Device Physics of Two-Dimensional Crystalline Materials

Thesis (Ph.D.)--University of Washington, 2016-07

Environmental impacts of freshwater use and suspended solids in life cycle assessment

Perturbation of natural ecosystems, namely by increasing freshwater use and its degradative use, as well as topsoil erosion by water of land-use production systems, have been emerging as topics of high environmental concern. Freshwater use has become a focus of attention in the last few years for all stakeholders involved in the production of goods, mainly agro-industrial and forest-based products, which are freshwater-intensive consumers, requiring large inputs of green and blue water. This thesis presents a global review on the available Water Footprint Assessment and Life Cycle Assessment (LCA)-based methods for measuring and assessing the environmental relevance of freshwater resources use, based on a life cycle perspective. Using some of the available midpoint LCA-based methods, the freshwater use-related impacts of a Portuguese wine (white ‘vinho verde’) were assessed. However, the relevance of environmental green water has been neglected because of the absence of a comprehensive impact assessment method associated with green water flows. To overcome this constraint, this thesis helps to improve and enhance the LCA-based methods by providing a midpoint and spatially explicit Life Cycle Impact Assessment (LCIA) method for assessing impacts on terrestrial green water flow and addressing reductions in surface blue water production caused by reductions in surface runoff due to land-use production systems. The applicability of the proposed method is illustrated by a case study on Eucalyptus globulus conducted in Portugal, as the growth of short rotation forestry is largely dependent on local precipitation. Topsoil erosion by water has been characterised as one of the most upsetting problems for rivers. Because of this, this thesis also focuses on the ecosystem impacts caused by suspended solids (SS) from topsoil erosion that reach freshwater systems. A framework to conduct a spatially distributed SS delivery to freshwater streams and a fate and effect LCIA method to derive site-specific characterisation factors (CFs) for endpoint damage on aquatic ecosystem diversity, namely on algae, macrophyte, and macroinvertebrates organisms, were developed. The applicability of this framework, combined with the derived site-specific CFs, is shown by conducting a case study on E. globulus stands located in Portugal as an example of a land use based system. A spatially explicit LCA assessment was shown to be necessary, since the impacts associated with both green water flows and SS vary greatly as a function of spatial location.

Degradation toolkit for predicting the amount of degradation of particulate solids in lean phase pneumatic conveyors

Abstract not available

Nuclear relaxation in low fields and the study of ultraslow atomic motions in solids

U of I Only

Dust recovery practice at blast furnaces; an evaluation of settleable solids formation and recovery at mills in the Ohio Valley and a suggested proceedure [sic] for defining performance of wastewater clarifiers.

"Reference data publication."

Octane improvement of gasoline with porous solids

In this work is performed the study of the hexane isomers separation with MOFs in order to improve the octane number of gasoline. The studies were performed with MOFs: MIL-125-Amine, MIL-53(Fe)-Cl, MIL-53(Fe)-Br and Fe-TazBz(DMF). It was observed that higher loadings were obtained for high pressure and low temperature. With MOFs like MIL-53(Fe)-Cl and MIL-53(Fe)-Br the components weren’t separated. In MIL-125-Amine hexane isomers were separated according to their boiling point, but the selectivity was small. The best result was obtained with MOF Fe-TazBz(DMF), because of the higher affinity of n-hex with this MOF, the separation from the other isomers was easier.

Deposition of Intrinsic a-Si:H by ECR-CVD to Passivate the Crystalline Silicon Heterointerface in HIT Solar Cells

We have deposited intrinsic amorphous silicon (a-Si:H) using the electron cyclotron resonance (ECR) chemical vapor deposition technique in order to analyze the a-Si:H/c-Si heterointerface and assess the possible application in heterojunction with intrinsic thin layer (HIT) solar cells. Physical characterization of the deposited films shows that the hydrogen content is in the 15-30% range, depending on deposition temperature. The optical bandgap value is always comprised within the range 1.9- 2.2 eV. Minority carrier lifetime measurements performed on the heterostructures reach high values up to 1.3 ms, indicating a well-passivated a-Si:H/c-Si heterointerface for deposition temperatures as low as 100°C. In addition, we prove that the metal-oxide- semiconductor conductance method to obtain interface trap distribution can be applied to the a-Si:H/c-Si heterointerface, since the intrinsic a-Si:H layer behaves as an insulator at low or negative bias. Values for the minimum of D_it as low as 8 × 10^10 cm^2 · eV^-1 were obtained for our samples, pointing to good surface passivation properties of ECR-deposited a-Si:H for HIT solar cell applications.

