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 Degree Discipline: Materials Science and Engineering
 Degree Level: Doctoral
 Collection: UNT Theses and Dissertations
Barrier and long term creep properties of polymer nanocomposites.

Barrier and long term creep properties of polymer nanocomposites.

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Date: December 2004
Creator: Ranade, Ajit
Description: 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 ...
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Biocompatible Hybrid Nanomaterials Involving Polymers and Hydrogels Interfaced with Phosphorescent Complexes and Toxin-Free Metallic Nanoparticles for Biomedical Applications

Biocompatible Hybrid Nanomaterials Involving Polymers and Hydrogels Interfaced with Phosphorescent Complexes and Toxin-Free Metallic Nanoparticles for Biomedical Applications

Date: August 2011
Creator: Marpu, Sreekar B.
Description: The major topics discussed are all relevant to interfacing brightly phosphorescent and non-luminescent coinage metal complexes of [Ag(I) and Au(I)] with biopolymers and thermoresponsive gels for making hybrid nanomaterials with an explanation on syntheses, characterization and their significance in biomedical fields. Experimental results and ongoing work on determining outreaching consequences of these hybrid nanomaterials for various biomedical applications like cancer therapy, bio-imaging and antibacterial abilities are described. In vitro and in vivo studies have been performed on majority of the discussed hybrid nanomaterials and determined that the cytotoxicity or antibacterial activity are comparatively superior when compared to analogues in literature. Consequential differences are noticed in photoluminescence enhancement from hybrid phosphorescent hydrogels, phosphorescent complex ability to physically crosslink, Au(I) sulfides tendency to form NIR (near-infrared) absorbing AuNPs compared to any similar work in literature. Syntheses of these hybrid nanomaterials has been thoroughly investigated and it is determined that either metallic nanoparticles syntheses or syntheses of phosphorescent hydrogels can be carried in single step without involving any hazardous reducing agents or crosslinkers or stabilizers that are commonly employed during multiple step syntheses protocols for syntheses of similar materials in literature. These astounding results that have been discovered within studies of hybrid nanomaterials ...
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Biodegradable Poly(hydroxy Butyrate-co-valerate) Nanocomposites And Blends With Poly(butylene Adipate-co-terephthalate) For Sensor Applications

Biodegradable Poly(hydroxy Butyrate-co-valerate) Nanocomposites And Blends With Poly(butylene Adipate-co-terephthalate) For Sensor Applications

Date: December 2011
Creator: Vidhate, Shailesh.
Description: The utilization of biodegradable polymers is critical for developing “cradle to cradle” mindset with ecological, social and economic consequences. Poly(hydroxy butyrate-co-valerate) (PHBV) shows significant potential for many applications with a polypropylene equivalent mechanical performance. However, it has limitations including high crystallinity, brittleness, small processing window, etc. which need to be overcome before converting them into useful products. Further the development of biodegradable strain sensing polymer sensors for structural health monitoring has been a growing need. In this dissertation I utilize carbon nanotubes as a self sensing dispersed nanofiller. The impact of its addition on PHBV and a blend of PHBV with poly(butylene adipate-co-terephthalate) (PBAT) polymer was examined. Nanocomposites and blends of PHBV, PBAT, and MWCNTs were prepared by melt-blending. The effect of MWCNTs on PHBV crystallinity, crystalline phase, quasi-static and dynamic mechanical property was studied concurrently with piezoresistive response. In PHBV/PBAT blends a rare phenomenon of melting point elevation by the addition of low melting point PBAT was observed. The blends of these two semicrystalline aliphatic and aromatic polyesters were investigated by using differential scanning calorimetry, small angle X-ray scattering, dynamic mechanical analysis, surface energy measurement by contact angle method, polarized optical and scanning electron microscopy, and rheology. The study ...
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Bulk and interfacial effects on density in polymer nanocomposites

Bulk and interfacial effects on density in polymer nanocomposites

Date: May 2007
Creator: Sahu, Laxmi Kumari
Description: The barrier properties of polymers are a significant factor in determining the shelf or device lifetime in polymer packaging. Nanocomposites developed from the dispersion of nanometer thick platelets into a host polymer matrix have shown much promise. The magnitude of the benefit on permeability has been different depending on the polymer investigated or the degree of dispersion of the platelet in the polymer. In this dissertation, the effect of density changes in the bulk and at the polymer-platelet interface on permeability of polymer nanocomposites is investigated. Nanocomposites of nylon, PET, and PEN were processed by extrusion. Montmorillonite layered silicate (MLS) in a range of concentrations from 1 to 5% was blended with all three resins. Dispersion of the MLS in the matrix was investigated by using one or a combination of X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Variation in bulk density via crystallization was analyzed using differential scanning calorimetry (DSC) and polarized optical microscopy. Interfacial densification was investigated using force modulation atomic force microscopy (AFM) and ellipsometry. Mechanical properties are reported. Permeability of all films was measured in an in-house built permeability measurement system. The effect of polymer orientation and induced defects on permeability ...
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Carrier Mobility, Charge Trapping Effects on the Efficiency of Heavily Doped Organic Light-Emitting Diodes, and EU(lll) Based Red OLEDs

