Materials & Nanotechnology Doctoral Work

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The Development, Characterization and Testing of Mg-rich Primers
(North Dakota State University, 2012) Battocchi, Dante
Aluminum alloys are widely used in aircraft industry for their strength and light weight. Those alloys that are hardened by precipitation, especially the Copper-rich of the 2000 series, are prone to corrosion and are protected against it using chromate containing coatings. The primary component of these coating systems is Chromium 6+ (CrVI) that has been found to be very toxic in the environment and carcinogenic, toxic and mutagenic in humans. The Mg-rich primer development is the result of a successful multi-year project funded by the US Air-force with its objective the replacement of coatings based on CrVI with a class of coatings less toxic and with comparable protective performances. The Mg rich primer fulfilled the USAF requirements and it is currently undergoing commercial and military qualifications testing. The use of Mg as one of the active pigments in coatings allows the primer to protect the underlying Al sacrificially, not considered possible for this substrate until now. Mg is anodic to most of the other structural metals and when particulate Mg became available commercially, the concept of the primer was first developed by analogy to Zn-rich coatings for steel. When Mg and Al are in contact and immersed in a corrosive environment, magnesium corrodes preferentially and protects the aluminum.
Synthesis of Sustainable Polymers from Vegetable Oil: Applications in Coatings and Nanoparticle Surface Modification
(North Dakota State University, 2013) Kalita, Harjyoti
Polymeric materials are increasing being used in many household, industrial, and health and personal care products. These materials, being either non-degradable or slow degradable, remain in the environment for a long time and are posing increasingly significant threats to the ecosystem components including mammals, birds, fish, reptiles, and crustaceans. Renewable resource based materials are the best raw materials for the development of sustainable products. Vegetable oil and polyglycol based novel copolymers have been synthesized in this research. Poly(2-VOES-r-TEGEVE) copolymers were synthesized from 2-(vinyloxyethyl) soyate (2-VEOS) and tri(ethylene glycol) ethyl vinyl ether (TEGEVE) via cationic polymerization. They were used in waterborne coating as self-dispersible polymers and as surfmers. Four different copolymers were synthesized having 2-VOES wt% as 10, 15, 25, 50 and rest being TEGEVE. In addition to that water insoluble poly(2-VOES) copolymers were synthesized from soybean oil. All copolymers were used as self-dispersible polymers and their coating property were analyzed by measuring glass transition temperature, drying time, gloss, transparency, contact angle, hysteresis, tensile strength, and hardness. Results showed that the coatings can be cured by autoxidation drying process within 6.1 to 8.2 h. Results also showed high transparency (coated in glass panel) with maximum 2% absorbance which is comparable to uncoated substrate (clean glass). Copolymer having 2-VOES wt% 15 and 50 were used as surfmers to disperse poly(2-VOES) and they were cured using autoxidation method. Results showed that the curing of film can be achieved within 2.6 to 8.0 h. High gloss and transparency confirmed that the surfmers get copolymerized with poly(2-VOES). Another set of poly(2-VOES-r-TEGEVE) copolymers with 2-VOES wt% 15, 25, 50, 75 and 85 were synthesized and then functionalized with a carboxyl group. These carboxyl functionalized polymer were used to coat nanoscale zero-valent iron (NZVI) to enhance their colloidal stability in aqueous media with an objective of using the coated particles for groundwater remediation. Structure property analysis of the coated NZVI showed that carboxyl functional copolymer with 15 wt% 2-VOES and 85 wt% TEGEVE had the best colloidal stability of the coated NZVI (CNZVI). Treatability study with CNZVI was carried out using trichloroethylene (TCE) and arsenic [As(V)] as model contaminants. Treatability data indicated that CNZVI can degrade 85 % of TCE (initial concentration 15 mgL-1) within 6 h and remove 99% of As(V) (initial concentration 15 mgL-1) within 0.5 h. Results also showed that CNZVI has higher contaminant (TCE and arsenic) removable rate compared to NZVI. The biodegradation behaviors of carboxyl functionalized poly(2-VOES-r-TEGEVE) copolymers were analyzed by respirometric, microbial growth, and gel permeation chromatography (GPC) studies. Respirometic test confirmed 90% degradations of carboxyl functionalized poly(2-VOES-r-TEGEVE) copolymers within 28 d. Microbial growth and GPC studies also support the data obtained from respirometic tests.
