Chemical Engineering Commons^™

The Role Of Biological Fluid And Dynamic Flow In The Behavior And Cellular Interactions Of Gold Nanoparticles, Emily K. Breitner, Saber M. Hussain, Kristen K. Comfort

Chemical and Materials Engineering Faculty Publications

Background: Due to their distinctive physicochemical properties, nanoparticles (NPs) have proven to be extremely advantageous for product and application development, but are also capable of inducing detrimental outcomes in biological systems. Standard in vitro methodologies are currently the primary means for evaluating NP safety, as vast quantities of particles exist that require appraisal. However, cell-based models are plagued by the fact that they are not representative of complex physiological systems. The need for a more accurate exposure model is highlighted by the fact that NP behavior and subsequent bioresponses are highly dependent upon their surroundings. Therefore, standard in vitro models …

Characterization Of Iron Phthalocyanine As The Cathode Active Material For Lithium-Ion Batteries, Sarwan S. Sandhu, Joseph P. Fellner

Chemical and Materials Engineering Faculty Publications

The developed thermodynamic functions for the determination of Gibbs free energy, enthalpy, and entropy of formation of solid lithium-iron phthalocyanine (LixFePc) from solid lithium and iron phthalocyanine as a function of x, defined as g-moles of the intercalated lithium per g-mole of iron phthalocyanine, at a fixed set of temperature and pressure conditions are presented. In addition, a proposed expression for the evaluation of lithium diffusion coefficient in solid iron phthalocyanine as a function of both x and temperature, and the experimental results from the ongoing research/development work on the lithium/iron phthalocyanine cells are included.

Electrode Side Reactions, Capacity Loss And Mechanical Degradation In Lithium-Ion Batteries, Jiagang Xu, Rutooj D. Deshpande, Jie Pan, Yang-Tse Cheng, Vincent S. Battaglia

Chemical and Materials Engineering Faculty Publications

For advancing lithium-ion battery (LIB) technologies, a detailed understanding of battery degradation mechanisms is important. In this article, experimental observations are provided to elucidate the relation between side reactions, mechanical degradation, and capacity loss in LIBs. Graphite/Li(Ni_1/3Mn_1/3Co_1/3)O₂ cells of two very different initial anode/cathode capacity ratios (R, both R > 1) are assembled to investigate the electrochemical behavior. The initial charge capacity of the cathode is observed to be affected by the anode loading, indicating that the electrolyte reactions on the anode affect the electrolyte reactions on the cathode. Additionally, the rate of “marching” …

A Quantitative Perspective On Surface Marker Selection For The Isolation Of Functional Tumor Cells, Calvin F. Cahall, Jacob L. Lilly, Edward A. Hirschowitz, Brad J. Berron

Chemical and Materials Engineering Faculty Publications

Much effort has gone into developing fluid biopsies of patient peripheral blood for the monitoring of metastatic cancers. One common approach is to isolate and analyze tumor cells in the peripheral blood. Widespread clinical implementation of this approach has been hindered by the current choice of targeting epithelial markers known to be highly variable in primary tumor sites. Here, we review current antigen-based tumor cell isolation strategies and offer biological context for commonly studied cancer surface markers. Expression levels of the most common markers are quantitated for three breast cancer and two non-small cell lung cancer (NSCLC) lineage models. These …

Electromagnetic Induction By Ferrofluid In An Oscillating Heating Pipe, John Gabriel Monroe, Erick S. Vasquez, Zachary S. Aspin, Keisha B. Walters, Matthew J. Berg, Scott M. Thompson

Chemical and Materials Engineering Faculty Publications

No abstract provided.

