Recent commercial developments have created a need for alternative materials and methods for imparting oil/grease resistance to paper and/or paperboard used in packaging. The performance of a novel grease resistant functional coating comprised of polyvinyl alcohol (PVA), sodium tetraborate pentahydrate (borate) and acetonedicarboxylic acid (ACDA) and the application of said coating by means of flexographic press is presented herein. Application criteria is developed, testing procedures described, and performance assessment of the developed coating materials are made. SEM images along with contact angle data suggest that coating performance is probably attributable to decreased mean pore size in conjunction with a slightly increased surface contact angle facilitated by crosslinking of PVA molecules by both borate ions and ACDA.

Recent progress in layered transition metal dichalcogenides (TMDs) has led to various promising electronic and optoelectronic applications. However, the structure of materials plays a critical role in electronic and optoelectronic devices, and determines performance. Electronic and optoelectronic devices typically consist of multiple layers that form electrical homojunctions or heterojunctions. Therefore, in a device it can be expected that a WS2 layer may serve as the substrate for a subsequent layer in a multilayer device stack and determine how the layer grows. In transistor structures, roughness at the channel/gate dielectric interface introduces field variations and charge scattering. Therefore, understanding the relations between processing, surface morphology and properties is important. In this project, the effects of pulsed laser deposition (PLD) processing conditions on the surface morphology of few layered WS2 films were studied. WS2 films were synthesized under processing conditions that represent the extremes of surface supersaturation and kinetic energy transfer from the flux to the growing films, and evolution of the surface morphology was studied. The specific conditions were 1Hz/50mJ, 10Hz/50mJ, 1Hz/300mJ, and 10Hz/300mJ respectively. Combining AFM, XRD and Raman analyses, it was determined that deposition at 10Hz/300mJ, provided the best structural properties and surface morphology. Growth appeared to be 3D-cluster, …

Two series monodispersed nanoparticles of hydroxylpropyl cellulose (HPC) and functionalized poly-N-isopropylamide (PNIPAM) particles have been synthesized and used as building blocks for creating three-dimensional networks, with two levels of structural hierarchy. The first level is HPC nanoparticles were made from methacrylated or degradable cross-linker attached HPC. These nanoparticles could be stabilized at room temperature by residual methacrylate or degradable groups are present both within and on the exterior of HPC nanoparticles. Controlled release studies have been performed on the particle and networks .The nearly monodispersed nanoparticles have been synthesized on the basis of a natural polymer of hydropropylcellulose (HPC) with a high molecular weight using the precipitation polymerization method and self-assembly of these particles in water results in bright colors. The HPC nanoparticles can be potential using as crosslinkers to increase the hydrogels mechanical properties, such as high transparency and rapid swelling/de-swelling kinetics. The central idea is to prepare colloidal particles containing C=C bonds and to use them as monomers - vinylparticles, to form stable particle assemblies with various architectures. This is accomplished by mixing an aqueous suspension of hydrogel nanoparticles (PNIPAM-co-allylamine) with the organic solvent (dichloromethane) to grow columnar crystals. The hydrogels with such a unique crystal structure behavior …

Lithium-sulfur (Li-S) batteries are faced with practical drawbacks of poor cycle life and low charge efficiency which hinder their advancements. Those drawbacks are primarily caused by the intrinsic issues of the cathodes (sulfur) and the anodes (Li metal). In attempt to resolve the issues found on the cathodes, this work discusses the method to prepare a binder-free three-dimensional carbon nanotubes-sulfur (3D CNTs-S) composite cathode by a facile and a scalable approach. Here, the 3D structure of CNTs serves as a conducting network to accommodate high loading amounts of active sulfur material. The efficient electron pathway and the short Li ions (Li+) diffusion length provided by the 3D CNTs offset the insulating properties of sulfur. As a result, high areal and specific capacities of 8.8 mAh cm−2 and 1068 mAh g−1, respectively, with the sulfur loading of 8.33 mg cm−2 are demonstrated; furthermore, the cells operated at a current density of 1.4 mA cm−2 (0.1 C) for up to 150 cycles. To address the issues existing on the anode part of Li-S batteries, this work also covers the novel approach to protect a Li metal anode with a thin layer of two-dimensional molybdenum disulfide (MoS2). With the protective layer of MoS2 …

