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Full-Text Articles in Engineering

Top-Down And Bottom-Up Fabrication Of Key Components In Miniature Energy Storage Devices, Wenhao Li Oct 2019

Top-Down And Bottom-Up Fabrication Of Key Components In Miniature Energy Storage Devices, Wenhao Li

Doctoral Dissertations

The advent of miniature electronic devices demands power sources of commensurate form factors. This spurs the research of micro energy storage devices, e.g., 3D microbatteries. A 3D microbattery contains nonplanar microelectrodes with high aspect ratio and high surface area, separated by a nanoscale electrolyte. The device takes up a total volume as small as 10 mm3, allowing it to serve on a chip and to provide power in-situ. The marriage of nanotechnology and electrochemical energy storage makes microbattery research a fascinating field with both scientific excitement and application prospect. However, successful fabrication of well-functioned key components …


Controlling Selectivities In Heterogeneously Catalyzed Aldol Reactions, Koushik Ponnuru Oct 2019

Controlling Selectivities In Heterogeneously Catalyzed Aldol Reactions, Koushik Ponnuru

Doctoral Dissertations

Aldol condensation is an important C-C bond formation reaction in chemical synthesis that finds versatile applications in bulk and fine chemical industries and has the potential for upgrading of biomass to fuels. However, aldol reactions pose a challenge for controlling the product selectivity by forming a mixture of desired and undesired self, cross, and poly-condensation products. Furthermore, a side reaction, the fission of aldol products resulting in an olefin and a carboxylic acid, has garnered attention recently as a route to isobutene from acetone. While a high level of selectivity control is achievable by homogeneous catalysis, selective solid catalysts, which …


Bioinspired Complex Nanoarchitectures By Dna Supramolecular Polymerization, Laura A. Lanier Oct 2019

Bioinspired Complex Nanoarchitectures By Dna Supramolecular Polymerization, Laura A. Lanier

Doctoral Dissertations

Bioinspired nanoarchitectures are of great interest for applications in fields such as nanomedicine, tissue engineering, and biosensing. With this interest, understanding how the physical properties of these complex nanostructures relate to their function is increasingly important. This dissertation describes the creation of complex nanoarchitectures with controlled structure and the investigation of the effect of nanocarrier physical properties on cell uptake for applications in nanomedicine. DNA self-assembly by supramolecular polymerization was chosen to create complex nanostructures of controlled architectures. We demonstrated that the supramolecular polymerization of DNA known as hybridization chain reaction (HCR) is in fact a living polymerization. The living …


Engineering Nanomaterials For Imaging And Therapy Of Bacteria And Biofilm-Associated Infections, Akash Gupta Oct 2019

Engineering Nanomaterials For Imaging And Therapy Of Bacteria And Biofilm-Associated Infections, Akash Gupta

Doctoral Dissertations

Infections caused by multidrug-resistant (MDR) bacteria pose a serious global burden of mortality, causing thousands of deaths each year. The “superbug” risk is further exacerbated by chronic infections generated from antibiotic-resistant biofilms that are highly resistant to available treatments. Synthetic macromolecules such as polymers and nanoparticles have emerged as promising antimicrobials. Moreover, ability to modulate nanomaterial interaction with bacterial cellular systems plays a pivotal role in improving the efficacy of the strategy. In the initial studies on engineering nanoparticle surface chemistry, I investigated the role played by surface ligands in determining the antimicrobial activity of the nanoparticles. In further study, …


Modeling And Simulation Of Driven Nanopatterning Of Bulk-Material And Thin-Film Surfaces, Ashish Kumar Oct 2019

Modeling And Simulation Of Driven Nanopatterning Of Bulk-Material And Thin-Film Surfaces, Ashish Kumar

Doctoral Dissertations

Material nanostructures such as nanowires, quantum dots, and nanorings have a wide variety of applications in electronic and photonic devices among numerous others. Assembling uniformly arranged and consistently sized nanostructure patterns on solid material surfaces is a major challenge for nanotechnology. This dissertation focuses on developing predictive models capable of simulation and analysis of such nanopattern formation on bulk material and strained thin film surfaces. Single-layer atomic clusters (islands) of sizes larger than a critical size on crystalline conducting substrates undergo morphological instabilities when driven by an externally applied electric field or thermal gradient. We have conducted a systematic and …


