Matching Items (10)
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- All Subjects: Condensed Matter Physics
- All Subjects: Polyurea
- Creators: Chamberlin, Ralph
Description
This dissertation is focused on material property exploration and analysis using computational quantum mechanics methods. Theoretical calculations were performed on the recently discovered hexahydride materials A2SiH6 (A=Rb, K) to calculate the lattice dynamics of the systems in order to check for structural stability, verify the experimental Raman and infrared spectrospcopy results, and obtain the theoretical free energies of formation. The electronic structure of the systems was calculated and the bonding and ionic properties of the systems were analyzed. The novel hexahydrides were compared to the important hydrogen storage material KSiH3. This showed that the hypervalent nature of the SiH62- ions reduced the Si-H bonding strength considerably. These hydrogen rich compounds could have promising energy applications as they link to alternative hydrogen fuel technology. The carbide systems Li-C (A=Li,Ca,Mg) were studied using \emph{ab initio} and evolutionary algorithms at high pressures. At ambient pressure Li2C2 and CaC2 are known to contain C22- dumbbell anions and CaC2 is polymorphic. At elevated pressure both CaC2 and Li2C2 display polymorphism. At ambient pressure the Mg-C system contains several experimentally known phases, however, all known phases are shown to be metastable with respect to the pure elements Mg and C. First principle investigation of the configurational space of these compounds via evolutionary algorithms results in a variety of metastable and unique structures. The binary compounds ZnSb and ZnAs are II-V electron-poor semiconductors with interesting thermoelectric properties. They contain rhomboid rings composed of Zn2Sb2 (Zn2As2) with multi-centered covalent bonds which are in turn covalently bonded to other rings via two-centered, two-electron bonds. Ionicity was explored via Bader charge analysis and it appears that the low ionicity that these materials display is a necessary condition of their multicentered bonding. Both compounds were found to have narrow, indirect band gaps with multi-valley valence and conduction bands; which are important characteristics for high thermopower in thermoelectric materials. Future work is needed to analyze the lattice properties of the II-V CdSb-type systems, especially in order to find the origin of the extremely low thermal conductivity that these systems display.
ContributorsBenson, Daryn Eugene (Author) / Häussermann, Ulrich (Thesis advisor) / Shumway, John (Thesis advisor) / Chamberlin, Ralph (Committee member) / Sankey, Otto (Committee member) / Treacy, Mike (Committee member) / Arizona State University (Publisher)
Created2013
Description
The heat transfer enhancements available from expanding the cross-section of a boiling microchannel are explored analytically and experimentally. Evaluation of the literature on critical heat flux in flow boiling and associated pressure drop behavior is presented with predictive critical heat flux (CHF) and pressure drop correlations. An optimum channel configuration allowing maximum CHF while reducing pressure drop is sought. A perturbation of the channel diameter is employed to examine CHF and pressure drop relationships from the literature with the aim of identifying those adequately general and suitable for use in a scenario with an expanding channel. Several CHF criteria are identified which predict an optimizable channel expansion, though many do not. Pressure drop relationships admit improvement with expansion, and no optimum presents itself. The relevant physical phenomena surrounding flow boiling pressure drop are considered, and a balance of dimensionless numbers is presented that may be of qualitative use. The design, fabrication, inspection, and experimental evaluation of four copper microchannel arrays of different channel expansion rates with R-134a refrigerant is presented. Optimum rates of expansion which maximize the critical heat flux are considered at multiple flow rates, and experimental results are presented demonstrating optima. The effect of expansion on the boiling number is considered, and experiments demonstrate that expansion produces a notable increase in the boiling number in the region explored, though no optima are observed. Significant decrease in the pressure drop across the evaporator is observed with the expanding channels, and no optima appear. Discussion of the significance of this finding is presented, along with possible avenues for future work.