This paper deals with various topics in micro electromechanical systems (MEMS) technology beginning with microactuation, MEMS processing, and MEMS design engineering. The fabrication and testing of three separate MEMS devices are described. The first two devices are a linear stepping motor and a continuous rotary motor, respectively; and were designed for the purpose of investigating the frictional and wear properties of silicon components. The third device is a bi-stable microrelay, in which electrical current conducts through a secondary circuit, via a novel probe-interconnect mechanism. The second half focuses on engineering a carbon nanotube / SU-8 photoepoxy nanocomposite for fabricating MEMS devices. A processing method for this material as well as the initial results of characterization, are discussed.

In this dissertation, nano-manufacturing of amorphous alloys for electro-catalytic applications is reported and the role of chemistry and active surface area on catalytic behavior is discussed. The catalytic activity of recently developed platinum and palladium-based metallic glasses was studied using cyclic voltammetry and localized electrochemical techniques. The synergistic effect between platinum and palladium was shown for amorphous alloys containing both these elements. The mechanism for superior catalytic behavior was investigated through electronic structure and surface chemical state of the alloys. A correlation between the work function and catalytic performance of the amorphous alloys with widely varying chemistries was established. To address the high cost associated with the noble-metal containing catalysts, the performance of non-noble Ni-P amorphous catalyst was evaluated for electro-catalysis. A facile pulsed electrodeposition approach was used for the nano-manufacturing of these amorphous catalysts. This nano-manufacturing route allowed the synthesis of fully amorphous nano-wires at room temperature for alloys with little or no noble-metal content. A wide range of nano-wires with varying aspect ratios from 25 to 120 was synthesized using commercially obtained anodic aluminum oxide (AAO) nano-molds. Cyclic voltammetry and chrono-amperometry demonstrated superior performance in terms of electrocatalytic activity and stability of the metallic glass nano-wires towards electro-oxidation …

Photoresist stripping with oxygen plasma ashing destroys the functional groups in organosilicate glass films and induce moisture uptake, causing low-k dielectric degradation. In this study, hexamethyldisilazane (HMDS), triethylchlorosilane and tripropylchlorosilane are used to repair the damage to organosilicate glass by the O2 plasma ashing process. The optimization of the surface functionalization of the organosilicate glass by the silanes and the thermal stability of the functionalized surfaces are investigated. These experimental results show that HMDS is a promising technique to repair the damage to OSG during the photoresist removal processing and that the heat treatment of the functionalized surfaces causes degradation of the silanes deteriorating the hydrophobicity of the films.

Sintering parameter effects on the microstructure of boron carbide and boron carbide/titanium diboride composites are investigated. The resulting microstructure and composition are characterized by scanning electron microscopy (SEM), x-ray microscopy (XRM) and x-ray diffraction (XRD). Starting powder size distribution effects on microstructure are present and effect the mechanical properties. Reactive spark plasma sintering introduces boron nitride (BN) intergranular films (IGF's) and their effects on fracture toughness, hardness and flexural strength are shown. Mechanical testing of Vickers hardness, 3-point bend and Chevron notch was done and the microstructural effects on the resulting mechanical properties are investigated.

Ruthenium and ruthenium dioxide thin films have shown great promise in various applications, such as thick film resistors, buffer layers for yttrium barium copper oxide (YBCO) superconducting thin films, and as electrodes in ferroelectric memories. Other potential applications in Si based complementary metal oxide semiconductor (CMOS) devices are currently being studied. The search for alternative metal-based gate electrodes as a replacement of poly-Si gates has intensified during the last few years. Metal gates are required to maintain scaling and performance of future CMOS devices. Ru based materials have many desirable properties and are good gate electrode candidates for future metal-oxide-semiconductor (MOS) device applications. Moreover, Ru and RuO2 are promising candidates as diffusion barriers for copper interconnects. In this thesis, the thermal stability and interfacial diffusion and reaction of both Ru and RuO2 thin films on HfO2 gate dielectrics were investigated using Rutherford backscattering spectrometry (RBS), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). An overview of Ru and RuO2/HfO2 interface integrity issues will be presented. In addition, the effects of C ion modification of RuO2 thin films on the physico-chemical and electrical properties are evaluated.