Analysis Of Particle Transport And Deposition Of Micron-Sized Particles In A 90° Bend Using A Two-Fluid Eulerian–Eulerian Approach, Erick S. Vasquez, Keisha B. Walters, D. Keith Walters

Chemical and Materials Engineering Faculty Publications

Two-phase flows involving dispersed particle and droplet phases are common in a variety of natural and industrial processes, such as aerosols, blood flow, emulsions, and gas-catalyst systems. For sufficiently dilute particle/aerosol phases, a simplified one-way coupling is often assumed, in which the continuous primary phase is unaffected by the presence of the dispersed secondary phase and standard CFD methods can be applied. To predict the transport and deposition of the particle phase, typically a Lagrangian particle-tracking or Eulerian one-fluid/two-phase drift-flux approach is used. Here, a full two-fluid Eulerian modeling approach is presented for coarse particles (>1 μm), in which …

Optimization Of Graphene-Based Materials Outperforming Host Epoxy Matrices, Liberata Guadagno, Marialuigia Raimondo, Luigi Vertuccio, Marco Mauro, Gaetano Guerra, Khalid Lafdi, Biagio De Vivo, Patrizia Lamberti, Giovanni Spinelli, Vincenzo Tucci

Chemical and Materials Engineering Faculty Publications

The degree of graphite exfoliation and edge-carboxylated layers can be controlled and balanced to design lightweight materials characterized by both low electrical percolation thresholds (EPT) and improved mechanical properties. So far, this challenging task has been undoubtedly very hard to achieve.

The results presented in this paper highlight the effect of exfoliation degree and the role of edge-carboxylated graphite layers to give self-assembled structures embedded in the polymeric matrix. Graphene layers inside the matrix may serve as building blocks of complex systems that could outperform the host matrix. Improvements in electrical percolation and mechanical performance have been obtained by a …

General Method To Predict Voltage-Dependent Ionic Conduction In A Solid Electrolyte Coating On Electrodes, Jie Pan, Yang-Tse Cheng, Yue Qi

Chemical and Materials Engineering Faculty Publications

Understanding the ionic conduction in solid electrolytes in contact with electrodes is vitally important to many applications, such as lithium ion batteries. The problem is complex because both the internal properties of the materials (e.g., electronic structure) and the characteristics of the externally contacting phases (e.g., voltage of the electrode) affect defect formation and transport. In this paper, we developed a method based on density functional theory to study the physics of defects in a solid electrolyte in equilibrium with an external environment. This method was then applied to predict the ionic conduction in lithium fluoride (LiF), in contact with …

Composition And Work Function Relationship In Os–Ru–W Ternary Alloys, Phillip D. Swartzentruber, Michael J. Detisch, Thomas John Balk

Chemical and Materials Engineering Faculty Publications

Os–Ru thin films with varying concentrations of W were sputter deposited in order to investigate their structure–property relationships. The films were analyzed with x-ray diffraction to investigate their crystal structures, and a Kelvin probe to investigate their work functions. An Os–Ru–W film with ∼30 at. % W yielded a work function maximum of approximately 5.38 eV. These results align well with other studies that found work function minima from thermionic emission data on M-type cathodes with varying amounts of W in the coatings. Furthermore, the results are consistent with other work explaining energy-level alignment and charge transfer of molecules on …

Computational Multiscale Modeling And Characterization Of Piezoresistivity In Fuzzy Fiber Reinforced Polymer Composites, Xiang Ren, Josh Burton, Gary D. Seidel, Khalid Lafdi

Chemical and Materials Engineering Faculty Publications

In this paper, the piezoresistive response (i.e. the change of resistance under the application of strain) of polymer composites reinforced by a novel material known as fuzzy fibers is characterized by using single tow piezoresistive fragmentation tests and modeled by using a 3D computational multiscale model based on the finite element analysis. In the characterization work, the fuzzy fiber tow is embedded in a dog-bone specimen infused by epoxy, with resistance and displacement measured simultaneously to obtain its piezoresistive response. An approximately linear and stable piezoresistive response is observed within the fuzzy fiber tow region yielding gauge factors on average …

Cytotoxic Activity Of Triazole-Containing Alkyl Ss-D-Glucopyranosides On A Human T-Cell Leukemia Cell Line, Edward Davis Oldham, Larissa M. Nunes, Armando Varela-Ramirez, Stephen E. Rankin, Barbara L. Knutson, Renato J. Aguilera, Hans-Joachim Lehmler

Chemical and Materials Engineering Faculty Publications

BACKGROUND: Simple glycoside surfactants represent a class of chemicals that are produced from renewable raw materials. They are considered to be environmentally safe and, therefore, are increasingly used as pharmaceuticals, detergents, and personal care products. Although they display low to moderate toxicity in cells in culture, the underlying mechanisms of surfactant-mediated cytotoxicity are poorly investigated.