Carrier Mobility, Charge Trapping Effects on the Efficiency of Heavily Doped Organic Light-Emitting Diodes, and EU(lll) Based Red OLEDs

Date: August 2010
Creator: Lin, Ming-Te
Description: Transient electroluminescence (EL) was used to measure the onset of emission delay in OLEDs based on transition metal, phosphorescent bis[3,5-bis(2-pyridyl)-1,2,4-triazolato] platinum(ΙΙ) and rare earth, phosphorescent Eu(hfa)3 with 4'-(p-tolyl)-2,2":6',2" terpyridine (ttrpy) doped into 4,4'-bis(carbazol-9-yl) triphenylamine (CBP), from which the carrier mobility was determined. For the Pt(ptp)2 doped CBP films in OLEDs with the structure: ITO/NPB (40nm)/mcp (10nm)/65% Pt(ptp)2:CBP (25nm)/TPBI (30nm)/Mg:Ag (100nm), where NPB=N, N'-bis(1-naphthyl)-N-N'-biphenyl-1, 1'-biphenyl-4, MCP= N, N'-dicarbazolyl-3,5-benzene, TPBI=1,3,5-tris(phenyl-2-benzimidazolyl)-benzene, delayed recombination was observed and based on its dependence on frequency and duty cycle, ascribed to trapping and de-trapping processes at the interface of the emissive layer and electron blocker. The result suggests that the exciton recombination zone is at, or close to the interface between the emissive layer and electron blocker. The lifetime of the thin films of phosphorescent emitter Pt(ptp)2 were studied for comparison with rare earth emitter Eu(hfa)3. The lifetime of 65% Pt(ptp)2:CBP co-film was around 638 nanoseconds at the emission peak of 572nm, and the lifetime of neat Eu(hfa)3 film was obtained around 1 millisecond at 616 nm, which supports the enhanced efficiency obtained from the Pt(ptp)2 devices. The long lifetime and narrow emission of the rare earth dopant Eu(hfa)3 is a fundamental factor limiting device performance. Red ...
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Characterization and mechanical properties of nanoscale precipitates in modified Al-Si-Cu alloys using transmission electron microscopy and 3D atom probe tomography.

Characterization and mechanical properties of nanoscale precipitates in modified Al-Si-Cu alloys using transmission electron microscopy and 3D atom probe tomography.

Date: May 2007
Creator: Hwang, Junyeon
Description: Among the commercial aluminum alloys, aluminum 319 (Al-7wt%Si-4wt%Cu) type alloys are popularly used in automobile engine parts. These alloys have good casting characteristics and excellent mechanical properties resulting from a suitable heat treatment. To get a high strength in the 319 type alloys, grain refining, reducing the porosity, solid solution hardening, and precipitation hardening are preferred. All experimental variables such as solidification condition, composition, and heat treatment are influence on the precipitation behavior; however, precipitation hardening is the most significant because excess alloying elements from supersaturated solid solution form fine particles which act as obstacles to dislocation movement. The challenges of the 319 type alloys arise due to small size of precipitate and complex aging response caused by multi components. It is important to determine the chemical composition, crystal structure, and orientation relationship as well as precipitate morphology in order to understand the precipitation behavior and strengthening mechanism. In this study, the mechanical properties and microstructure were investigated using transmission electron microscopy and three dimensional atom probe tomography. The Mn and Mg effects on the microstructure and mechanical properties are discussed with crystallographic study on the iron intermetallic phases. The microstructural evolution and nucleation study on the precipitates in the ...
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Definition of brittleness: Connections between mechanical and tribological properties of polymers.

Definition of brittleness: Connections between mechanical and tribological properties of polymers.

Date: August 2008
Creator: Hagg Lobland, Haley E.
Description: The increasing use of polymer-based materials (PBMs) across all types of industry has not been matched by sufficient improvements in understanding of polymer tribology: friction, wear, and lubrication. Further, viscoelasticity of PBMs complicates characterization of their behavior. Using data from micro-scratch testing, it was determined that viscoelastic recovery (healing) in sliding wear is independent of the indenter force within a defined range of load values. Strain hardening in sliding wear was observed for all materials-including polymers and composites with a wide variety of chemical structures-with the exception of polystyrene (PS). The healing in sliding wear was connected to free volume in polymers by using pressure-volume-temperature (P-V-T) results and the Hartmann equation of state. A linear relationship was found for all polymers studied with again the exception of PS. The exceptional behavior of PS has been attributed qualitatively to brittleness. In pursuit of a precise description of such, a quantitative definition of brittleness has been defined in terms of the elongation at break and storage modulus-a combination of parameters derived from both static and dynamic mechanical testing. Furthermore, a relationship between sliding wear recovery and brittleness for all PBMs including PS is demonstrated. The definition of brittleness may be used as ...
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Device Engineering for Enhanced Efficiency from Platinum(II) Phosphorescent OLEDs