High entropy alloys (HEAs) are a relatively new class of solid solution alloys that contain multiple principal elements to take advantage of their high configurational entropy, sluggish diffusion, lattice distortion, and the cocktail effect. In recent development, work hardening mechanisms known as twinning induced plasticity (TWIP) and transformation induced plasticity (TRIP) have been found active in Al0.3CoCrFeNi (molar fraction) and Fe50Mn30Co10Cr10 (at %) HEA compositions. Friction-stir processing was done to increase the mechanical properties and improve the microstructure of the alloys for the purpose of high strain rate performance. Quasi-static tensile tests as well as top-hat geometry Split-Hopkinson pressure bar tests were conducted to view the mechanical properties as well as view the microstructural evolution at dynamic strain rates. Overall, the Al0.3CoCrFeNi condition after friction-stir processing and heat treatment has proved to have the best mechanical properties, and selecting from the conditions in this study, Al0.3CoCrFeNi has better shear localization resistance.

One of the final steps in fabricating microelectromechanical devices often involves a liquid etch release process. Capillary forces during the liquid evaporation stage after the wet etch process can pull two surfaces together resulting in adhesion of suspended microstructures to the supporting substrate. This release related adhesion can greatly reduce yields. In this report, a wet etch release method that uses polystyrene microspheres in the final rinse liquid is investigated. The polystyrene microspheres act as physical barriers between the substrate and suspended microstructures during the final liquid evaporation phase. A plasma ashing process is utilized to completely remove the polystyrene microspheres from the microstructure surfaces. Using this process, release yields > 90% were achieved. It is found that the surface roughness of gold surfaces increases while that of the silicon is reduced due to a thin oxide that grows on the silicon surface during the plasma process.

Through a series of carefully designed experiments, characterization and some modeling tools, this work is aimed at studying the role of thermal profiles on different microstructural zones and associated properties like strength and corrosion through a variation of weld parameters, thermal boundary conditions and material temper. Two different alloys belonging to the Al-Cu and Al-Cu-Li system in different temper conditions- peak aged (T8) and annealed (O) were used. A 3D-thermal pseudo mechanical (TPM) model is developed for the FSW process using heat transfer module in COMSOL Multiphysics and is based on a heat source wherein the temperature dependent yield shear stress is used for the heat generation. The precipitation and coarsening model is based on the Kampmann and Wagner theoretical framework and accounts for the competition between the various nucleation sites for both metastable and equilibrium precipitates. The model predicts different precipitate mean radius and volume fraction for the various zones in the friction stir welded material. A model for the yield strength is developed which considers contributions from different strengthening mechanisms. The predictions of the each models have been verified against experimental data and literature. At constant advance per rotation, the peak temperature decreases with a decrease in traverse …

Methylsilsesquioxane (MSQ) and organosilicate glass (OSG) are the materials under this study because they exhibit the dielectric constant values necessary for future IC technology requirements. Obtaining a low-k dielectric value is critical for the IC industry in order to cope time delay and cross talking issues. These materials exhibit attractive dielectric value, but there are problems replacing conventional SiO2, because of their chemical, mechanical and electrical instability after plasma processing. Several techniques have been suggested to mitigate process damage but supercritical silylation offers a rapid single repair step solution to this problem. Different ash and etch damaged samples were employed in this study to optimize an effective method to repair the low-k dielectric material and seal the surface pores via supercritical fluid processing with various trialkylchlorosilanes. Fourier transform infrared spectroscopy (FTIR), contact angle, capacitance- voltage measurements, and x-ray photoemission spectroscopy, dynamic secondary ion mass spectroscopy (DSIMS), characterized the films. The hydrophobicity and dielectric constant after exposure to elevated temperatures and ambient conditions were monitored and shown to be stable. The samples were treated with a series of silylating agents of the form R3-Si-Cl where R is an alkyl groups (e.g. ethyl, propyl, isopropyl). Reactivity with the surface hydroxyls was inversely …