Biomimetic Nanoclay Scaffolds for Bone Tissue Engineering
(North Dakota State University, 2014) Ambre, Avinash Harishchandra
Tissue engineering offers a significant potential alternative to conventional methods for rectifying tissue defects by evoking natural regeneration process via interactions between cells and 3D porous scaffolds. Imparting adequate mechanical properties to biodegradable scaffolds for bone tissue engineering is an important challenge and extends from molecular to macroscale. This work focuses on the use of sodium montmorillonite (Na-MMT) to design polymer composite scaffolds having enhanced mechanical properties along with multiple interdependent properties. Materials design beginning at the molecular level was used in which Na-MMT clay was modified with three different unnatural amino acids and further characterized using Fourier Transform Infrared (FTIR) spectroscopy, X-ray diffraction (XRD). Based on improved bicompatibility with human osteoblasts (bone cells) and intermediate increase in d-spacing of MMT clay (shown by XRD), 5-aminovaleric acid modified clay was further used to prepare biopolymer (chitosan-polygalacturonic acid complex) scaffolds. Osteoblast proliferation in biopolymer scaffolds containing 5-aminovaleric acid modified clay was similar to biopolymer scaffolds containing hydroxyapatite (HAP). A novel process based on biomineralization in bone was designed to prepare 5-aminovaleric acid modified clay capable of imparting multiple properties to the scaffolds. Bone-like apatite was mineralized in modified clay and a novel nanoclay-HAP hybrid (in situ HAPclay) was obtained. FTIR spectroscopy indicated a molecular level organic-inorganic association between the intercalated 5-aminovaleric acid and mineralized HAP. Osteoblasts formed clusters on biopolymer composite films prepared with different weight percent compositions of in situ HAPclay. Human MSCs formed mineralized nodules on composite films and mineralized extracellular matrix (ECM) in composite scaffolds without the use of osteogenic supplements. Polycaprolactone (PCL), a synthetic polymer, was used for preparing composites (films and scaffolds) containing in situ HAPclay. Composite films showed significantly improved nanomechanical properties. Human MSCs formed mineralized ECM on films in absence of osteogenic supplements and were able to infiltrate the scaffolds. Atomic force microscopy imaging of mineralized ECM formed on composite films showed similarities in dimensions, arrangement of collagen and apatite with their natural bone counterparts. This work indicates the potential of in situ HAPclay to impart polymeric scaffolds with osteoinductive, osteoconductive abilities and improve their mechanical properties besides emphasizing nanoclays as cell-instructive materials.
Laser-Assisted Advanced Assembly for MEMS Fabrication
(North Dakota State University, 2014) Atanasov, Yuriy Andreev
Micro Electro-Mechanical Systems (MEMS) are currently fabricated using methods originally designed for manufacturing semiconductor devices, using minimum if any assembly at all. The inherited limitations of this approach narrow the materials that can be employed and reduce the design complexity, imposing limitations on MEMS functionality. The proposed Laser-Assisted Advanced Assembly (LA3) method solves these problems by first fabricating components followed by assembly of a MEMS device. Components are micro-machined using a laser or by photolithography followed by wet/dry etching out of any material available in a thin sheet form. A wide range of materials can be utilized, including biocompatible metals, ceramics, polymers, composites, semiconductors, and materials with special properties such as memory shape alloys, thermoelectric, ferromagnetic, piezoelectric, and more. The approach proposed allows enhancing the structural and mechanical properties of the starting materials through heat treatment, tribological coatings, surface modifications, bio-functionalization, and more, a limited, even unavailable possibility with existing methods. Components are transferred to the substrate for assembly using the thermo-mechanical Selective Laser Assisted Die Transfer (tmSLADT) mechanism for microchips assembly, already demonstrated by our team. Therefore, the mechanical and electronic part of the MEMS can be fabricated using the same equipment/method. The viability of the Laser-Assisted Advanced Assembly technique for MEMS is demonstrated by fabricating magnetic switches for embedding in a conductive carbon-fiber metamaterial for use in an Electromagnetic-Responsive Mobile Cyber-Physical System (E-RMCPS), which is expected to improve the wireless communication system efficiency within a battery-powered device.