ContributorsMiner, Mark (Author) / Phelan, Patrick E (Thesis advisor) / Baer, Steven (Committee member) / Chamberlin, Ralph (Committee member) / Chen, Kangping (Committee member) / Herrmann, Marcus (Committee member) / Arizona State University (Publisher)
Created2013
Description
A series of Molybdenum-Copper bilayers were studied for use in 120mK superconducting transition edge sensors for spectrometer applications. The Transition temperature (TC) was tuned to the desired temperature using the proximity effect, by adjusting the thickness of a normal copper layer in direct contact with the superconducting molybdenum layer in a proximitized bilayer structure. The bilayers have a fixed normal metal thickness dCu=1250 Å, on top of a variable superconductor thickness 650 Å ≤ dMo ≤ 1000 Å. Material characterization techniques including X-ray Diffraction (XRD), Rutherford Backscattering Spectroscopy (RBS), Atomic Force Microscopy (AFM), and 4-point electrical characterization are used to characterize the films. Film TC are compared with the results of the Usadel proximity theory. The results of RBS analysis demonstrated that some Argon-contamination is observed at the Mo film-substrate interface, which correlates with bilayer surface roughness (as observed with AFM), reduced crystalline quality (via XRD Rocking Curve), and a deviation from the theoretical expected TC for a bilayer. The Argon contamination is presumably the cause of interface roughness, reducing the interface transmission coefficient in the Usadel model, and producing the discrepancy from the expected TC.
ContributorsKopas, Cameron (Author) / Newman, Nathan (Thesis advisor) / Singh, Rakesh (Committee member) / Chamberlin, Ralph (Committee member) / Arizona State University (Publisher)
Created2014
Description
Recent literature indicates potential benefits in microchannel cooling if an inlet orifice is used to suppress pressure oscillations that develop under two-phase conditions. This study investigates the costs and benefits of using an adjustable microchannel inlet orifice. The focus is on orifice effect during steady-state boiling and critical heat flux (CHF) in the channels using R134a in a pumped refrigerant loop (PRL). To change orifice size, a dam controlled with a micrometer was placed in front of 31 parallel microchannels. Each channel had a hydraulic diameter of 0.235 mm and a length of 1.33 cm. For steady state two-phase conditions, mass fluxes of 300 kg m-2 s-1 and 600 kg m-2 s-1were investigated. For orifice sizes with a hydraulic diameter to unrestricted hydraulic diameter (Dh:Dh,ur) ratio less than 35 percent, oscillations were reduced and wall temperatures fell up to 1.5 °C. Critical heat flux data were obtained for 7 orifice sizes with mass fluxes from 186 kg m-2 s-1 to 847 kg m-2 s-1. For all mass fluxes and inlet conditions tested, CHF values for a Dh:Dh,ur ratio of 1.8 percent became increasingly lower (up to 37 W cm-2 less) than those obtained with larger orifices. An optimum orifice size with Dh:Dh,ur of 35 percent emerged, offering up to 5 W cm-2 increase in CHF over unrestricted conditions at the highest mass flux tested, 847 kg m-2 s-1. These improvements in cooling ability with inlet orifices in place under both steady-state and impending CHF conditions are modest, leading to the conclusion that inlet orifices are only mildly effective at improving heat transfer coefficients. Stability of the PRL used for experimentation was also studied and improved. A vapor compression cycle's (VCC) proportional, integral, and derivative controller was found to adversely affect stability within the PRL and cause premature CHF. Replacing the VCC with an ice water heat sink maintained steady pumped loop system pressures and mass flow rates. The ice water heat sink was shown to have energy cost savings over the use of a directly coupled VCC for removing heat from the PRL.