The incorporation of fluorine into SiO2 has been shown to reduce the dielectric constant of the existing materials by reducing the electrical polarizability. However, the incorporation of fluorine has also been shown to decrease film stability. Therefore, new efforts have been made to find different ways to further decrease the relative dielectric constant value of the existing low-k materials. One way to reduce the dielectric constant is by decreasing its density. This reduces the amount of polarizable materials. A good approach is increasing porosity of the film. Recently, fluorinated silica xerogel films have been identified as potential candidates for applications such as interlayer dielectric materials in CMOS technology. In addition to their low dielectric constants, these films present properties such as low refractive indices, low thermal conductivities, and high surface areas. Another approach to lower k is incorporating lighter atoms such as hydrogen or carbon. Silsesquioxane based materials are among them. However, additional integration issues such as damage to these materials caused by plasma etch, plasma ash, and wet etch processes are yet to be overcome. This dissertation reports the effects of triethoxyfluorosilane-based (TEFS) xerogel films when reacted with silylation agents. TEFS films were employed because they form robust silica …

The barrier properties and long term strength retention of polymers are of significant importance in a number of applications. Enhanced lifetime food packaging, substrates for OLED based flexible displays and long duration scientific balloons are among them. Higher material requirements in these applications drive the need for an accurate measurement system. Therefore, a new system was engineered with enhanced sensitivity and accuracy. Permeability of polymers is affected by permeant solubility and diffusion. One effort to decrease diffusion rates is via increasing the transport path length. We explore this through dispersion of layered silicates into polymers. Layered silicates with effective aspect ratio of 1000:1 have shown promise in improving the barrier and mechanical properties of polymers. The surface of these inorganic silicates was modified with surfactants to improve the interaction with organic polymers. The micro and nanoscale dispersion of the layered silicates was probed using optical and transmission microscopy as well as x-ray diffraction. Thermal transitions were analyzed using differential scanning calorimetry. Mechanical and permeability measurements were correlated to the dispersion and increased density. The essential structure-property relationships were established by comparing semicrystalline and amorphous polymers. Semicrystalline polymers selected were nylon-6 and polyethylene terephthalate. The amorphous polymer was polyethylene terphthalate-glycol. Densification …

This dissertation tested the hypothesis that pulsed laser deposition (PLD) could be used to create targeted dopant profiles in few layered WS2 films based on congruent evaporation of the target. At the growth temperatures used, 3D Volmer-Weber growth was observed. Increased energy transfer from the PLD plume to the growing films degraded stoichiometry (desorption of sulfur) and mobility. Sulfur vacancies act as donors and produce intrinsic n-type conductivity. Post deposition annealing significantly improved the crystallinity, which was accompanied by a mobility increase from 6.5 to 19.5 cm2/Vs. Preparation conditions that resulted in excess sulfur, possibly in the form of interstitials, resulted in p-type conductivity. Current-voltage studies indicated that Ohmic contacts were governed by surface properties and tunneling. Extrinsic p-type doping of few layered WS2 films with Nb via pulsed laser deposition using ablation targets fabricated from WS2, S and Nb powders is demonstrated. The undoped controls were n-type, and exhibited a Hall mobility of 0.4 cm2/Vs. Films doped at 0.5 and 1.1 atomic percentages niobium were p-type, and characterized by Fermi levels at 0.31 eV and 0.18 eV from the valence band edge. That is, the Fermi level moved closer to the valence band edge with increased doping. With increased …