Synthesis and Characterization of Novel Hierarchically Functionalized Carbon Nanofibers for Energy Conversion and Storage Applications
(North Dakota State University, 2014) Zhou, Zhengping
Among various energy conversion and storage devices available in the market, supercapacitors are deemed as an effective, competitive solution to the increasing demand for high-power density energy-storage devices. Yet, supercapacitors usually carry relatively low energy density compared to batteries. Nanostructured electrode materials are expected being able to greatly enhance the electrochemical performance of supercapacitors. This research aims at rational synthesis and electrochemical characterization of novel hierarchically functionalized carbon nanofibers (CNFs) for use as advanced electrode materials of supercapacitors. These novel CNFs [(i.e., graphene-beaded CNFs (G/CNFs) and carbon nanotube (CNT)-grown CNFs (CNT/CNFs)] were successfully synthesized. The unique synthesis routes consist of electrospinning the precursor polymer nanofibers, followed by controlled carbonization, chemical vapor deposition (CVD) for CNT growth, and in situ polymerization for coating nanostructured conducting polymer. These new electrode materials carry the advantages of G/CNFs and CNT/CNFs (e.g., unique nanostructural continuity, large specific surface area, low intrinsic contact electric resistance, etc.) and conducting polymers (e.g., high pseudocapacitance), and therefore show excellent electrochemical performance including high specific capacitance, superior energy and power densities, and excellent cyclability. In addition, this work also provides the experimental study on parameter dependency of conic angle in electrospinning and scalable fabrication of core-shell nanofibers via needleless emulsion electrospinning.
Multicomponent Doped Barium Strontium Titanate Thin Films for Tunable Microwave Applications
(North Dakota State University, 2014) Alema, Fikadu Legesse
In recent years there has been enormous progress in the development of barium strontium titanate (BST) films for tunable microwave applications. However, the properties of BST films still remain inferior compared to bulk materials, limiting their use for microwave technology. Understanding the film/substrate mismatch, microstructure, and stoichiometry of BST films and finding the necessary remedies are vital. In this work, BST films were deposited via radio frequency magnetron sputtering method and characterized both analytically and electrically with the aim of optimizing their properties. The stoichiometry, crystal structure, and phase purity of the films were studied by varying the oxygen partial pressure (OPP) and total gas pressure (TGP) in the chamber. A better stoichiometric match between film and target was achieved when the TGP is high (> 30 mTorr). However, the O2/Ar ratio should be adjusted as exceeding a threshold of 2 mTorr in OPP facilitates the formation of secondary phases. The growth of crystalline film on platinized substrates was achieved only with a lower temperature grown buffer layer, which acts as a seed layer by crystallizing when the temperature increases. Concurrent Mg/Nb doping has significantly improved the properties of BST thin films. The doped film has shown an average tunability of 53%, which is only ~8 % lower than the value for the undoped film. This drop is associated with the Mg ions whose detrimental effects are partially compensated by Nb ions. Conversely, the doping has reduced the dielectric loss by ~40 % leading to a higher figure of merit. Moreover, the two dopants ensure a charge neutrality condition which resulted in significant leakage current reduction. The presence of large amounts of empty shallow traps related to NbTi localize the free carriers injected from the contacts; thus increase the device control voltage substantially (>10 V). A combinatorial thin film synthesis method based on co-sputtering of two BST sources doped with Mg/Nb and Ce, respectively, was applied. The composition and the dielectric properties of the deposited film were correlated and the optimal concentration of dopants corresponding to high tunability and low dielectric loss was determined in a timely fashion.
Optical Properties and Ensemble Characteristics of Size Purified Silicon Nanocrystals
(North Dakota State University, 2014) Miller, Joseph Bradley
Nanotechnology is at the forefront of current scienti c research and nanocrystals are being hailed as the `arti cial' atoms of the 21st century. Semiconducting silicon nanocrystals (SiNCs) are prime candidates for potential commercial applications because of silicon's already ubiquitous presence in the semiconductor industry, nontoxicity and abundance in nature. For realization of these potential applications, the properties and behavior of SiNCs need to be understood and enhanced. In this report, some of the main SiNC synthesis schemes are discussed, including those we are currently experimenting with to create our own SiNCs and the one utilized to create the SiNCs used in this study. The underlying physics that governs the unique behavior of SiNCs is then presented. The properties of the as-produced SiNCs are determined to depend strongly on surface passivation and environment. Size puri cation, an important aspect of nanomaterial utilization, was successfully performed on our SiNCs though density gradient ultracentrifugation. We demonstrate that the size-puri ed fractions exhibit an enhanced ability for colloidal self-assembly, with better aligned nanocrystal energy levels which promotes greater photostability in close-packed lms and produces a slight increase in photoluminescence (PL) quantum yield. The qualities displayed by the fractions are exploited to form SiNC clusters that exhibit photostable PL. An analysis of SiNC cluster (from individual nanocrystals to collections of more than one thousand) blinking and PL shows an improvement in their PL emitting `on' times. Pure SiNC lms and SiNC-polymer nanocomposites are created and the dependence of their PL on temperature is measured. For such nanocomposites, the coupling between the `co ee-ring' e ect and liquid-liquid phase separation is also examined for ternary mixtures of solvent, polymer and semiconducting nanocrystal. We discover that with the right SiNC-polymer concentration and polymer molecular weight, phase separation can be supressed; we use this to build a prototype nanocomposite printing device. Finally, the nanocrystals are PEGylated and introduced into an aqueous biological environment to demonstrate their potential for use in biological labelling and sensing devices. The development of superlattice structures from monodisperse SiNC fractions and their use in solid-state lighting and solar cell applications are also explored.
