Poly(vinyl chloride)(PVC) wire and cable insulation has poor thermal stability, causing the plasticizer to separate from the PVC chain and produce an oily residue, lowering the tensile elongation at break and thus increasing brittleness. We have added 4 wt.% of three different types of cross-linking agents and antioxidants, as well as mixtures of both, to improve the thermal stability of the plasticizer and tensile properties of PVC after thermal exposure. We performed tensile tests, tribological tests, profilometry, scanning electron microscopy(SEM) and water absorption determination before and after thermal exposure at 136 ℃ for 1 week. After adding the agents, elongation at break increased by 10 to 20 % while the wear rate and water absorption were lower than for the control sample. Less voids are seen in the SEM images after adding these two kinds of agents. The thermal resistance of the PVC cable insulation is best enhanced by combinations of cross-linking agents and antioxidants.

The push for electronic devices on smaller and smaller scales has driven research in the direction of transition metal dichalcogenides (TMD) as new ultra-thin semiconducting materials. These ‘two-dimensional' (2D) materials are typically on the order of a few nanometers in thickness with a minimum all the way down to monolayer. These materials have several layer-dependent properties such as a transition to direct band gap at single-layer. In addition, their lack of dangling bonding and remarkable response to electric fields makes them promising candidates for future electronic devices. For the purposes of this work, two 2D TMDs were studied, MoS2 and MoTe2. This dissertation comprises of three sections, which report on exploration of charge lifetimes, investigation environmental stability at elevated temperatures in air, and establishing feasibility of UV laser annealing for large area processing of 2D TMDs, providing a necessary knowledge needed for practical use of these 2D TMDs in optoelectronic and electronic devices. (1) A study investigating the layer-dependence on the lifetime of photo-generated electrons in exfoliated 2D MoTe2 was performed. The photo-generated lifetimes of excited electrons were found to be strongly surface dependent, implying recombination events are dominated by Shockley-Read-Hall effects (SRH). Given this, the measured lifetime was shown …

My work focuses on taking waste wire-grade PVC = poly(vinyl chloride) and waste XLPE = cross-linked polyethylene and recycle them into small wire/cable spool technology in order to reduce waste cost and reduce cost of spool production. The PVC and XLPE were provided by Encore Wire Corp. of McKinney, TX; they have also defined the standard to which I am comparing my results. The end goal is to incorporate as much PVC and XLPE into the spools while maintaining material toughness, impact resistance, as well as cost-effectiveness in the implementation of the waste materials. The work has been divided into two primary sections, the first is focused on improving material strength through the addition of ceramic fillers. The second section is focused on adding PVC and XLPE into a stronger and highly cohesive polymer matrix and optimizing the concentration of the waste products. Since XLPE is non-polar while PVC is strongly polar, compatibilizers such as CPE (chlorinated polyethylene) and MA-DCP (maleic anhydride with dicumyl peroxide) were used to improve interactions between polar and non-polar constituents. Testing involved the tensile mechanical properties, tribology and thermal properties, namely dynamic mechanical analysis (DMA) and evaluation of thermal degradation by thermogravimetric analysis (TGA). Combining …

Brittleness of a polymeric material has a direct relationship with the material's performance and furthermore shares an inverse relationship with that material's flexibility. The concept of flexibility of materials has been understood but merely explained with a hand-waving manner. Thus, it has never been defined by a calculation, thereby lacking the ability to determine a definite quantitative value for this characteristic. Herein, an equation is presented and proven which makes determining the value of flexibility possible. Such an equation could be used to predict a material's flexibility prior to testing it, thus saving money and valuable time for those in research and in industry. Substantiating evidence showing the relationship between flexibility of polymers and their respective mechanical properties is presented. Further relating the known tensile properties of a given polymer to its flexibility is expanded upon by proving its relationship to the linear coefficient of thermal expansion for each polymer. Additionally, determining flexibility for polymers whose chemical structures have been compromised by respective solvents has also been investigated to predict a solvent's impact on a polymer after exposure. Polymers examined through literature include polycarbonate (PC), polystyrene (PS), teflon (PTFE), styrene acrylonitrile (SAN), acrylonitrile butadiene styrene (ABS), poly(ethersulfone) (PES), low density …