RESULTS: We synthesized a series of triazole-linked (fluoro)alkyl β-glucopyranosides using the copper-catalyzed azide-alkyne reaction, one of many popular "click" reactions that enable efficient preparation of structurally diverse compounds, and investigate the toxicity of this novel class of surfactant in the Jurkat cell line. Similar to …

Temporally And Spatially Resolved Plasma Spectroscopy In Pulsed Laser Deposition Of Ultra-Thin Boron Nitride Films, Nicholas R. Glavin, Christopher Muratore, Michael L. Jespersen, Jianjun Hu, Timothy S. Fisher, Andrey A. Voevodin

Chemical and Materials Engineering Faculty Publications

Physical vapor deposition (PVD) has recently been investigated as a viable, alternative growth technique for two-dimensional materials with multiple benefits over other vapor deposition synthesis methods. The high kinetic energies and chemical reactivities of the condensing species formed from PVD processes can facilitate growth over large areas and at reduced substrate temperatures. In this study, chemistry, kinetic energies, time of flight data, and spatial distributions within a PVD plasma plume ablated from aboron nitride (BN) target by a KrF laser at different pressures of nitrogen gas were investigated. Time resolved spectroscopy and wavelength specific imaging were used to identify and …

The Future Of Carbon-Based Scaffolds In Foot And Ankle Surgery, Jarema S. Czarnecki, Khalid Lafdi, Panagiotis A. Tsonis

Chemical and Materials Engineering Faculty Publications

Autologous grafts have been the gold standard in tissue replacement and the most accurate means of recapitulating both the biological and mechanical properties of tissue. However, autologous grafts have had complications and drawbacks. Skin grafting, a prime example of an autologous tissue graft, has been limited by the size of graft, availability, and secondary donor site morbidity. Use of cadaveric tissues circumvents several limitations of autologous grafts; however, sterilization processes used to reduce the risk of disease transmission potentially weaken tissues and eliminate living cells and some growth factors from scaffolds, making them suboptimal tissue replacements. Chemical cross-linkage of tissue …

Effects Of Disorder State And Interfacial Layer On Thermal Transport In Copper/Diamond System, Vikas Sinha, Jaime J. Gengler, Christopher Muratore, Jonathan E. Spowart

Chemical and Materials Engineering Faculty Publications

The characterization of Cu/diamond interface thermal conductance (h_c) along with an improved understanding of factors affecting it are becoming increasingly important, as Cu-diamond composites are being considered for electronic packaging applications. In this study, ∼90 nm thick Cu layers weredeposited on synthetic and natural single crystal diamond substrates. In several specimens, a Ti-interface layer of thickness ≤3.5 nm was sputtered between the diamond substrate and the Cu top layer. The h_c across Cu/diamond interfaces for specimens with and without a Ti-interface layer was determined usingtime-domain thermoreflectance. The h_c is ∼2× higher for similar interfacial layers on …

Interfacial Polymerization For Colorimetric Labeling Of Protein Expression In Cells, Jacob L. Lilly, Phillip R. Sheldon, Liv J. Hoversten, Gabriela Romero, Vivek Balasubramaniam, Brad J. Berron