Experimental Evaluation of Multiscale Behavior of Human Bone
(North Dakota State University, 2014) Gu, Chunju
Bone is the most important structural member of the human body. It has a unique hierarchical structure and its primary constituents, collagen molecules and hydroxyapatite, are arranged in a staggered pattern at nanometer scale. Osteogenesis imperfecta (OI) is an inheritable disease characterized by the fragility of bones and other tissues rich in the type I collagen. OI provides an interesting platform for investigating how alterations of collagen at the molecular level cause changes in the structure of bone. In this dissertation, multi-scale-, particularly nanometer and sub-micro scale-, behaviors of both normal and OI (putative type I) human bones have been evaluated experimentally. Since chemical treatment influences collagen or mineral structure, we have used ―undisturbed bone samples‖ that are not subjected to any chemicals as previously done in literature. Photoacoustic-Fourier transform infrared spectroscopy (PA-FTIR) experiments reveal orientational differences in stoichiometry of hydroxyapatite. FTIR, electron microscopy, scanning probe microscopy, and nanomechanical tests also show that the OI disease results in a distorted microstructure in bone and that the mineralization of hydroxyapatite in OI is also altered. Modulus mapping test displays the distribution of mineralized fibril and extrafibrillar mineral according to the spatial variation of elastic properties. Dynamic nanomechanical behaviors of OI bone and normal bone indicates that the viscoelasticity of intact bone is mostly determined by the mineral. Also investigated are molecular composition and nanomechanical properties of different anatomical positions in the diaphysis of an OI human tibia. Our study on OI bone describes unique differences in collagen as previously described but also elaborates on unique influence of the non-collagenous proteins on mineralization of bone in OI. The fundamental premise of this work is investigation of the molecular basis of this highly debilitating bone disease.
Synthesis, Characterization, and Modeling of New Molecule-Based Magnets
(North Dakota State University, 2015) Olson, Christopher Samuel
The chemical bond and its role as a mediator of magnetic exchange interaction remains an important aspect in the study of magnetic insulators and semiconductors. The M[TCNE] (M = transition metal, TCNE = tetracyanoethylene) class of organic-based magnets has attracted considerable interest since VII[TCNE]x (x ~ 2) exhibits one of the highest critical temperatures for its class – Tc ~ 400 K – in addition to highly spin-polarized conduction and valance bands (Eg ~ 0.5 eV), thus foreseeing potential spintronic application. The magneto-structural factors underlying this exceptional behavior remain elusive, however, due to the amorphous nature of the material. To address this, a novel synthetic route was utilized to produce new polycrystalline M[TCNE] solids (whose crystal structures have been resolved) with varying transition metal centers (Ni, Mn, Fe) and lattice dimensionality (2D-3D), exhibiting a wide range of Tc (40-170 K). Spectroscopic and magnetometric studies were performed and demonstrate that in 2D [MII(TCNE)(NCMe)2]X structures (M = Ni, Mn, Fe; X = diamagnetic anion), strong ligand-to-metal transfer of electron density from the organic TCNE radical plays a significant role in the formation of magnetic exchange pathways, while single-ion anisotropy strongly influences the critical temperature and below-Tc spin disorder for magnets in this material class. Additionally, using quantum-computational modeling, magnetic spin-density transfer trends, spin-polarized electronic structures, and electronic exchange coupling constants have been identified and interpreted in terms of 3d-orbital filling and dimensionality of magnetic interaction. These findings offer new perspectives on the stabilization of magnetic order in M[TCNE] solids.
Synthesis of Cellulose Nanofiber Composites for Mechanical Reinforcement and Other Advanced Applications
(North Dakota State University, 2015) Xu, Xuezhu
Cellulose nanofibers from bioresources have attracted intensive research interest in recent years due to their unique combination of properties including high strength and modulus, low density, biocompatibility/biodegradability and rich surface chemistry for functionalization. The nanofibers have been widely studied as nanoreinforcements in polymer nanocomposites; while the nanocomposite research is still very active, new research directions of using the nanofibers for hydrogels/aerogels, template for nanoparticle synthesis, scaffold, carbon materials, nanopaper, etc. have emerged. In this Ph.D. thesis, fundamental studies and application developments are performed on three types of cellulose nanofibers, i.e. cellulose nanocrystals (CNCs), cellulose nanofibrils (CNFs) and bacterial cellulose (BC). First CNCs and CNFs are systematically compared in terms of their effects on the mechanical properties, crystallization and failure behavior of the nanocomposites, which provides a guideline for the design of cellulose nanofiber reinforced composites. Second, CNFs and BC are used to develop core-shell carbon fibers and flexible carbon aerogels for energy storage applications. This part is focused on developing nanocarbon materials with multi-scale features. Lastly, hybrid CNC/CNF nanopaper with superior optical, mechanical, and electrical properties is developed and its application is demonstrated on a LED device.