The current study focuses on phase stability and evolution in the titanium-zinc titanium-copper and titanium-antimony systems. The study utilized the Laser Engineering Net Shaping (LENS™) processing technique to deposit compositionally graded samples of three binary system in order to allow the assessment of phase stability and evolution as a function of composition and temperature the material is subjected to. Through LENS™ processing it was possible to create graded samples from Ti-xSb (up to 13wt%) and Ti-xCu (up to 16wt%). The LENS™ deposited gradient were solutionized, and step quenched to specific aging temperature, and the resulting microstructures and phase were characterized utilizing XRD, EDS, SEM, FIB and TEM. The Ti-Zn system proved incapable of being LENS™ deposited due to the low vaporization temperature of Zn; however, a novel processing approach was developed to drip liquid Zn onto Ti powder at temperatures above β transus temperature of Ti (882 ◦C) and below the vaporization temperature of Zn (907 ◦C). The product of this processing technique was characterized in a similar way as the graded LENS™ depositions. From measurements performed on Ti-Sb it seems that Sb could be a potential α stabilizer in Ti due to the presence of a mostly homogeneous α …

Polymer nanocomposites are a going part of Materials Science and Engineering. These new composite materials exhibit dimensional and thermal stability of inorganic materials and toughness and dielectric properties of polymers. Development of nanocomposites become an important approach to create high-performance composite materials. In this study silica, fly ash, silica nanotubes and carbon black particles have been added to modify polyurethane foam and thermoplastic polyurethanes. It has been found that the addition of silica can diminish the size of foam bubbles, resulting in an increased stiffness of the material, increase of the compressive strength, and greater resistance to deformation. However, the uniformity of bubbles is reduced, resulting in increased friction of the material. Fly ash added to the foam can make bubbles smaller and improve uniformity of cells. Therefore, the material stiffness and compressive strength, resistance to deformation, and has little impact on the dynamic friction of the material. Adding nanotubes make bubble size unequal, and the arrangement of the bubble uneven, resulting in decreased strength of the material, while the friction increases. After the addition of carbon black to the polyurethane foam, due to the special surface structure of the carbon black, the foam generates more bubbles during the foaming …

Mg alloys have spurred a renewed academic and industrial interest because of their ultra-light-weight and high specific strength properties. Hexagonal close packed Mg has low deformability and a high plastic anisotropy between basal and non-basal slip systems at room temperature. Alloying with Li and other elements is believed to counter this deficiency by activating non-basal slip by reducing their nucleation stress. In this work I study how Li addition affects deformation mechanisms in Mg using atomistic simulations. In the first part, I create a reliable and transferable concentration dependent embedded atom method (CD-EAM) potential for my molecular dynamics study of deformation. This potential describes the Mg-Li phase diagram, which accurately describes the phase stability as a function of Li concentration and temperature. Also, it reproduces the heat of mixing, lattice parameters, and bulk moduli of the alloy as a function of Li concentration. Most importantly, our CD-EAM potential reproduces the variation of stacking fault energy for basal, prismatic, and pyramidal slip systems that influences the deformation mechanisms as a function of Li concentration. This success of CD-EAM Mg-Li potential in reproducing different properties, as compared to literature data, shows its reliability and transferability. Next, I use this newly created potential …