ContributorsOdom, Brent A (Author) / Phelan, Patrick E (Thesis advisor) / Herrmann, Marcus (Committee member) / Trimble, Steve (Committee member) / Tasooji, Amaneh (Committee member) / Holcomb, Don (Committee member) / Arizona State University (Publisher)
Created2012
Description
In this dissertation, in-situ X-ray and ultraviolet photoemission spectroscopy have been employed to study the interface chemistry and electronic structure of potential high-k gate stack materials. In these gate stack materials, HfO2 and La2O3 are selected as high-k dielectrics, VO2 and ZnO serve as potential channel layer materials. The gate stack structures have been prepared using a reactive electron beam system and a plasma enhanced atomic layer deposition system. Three interrelated issues represent the central themes of the research: 1) the interface band alignment, 2) candidate high-k materials, and 3) band bending, internal electric fields, and charge transfer. 1) The most highlighted issue is the band alignment of specific high-k structures. Band alignment relationships were deduced by analysis of XPS and UPS spectra for three different structures: a) HfO2/VO2/SiO2/Si, b) HfO2-La2O3/ZnO/SiO2/Si, and c) HfO2/VO2/ HfO2/SiO2/Si. The valence band offset of HfO2/VO2, ZnO/SiO2 and HfO2/SiO2 are determined to be 3.4 ± 0.1, 1.5 ± 0.1, and 0.7 ± 0.1 eV. The valence band offset between HfO2-La2O3 and ZnO was almost negligible. Two band alignment models, the electron affinity model and the charge neutrality level model, are discussed. The results show the charge neutrality model is preferred to describe these structures. 2) High-k candidate materials were studied through comparison of pure Hf oxide, pure La oxide, and alloyed Hf-La oxide films. An issue with the application of pure HfO2 is crystallization which may increase the leakage current in gate stack structures. An issue with the application of pure La2O3 is the presence of carbon contamination in the film. Our study shows that the alloyed Hf-La oxide films exhibit an amorphous structure along with reduced carbon contamination. 3) Band bending and internal electric fields in the gate stack structure were observed by XPS and UPS and indicate the charge transfer during the growth and process. The oxygen plasma may induce excess oxygen species with negative charges, which could be removed by He plasma treatment. The final HfO2 capping layer deposition may reduce the internal potential inside the structures. The band structure was approaching to a flat band condition.
ContributorsZhu, Chiyu (Author) / Nemanich, Robert (Thesis advisor) / Chamberlin, Ralph (Committee member) / Chen, Tingyong (Committee member) / Ponce, Fernando (Committee member) / Smith, David (Committee member) / Arizona State University (Publisher)
Created2012
Description
The exceptional mechanical properties of polymers with heterogeneous structure, such as the high toughness of polyethylene and the excellent blast-protection capability of polyurea, are strongly related to their morphology and nanoscale structure. Different polymer microstructures, such as semicrystalline morphology and segregated nanophases, lead to coordinated molecular motions during deformation in order to preserve compatibility between the different material phases. To study molecular relaxation in polyethylene, a coarse-grained model of polyethylene was calibrated to match the local structural variable distributions sampled from supercooled atomistic melts. The coarse-grained model accurately reproduces structural properties, e.g., the local structure of both the amorphous and crystalline phases, and thermal properties, e.g., glass transition and melt temperatures, and dynamic properties: including the vastly different relaxation time scales of the amorphous and crystalline phases. A hybrid Monte Carlo routine was developed to generate realistic semicrystalline configurations of polyethylene. The generated systems accurately predict the activation energy of the alpha relaxation process within the crystalline phase. Furthermore, the models show that connectivity to long chain segments in the amorphous phase increases the energy barrier for chain slip within crystalline phase. This prediction can guide the development of tougher semicrystalline polymers by providing a fundamental understanding of how nanoscale morphology contributes to chain mobility. In a different study, the macroscopic shock response of polyurea, a phase segregated copolymer, was analyzed using density functional theory (DFT) molecular dynamics (MD) simulations and classical MD simulations. The two models predict the shock response consistently up to shock pressures of 15 GPa, beyond which the DFT-based simulations predict a softer response. From the DFT simulations, an analysis of bond scission was performed as a first step in developing a more fundamental understanding of how shock induced material transformations effect the shock response and pressure dependent strength of polyurea subjected to extreme shocks.