Amorphous-Crystalline Brush Block Copolymers: Phase Behavior, Rheology And Composite Design, Gayathri Kopanati Oct 2019

Amorphous-Crystalline Brush Block Copolymers: Phase Behavior, Rheology And Composite Design, Gayathri Kopanati

Doctoral Dissertations

Bottlebrush block copolymers are polymers with chemically distinct polymer side chains grafted onto a common backbone. The unique architecture induced properties make these materials attractive for applications such as photonic materials, stimuli responsive actuators and drug delivery vehicles to name a few. This dissertation primarily investigates the phase transitions and rheological behavior of amorphous-crystalline bottlebrush brush block copolymers and their composites. The temperature induced phase behavior is investigated using time resolved synchrotron X-ray source. Irrespective of volume fraction and backbone length, the samples display strong segregation even at high temperatures (200 °C) and there is no accessible order-disorder transition in …


A Synthetic Human Brain Ecm Hydrogel For Tight Control Of Astrocyte Activation, Sualyneth Galarza Oct 2019

A Synthetic Human Brain Ecm Hydrogel For Tight Control Of Astrocyte Activation, Sualyneth Galarza

Doctoral Dissertations

Bioengineers have aimed to design instructive extracellular matrix (ECM) models that can tailor the protein composition and biomechanics of the brain in vitro in order to study how astrocytes remodel the brain during trauma and inflammation. However, these parameters cannot be independently controlled in protein-based models, and although tunable in synthetic systems, current astrocyte cultures fail to retain their characteristic stellate morphology without becoming activated. To this date, there is no biomaterial model that can retain astrocyte quiescence in vitro. This dissertation sought to develop such an in vitro model that would enable the study of specific ECM factors …


Polymeric Impulsive Actuation Mechanisms: Development, Characterization, And Modeling, Yongjin Kim Oct 2019

Polymeric Impulsive Actuation Mechanisms: Development, Characterization, And Modeling, Yongjin Kim

Doctoral Dissertations

Recent advances in the field of biomedical and life-sciences are increasingly demanding more life-like actuation with higher degrees of freedom in motion at small scales. Many researchers have developed various solutions to satisfy these emerging requirements. In many cases, new solutions are made possible with the development of novel polymeric actuators. Advances in polymeric actuation not only addressed problems concerning low degree of freedom in motion, large system size, and bio-incompatibility associated with conventional actuators, but also led to the discovery of novel applications, which were previously unattainable with conventional engineered systems. This dissertation focuses on developing novel actuation mechanisms …


Interfacial Interactions And Dynamic Adhesion Of Synthetic And Living Colloids In Flow, Molly Shave Aug 2019

Interfacial Interactions And Dynamic Adhesion Of Synthetic And Living Colloids In Flow, Molly Shave

Doctoral Dissertations

This thesis focuses on the interactions between flowing particles and a surface, where hydrodynamics couples with chemical interactions in order to modify the way they come into play. First this thesis shows how electrostatic chemical heterogeneities on a flowing particle affect the interactions with a wall, using a highly tunable electrostatically heterogenous system produced by adsorbing small amounts of cationic polyelectrolytes onto silica particles in suspension and studying their behavior in flow over the fixed surface. By comparing this behavior to a system with equivalent chemical heterogeneity on a channel wall it was shown that the rotation of a particle …


Double-Network Materials Via Frontal Polymerization & Supercritical Co2 Processing, Matthew Joseph Lampe Jul 2019

Double-Network Materials Via Frontal Polymerization & Supercritical Co2 Processing, Matthew Joseph Lampe

Doctoral Dissertations

This dissertation presents work focused on producing materials in non-equilibrium states by taking advantage of novel processing techniques. First, epoxy-based resins which can undergo radically promoted, cationic, thermal, frontal polymerization are investigated for their potential use as adhesives. These resins are found to be capable of sustaining propagating polymerization fronts between several different substrate materials, resulting in high levels of adhesion in some cases. In addition, a similar frontal resin was developed that can undergo sequential gelation and frontal polymerization. The gels are formed by radically crosslinking acrylate monomers within the epoxy resin. These gels can then be manipulated, and …


Rheological Investigations Of Self-Assembled Block Copolymer Nanocomposites With Complex Architectures, Benjamin Yavitt Jul 2019