The relatively low oxidation resistance and subsequent surface embrittlement have often limited the use of titanium alloys in elevated temperature structural applications. Although extensive effort is spent to investigate the high temperature oxidation performance of titanium alloys, the studies are often constrained to complex technical titanium alloys and neither the mechanisms associated with evolution of the oxide scale nor the effect of oxygen ingress on the microstructure of the base metal are well-understood. In addition lack of systematic oxidation studies across a wider domain of the alloy composition has complicated the determination of composition-mechanism-property relationships. Clearly, it would be ideal to assess the influence of composition and exposure time on the oxidation resistance, independent of experimental variabilities regarding time, temperature and atmosphere as the potential source of error. Such studies might also provide a series of metrics (e.g., hardness, scale, etc) that could be interpreted together and related to the alloy composition. In this thesis a novel combinatorial approach was adopted whereby a series of compositionally graded specimens, (Ti-xMo, Ti-xCr, Ti-xAl and Ti-xW) were prepared using Laser Engineered Net Shaping (LENS™) technology and exposed to still-air at 650 °C. A suite of the state-of-the-art characterization techniques were employed to assess …

In-situ x-ray photoemission (XPS) and ex-situ FTIR studies of nanoporous organosilicate glass (OSG) films point to the separate roles of radicals vs. VUV photons in the carbon abstraction. The studies indicate that reaction with O2 in presence of VUV photons (~123 nm) result in significant carbon abstraction within the bulk and that the kinetics of this process is diffusion-limited. In contrast, OSG exposed to atomic O (no VUV) results in Si-C bond scission and Si-O bond formation, but this process is self-limiting after formation of ~1 nm thick SiO2 surface layer that inhibits further diffusion. Therefore, the diffusion-dominated kinetics of carbon abstraction observed for OSG exposed to O2 plasma is definitively attributed to the diffusion of O2 down OSG nanopores, reacting at photo-activated sites, rather than to the diffusion of atomic O. Pretreatment of OSG by 900 eV Ar+ ion bombardment also results in formation of 1 nm thick SiO2-like surface overlayer that inhibits O2 diffusion, inhibiting VUV+O2 and O2 plasma-induced reactions, and that the effectiveness of this treatment increases with ion kinetic energy. On the contrary, organosilicate glass (OSG) films with backbone carbon (-Si-R-Si-) exhibit significantly enhanced resistance to carbon loss upon exposure to O2 plasma, radicals and VUV+O2 …

Since their discovery in the 1930s, polymeric foams have been widely used in the industry for a variety of applications such as acoustical and thermal insulation, filters, absorbents etc. The reason for this ascending trend can be attributed to factors such as cost, ease of processing and a high strength to weight ratio compared to non-foamed polymers. The purpose of this project was to develop an “indestructible” material made of polycarbonate (PC) for industrial applications. Due to the high price of polycarbonate, two foaming methods were investigated to reduce the amount of material used. Samples were foamed physically in supercritical CO2 or chemically with 5-phenyl-1H-tetrazole. After thermal characterization of the foams in differential scanning calorimetry (DSC), we saw that none of the foaming methods had an influence on the glass transition of polycarbonate. Micrographs taken in scanning electron microscopy (SEM) showed that foams obtained in physical and chemical foaming had different structures. Indeed, samples foamed in supercritical CO2 exhibited a microcellular opened-cell structure with a high cell density and a homogeneous cell distribution. On the other hand, samples foamed with 5-phenyl-1H-tetrazole had a macrocellular closed-cell structure with a much smaller cell density and a random cell distribution. Compression testing showed …

The effect of friction stir processing (FSP) on the mechanical wear behavior was investigated for Ti-1Al-8V-5Fe (Ti-185) and stainless steel (Incoloy® A-286) alloys. The Ti-185 and A-286 alloys were tested in different processing conditions, including as rolled (AR), AR+FSP, and AR+FSP+aged. A high frequency reciprocating rig was used to simulate fretting-type wear of these alloys at room temperature. The Vickers micro-hardness and wear rates were calculated and compared for each processing condition. It was determined that along with increasing hardness in the stir zones, FSP resulted in improved wear resistance for both alloys. Specifically, wear rates in the stir zones were reduced to lowest values of 1.6 x 10-5 and 5.8 x 10-7 mm3/N·m for the AR+FSP+aged Ti-185 and A-286 alloys, respectively, despite lower hardness for A-286 alloy. Mechanistic studies were conducted to determine the reason behind these improvements in wear resistance and the effect of FSP on the microstructural evolution during wear. For the Ti-185 alloy, x-ray diffraction revealed that there was a phase transformation from β-Ti (AR+FSP) to α-Ti (AR+FSP+aged). This phase decomposition resulted in the harder and stiffer Ti phase responsible for lowering of wear rate in Ti-185. While x-ray diffraction confirmed the A-286 alloy retains its …