ContributorsLi, Yiyang (Author) / Oswald, Jay (Thesis advisor) / Rajan, Subramaniam D. (Committee member) / Solanki, Kiran (Committee member) / Chamberlin, Ralph (Committee member) / Rajagopalan, Jagannathan (Committee member) / Arizona State University (Publisher)
Created2017
Description
Improved knowledge connecting the chemistry, structure, and properties of polymers is necessary to develop advanced materials in a materials-by-design approach. Molecular dynamics (MD) simulations can provide tremendous insight into how the fine details of chemistry, molecular architecture, and microstructure affect many physical properties; however, they face well-known restrictions in their applicable temporal and spatial scales. These limitations have motivated the development of computationally-efficient, coarse-grained methods to investigate how microstructural details affect thermophysical properties. In this dissertation, I summarize my research work in structure-based coarse-graining methods to establish the link between molecular-scale structure and macroscopic properties of two different polymers. Systematically coarse-grained models were developed to study the viscoelastic stress response of polyurea, a copolymer that segregates into rigid and viscous phases, at time scales characteristic of blast and impact loading. With the application of appropriate scaling parameters, the coarse-grained models can predict viscoelastic properties with a speed up of 5-6 orders of magnitude relative to the atomistic MD models. Coarse-grained models of polyethylene were also created to investigate the thermomechanical material response under shock loading. As structure-based coarse-grained methods are generally not transferable to states different from which they were calibrated at, their applicability for modeling non-equilibrium processes such as shock and impact is highly limited. To address this problem, a new model is developed that incorporates many-body interactions and is calibrated across a range of different thermodynamic states using a least square minimization scheme. The new model is validated by comparing shock Hugoniot properties with atomistic and experimental data for polyethylene. Lastly, a high fidelity coarse-grained model of polyethylene was constructed that reproduces the joint-probability distributions of structural variables such as the distributions of bond lengths and bond angles between sequential coarse-grained sites along polymer chains. This new model accurately represents the structure of both the amorphous and crystal phases of polyethylene and enabling investigation of how polymer processing such as cold-drawing and bulk crystallization affect material structure at significantly larger time and length scales than traditional molecular simulations.
ContributorsAgrawal, Vipin (Author) / Oswald, Jay (Thesis advisor) / Peralta, Pedro (Committee member) / Chamberlin, Ralph (Committee member) / Solanki, Kiran (Committee member) / Jiao, Yang (Committee member) / Arizona State University (Publisher)
Created2016
Description
Microwave properties of low-loss commercial dielectric materials are optimized by adding transition-metal dopants or alloying agents (i.e. Ni, Co, Mn) to tune the temperature coefficient of resonant frequency (τf) to zero. This occurs as a result of the temperature dependence of dielectric constant offsetting the thermal expansion. At cryogenic temperatures, the microwave loss in these dielectric materials is dominated by electron paramagnetic resonance (EPR) loss, which results from the spin-excitations of d-shell electron spins in exchange-coupled clusters. We show that the origin of the observed magnetically-induced shifts in the dielectric resonator frequency originates from the same mechanism, as described by the Kramers-Kronig relations. The temperature coefficient of resonator frequency, τf, is related to three material parameters according to the equation, τf = - (½ τε + ½ τµ + αL), where τε, τµ, and αL are the temperature coefficient of dielectric constant, magnetic permeability, and lattice constant, respectively. Each of these parameters for dielectric materials of interest are measured experimentally. These results, in combination with density functional simulations, developed a much improved understanding of the fundamental mechanisms responsible for τf. The same experimental methods have been used to characterize in-situ the physical nature and concentration of performance-degrading point defects in the dielectrics of superconducting planar microwave resonators.