First Principle Study on Interfacial Energetic Alignment and Charge Transfer in Quantum Dots Functionalized via Metal-Organic Dye
(North Dakota State University, 2016) Cui, Peng
Quantum dots (QDs) are promising materials for applications in solar energy conversion because of tunable band gap, multi-exciton generation, photon-upconversion, etc. One of the main challenges of increasing solar energy conversion is to extend the lifetime of photoexcited charge-carriers in conduction band, and one of the strategies is to functionalize QD with mediator molecules. Functionalizing QD with metal-organic dye serves as the additional channel of manipulating charge transfer – the key process increasing solar energy conversion. When metal-organic dye is attached to QD, the interfacial charge transfer direction as well as the rates are determined by a balance between the energetic alignment, QD-dye interaction as well as charge-carrier relaxation dynamics. In this dissertation, we explore the effect of dye functionalization on these elements. We change the metal ion, organic ligands as well as binding geometry of dye, size of QD, polarity of solvent, and use density functional theory to study their effects on energetic alignment. Embedding density functional calculation is used to study the dipole interaction between QD and dye providing additional controllability on charge transfer excitation. At last, we apply Tully surface hopping scheme in combining with density functional theory in time domain to study the charge-carrier relaxation dynamics and charge transfer across the heterogeneous interface in QD/dye nanocrystal composite.
Properties of Block-Copolymer Interfaces
(North Dakota State University, 2016) Rozairo, Damith P.
There is considerable interest in the fabrication and mechanism of soft spheres and capsules because of their use in a large number of applications ranging from targeted drug delivery systems to cosmetically active agents. The performance of these soft spheres depends on the enhancement of the mechanical properties of these materials. This dissertation is focused on studying the fundamental physics of these soft spheres. First, we study a simple fluid-fluid system covered by a diblock copolymer. Specifically, we use laser confocal microscopy to adapt a sessile drop geometry to a measurement of the static properties of an ensemble of polystyrene-b-poly(ethylene oxide) (PS-PEO) stabilized oil droplets. We present a simple model derived from Bashforth-Adams model for sessile drops. This method can be used to measure the surface tension of any fluid-fluid interface using a simple optical microscope without looking at the full geometry of a deformed droplet. We then synthesize a polystyrene-b-poly(acrylic acid)-b-polystyrene (PS-PAA-PS) elastic-shell-coated emulsion drop that shows an identical deformation to the fluid-like PS-PEO droplets. Both systems, in sessile geometry, can be related to their basic material properties through appropriate modeling. We find that the elastic shell is dominated by its surface tension, easily enabling it to match the static response of a purely fluid drop. Motivated by the sessile drop geometry, we study how these idealized cargo carrying spheres interact with a hard wall. As a polymer covered droplet approaches a flat wall, it buckles in and traps an amount of the outer fluid. This fluid is slowly drained out through a narrow channel covered with a polymer brush. A simple scaling model predicts the drainage rate of the fluid through the polymer brush. Finally, we look at how a long diblock copolymer (PS-PEO) molecule is packed at an oil-water interface and how it affects the surface tension. We find that as the polymer to oil concentration is reduced, it goes from the critical concentration at which no more chains can be fitted to the bare oil interface quickly. Furthermore, we find that the outer brush thickness (PEO) increases as the PS-PEO concentration is increased.