Chemical and Materials Engineering Faculty Publications

Determining the location of rare proteins in cells typically requires the use of on-sample amplification. Antibody based recognition and enzymatic amplification is used to produce large amounts of visible label at the site of protein expression, but these techniques suffer from the presence of nonspecific reactivity in the biological sample and from poor spatial control over the label. Polymerization based amplification is a recently developed alternative means of creating an on-sample amplification for fluorescence applications, while not suffering from endogenous labels or loss of signal localization. This manuscript builds upon polymerization based amplification by developing a stable, archivable, and colorimetric …

Field-Limited Migration Of Li-Ions In Li-Ion Battery, Fuqian Yang

Chemical and Materials Engineering Faculty Publications

The migration of Li-ions in lithium-ion battery cannot be simply described by Fick's second law; the interactions among ionic migration, field, and stress need to be taken into account when analyzing the migration of Li-ions. Using the theory of thermal activation process, the flux for ionic migration under concurrent action of electric field and mechanical stress is found to be a nonlinear function of the gradient of electric potential and the gradient of stress. Electric field can either accelerate or retard the growth of the lithiation layer, depending on polarity of the field.

Growth And Properties Of Carbon Microcoils And Nanocoils, Muneaki Hikita, Robyn Bradford, Khalid Lafdi

Chemical and Materials Engineering Faculty Publications

Various types of coiled carbon filaments have been synthesized using chemical vapor deposition and other methods. These carbon filaments exhibit unique electrical and mechanical properties due to their versatile shapes and structures. To form coiled shapes, different types of catalyst compositions and reactive gases have been explored. Generally, coiled carbon filaments are classified by coil diameter and shape (e.g., microcoil and nanocoil). In this review, coiled carbon filaments are classified into three growth mechanism categories:

(1) bidirectional double helical growth;

(2) bidirectional twisted growth; and

(3) tip single helical or twisted growth.

Next, their synthesis methods and hypothetical growth mechanisms …

Slow Release Of Ions From Internalized Silver Nanoparticles Modifies The Epidermal Growth Factor Signaling Response, Kristen K. Comfort, Elizabeth I. Maurer, Saber M. Hussain

Chemical and Materials Engineering Faculty Publications

Due to their distinctive physiochemical properties, including a robust antibacterial activity and plasmonic capability, hundreds of consumer and medical products contain colloidal silver nanoparticles (AgNPs). However, even at sub-toxic dosages, AgNPs are able to disrupt cell functionality, through a yet unknown mechanism. Moreover, internalized AgNPs have the potential to prolong this disruption, even after the removal of excess particles. In the present study, we evaluated the impact, mechanism of action, and continual effects of 50 nm AgNP exposure on epidermal growth factor (EGF) signal transduction within a human keratinocyte (HaCaT) cell line. After AgNP expose, EGF signaling was initially obstructed …

The Stochastic Dynamics Of Tethered Microcantilevers In A Viscous Fluid, Brian A. Robbins, Milad Radiom, William A. Ducker, John Y. Walz, Mark R. Paul

Chemical and Materials Engineering Faculty Publications

We explore and quantify the coupled dynamics of a pair of micron scale cantilevers immersed in a viscous fluid that are also directly tethered to one another at their tips by a spring force. The spring force, for example, could represent the molecular stiffness or elasticity of a biomolecule or material tethered between the cantilevers. We use deterministic numerical simulations with the fluctuation-dissipation theorem to compute the stochastic dynamics of the cantilever pair for the conditions of experiment when driven only by Brownian motion. We validate our approach by comparing directly with experimental measurements in the absence of the tether …

Oxidation-Resistant, Solution-Processed Plasmonic Ni Nanochain-SioX (X < 2) Selective Solar Thermal Absorbers, Xiaobai Yu, Xiaoxin Wang, Qinglin Zhang, Juchuan Li, Jifeng Liu