Rheological Investigations Of Self-Assembled Block Copolymer Nanocomposites With Complex Architectures, Benjamin Yavitt

Doctoral Dissertations

The self-assembly of block copolymers (BCP) into microphase separated structures is an attractive route to template and assemble functional nanoparticles (NP) into highly ordered nanocomposites and is central to the “bottom up” fabrication of future materials with tunable electronic, optical, magnetic, and mechanical properties. The optimization of the co-assembly requires an understanding of the fundamentals of phase behavior, intermolecular interactions and dynamics of the polymeric structure. Rheology is a novel characterization tool to investigate these processes in such systems that are not accessible by other means. With the combination of X-ray scattering techniques, structure-property relationships are determined as a function …


Quantitative Probing Of Vacancies And Ions Dynamics In Electroactive Oxide Materials, Jiaxin Zhu Mar 2019

Quantitative Probing Of Vacancies And Ions Dynamics In Electroactive Oxide Materials, Jiaxin Zhu

Doctoral Dissertations

Oxygen vacancy and ion dynamics in functional oxides are critical factors influencing electrical conductivity and electrochemical activity of oxides assemblies. The recent advancements in deposition and fabrication of oxide heterostructured films with atomic-level precision has led to discovery of intriguing physical properties and new artificial materials. While still under debate, researchers most often attribute these observed behaviors to unique oxygen vacancy distributions in the substrate near heterointerfaces. In electroactive oxides devices such as solid oxide cells (SOCs), oxygen vacancy and ion transport at the triple-phase boundary determines the performance of the device. This complex process motivates numerous remaining questions regarding …


Targeted Design Of Co-Continuous Nanostructures In Copolymers, Di Zeng Mar 2019

Targeted Design Of Co-Continuous Nanostructures In Copolymers, Di Zeng

Doctoral Dissertations

Microphase separated copolymers with nano-scale morphologies are critically important in designing next generation materials. Cocontinuous nanoscale structures, in which domains of multiple different phases each simultaneously percolate in three dimensions, provide opportunities to synergistically combine properties of the constituent polymers in a wide variety of contexts. While cocontinuous nanostructures are fabricated through equilibrium self-assembly of block or graft copolymers and kinetically trapped phase separation of polymer blends or crosslinked copolymer networks, their formation is highly sensitive to changes in chemical details, synthesis and/or processing conditions, bringing practical challenges to generalization to multiple systems. In this dissertation, we focus on transforming …


Synthesis And Molecular Transport Studies In Zeolites And Nanoporous Membranes, Vivek Vattipalli Mar 2019

Synthesis And Molecular Transport Studies In Zeolites And Nanoporous Membranes, Vivek Vattipalli

Doctoral Dissertations

The advent of nanoporous materials such as zeolites and nanoporous membranes has provided cost-effective solutions to some of the most pressing problems of the 20th century such as the conversion of crude oil into fuels and valuable chemicals. Hierarchical zeolites and mesoporous inorganic membranes are showing great promise in addressing new problems such as the conversion of biomass into value-added chemicals and development of energy-efficient separation processes. The synthesis and fundamental aspects of molecular transport in these new materials with hierarchical porosities need to be better understood in order to rationally develop them for these desired applications. Pore narrowing …


Chemical Stability And Performance Influence Of Choice Substituents And Core Conjugation Of Organic Semiconductors, Jack Ly Mar 2019

Chemical Stability And Performance Influence Of Choice Substituents And Core Conjugation Of Organic Semiconductors, Jack Ly

Doctoral Dissertations

Realizing organic based active materials for electronic devices, such as thin film transistors and photovoltaics, has been long sought after. Advancement in the field driven by chemists, engineers, and physicists alike have bolstered organic based semiconductor performance levels to rival those of traditional inorganic amorphous silicon-based devices. Within the field of organic semiconductors (OSC), two categories of active materials may be generalized: (1) polymer and (2) small molecule semiconductors. Each class of OSC inherently have their own advantages and disadvantages. Polymer semiconductors (PSC) allow a wide range in tunability via choice monomers and side chain engineering to illicit desirable energy …


Direct Printing Of Conductive Inks For Organic Electronics And Wearable Microfluidics, Aditi Naik Mar 2019

Direct Printing Of Conductive Inks For Organic Electronics And Wearable Microfluidics, Aditi Naik