An Insilico Design of Nanoclay Based Nanocomposites and Scaffolds In Bone Tissue Engineering
(North Dakota State University, 2016) Sharma, Anurag
A multiscale in silico approach to design polymer nanocomposites and scaffolds for bone tissue engineering applications is described in this study. This study focuses on the role of biomaterials design and selection, structural integrity and mechanical properties evolution during degradation and tissue regeneration in the successful design of polymer nanocomposite scaffolds. Polymer nanocomposite scaffolds are synthesized using aminoacid modified montmorillonite nanoclay with biomineralized hydroxyapatite and polycaprolactone (PCL/in situ HAPclay). Representative molecular models of polymer nanocomposite system are systematically developed using molecular dynamics (MD) technique and successfully validated using material characterization techniques. The constant force steered molecular dynamics (fSMD) simulation results indicate a two-phase nanomechanical behavior of the polymer nanocomposite. The MD and fSMD simulations results provide quantitative contributions of molecular interactions between different constituents of representative models and their effect on nanomechanical responses of nanoclay based polymer nanocomposite system. A finite element (FE) model of PCL/in situ HAPclay scaffold is built using micro-computed tomography images and bridging the nanomechanical properties obtained from fSMD simulations into the FE model. A new reduction factor, K is introduced into modeling results to consider the effect of wall porosity of the polymer scaffold. The effect of accelerated degradation under alkaline conditions and human osteoblast cells culture on the evolution of mechanical properties of scaffolds are studied and the damage mechanics based analytical models are developed. Finally, the novel multiscale models are developed that incorporate the complex molecular and microstructural properties, mechanical properties at nanoscale and structural levels and mechanical properties evolution during degradation and tissue formation in the polymer nanocomposite scaffold. Overall, this study provides a leap into methodologies for in silico design of biomaterials for bone tissue engineering applications. Furthermore, as a part of this work, a molecular dynamics study of rice DNA in the presence of single walled carbon nanotube is carried out to understand the role played by molecular interactions in the conformation changes of rice DNA. The simulations results showed wrapping of DNA onto SWCNT, breaking and forming of hydrogen bonds due to unzipping of Watson–Crick (WC) nucleobase pairs and forming of new non-WC nucleobase pairs in DNA.
Agricultural Residues and Other Carbon-Based Resources as Feedstocks for Supercapacitor Electrodes
(North Dakota State University, 2017) Wang, Yong
Agricultural residues are generally considered as renewable, economical and environmental-friendly sources to produce carbon-based materials with many advanced applications. Agricultural residues and by-products generated from the agricultural industry, such as distiller's dried grains with solubles (DDGS), are produced every year on a large scale but lack of proper utilization. As a result, seeking high-value applications based on agricultural residues is essential for the promotion of the economy in agricultural states like North Dakota, USA. With the fast development of nanotechnology in recent years, carbon-based nanomaterials have attracted intense research interests in the fields of chemistry, materials science and condensed matter physics due to many unique properties (e.g., chemical and thermal stability, electrical conductivity, mechanical strength, etc.). The development of low-cost nanomaterials using agricultural residues as feedstocks can be a promising route for the sustainable development of the agricultural industry. In this dissertation, the preparation of carbon-based materials from agricultural residues is explored. Many advanced applications are investigated, especially in the field of energy storage devices. The development of porous activate carbons were investigated in detail, and their application as electrode materials of supercapacitors was demonstrated. Hydrothermal carbonization of biomass to produce carbonaceous materials was also covered in this dissertation. In addition to traditional raw materials such as cellulose produced from wood industry, novel material sources such as bacterial cellulose were used to prepare nanocomposites that can be used for the electrodes of supercapacitors. This dissertation contributes to the sustainable development of the agricultural industry in North Dakota.
Silicon Nanocrystals: Optical Properties and Self Assembly
(North Dakota State University, 2018) Brown, Samuel
Silicon nanocrystal’s (SiNCs) size dependent optical properties and nontoxic nature portend potential applications across a broad range of industries. With any of these applications, a thorough understanding of SiNC photophysics is desirable to tune their optical properties while optimizing quantum yield. However, a detailed understanding of the photoluminescence (PL) from SiNCs is convoluted by the complexity of the decay mechanisms, including a stretched-exponential relaxation and the presence of both nanosecond and microsecond decays. In this dissertation, a brief history of semiconductor nanocrystals is given, leading up to the first discovery of room temperature PL in SiNCs. This is then followed by an introduction to the various nanocrystal synthetic schemes and a discussion of quantum dot photophysics in general. Three different studies on the PL from SiNCs are then presented. In the first study, the stretched nature of the time dependent PL is analyzed via chromatically-resolved and full-spectrum PL decay measurements. The second study analyzes the size dependence of the bimodal PL decay, where the amplitude of the nanosecond and microsecond decay are related to nanocrystal size, while the third project analyzes the temperature and microstructure dependencies of the PL from SiNC solids. After an indepth look at the PL from SiNCs, this report examines preliminary results of SiNC and silver nanocrystal self-assembly. When compared to metal and metal chalcogenide nanoparticles, there is a dearth of literature on the self-assembly of SiNCs. To understand these phenomena, we analyze the size dependent ability of SiNCs to form a ‘superlattice’ and compare this with silver nanocrystals. Although the results on self-assembly are still somewhat preliminary, it appears that factors such as SiNC concentration and size dispersity play a key role in SiNC self-assembly, while suggesting intrinsic differences between the self-assembly of SiNCs and silver nanocrystals. Finally, at the end of this dissertation, a corollary project is presented on the computational analysis of fluorescent silver nanoclusters (AgNCs). Due to their small size and non-toxic nature, AgNCs are an ideal fluorophore for biological systems, yet there is a limited understanding of their photophysics, which is the focus of this part of the dissertation.