Chemical and Materials Engineering Faculty Publications

Metal oxidation at high temperatures has long been a challenge in cermet solar thermal absorbers, which impedes the development of atmospherically stable, high-temperature, high-performance concentrated solar power (CSP) systems. In this work, we demonstrate solution-processed Ni nanochain-SiO_x (x < 2) and Ni nanochain-SiO₂ selective solar thermal absorbers that exhibit a strong anti-oxidation behavior up to 600 °C in air. The thermal stability is far superior to previously reported Ni nanoparticle-Al₂O₃ selective solar thermal absorbers, which readily oxidize at 450 °C. The SiO_x (x < 2) and SiO₂ matrices are derived from hydrogen silsesquioxane and tetraethyl orthosilicate precursors, respectively, which comprise Si-O cage-like …

A Non-Destructive Method For Measuring The Mechanical Properties Of Ultrathin Films Prepared By Atomic Layer Deposition, Qinglin Zhang, Xingcheng Xiao, Yang-Tse Cheng, Mark W. Verbrugge

Chemical and Materials Engineering Faculty Publications

The mechanical properties of ultrathin films synthesized by atomic layer deposition (ALD) are critical for the liability of their coated devices. However, it has been a challenge to reliably measure critical properties of ALD films due to the influence from the substrate. In this work, we use the laser acoustic wave (LAW) technique, a non-destructive method, to measure the elastic properties of ultrathin Al₂O₃ films by ALD. The measured properties are consistent with previous work using other approaches. The LAW method can be easily applied to measure the mechanical properties of various ALD thin films for multiple …

Photo-Sensitivity Of Large Area Physical Vapor Deposited Mono And Bilayer Mos2, Baoming Wang, Christopher Muratore, Andrey A. Voevodin, M. Amanul Haque

Chemical and Materials Engineering Faculty Publications

We present photosensitivity in large area physical vapour deposited mono and bi-layer MoS2 films. Photo-voltaic effect was observed in single layer MoS2 without any apparent rectifying junctions, making device fabrication straightforward. For bi-layers, no such effect was present, suggesting strong size effect in light-matter interaction. The photo-voltaic effect was observed to highly direction dependent in the film plane, which suggests that the oblique deposition configuration plays a key role in developing the rectifying potential gradient. To the best of our knowledge, this is the first report of any large area and transfer free MoS2 photo device with performance comparable to …

Correlation Between Microstructure And Thermionic Electron Emission From Os-Ru Thin Films On Dispenser Cathodes, Phillip D. Swartzentruber, Thomas John Balk, Michael P. Effgen

Chemical and Materials Engineering Faculty Publications

Osmium-ruthenium films with different microstructures were deposited onto dispenser cathodes and subjected to 1000 h of close-spaced diode testing. Tailored microstructures were achieved by applying substrate biasing during deposition, and these were evaluated with scanning electron microscopy, x-ray diffraction, and energy dispersive x-ray spectroscopy before and after close-spaced diode testing. Knee temperatures determined from the close-spaced diode test data were used to evaluate cathode performance. Cathodes with a large {10-11} Os-Ru film texture possessed comparatively low knee temperatures. Furthermore, a low knee temperature correlated with a low effective work function as calculated from the close-spaced diode data. It is proposed …

Influence Of Nanofiller Morphology On The Viscoelastic Properties Of Cnf/Epoxy Resins, Liberata Guadagno, Marialuigia Raimondo, Khalid Lafdi, Annalisa Fierro, Salvatore Rosolia, Maria Rossella Nobile

Chemical and Materials Engineering Faculty Publications

In this paper we discuss the viscoelastic properties of CNF/Epoxy-Amine Resins for structural applications. The use of reactive diluent inside the unfilled and nanofilled epoxy mixture as proven to be of benefit to strongly decrease the viscosity.