Doctoral Dissertations

This dissertation examines the direct printing of conductive inks on polymeric substrates for applications in organic electronics, microfluidic valving systems, and wearable sweat sensors. The inexpensive production of solution-based electrodes with high electrical conductivity is necessary to enable the next-generation of printed, flexible, and organic electronics. Specifically, the optimization and printing of liquid-phase graphene ink and nanoparticle-based silver ink by soft nanoimprint lithography and inkjet-printing is discussed to achieve printed functional devices. Using scalable low-cost patterning systems, these flexible applications are compatible with roll-to-roll processing, enabling large-scale manufacturing. This research expands the knowledge of high-resolution printing optimization for the direct …


The Investigation Of Surface Barrier During Molecular Transport In Hierarchical Zeolites, Xiaoduo Qi Mar 2019

The Investigation Of Surface Barrier During Molecular Transport In Hierarchical Zeolites, Xiaoduo Qi

Doctoral Dissertations

Hierarchical zeolites with micropore lengths on the order of nanometers have been synthesized with the aim of reducing mass transfer limitation. However, due to large external surface to volume ratios, the mass transport in these materials can be hindered by a secondary rate limitation step imposed on the external surface of the zeolites. This has led to the general phenomenon referred to as “surface barriers”, which cause the enhancement in mass transport being far lower than expected. In order to fully unlock the potential of hierarchical zeolites, it is imperative to fundamentally understand the molecular transport in these new types …


Plenum-To-Plenum Heat Transfer Characteristics Under Natural Circulation In A Scaled-Down Prismatic Modular Reactor, Salman Mohammed Alshehri Jan 2019

Plenum-To-Plenum Heat Transfer Characteristics Under Natural Circulation In A Scaled-Down Prismatic Modular Reactor, Salman Mohammed Alshehri

Doctoral Dissertations

“Gas-cooled reactor (GCR) is being developed under the Next Generation Nuclear Plant Program (NGNP) in nuclear engineering studies. As the world searches for an energy source with high energy density, clean, abundant, and storable nature to avoid global warming issues, GCR seems to be a promising solution, particularly the possibility of producing hydrogen. Studying and developing the safety analysis and GCR technologies are required for the optimum design and safety of GCR system. Multiphase Reactors Engineering and Applications Laboratory (mReal) at Missouri University of Science and Technology (S&T) has developed a natural convection heat transfer test facility with one riser …


Computational Fluid Dynamics Modeling And Comparison Of Advanced Techniques For Heat Transfer Augmentation For Nuclear Applications, Salman Mohammed Alzahrani Jan 2019

Computational Fluid Dynamics Modeling And Comparison Of Advanced Techniques For Heat Transfer Augmentation For Nuclear Applications, Salman Mohammed Alzahrani

Doctoral Dissertations

“Passive safety is the most important feature of NuScale’s reactor designs. Twist tape is one passive heat enhance heat technique. The present research investigated thermo-hydraulic characteristics of natural and forced convection of water under different configurations of twisted tape inserted in tube as well as NuScale rod bundles for uniform wall heat flux using computational fluid dynamics (CFD) using ANSYS Fluent 18.1. Results for twist tape inserted in tube under natural circulation showed that heat transfer enhanced and pressure drop increased to 28% and 102.8% over the plain tube respectively. Regularly spaced tapes, and different widths of the twisted tapes …


Development Of Functional Ionic Liquids For Separation And Recovery Of Rare Earth Elements, Mostafa Khodakarami Jan 2019

Development Of Functional Ionic Liquids For Separation And Recovery Of Rare Earth Elements, Mostafa Khodakarami

Doctoral Dissertations

“This research focused on the design and synthesis of task-specific ionic liquids for enhanced extraction and separation of rare earth elements (REEs). Two novel ammonium-based functional ionic liquids (FILs) with oxygen donating groups: trioctyl(2-ethoxy-2-oxoethyl)ammonium dihexyl diglycolamate, [OcGBOEt][DHDGA], and tricaprylmethylammonium dihexyl diglycolamate, [A336][DHDGA] were synthesized and tested for the recovery and separation of selected REEs from aqueous solutions. Functionalities with different denticities were incorporated into both anionic and cationic parts of ionic liquids, which are solely composed of incinerable atoms including C, H, O, and N. The structural, physical, and chemical properties of the synthesized FILs were studied using nuclear magnetic …