Lattice Gases with Molecular Dynamics Collision Operator
(North Dakota State University, 2018) Parsa, Mohammad Reza
The purpose of this dissertation is to provide a direct microscopic underpinning for lattice Boltzmann (and lattice gas) methods. Lattice gases are idealized discrete models that conserve mass and momentum. These conservation laws imply, through the formalism of kinetic theory, that on a macroscopic scale these methods recover the continuity and Navier-Stokes equations. As part of the kinetic theory approach, an ensemble average of the lattice gas is taken leading to a lattice Boltzmann equation. These lattice Boltzmann equations can be implemented directly leading to the new how ubiquitous lattice Boltzmann methods. In this dissertation we step away from justifying lattice Boltzmann methods and the ability of recovering suitable macroscopic equations. Rather, their correspondence to coarse-grained Molecular Dynamics simulations is examine and can be cast in the form of a lattice gas evolution equation. We call this lattice gas the Molecular Dynamic Lattice Gas (MDLG). We use this MDLG to derive the exact formulation for lattice Boltzmann equilibrium distributions, relaxation parameters, and fluctuating properties.
An Electron Energy-Loss Spectroscopic Investigation of Molecular Interactions at Hydroxyapatite-Collagen Interfaces in Healthy and Diseased (Osteogenesis Imperfecta) Human Bone and Biomineralized Tissue-Engineered Bone
(North Dakota State University, 2018) Payne, Scott Andrew
At its primary level (nm scale) bone is a nanocomposite consisting of a mineral (hydroxyapatite) phase which gives bone its strength and an organic (type I collagen) phase giving bone its fracture toughness. Hydroxyapatite, (HAP) Ca10(PO4)6(OH)2, is the most abundant mineral in the human body. Bone tissue has a complex hierarchical structure spanning multiple length scales (cm to nm). Characterization of mineral composition in biomineralized tissues such as bone at their primary level, is very challenging and requires instrumentation with nanometer-scale spatial resolution. Transmission electron microscopy (TEM) combines high spatial resolution with visual correlation of diffraction and elemental-composition data. Electron energy-loss spectroscopy (EELS) is a sensitive technique used to probe electronic structure at the molecular level. TEM-based EELS is the only available technique that can provide information about the chemical and coordination environment of minerals with nm scale spatial resolution. Prior studies in our group has developed a method to create biomimetic HAP using biomineralization routes inside the clay galleries of montmorillonite clay modified with amino acids (in-situ HAPclay). Incorporation of in-situ HAPclay into polymer scaffolds and seeding with human mesenchymal stem cells has enabled the cells towards differentiation into osteoblastic lineages without differentiating media. Because of the importance of these materials for bioengineering applications, TEM-EELS was used to evaluate differences and similarities among HAP, biomimetic in-situ HAPclay, modified MMT clay, and β-tricalcium phosphate. Osteogenesis imperfecta (OI), also known as brittle bone disease, is an inheritable disease characterized by increased bone fragility, low bone mass, and bone deformity caused primarily by mutation in collagen type I genes and is expressed as changes in structure and mechanics at the macrostructural level of bone. Therefore the mineralization of HAP in OI bone and the molecular basis of OI bone disease makes this an interesting system for molecular-level investigations. Small changes in the valence band and outer electronic structures of the diseased bone have been revealed through EELS. These small changes observed in the electron energy-loss spectra of the OI bone appear to play important biological roles towards development of the disease.