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 …

Continuous Ultra-Thin Mos2 Films Grown By Low-Temperature Physical Vapor Deposition, Christopher Muratore, Jianjun Hu, Baoming Wang, M. Amanul Haque, John E. Bultman, Michael L. Jespersen, Michael E. Mcconney, R. D. Naguy

Chemical and Materials Engineering Faculty Publications

Uniform growth of pristine two dimensional (2D) materials over large areas at lower temperatures without sacrifice of their unique physical properties is a critical pre-requisite for seamless integration of next-generation van der Waals heterostructures into functional devices. This Letter describes a vapor phasegrowth technique for precisely controlled synthesis of continuous, uniform molecular layers of MoS2 on silicon dioxide and highly oriented pyrolitic graphite substrates of over several square centimeters at 350 °C. Synthesis of few-layer MoS2 in this ultra-high vacuum physical vapor deposition process yieldsmaterials with key optical and electronic properties identical to exfoliated layers. The films are composed of …

Optical Properties Of Carbon Microcoils, Muneaki Hikita, Li Cao, Khalid Lafdi

Chemical and Materials Engineering Faculty Publications

Carbon microcoils (CMCs) have emerged as versatile material artifacts for a variety of applications due to their helical and spiral structures. Embedded in matrix, CMCs have already been demonstrated for their potential tactile/proximity sensor application. In this study, CMCs were prepared using a conventional chemical vapor deposition method, and then were functionalized with octadecylamine.

Upon photoexcitation, the functionalized CMCs exhibited photoluminescence in the visible region, which has never been found before. Similar to carbon based nanoparticles, the photoluminescence of CMCs was attributed to electron-hole radiative recombination after surface passivation. The results suggested that this kind of fluorescent functionalized CMCs might …

Domain Engineering Of Physical Vapor Deposited Two-Dimensional Materials, Tarek Alam, Baoming Wang, Raghu Pulavarthy, M. Amanul Haque, Christopher Muratore, Nicholas R. Glavin, Ajit K. Roy, Andrey A. Voevodin

Chemical and Materials Engineering Faculty Publications

Physical vapor deposited two-dimensional (2D) materials span larger areas compared to exfoliated flakes, but suffer from very small grain or domain sizes. In this letter, we fabricate freestanding molybdenum disulfide (MoS2) and amorphous boron nitride (BN) specimens to expose both surfaces. We performed in situ heating in a transmission electron microscope to observe the domain restructuring in real time. The freestanding MoS2 specimens showed up to 100× increase in domain size, while the amorphous BN transformed in to polycrystalline hexagonal BN (h-BN) at temperatures around 600 °C much lower than the 850–1000 °C range cited in the literature.

Less Is More: Long-Term In Vitro Exposure To Low Levels Of Silver Nanoparticles Provides New Insights For Nanomaterial Evaluation, Kristen K. Comfort, Laura K. Braydich-Stolle, Elizabeth I. Maurer, Saber M. Hussain

Chemical and Materials Engineering Faculty Publications

In view of the vast number of new nanomaterials (NMs) that require testing and the constraints associated with animal models, the majority of studies to elucidate nanotoxicological effects have occurred in vitro, with limited correlation and applicability to in vivo systems and realistic, occupational exposure scenarios.

In this study, we developed and implemented a chronic in vitromodel coupled with lower, regulatory dosages in order to provide a more realistic assessment of NM-dependent consequences and illuminate the implications of long-term NM exposure. When keratinocytes were exposed to 50 nm silver nanoparticles (Ag-NPs), we determined that chronically dosed cells operated …

Physiological Fluid Specific Agglomeration Patterns Diminish Gold Nanorod Photothermal Characteristics, Kristen K. Comfort, Jared W. Speltz, Bradley M. Stacy, Larry R. Dosser, Saber M. Hussain

Chemical and Materials Engineering Faculty Publications

Investigations into the use of gold nanorods (Au-NRs) for biological applications are growing exponentially due to their distinctive physicochemical properties, which make them advantageous over other nanomaterials. Au-NRs are particularly renowned for their plasmonic characteristics, which generate a robust photothermal response when stimulated with light at a wavelength matching their surface plasmon resonance. Numerous reports have explored this nanophotonic phenomenon for temperature driven therapies; however, to date there is a significant knowledge gap pertaining to the kinetic heating profile of Au-NRs within a controlled physiological setting. In the present study, the impact of environmental composition on Au-NR behavior and degree …