The current understanding of the mechanical properties and deformation behavior of some individual phases in titanium alloys is limited due to the fine scale at which these phases precipitate within the β-phase matrix. The α and ω phases represent the most widely observed phases in titanium alloys depending on the alloy composition and also the heat treatment procedure adopted during processing. The possibility of precipitating ω-phase depends on the content of the β-stabilizers within the system. Although a significant compositional partitioning occurs within ω-phase upon aging treatment, the knowledge of ω-phase mechanical properties as a function of composition is very limited. The initial part of the current work focuses on the effect of common β-stabilizers elements on the phase stability and mechanical properties of the ω-phase using first-principles calculations. A relation between the bonding nature, the phase stability, and elastic properties was proposed. Thereafter αʺ martensitic phase was investigated in Ti-Nb and Ti-Nb-O alloys. The phase stability and martensitic start temperature of αʺ-phase was studied as a function of Nb and oxygen content. Also, the effect of the lattice shear distortion induced by oxygen atom on stabilizing β-phase was investigated. Subsequently the effect of the β-stabilizers' elements on stacking faults …

In the current study, we have investigated the cyclic loading behavior of conventional as well as novel alloy system exhibiting fine and ultrafine-grained structure. While in case of conventional alloy systems (here aluminum alloy AA5024), the effect of three different grain sizes was investigated. Improvement in fatigue properties was observed with decreasing grain size. The unique microstructure produced via Friction stir processing was responsible for the improved fatigue response. Additionally, microstructures consisting of a high fraction of special boundaries within the fine and ultrafine-grained regime were also subjected to cyclic loading. The hierarchical features introduced in the eutectic high entropy alloy deflected the persistent slip bands, responsible for fatigue cracking, thus resulted in delayed crack initiation and improved fatigue life. The selective nature of fatigue was learnt in the fine grain Al0.5CoCrFeNi, where the introduction of hierarchical features did not result in improved fatigue properties. The weak links in the microstructure, while not affecting the tensile properties, got exposed during cyclic loading. Further study on the medium entropy alloy revealed the inherent reason for the improved fatigue properties. The medium entropy alloys utilized the benefit of UFG single-phase FCC matrix. The UFG matrix showed signs of transformation of FCC phase …

I have used computer simulations to investigate the behavior of polymeric materials at the molecular level. The simulations were performed using the molecular dynamics method with Lennard-Jones potentials defining the interactions between particles in the system. Significant effort was put into the creation of realistic materials on the computer. For this purpose, an algorithm was developed based on the step-wise polymerization process. The resulting computer-generated materials (CGMs) exhibit several features of real materials, such as molecular weight distribution and presence of chain entanglements. The effect of the addition of a liquid crystalline (LC) phase to the flexible matrix was also studied. The concentration and distribution of the second phase (2P) were found to influence the mechanical and tribological properties of the CGMs. The size of the 2P agglomerates was found to have negligible influence on the properties within the studied range. Moreover, although the 2P reinforcement increases the modulus, it favors crack formation and propagation. Regions of high LC concentration exhibit high probability of becoming part of the crack propagation path. Simulations of the tensile deformation under a uniaxial force have shown that the molecular deformation mechanisms developing in the material depend on several variables, such as the magnitude of …

High entropy alloys (HEAs) based on refractory elements have shown a great potential for high temperature structural applications. In particular, the ones containing Al, exhibits a microstructure similar to the γ-γ' in Ni-based superalloys. While these alloys exhibit impressive strengths at room temperature (RT) and at elevated temperatures, the continuous B2 matrix in these alloys is likely to be responsible for their brittle behavior at RT. Phase stability of five such alloys are studied by thermo-mechanical treatments and characterization techniques using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Two of these alloys showed an inverted microstructure, where the disordered BCC phase becomes continuous, and therefore, they were characterized in detail using SEM, TEM, atom probe tomography (APT) and synchrotron x-ray diffraction experiments. The phenomenon of phase inversion lead to a better combination of strength and ductility as compared to the non-inverted microstructure.To enhance the stability of B2 intermetallic phase which provides the strength when present in a BCC matrix, multicomponent B2 phase compositions stable at 1000°C in some of the above studied alloys, were melted separately. The aim was to establish a single phase B2 at 1000°C and understand the mechanical behavior of these single-phase multicomponent B2 intermetallic …