Evaluating Mechanisms of Metastasis of Prostate Cancer to Bone Using 3D Bone-Mimetic Tissue Engineered Scaffolds
(North Dakota State University, 2018) Molla, MD Shahjahan
The complex nature of cancer metastasis necessitates the development of a cancer model based on specific metastatic stages. In this dissertation, we report a polymer-nanoclay based in vitro tumor model which recapitulates early stage of prostate cancer skeletal metastasis. A unique cell culture system termed as ‘sequential culture’ has been applied to create a bone-mimetic niche for colonization of prostate cancer cells. Sequentially cultured MDA PCa 2b cells with MSCs formed self-organized multicellular tumoroids with distinct tight cellular junctions and hypoxic core regions. Further, the sequentially cultured PC-3 cell formed multicellular tumoroid like clusters. We performed immunocytochemical confocal microscopy, qRT-PCR, ELISA assays, nanomechanical evaluation and SEM imaging to characterize our tumor model. We observed that in the in vitro model that MSCs differentiated to matured osteoblasts, EMT (epithelial to mesenchymal transition) was inhibited, MET was enhanced, and hypoxia increased angiogenesis when prostate cancer cells were sequentially cultured with MSCs. We also studied the effect of prostate cancer metastasis on bone microenvironment using different prostate cancer cell lines. We found that the less metastatic MDA PCa 2b cells inhibited mineralized collagen formation whereas, highly metastatic PC-3 cells enhanced mineralized collagen formation. All the experimental results indicated osteoblastic bone formation by PC-3 cells and osteolytic bone resorption by MDA PCa 2b cells. Cancer metastasis is a complex process requiring dramatic remodeling of the cell cytoskeleton. Bone metastasis is characterized by complex biochemical, morphological, pathophysiological, and genetic changes to cancer cells as they colonize at remote bone sites. These changes can be captured in sum by changes to nanomechanical properties of cancer cells during metastasis. Using a specially designed nanoindentation apparatus, we observed significant softening of prostate cancer cells during MET and then further softening during the disease progression at the metastatic site. We observed a substantial reduction in elastic modulus of prostate cancer cells during MET arising from actin reorganization and depolymerization. This is the first study that reveals changes to nanomechanical characteristics of prostate cancer cells with correlation to cytoskeletal changes during MET and progression of the disease at the metastatic bone site.
Flexible Nanocomposite Thin Films for Electronic Devices
(North Dakota State University, 2019) Alzaid, Meshal Mufleh
Electronic technology is moving towards flexible, durable, and smaller devices with multifunctional capability. To accelerate this movement, creating materials with outstanding properties is critical. Nanocomposites based on single wall carbon nanotubes (SWCNTs) have received considerable attention because of their unique mechanical and electrical properties. When SWCNTs are formed as a sheet, they provide large contact area and ease of control, especially when incorporated into a flexible format. However, when SWCNT films are adhered to an elastic substrate, there are challenges with their use in flexible electronics, such as a reduction Young’s modulus under deformation. SWCNT films can undergo plastic behavior at even a small strain because individual SWCNTs slide past each other in response to deformation. To address these challenges, a strain-induced elastic buckling instability for mechanical measurements (SIEBIMM) method was used to query SWCNT film mechanics. The buckling wavelength and the film thickness are two main factors that influence the mechanics of nanocomposite thin films adhered to elastomeric substrates. SWCNT films coated with a second nanomaterial, such as a polymer thin film or nanocrystals (NCs), have shown a significant enhancement in elasticity. The studies described in this dissertation demonstrate that polymer thin film can reduce the strain softening of SWCNT films, where both yield strain and Young’s modulus increase with the introduction of SWCNT-polymer layers. Specifically, the films started to exhibit a strong synergy between SWCNT and polymer at a film thickness of around 20 nm, which is attributed to the thickness approaching the characteristic interfacial width between the two materials. Both a ‘passive’ polymer thin film (for example, polystyrene-PS) and an ‘active’ polymer thin film, the conducting polymer poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate)(PEDOT:PSS), were investigated, spanning a bilayer to the bulk limit of SWCNT-polymer multilayers. In addition, ultrathin SWCNT films coated with colloidal NCs have also been investigated. We have utilized two approaches to coat SWCNT films with NCs: Langmuir-Blodgett (LB) and spray coating. Both Si and CdSe nanocrystals showed a roughly two-fold enhancement in film elasticity, which was attributed to an excluded volume effect that prevents the SWCNT rearrangement under an applied strain.
Non-Thermal Plasma Synthesis of Luminescent Silicon Nanocrystals from Cylclohexasilane
(North Dakota State University, 2019) Pringle, Todd Andrew
In this report we establish cyclohexasilane (CHS) as a reliable precursor for non-thermal plasma synthesis of high quality photoluminescent silicon nanocrystals (SiNCs). We demonstrate that this synthesis approach can produce high quality, size tunable silicon quantum dots with quantum yields exceeding 60% as synthesized (subsequent work in our group has measured over 70% quantum yield after density gradient ultracentrifugation size purification).After a brief background on non-thermal plasma synthesis, the characterization methods used in this study, and an overview of CHS, we report at length on our development of the apparatus used, and our exploration of the controllable processing parameters of the synthesis method. We describe our successes and challenges with size tuning, sample collection, and passivation. Finally, we discuss preliminary studies we performed to identify promising future research areas. Novel reactor designs, blue light passivation, and magnetic confinement of plasma are described briefly to entice future researchers.

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