Mechanical properties of structural materials are highly correlated to their microstructure. The relationship between microstructure and mechanical properties can be established experimentally. The growing need for structural materials in industry promotes the study of microstructural evolution of materials by design using computational approaches. This thesis presents the microstructural evolution of two different structural materials. The first uses a genetic algorithm approach to study the microstructural evolution of a high-temperature nickel-based oxide-dispersion-strengthened (ODS) alloy. The chosen Ni-20Cr ODS system has nano Y2O3 particles for dispersion strengthening and submicron Al2O3 for composite strengthening. Synergistic effects through the interaction of small dispersoids and large reinforcements improved high-temperature strength. Optimization considered different weight factors on low temperature strength, ductility, and high temperature strength. Simulation revealed optimal size and volume fraction of dispersoids and reinforced particles. Ni-20Cr-based alloys were developed via mechanical alloying for computational optimization and validation. The Ni-20Cr-1.2Y2O3-5Al2O3 alloy exhibited significant reduction in the minimum creep rate (on the order of 10-9 s-1) at 800oC and 100 MPa. The second considers the microstructural evolution of AA 7050 alloy during friction stir welding (FSW). Modeling the FSW process includes thermal, material flow, microstructural and strength modeling. Three-dimensional material flow and heat transfer model was …

Lack of crystalline order and microstructural features such as grain/grain-boundary in metallic glasses results in a suite of remarkable attributes including very high strength, close to theoretical elasticity, high corrosion and wear resistance, and soft magnetic properties. By altering the morphology and tuning of composition, MGs may be transformed into high-performance catalytic materials. In this study, the catalytic properties of metallic glass powders were demonstrated in dissociating toxic organic chemicals such as AZO dye. BMG powders showed superior performance compared to state of the art crystalline iron because of their high catalytic activity, durability, and reusability. To enhance the catalytic properties, high energy mechanical milling was performed to increase the surface area and defect density. Iron-based bulk metallic glass (BMG) of composition Fe48Cr15Mo14Y2C15B6 was used because of its low cost and ability to make large surface area by high energy ball milling. AZO dye was degraded in less than 20 minutes for the 9 hours milled Fe-BMG. However, subsequent increase in ball milling time resulted in devitrification and loss of catalytic activity as measured using UV-Visible spectroscopy. Aluminum-based bulk metallic glass (Al-BMG) powder of composition Al82Fe3Ni8Y7 was synthesized by arc-melting the constituent elements followed by gas-atomization. The particle size and …

In this thesis, I utilize first principles density functional theory (DFT) based calculations to investigate the structure and electronic properties including charge transfer behaviors and work function of two types of materials: pentacene based organic semiconductors and ZnO transparent conducting oxides, with an aim to search for high mobility n-type organic semiconductors and fine tuning work functions of ZnO through surface modifications. Based on DFT calculations of numerous structure combinations, I proposed a pentacene and perfluoro-pentacene alternating hybrid structures as a new type of n-type semiconductor. Based on the DFT calculations and Marcus charge transfer theory analysis, the new structure has high charge mobility and can be a promising new n-type organic semiconductor material. DFT calculations have been used to systematically investigate the effect of surface organic absorbate and surface defects on the work function of ZnO. It was found that increasing surface coverage of organic groups and decreasing surface defects lead to decrease of work functions, in excellent agreement with experimental results. First principles based calculations thus can greatly contribute to the investigating and designing of new electronic materials.

