological weapons, it is of interest to develop multifunctional materials combining the high energy density of metal fuels with the biocidal activity of halogens. A challenge of this effort is to design and prepare powder-like Al-I2 materials which …

Separation Of Various Organic-Organic And Aqueous-Organic Solutions Via Pervaporation, John Tang

Dissertations

Pervaporation, an energy saving separation process, can be useful in pharmaceutical processing. However, the organic solvents involved in pharmaceutical product synthesis are chemically demanding; very few polymers are able to withstand them. An ideal membrane would be polymeric having a high thermal, chemical and mechanical stability. Such a membrane is made of a copolymer of polydimethyldioxole and tetrafluoroethylene known as PDD-TFE of the CMS-3 variety with a very high free volume. This novel membrane is used to separate a variety of organic-organic and aqueous-organic mixtures. An earlier study based on water-ethanol-isopropanol has shown evidence that the membrane selectivity may be …

Particle Engineering Via Surface Modification During Micronization For Pharmaceutical Applications, Xi Han

Dissertations

Improving the dissolution rate of Biopharmaceutics Classification System (BCS) class II drugs is an important research area. Micronization which can increase the specific surface area is a promising method to improve the dissolution rate. Micronization alone, however, can lead to downstream processing problems related to poor flow and dispersion properties. The importance of the flowability of pharmaceutical powders is well-documented in the literature. It is, therefore, important to develop a method that can simultaneously overcome these processing issues and allow for micronizing the API. In this work, dry particle coating technique is investigated in the context of micronizing API powders …

Mathematical Modeling Of Heavy Metals Diffusion And Removal From Cylindrical Cement Forms Coated With Bio-Film, Mojdeh Tabatabaie

Dissertations

A mathematical model is developed to predict bioleachi ng of heavy metals from long cylindrical shape cementitious samples. In this model, the metal concentration difference within the solid and its surface is considered as the main driving force for transport of metals to the surface of a sample at a given temperature and pressure. Fick’s first and second law are applied to explain the motion of contaminants in a long and uniform cylindrical solid. In addition, the model considers Michaelis-Menten type kinetics, a special case of the widely accepted Langmuir-Hinshelwood reaction mechanism, at the surface of the encapsulating cylinder. The …

Gravure Printability Of Indium Tin Oxide Nanoparticles On Glass And Pet Films For Applications In Printed Electronics, Dania Awni Alsaid

Dissertations

The advancements in the field of solution processable electro-active materials and their ability to be printed on different substrates have led to the evolution of printed electronics. In this field, electronic components are manufactured with conventional printing methods. Transparent electrodes made from indium tin oxide (ITO) are part of many electronic devices. Currently in industry, highly conductive ITO films are prepared by sputtering. The sputtering and then patterning of ITO films is a sophisticated process that consumes high energy, generates waste and produces films with limited flexibility. Therefore, there is a need to investigate processing methods for creating ITO films …

Inkjet Printability Of Electronic Materials Important To The Manufacture Of Fully Printed Otfts, Sooman Lim

Dissertations

In this study, the inkjet printability of materials important to fabricating OTFTs was researched. In order to understand the jetting evolution of inkjet printed inks, simulations were performed with a nano copper and nano particle silver ink. To predict the inkjettability of the nano copper ink, Z and Oh numbers at different temperatures were determined. The results from the simulation studies were compared to experimental results obtained using a Dimatix inkjet printer. For the semiconductor ink, the inkjet printability of two organic semiconductors, P2TDC17FT4 (poly[(3,7-diheptadecylthieno[3,2-b]thieno[2',3':4,5]thieno[2,3-d]thiophene-2,6-diyl)[2,2'-bithiophene]-5,5'-diyl] dissolved in 1,2-dichlorobenzene and P3HT (poly-3 hexylthiophene) were compared to determine the relationship between drop …

Investigation Of The Fracture Phenomena During The Milling Process Of Inorganic Particulates And Brittle Fracture Of Polymer Composites Using Fractal Theory, Zheng Qian

Dissertations

This dissertation investigates the applicability and usefulness of applying Fractal mathematics and to the fracture of brittle particulates in Fluid Energy Mill devices, and in particular quantifying the resulting power law particle size distributions, examining the Surface Fractal Dimension of milled particulates, and relating the Izod Impact Strength values of composites of polypropylene and Calcium carbonate particulates which are large un-milled, small milled, as well as small and produced by the simultaneous milling and coating with nano-silica to the Surface Fractal Dimension of the impact fracture surfaces.