Hafnium based high-κ dielectrics are considered potential candidates to replace SiO2 or SiON as the gate dielectric in complementary metal oxide semiconductor (CMOS) devices. Hydrogen is one of the most significant elements in semiconductor technology because of its pervasiveness in various deposition and optimization processes of electronic structures. Therefore, it is important to understand the properties and behavior of hydrogen in semiconductors with the final aim of controlling and using hydrogen to improve electronic performance of electronic structures. Trap transformations under annealing treatments in hydrogen ambient normally involve passivation of traps at thermal SiO2/Si interfaces by hydrogen. High-κ dielectric films are believed to exhibit significantly higher charge trapping affinity than SiO2. In this thesis, study of hydrogen trapping in alternate gate dielectric candidates such as HfO2 during annealing in hydrogen ambient is presented. Rutherford backscattering spectroscopy (RBS), elastic recoil detection analysis (ERDA) and nuclear reaction analysis (NRA) were used to characterize these thin dielectric materials. It was demonstrated that hydrogen trapping in bulk HfO2 is significantly reduced for pre-oxidized HfO2 prior to forming gas anneals. This strong dependence on oxygen pre-processing is believed to be due to oxygen vacancies/deficiencies and hydrogen-carbon impurity complexes that originate from organic precursors used in …

Geckos are famous for the skill of switchable adhesion that they use to stick on various surface while keep their fingers super clean. In the dissertation, a unique mechanism was discovered to explain gecko self-cleaning phenomena. Using atomic force microscopy (AFM), we managed to compare the microparticle-substrate adhesion and the microparticle-seta adhesion with a single seta bonded to the AFM cantilever. A dynamic effect was approved that high pulling-off speed could increase the microparticle-substrate adhesion and thus the self-cleaning appears at high moving speed. Based on the self-cleaning theory, a gecko-inspired N-doped graphene surface with switchable adhesion was achieved, which was designed into a bio-inspired micromanipulator with a success rate over 90%. When electrical bias was applied on this biomimetic surface, the charge concentration induced an electrical double layer (ELD) on the convex surfaces, which attracts polar water molecules to form a water bridge on it, significantly enhancing the adhesion on the wrinkled graphene surface, mimicking the capillary force on beetle feet. Therefore, the bio-inspired adhesive surface can be controlled with speed, electrical bias, humidity and different material surfaces. The water attraction phenomenon on the polarized surface was further tested for the potential application of water collection and evaporation in …

High entropy alloys (HEAs) are a new class of solid solution alloys that contain multiple principal elements and possess excellent mechanical properties, from corrosion resistance to fatigue and wear resistance. Even more recently, twinning induced plasticity (TWIP) and transformation induced plasticity (TRIP) non-equiatomic high entropy alloys have been engineered, promising increased strength and ductility as compared to their equiatomic counterparts. However, impact and fracture resistance of these HEAs has not been studied as much as their other mechanical properties. In this thesis, the hardness, tensile properties, and Charpy impact energy of Al0.3CoCrFeNi, a TWIP HEA, and 50Fe-30Mn-10Co-10Cr (at.%), a TRIP HEA, was explored. First, three processing conditions, (1) as-received, (2) recrystallized, and (3) peak hardness, were chosen for each alloy and verified with Vickers microhardness measurements. Next, the tensile properties of each alloy and condition were investigated. Charpy impact specimen size was then selected based on the final plate thickness, and the machined samples were tested. Plastic zone size and change in sample thickness in the deformed region of each condition after testing was measured. Post-impact test inspection of the samples in all conditions showed that the samples were in tension near the V-notch root and in compression at the …

The thesis studied quantized conductance in nanocontacts formed between two thin gold wires with one of the wires coated by alkainthiol self assembly monolayers (SAM), by using the cross-wire junction. Using the Lorenz force as the driving force, we can bring the two wires in contact in a controlled manner. We observed conductance with steps of 2e2 / h. The conductance plateaus last several seconds. The stability of the junction is attributed to the fact that the coating of SAM improves the stability and capability of the formed contact.