Tissue engineering merges the disciplines of study like cell biology, materials science, engineering and surgery to enable growth of new living tissues on scaffolding constructed from implanted polymeric materials. One of the most important aspects of tissue engineering related to material science is design of the polymer scaffolds. The polymer scaffolds needs to have some specific mechanical strength over certain period of time. In this work bioresorbable aliphatic polymers (PCL and PLLA) were blended using extrusion and solution methods. These blends were then extruded and electrospun into fibers. The fibers were then subjected to FDA standard in vitro immersion degradation tests where its mechanical strength, water absorption, weight loss were observed during the eight weeks. The results indicate that the mechanical strength and rate of degradation can be tailored by changing the ratio of PCL and PLLA in the blend. Processing influences these parameters, with the loss of mechanical strength and rate of degradation being higher in electrospun fibers compared to those extruded. A second effort in this thesis addressed the potential separation of the scaffold from the tissue (loss of apposition) due to the differences in their low strain responses. This hypothesis that using knit with low tension will …

Graphene has attracted significant research attention for next generation of semiconductor devices due to its high electron mobility and compatibility with planar semiconductor processing. In this dissertation, the influences of Ohmic metals and high dielectric (high-k) constant aluminum oxide (Al2O3) deposition on the structural and electrical properties of multi-layer epitaxial graphene (MLG) grown by graphitization of silicon carbide (SiC) substrates have been investigated. Uniform MLG was successfully grown by sublimation of silicon from epitaxy-ready, Si and C terminated, 6H-SiC wafers in high-vacuum and argon atmosphere. The graphene formation was accompanied by a significant enhancement of Ohmic behavior, and, was found to be sensitive to the temperature ramp-up rate and annealing time. High-resolution transmission electron microscopy (HRTEM) showed that the interface between the metal and SiC remained sharp and free of macroscopic defects even after 30 min, 1430 °C anneals. The impact of high dielectric constant Al2O3 and its deposition by radio frequency (RF) magnetron sputtering on the structural and electrical properties of MLG is discussed. HRTEM analysis confirms that the Al2O3/MLG interface is relatively sharp and that thickness approximation of the MLG using angle resolved X-ray photoelectron spectroscopy (ARXPS) as well as variable-angle spectroscopic ellipsometry (VASE) is accurate. The totality …

This thesis examines the value of using dispersed conductive fillers as a stress/strain sensing material. The effect of the intrinsic conductivity of the filler on the ability to be effective and the influence of filler concentration on the conductivity are also examined. To meet these objectives, nanocomposites of polyvinylidene fluoride (PVDF) with carbon nanofibers (CNFs) and carbon nanotubes (CNTs) were prepared by melt-blending using a twin screw extruder. Since PVDF has a potential to be piezoresistive based on the type of crystalline phase, the effect of CNFs on PVDF crystallinity, crystalline phase, quasi static and dynamic mechanical property was studied concurrently with piezoresponse. Three time dependencies were examined for PVDF/CNTs nanocomposites: quasi-static, transient and cyclic fatigue. The transient response of the strain with time showed viscoelastic behavior and was modeled by the 4-element Burger model. Under quasi-static loading the resistance showed negative pressure coefficient below yield but changed to a positive pressure coefficient after yield. Under cyclic load, the stress-time and resistance-time were synchronous but the resistance peak value decreased with increasing cycles, which was attributed to charge storage in the nanocomposite. The outcomes of this thesis indicate that a new piezoresponsive system based on filled polymers is a viable …

The current understanding of the atomic scale phenomenon associated with the influence of beta phase instabilities on the evolution of microstructure in titanium alloys is limited due to their complex nature. Such beta phase instabilities include phase separation and precipitation of nano-scale omega and alpha phases in the beta matrix. The initial part of the present study focuses on omega precipitation within the beta matrix of model binary titanium molybdenum (Ti-Mo) alloys. Direct atomic scale observation of pre-transition omega-like embryos in quenched alloys, using aberration-corrected high resolution scanning transmission electron microscopy and atom probe tomography (APT) was compared and contrasted with the results of first principles computations performed using the Vienna ab initio simulation package (VASP) to present a novel mechanism of these special class of phase transformation. Thereafter the beta phase separation and subsequent alpha phase nucleation in a Ti-Mo-Al ternary alloy was investigated by coupling in-situ high energy synchrotron x-ray diffraction with ex-situ characterization studies performed using aberration corrected transmission electron microscopy and APT to develop a deeper understanding of the mechanism of transformation. Subsequently the formation of the omega phase in the presence of simultaneous development of compositional phase separation within the beta matrix phase of a …