ContributorsZhang, Shengke (Author) / Newman, Nathan (Thesis advisor) / Alford, Terry L. (Committee member) / Chamberlin, Ralph (Committee member) / Flores, Marco (Committee member) / Singh, Rakesh K. (Committee member) / Arizona State University (Publisher)
Created2016
Description
Multifunctional oxide thin-films grown on silicon and several oxide substrates have been characterized using High Resolution (Scanning) Transmission Electron Microscopy (HRTEM), Energy-Dispersive X-ray Spectroscopy (EDX), and Electron Energy-Loss Spectroscopy (EELS). Oxide thin films grown on SrTiO3/Si pseudo-substrate showed the presence of amorphised SrTiO3 (STO) at the STO/Si interface. Oxide/oxide interfaces were observed to be atomically clean with very few defects.
Al-doped SrTiO3 thin films grown on Si were of high crystalline quality. The Ti/O ratio estimated from EELS line scans revealed that substitution of Ti by Al created associated O vacancies. The strength of the crystal field in STO was measured using EELS, and decreased by ~1.0 eV as Ti4+ was substituted by Al3+. The damping of O-K EELS peaks confirmed the rise in oxygen vacancies. For Co-substituted STO films grown on Si, the EDS and EELS spectra across samples showed Co doping was quite random. The substitution of Ti4+ with Co3+ or Co2+ created associated oxygen vacancies for charge balance. Presence of oxygen vacancies was also confirmed by shift of Ti-L EELS peaks towards lower energy by ~0.4 eV. The crystal-field strength decreased by ~0.6 eV as Ti4+ was partially substituted by Co3+ or Co2+.
Spinel Co3O4 thin films grown on MgAl2O4 (110) were observed to have excellent crystalline quality. The structure of the Co3O4/MgAl2O4 interface was determined using HRTEM and image simulations. It was found that MgAl2O4 substrate is terminated with Al and oxygen. Stacking faults and associated strain fields in spinel Co3O4 were found along [111], [001], and [113] using Geometrical Phase Analysis.
NbO2 films on STO (111) were observed to be tetragonal with lattice parameter of 13.8 Å and NbO films on LSAT (111) were observed to be cubic with lattice parameter of 4.26 Å. HRTEM showed formation of high quality NbOx films and excellent coherent interface. HRTEM of SrAl4 on LAO (001) confirmed an island growth mode. The SrAl4 islands were highly crystalline with excellent epitaxial registry with LAO. By comparing HRTEM images with image simulations, the interface structure was determined to consist of Sr-terminated SrAl4 (001) on AlO2-terminated LAO (001).
Al-doped SrTiO3 thin films grown on Si were of high crystalline quality. The Ti/O ratio estimated from EELS line scans revealed that substitution of Ti by Al created associated O vacancies. The strength of the crystal field in STO was measured using EELS, and decreased by ~1.0 eV as Ti4+ was substituted by Al3+. The damping of O-K EELS peaks confirmed the rise in oxygen vacancies. For Co-substituted STO films grown on Si, the EDS and EELS spectra across samples showed Co doping was quite random. The substitution of Ti4+ with Co3+ or Co2+ created associated oxygen vacancies for charge balance. Presence of oxygen vacancies was also confirmed by shift of Ti-L EELS peaks towards lower energy by ~0.4 eV. The crystal-field strength decreased by ~0.6 eV as Ti4+ was partially substituted by Co3+ or Co2+.
Spinel Co3O4 thin films grown on MgAl2O4 (110) were observed to have excellent crystalline quality. The structure of the Co3O4/MgAl2O4 interface was determined using HRTEM and image simulations. It was found that MgAl2O4 substrate is terminated with Al and oxygen. Stacking faults and associated strain fields in spinel Co3O4 were found along [111], [001], and [113] using Geometrical Phase Analysis.