Characterization Of A Green Electric Solid Propellant For Electric Propulsion, Matthew Scott Glascock Jan 2019

Characterization Of A Green Electric Solid Propellant For Electric Propulsion, Matthew Scott Glascock

Doctoral Dissertations

"Electric solid propellants are advanced solid chemical rocket propellants that can be controlled (ignited, throttled and extinguished) through the application and removal of an electric current. These propellants are also being considered for use in ablative pulsed plasma thruster and multimode systems. In this work, the behavior and performance of a novel green electric solid propellant operating in an electrothermal ablation-fed pulsed plasma thruster was investigated. Using an inverted pendulum micro-Newton thrust stand, the impulse bit and specific impulse of the device using the electric solid propellant were measured for short-duration and long-duration runs to end-of-life, at energy levels of …


Novel Insights Into Low Salinity Water Flooding Enhanced Oil Recovery In Sandstone Reservoirs, Hasan N. Al-Saedi Jan 2019

Novel Insights Into Low Salinity Water Flooding Enhanced Oil Recovery In Sandstone Reservoirs, Hasan N. Al-Saedi

Doctoral Dissertations

"Ever growing global energy demand and the natural decline in oil production from mature oil fields have been the main incentives to search for methods to increase recovery efficiency for several decades. Water flooding is extensively applied worldwide to improve oil recovery. The recent drop in oil prices has turned the oil industry to the cheapest improved oil recovery (IOR) techniques, such as low salinity (LS) waterflooding. Also, the reduction in reservoir energy and the friendly environmental aspects of low salinity water flooding (LSWF) provide additional incentives for its use. That LS water requires decreasing only the active divalent cations …


Insights Into Well Performance And Completion Optimization Using A Coupled Fracfocus And Drillinginfo Database, Mustafa A. Al-Alwani Jan 2019

Insights Into Well Performance And Completion Optimization Using A Coupled Fracfocus And Drillinginfo Database, Mustafa A. Al-Alwani

Doctoral Dissertations

“The hydraulic fracturing designs, drilling, and completion trends are undergoing continuous change as the oil and gas industry pushing the boundaries of the traditional designs to increase wells productivity and meet the energy demand. The lateral length in addition to the amount of proppant and water used in well stimulation have witnessed a paradigm shift over the past few years. The motivation for this work began with a desire to better understand well performance as a function of the type of fracturing fluid treatment applied. An early objective was to compare whether East Texas Cotton Valley wells stimulated with water …


Intelligent Data-Driven Decision-Making To Mitigate Or Stop Lost Circulation, Husam Hasan Alkinani Jan 2019

Intelligent Data-Driven Decision-Making To Mitigate Or Stop Lost Circulation, Husam Hasan Alkinani

Doctoral Dissertations

”Lost circulation is a challenging problem in the oil and gas industry. Each year, millions of dollars are spent to mitigate or stop this problem. The aim of this work is to utilize machine learning and other intelligent solutions to help to make better decision to mitigate or stop lost circulation. A detailed literature review on the applications of decision tree analysis, expected monetary value, and artificial neural networks in the oil and gas industry was provided. Data for more than 3000 wells were gathered from many sources around the world. Detailed economics and probability analyses for lost circulation treatments’ …


Characterization Of Aerosols In An Underground Mine, Arash A. Habibi Jan 2019

Characterization Of Aerosols In An Underground Mine, Arash A. Habibi

Doctoral Dissertations

“Diesel-powered engines are a common source of submicron carbon-rich particles. Characterizing morphological and physical attributes of diesel agglomerates is therefore of great importance to be able to identify the source and improve removal technology. Size-segregated sampling was conducted in two phases of underground experiments. Scanning transmission electron microscopy and fast mobility particle sizers were used to determine the size distribution of agglomerates based on particle mobility and projected area diameter. Controlled zone sampling test results were used to determine the morphological characteristics of agglomerates for specific types of diesel equipment both with and without removal strategies. Changes in fractal dimension, …


Experimental Study On Enhanced Oil Recovery (Eor) Mechanisms Of Nanogel Combining With Low Salinity Water For Carbonate Reservoirs, Pu Han Jan 2019