First, the dissertation examines the behavior of un-coated and micron-sized wax pre-coated particulates …

Desalination Of Brine And Produced Water By Membrane Distillation At Lower As Well As Higher Temperatures And Pressures, Dhananjay Singh

Dissertations

Direct contact membrane distillation (DCMD)-based desalination process is a thermally- driven separation process where a hydrophobic microporous membrane separates a hot brine feed and a cold distillate which condenses the water vapor from the hot brine passing through the membrane pores. So far, DCMD has been explored for hot brines and other aqueous solutions below 100oC. For feed solutions above 100oC, DCMD has an extra advantage over other conventional separation processes like reverse osmosis (RO) which requires cooling of the feed solution costing additional energy; further, RO can not utilize the heat available in the feed solution. Produced water obtained …

Single And Multiphase Mixing In Partially Filled Stirred Vessels, Shilan Motamedvaziri

Dissertations

In many industrial applications, mixing vessels have a liquid height-to-tank diameter ratio, H/T, equal to, or larger than 1. However, there are many instances where this ratio is lower than 1, as in all those cases in which the vessel is either emptied or filled. Even when H/T<1, sufficient agitation must still be provided in order to attain the desired process objectives. When the impeller submergence is reduced as a result of lowering the liquid level, the fluid dynamics of even a single-phase stirred liquid can become quite complex, with different regimes possibly existing depending on the geometric characteristics of the system (such as impeller clearance, liquid height, or liquid submergence above the impeller). The objectives of this work were to study in detail the hydrodynamic changes that occur when H/T is decreased, and to determine the minimum liquid levels and the critical impeller submergence for different impeller off-bottom distances, impeller diameters and agitation speeds where adequate mixing process can still be achieved, both in a single liquid phase and in solid-liquid suspensions.

Flat-bottomed, baffled vessels (5L, 12L, 20L and 170L) equipped with a single disk turbine (DT) of four different sizes placed at five different impeller off-bottom clearances were used here to study the system's hydrodynamics and related mixing phenomena. A number of experimental tools were used to analyze the systems under investigation, including: …

Hot-Melt Mixing Of Partially Miscible Active Pharmaceutical Ingredient-Polymer Mixtures, Min Yang

Dissertations

Solid dispersion/solution processes for producing pharmaceutical oral dosages such as hot-met extrusion (HME) have received increasing attention by industry and academe because they can enhance drugs’ solubility and even bioavailability to a great extent by converting drugs from crystalline to amorphous form. HME can be carried out at two process temperature regimes: one where T_process > T_m of the drug and the T_g of the polymer (or the T_m for the case of semi-crystalline polymers); the other at T_m > T_process > T_g (T_m for the case of semi-crystalline polymer). Processing below the drug’s …

Theoretical Prediction Of Drug Release In Gi Tract From Spherical Matrix Systems, Naga Lakshmi Ramana Susarla

Dissertations

The significance of controlled release drug delivery systems (CRDDS) lies in their ability to deliver the drug at a steady rate thus reducing the dosage interval and providing a prolonged pharmacodynamic effect. But despite the steadily increasing practical importance of these devices, little is known regarding their underlying drug release mechanisms. Mathematical modeling of these drug delivery systems could help us understand the underlying mass transport mechanisms involved in the control of drug release. Mathematical modeling also plays an important role in providing us with valuable information such as the amount of drug released during a certain period of time …

Effects Of Operating And Geometric Variables On Hydrodynamics And Tablet Dissolution In Standard And Modified Dissolution Testing Apparatuses 2, Yimin Wang

Dissertations

Dissolution testing is routinely conducted in the pharmaceutical industry to provide critical in vitro drug release information for quality control purposes, and especially to assess batch-to-batch consistency of solid oral dosage forms such as tablets. Among the different types of apparatuses listed in the United States Pharmacopoeia (USP), the most commonly used dissolution system for solid dosage forms is the USP Dissolution Testing Apparatus 2, consisting of an unbaffled, hemispherical-bottomed vessel equipped with a 2-blade radial impeller.

Despite its extensive use in industry and a large body of work, some key aspects of the hydrodynamics of Apparatus 2 have received …

Multifunctional Reactive Nanocomposite Materials, Demitrios Stamatis

Dissertations

Many multifunctional nanocomposite materials have been developed for use in propellants, explosives, pyrotechnics, and reactive structures. These materials exhibit high reaction rates due to their developed reaction interfacial area. Two applications addressed in this work include nanocomposite powders prepared by arrested reactive milling (ARM) for burn rate modifiers and reactive structures. In burn rate modifiers, addition of reactive nanocomposite powders to aluminized propellants increases the burn rate of aluminum and thus the overall reaction rate of an energetic formulation. Replacing only a small fraction of aluminum by 8Al•MoO₃ and 2B•Ti nanocomposite powders enhances the reaction rate with little change …

Effect Of Dry Particle Coating On The Properties Of Cohesive Pharmaceutical Powders, Lauren Elizabeth Beach

Dissertations

Engineered particles, which have undergone surface modification via dry coating, have been previously shown to have improved flow and handling properties. The improvements in these properties can be applied and are very useful for a number of industrial applications, in this case the pharmaceutical industry. This work investigates the effect of dry particle coating to improve the flowability of cohesive active pharmaceutical ingredient (API) powders and their blends. Improving the flow properties of cohesive API powders can significantly improve their handling and subsequent use for pharmaceutical processes such as formulation and manufacturing processing operations. Although it has been shown that …

Electrodeless Electro Hydrodynamic Printing Of Personalized Drug Dosages, Ezinwa Okeoma Elele