Commercial superalloys like Rene88DT are used in high temperature applications like turbine disk in aircraft jet engines due to their excellent high temperature properties, including strength, ductility, improved fracture toughness, fatigue resistance, enhanced creep and oxidation resistance. Typically this alloy's microstructure has L12-ordered precipitates dispersed in disordered face-centered cubic γ matrix. A typical industrially relevant heat-treatment often leads to the formation of multiple size ranges of γ¢ precipitates presumably arising from multiple nucleation bursts during the continuous cooling process. The morphology and distribution of these γ′ precipitates inside γ matrix influences the mechanical properties of these materials. Therefore, the study of thermodynamic and kinetic factors influencing the evolution of these precipitates and subsequent effects is both relevant for commercial applications as well as for a fundamental understanding of the underlying phase transformations. The present research is primarily focused on understanding the mechanism of formation of different generations of γ′ precipitates during continuous cooling by coupling scanning electron microscopy (SEM), energy filtered TEM and atom probe tomography (APT). In addition, the phase transformations leading to nucleation of γ′ phase has been a topic of controversy for decades. The present work, for the first time, gives a novel insight into the mechanism …

The objective of this thesis is to investigate the effects of adding natural fiber (kenaf fiber, retted kenaf fiber, and sugarcane fiber) into polymer materials. The effects are obtained by considering three main parts. 1. Performance in thermoplastic composites. The effect of fiber retting on polymer composite crystallization and mechanical performance was investigated. PHBV/PBAT in 80/20 blend ratio was modified using 5% by weight kenaf fiber. Dynamic mechanical analysis of the composites was done to investigate the glass transition and the modulus at sub-ambient and ambient temperatures. ESEM was conducted to analyze fiber topography which revealed smoother surfaces on the pectinase retted fibers. 2. Performance in thermoset composites. The effect of the incorporation of natural fibers of kenaf and of sugarcane combined with the polyester resin matrix is investigated. A comparison of mechanical properties of kenaf polyester composite, sugarcane polyester composite and pure polyester in tensile, bending, dynamic mechanical thermal analysis (DMA) and moisture test on performance is measured.. 3. Performance in sandwich composites. The comparison of the performance characteristics and mechanical properties of natural fiber composites panels with soft and rigid foam cores are evaluated. A thorough test of the mechanical behavior of composites sandwich materials in tensile, bending …

Amorphous materials are used as soft magnetic materials and also as surface coatings to improve the surface properties. Furthermore, the nanocrystalline materials derived from their amorphous precursors show superior soft magnetic properties than amorphous counter parts for transformer core applications. In the present work, laser based processing of amorphous materials will be presented. Conventionally, the nanocrystalline materials are synthesized by furnace heat treatment of amorphous precursors. Fe-based amorphous/nanocrystalline materials due to their low cost and superior magnetic properties are the most widely used soft magnetic materials. However, achieving nanocrystalline microstructure in Fe-Si-B ternary system becomes very difficult owing its rapid growth rate at higher temperatures and sluggish diffusion at low temperature annealing. Hence, nanocrystallization in this system is achieved by using alloying additions (Cu and Nb) in the ternary Fe-Si-B system. Thus, increasing the cost and also resulting in reduction of saturation magnetization. laser processing technique is used to achieve extremely fine nanocrystalline microstructure in Fe-Si-B amorphous precursor. Microstructure-magnetic Property-laser processing co-relationship has been established for Fe-Si-B ternary system using analytical techniques. Laser processing improved the magnetic properties with significant increase in saturation magnetization and near zero coercivity values. Amorphous materials exhibit excellent corrosion resistance by virtue of their atomic …