Experimental Study On Enhanced Oil Recovery (Eor) Mechanisms Of Nanogel Combining With Low Salinity Water For Carbonate Reservoirs, Pu Han

Doctoral Dissertations

"Nanomaterials have been widely studied and applied in the oil and gas industry. Among the developed nanomaterials, nano-sized crosslinked polymeric gel particle (nanogel) has shown great potential in recovering residual oil and improving oil recovery. This dissertation carried out their potential EOR mechanisms and the synergetic effect between nanogel and low salinity water. Nanogel used in this study was synthesized through the suspension polymerization process in our lab. The morphology, size distribution, and zeta potential were studied for nanogel dispersed in brine with variable ionic strength. The injectivity of nanogel was elucidated at first to ensure their in-depth penetration ability. …


Investigating The Performance Of High Viscosity Friction Reducers Used For Proppant Transport During Hydraulic Fracturing, Mohammed Salem Ba Geri Jan 2019

Investigating The Performance Of High Viscosity Friction Reducers Used For Proppant Transport During Hydraulic Fracturing, Mohammed Salem Ba Geri

Doctoral Dissertations

"Over the last few recent years, high viscosity friction reducers (HVFRs) have been successfully used in the oil and gas industry across all premier shale plays in North America including Permian, Bakken, and Eagle Ford. However, selecting the most suitable fracture fluid system plays an essential role in proppant transport and minimizing or eliminating formation damage.

This study investigates the influence of the use of produced water on the rheological behavior of HVFRs compared to a traditional linear guar gel. Experimental rheological characterization was studied to investigate the viscoelastic property of HVFRs on proppant transport. In addition, the successful implication …


Thermomechanical Analysis Of Rock Asperity In Fractures Of Enhanced Geothermal Systems, Chao Zeng Jan 2019

Thermomechanical Analysis Of Rock Asperity In Fractures Of Enhanced Geothermal Systems, Chao Zeng

Doctoral Dissertations

"Enhanced Geothermal Systems (EGS) offer great potential for dramatically expanding the use of geothermal energy and become a promising supplement for fossil energy. The EGS is to extract heat by creating a subsurface system to which cold water can be added through injection wells. Injected water is heated by contact with rock and returns to the surface through production well. Fracture provides the primary conduit for fluid flow and heat transfer in natural rock. Fracture is propped by fracture roughness with varying heights which is called asperity. The stability of asperity determines fracture aperture and hence imposes substantial effect on …


Transient Multiphase Flow Simulation For Unloading Of Frac Hit Gas Wells, Miguel Angel Cedeno Moreno Jan 2019

Transient Multiphase Flow Simulation For Unloading Of Frac Hit Gas Wells, Miguel Angel Cedeno Moreno

Doctoral Dissertations

"This work seeks to develop a fully step-by-step transient multiphase flow simulation valid for unloading gas wells using nitrogen. It studies the behavior of nitrogen for unloading horizontal gas wells with gas injection in the annulus. The work investigates unloading non-Newtonian fluids such as those which invade offset wells when a frac hit occurs during hydraulic fracturing operations in unconventional wells. The effect of varying tubing depth and injection pressure are included in the study.

Results show that as the plastic viscosity increases, the nitrogen volume and time to unload will be increased. As tubing depth increases, the nitrogen volume …


The Effects Of Low Aspect Ratio And Heat Exchanging Internals On The Bubble Properties And Flow Regime In A Pilot-Plant Bubble/Slurry Bubble Column For Fischer-Tropsch Synthesis, Hayder Al-Naseri Jan 2019

The Effects Of Low Aspect Ratio And Heat Exchanging Internals On The Bubble Properties And Flow Regime In A Pilot-Plant Bubble/Slurry Bubble Column For Fischer-Tropsch Synthesis, Hayder Al-Naseri

Doctoral Dissertations

"Fischer-Tropsch synthesis (F-T) is a process utilized to convert the syngas mixture of CO and H2 to synthetic fuel and chemicals that executed commercially by using the bubble/slurry bubble column reactor. The experimental results reveal that the investigated parameters, in terms the presence of internals, and reducing the aspect ratio and the solids loading, increase the local gas holdup, interfacial area, bubble passage frequency, and decrease the bubble rise velocity, bubble chord length. Meanwhile, the aspect ratio H/D = 4, and 5 provide enough height to established the fully developed flow regime. As a result of the variation in …