Device Engineering for Enhanced Efficiency from Platinum(II) Phosphorescent OLEDs

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Date: August 2010
Creator: Li, Minghang
Description: Phosphorescent organic light emitting diodes (PHOLEDs) based on efficient electrophosphorescent dopant, platinum(II)-pyridyltriazolate complex, bis[3,5-bis(2-pyridyl)-1,2,4-triazolato]platinum(II) (Pt(ptp)2) have been studied and improved with respect to power efficiency, external efficiency, chromacity and efficiency roll-off. By studying the electrical and optical behavior of the doped devices and functionality of the various constituent layers, devices with a maximum EQE of 20.8±0.2 % and power efficiency of 45.1±0.9 lm/W (77lm/W with luminaries) have been engineered. This improvement compares to devices whose emission initially could only be detected by a photomultiplier tube in a darkened environment. These devices consisted of a 65 % bis[3,5-bis(2-pyridyl)-1,2,4-triazolato]platinum(II) (Pt(ptp)2) doped into 4,4'-bis(carbazol-9-yl)triphenylamine (CBP) an EML layer, a hole transporting layer/electron blocker of 1,1-bis[(di-4-tolylamino)phenyl]cyclohexane (TAPC), an electron transport layer of 1,3,5-tris(phenyl-2-benzimidazolyl)-benzene (TPBI), and a LiF/Al cathode. These devices show the acceptable range for warm white light quadrants and qualify to be called "warm white" even w/o adding another emissive layer. Dual EML devices composed of neat Pt(ptp)2 films emitting orange and CBP: Pt(ptp)2 film emitting blue-green produced a color rendering index (CRI) of 59 and color coordinates (CIE) of (0.47,0.49) at 1000Cd/m² with power efficiency of 12.6±0.2 lm/W and EQE of 10.8±0.2 %. Devices with two blue fluorescent emission layers as singlet ...
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Dynamic Adhesion and Self-cleaning Mechanisms of Gecko Setae and Spatulae

Dynamic Adhesion and Self-cleaning Mechanisms of Gecko Setae and Spatulae

Date: December 2013
Creator: Xu, Quan
Description: Geckos can freely climb on walls and ceilings against their body weight at speed of over 1ms-1. Switching between attachment and detachment seem simple and easy for geckos, without considering the surface to be dry or wet, smooth or rough, dirty or clean. In addition, gecko can shed dirt particles during use, keeping the adhesive pads clean. Mimicking this biological system can lead to a new class of dry adhesives for various applications. However, gecko’s unique dry self-cleaning mechanism remains unknown, which impedes the development of self-cleaning dry adhesives. In this dissertation we provide new evidence and self-cleaning mechanism to explain how gecko shed particles and keep its sticky feet clean. First we studied the dynamic enhancement observed between micro-sized particles and substrate under dry and wet conditions. The adhesion force of soft (polystyrene) and hard (SiO2 and Al2O3) micro-particles on soft (polystyrene) and hard (fused silica and sapphire) substrates was measured using an atomic force microscope (AFM) with retraction (z-piezo) speed ranging over 4 orders of magnitude. The adhesion is strongly enhanced by the dynamic effect. When the retraction speeds varies from 0.02 µm/s to 156 µm/s, the adhesion force increases by 10% ~ 50% in dry nitrogen while ...
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Effects of Plasma, Temperature and Chemical Reactions on Porous Low Dielectric Films for Semiconductor Devices

Effects of Plasma, Temperature and Chemical Reactions on Porous Low Dielectric Films for Semiconductor Devices

Date: December 2010
Creator: Osei-Yiadom, Eric
Description: Low-dielectric (k) films are one of the performance drivers for continued scaling of integrated circuit devices. These films are needed in microelectronic device interconnects to lower power consumption and minimize cross talk between metal lines that "interconnect" transistors. Low-k materials currently in production for the 45 and 65 nm node are most often organosilicate glasses (OSG) with dielectric constants near 2.8 and nominal porosities of 8-10%. The next generation of low-k materials will require k values 2.6 and below for the 45 nm device generation and beyond. The continuous decrease in device dimensions in ultra large scale integrated (ULSI) circuits have brought about the replacement of the silicon dioxide interconnect dielectric (ILD), which has a dielectric constant (k) of approximately 4.1, with low dielectric constant materials. Lowering the dielectric constant reduces the propagation delays, RC constant (R = the resistance of the metal lines; C = the line capacitance), and metal cross-talk between wires. In order to reduce the RC constants, a number of low-k materials have been studied for use as intermetal dielectrics. The k values of these dielectric materials can be lowered by replacing oxide films with carbon-based polymer films, incorporating hydrocarbon functional groups into oxide films (SiOCH ...
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