Dissertations

There is compelling evidence that variability in drug efficacy in individuals depends on their genetic fingerprints. These observations have given rise to the concept of personalized therapy whose ultimate goal is to develop medicinal agents designed for each niche of the population and individual patients according to their genetic background. The drawback in current pharmaceutical technologies is that most processes are designed to target large population and are unable to meet the demand of small-scale manufacturing of tailored therapeutics with diverse range of physical properties. One of the major challenges lie in developing efficient and cost effective methods of manufacturing …

Deagglomeration And Mixing Via The Rapid Expansion Of High Pressure And Supercritical Suspensions, Daniel To

Dissertations

Nano-materials are the focus of many research activities due to the desirable properties imparted from their small grain size and high interfacial surface area. However, these materials are highly cohesive powders in the dry state and typically form large agglomerates, leading to a diminished surface area or even grain growth, which minimizes the effectiveness of these nanomaterials. This dissertation addresses the issue of mixing nanopowders constituents by deagglomerating them and achieving simultaneous mixing so that even after inevitable reagglomeration, the effectiveness of large interfacial surface area may be preserved.

Nano-particle mixtures were prepared using the environmentally benign dry mixing methods …

Study Of The Heating And Ignition Of Metal Powder By Electrostatic Discharge, Ervin Beloni

Dissertations

The objective of this work was to understand the processes that lead to ESD stimulated ignition events in metal powders. Several metals were studied: Mg, Al, and Ti. A commercially available ESD test device was adapted for the present experiments. The ESD current and voltage were measured using inductance coils; the data were used to determine the electric circuit impedance, and energy transferred to the powder. A mode of the powder ignition (individual particles vs. dust cloud), ignition delays, burn times, and velocities of ignited and ejected particles were determined from optical measurements.

It was determined that the ESD energy …

Study Of Controlled Release Of Active Pharmaceutical Ingredients From Functionalized Nanoclays And Polymer Matrices, Jin Uk Ha

Dissertations

This dissertation contains the results of three related novel investigations in the field of structure-property-processing relationships of pharmaceutical polymer-based products. They are: a) modification of a pharmaceutical anionic nanoclay with two different Active Pharmaceutical Ingredients (APIs) to produce nanohybrid API carriers intended to be used alone or in acrylic polymer matrices, b) comparison of binary systems containing the above APIs in the selected acrylic polymers in terms of their miscibilities with the polymer, but in the absence of nanoclay, and c) comparison of the polymer/API binary systems with ternary polymer/API/Clay systems.

For the first study, the calcination method which can …

New Media Icc Profiles Construction And Concerns, Reem El Asaleh

Dissertations

With the advent of the modern digital technology, users can now capture an image and reproduce it between different media, such as display it on LCD monitor or tablet computer, print it on desktop printer or send it to a printing press. The challenge has been then to maintain the accuracy of image colors during this reproduction, which has led to the development of Color Management Systems. Using these systems, the color reproduction across-media will be accomplished using device ICC profiles that describe each device’s color characterization data in a standardized format based on International Color Consortium (ICC) specifications.

ICC …

Design Of Novel Drug Delivery System And Optimal Dosage Regimens, Kwang Seok Kim

Dissertations

Three representative drug delivery systems were analyzed to emphasize the roles of mathematical models and computer-aided simulations in pharmaceutical research. In the first project, a protocol was developed so that the optimal regimen, consisting of the intravenous boluses and subsequent infusion of theophylline, could be obtained once information on the pharmacokinetics became available. The method was based on a two-compartment model of the human body. A module was created and posted on a website for free access. The second project dealt with the transdermal heat-assisted delivery of corticosterone. Heat conduction and drug diffusion through the patch and the skin were …

Simulation, Synthesis, And Characterization Of Hydrogels And Nanocomposite Gels., Kamleshkumar J. Suthar

Dissertations

Stimuli-responsive gels are three-dimensional, cross-linked polymeric materials that undergo large physical change in response to the environmental stimuli, like temperature, pH, electrical potential, and irradiation. Ferrogels are colloidaldispersion of magnetic nanoparticles in the hydrogel network. The magnetic nanoparticles are attached to the polymeric network by different adhesive forces; as a result, it becomes sensitive to the applied magnetic field.

The main objective of this research is the simulation, synthesis, and characterization of the hydrogel and ferrogel. Simulation of the hydrogel response was performed for various environmental stimuli using a multiphysics finite element analysis software, COMSOL. The pH and electrical response …

Precipitation Of Micro/Nanoparticles In Enhanced High Energy Dissipation Mixing Systems, Giuseppe Di Benedetto

Dissertations

Crystallization is the most common unit operation used in the pharmaceutical industry to synthesize active ingredients. Rapid development of a drug candidate is dependent on the ability to produce a desired drug substance with consistent properties, These properties include stability and purity, which are directly affected by the crystallization process and which affect, in turn, bioavailability, drug dissolution rate, drug stability, and shelf life.

The objective of this work is to produce micro/nanoparticle crystals within existent glass-lined pharmaceutical stirred-tank reactors by modifying the current reactor configuration to include features that can increase the local rate of energy dissipation in the …