NbO2 films on STO (111) were observed to be tetragonal with lattice parameter of 13.8 Å and NbO films on LSAT (111) were observed to be cubic with lattice parameter of 4.26 Å. HRTEM showed formation of high quality NbOx films and excellent coherent interface. HRTEM of SrAl4 on LAO (001) confirmed an island growth mode. The SrAl4 islands were highly crystalline with excellent epitaxial registry with LAO. By comparing HRTEM images with image simulations, the interface structure was determined to consist of Sr-terminated SrAl4 (001) on AlO2-terminated LAO (001).
ContributorsDhamdhere, Ajit (Author) / Smith, David J. (Thesis advisor) / McCartney, Martha R. (Committee member) / Chamberlin, Ralph (Committee member) / Ponce, Fernando (Committee member) / Arizona State University (Publisher)
Created2015
Description
Proton and fluorine diffusivity and ionic conductivity of 2-fluoropyridinium triflate (2-FPTf) and proton and fluorine diffusivity, ionic conductivity, and viscosity of trifluoromethanesulfonic acid (TFMSA) monohydrate have been measured over a wide range of temperatures. Diffusivities were measured using the pulsed-gradient spin-echo (PGSE) technique on a 300 MHz NMR spectrometer. Conductivities were measured using electrochemical impedance spectroscopy (EIS) on standard equipment and viscosities were determined using a Cannon-Ubbelohde viscometer. For 2-FPTF, the diffusivity of mobile protons increased from 1.84+/-0.06 x 10(-11) m2/s at 55 degC to 1.64+/-0.05 x 10(-10) m2/s at 115 degC while the diffusivity of 2-fluoropyridine fluorines increased from 2.22+/-0.07 x 10(-11) m2/s at 70 degC to 9.40+/-0.28 x 10(-11) m2/s at 115 degC. For TFMSA monohydrate, the diffusivity of protons increased from 7.67+/-0.23 x 10(-11) m2/s at 40 degC to 3.92+/-0.12 x 10(-10) m2/s at 110 degC while the diffusivity of fluorines increased from 4.63+/-0.14 x 10(-11) m2/s at 40 degC to 2.79+/-0.08 x 10(-10) m2/s at 110 degC, protons diffusing approximately 1.5 times faster than fluorines over the entire temperature range. NMR spectra indicate that proton diffusion occurs via direct hopping from TFMSA molecule to molecule. The conductivity of 2-FPTf varied from 0.85+/-0.03 mS/cm to 35.9+/-1.08 mS/cm between 25 and 110 degC. The conductivity of TFMSA monohydrate varied from 6.60+/-0.2 mS/cm to 84.6+/-2.5 mS/cm between 23 and 139 degC and its viscosity varied from 27.5+/-1.4 mPa.s to 4.38+/-0.22 mPa.s between 49 and 121.5 degC, in good agreement with literature values. Temperature dependences of the measured properties showed Arrhenius behavior with activation energies for proton diffusion, fluorine diffusion and ionic conduction for 2-FPTf above the melting point of 16.9+/-0.8 kJ/mol, 48.0+/-2.4 kJ/mol and 27.8+/-1.4 kJ/mol respectively. Activation energies for proton diffusion, fluorine diffusion, ionic conduction and viscosity for TFMSA monohydrate were 23.4+/-1.2 kJ/mol, 26.0+/-1.3 kJ/mol, 22.1+/-1.1 kJ/mol, and 26.9+/-1.3 kJ/mol respectively. The degree of dissociation of the charged species, calculated using the Nernst-Einstein relation, varied from 13 to 24% for 2-FPTf and from 25 to 29% for TFMSA monohydrate over the temperature range.
ContributorsAbdullah, Mohammed Wahed (Author) / Marzke, Robert F (Thesis advisor) / Gervasio, Dominic (Committee member) / Chamberlin, Ralph (Committee member) / Alarcon, Ricardo (Committee member) / Arizona State University (Publisher)
Created2015