Synthesis and proton conduction properties of lanthanide amino-sulfophosphonates

Crystalline acid-functionalized metal phosphonates are potential candidates as proton conducting electrolytes. Their frameworks can be chemically modified to contain proton carriers such as acidic groups (P-OH; -SO3H, -COOH,…) and guest molecules (H2O, NH3,…) that generates hydrogen bond networks stable in a wide range of temperature [1,2]. In this work, focus is laid on properties derived from the combination of lanthanide ions with the amino-sulfophosphonate ligand (H2O3PCH2)2-N-(CH2)2-SO3H. Hightrough-put screening was followed to reach the optimal synthesis conditions under solvothermal conditions at 140 ºC. Isolated polycrystalline solids, Ln[(O3PCH2)2-NH-(CH2)2-SO3H].2H2O (Ln= La, Pr and Sm), crystallize in the monoclinic (La) and orthorhombic (Pr and Sm) systems with unit cell volume of ~2548 Å3. Preliminary proton conductivity measurements for Sm derivative have been carried out between 25º and 80 ºC at relative humidity (RH) values of 70 % and 95 %. The sample exhibits enhanced conductivity at high RH and T (Figure 1) and constant activation energies of 0.4 eV, typical of a Grothuss mechanism of proton.

Structure-properties correlations in divalent metal phosphonates

Crystalline metal phosphonates may offer acidic sites, structural flexibility and guest molecules (H2O, heterocyclics, etc.) which can act as proton carriers. In addition, some frameworks are also amenable for post‐synthesis modifications in order to enhance desired properties [1,2]. In this work, we present the synthesis and structural characterization of two hydroxyphosphonoacetates hybrids based on magnesium, [Mg5(O3PCHOHCOO)2(HO3PCHOHCOO)2·8H2O] [Mg5(HPAA)2(H1HPAA)2·8H2O], and zinc, [Zn6K(O3PCHOHCOO)4(OH)·6.5H2O] [Zn6K(HPAA)4(OH)·6.5H2O]. Both solids present three-dimensional frameworks and their crystal structures were solved ab initio from X-ray powder diffraction. The proton conductivity of [Zn6K(HPAA)4(OH)·6.5H2O] as well as ammonia derivatives of M(II)(HO3PCHOHCOO)·2H2O [M(II)=Zn, Mg] will be reported and discussed.

Obtenção de filtro cerâmico a partir da diatomita e casca de arroz carbonizada visando tratamento de efluente têxtil

The effluents released by the textile industry have high concentrations of alkali, carbohydrates, proteins, in addition to colors containing heavy metals. Therefore, a filter was prepared aiming primarily to the removal of color. In order to prepare this filter, rice hulls and diatomite were used, which have in their structure, basically amorphous hydrated silica. The silica exists in three crystalline forms: quartz, tridymite and cristobalite. In accordance with the above considerations, this study was divided into two stages; the first corresponds to the preparation of the filter and the second to carry out the tests in the effluent/filter in order to verify the efficiency of the color removal. First, the raw material was subjected to a chemical analysis and XRD, and then the diatomite was mixed, via humid, with a planetarium windmill with 20 %, 40 %, 60 % and 80 % of rice husk ash. To the mixture, 5 % carboxymethylcellulose (CMC) was added as a binder at room temperature. The samples were uniaxially compacted into metallic matrix of 0.3 x 0.1 cm² of area at a pressure of 167 MPa by means of hydraulic press and then sintered at temperatures of 1,000 °C, 1,200 °C and 1,400 °C for 1 h and submitted to granulometry test using laser, linear retraction, water absorption, apparent porosity and resistance to bending, DTA, TMA and XRD. To examine the pore structure of the samples scanning electron microscope (SEM) was used. Also tests were carried out in a mercury porosimeter to verify the average size of the pores and real density of the samples. In the second stage, samples of the effluent were collected from a local industry, whose name will be preserved, located in Igapó, in the State of Rio Grande do Norte - RN. The effluent was first pretreated before filtration and then subjected to a treatment of flotation. The effluent was then characterized before and after filtration, with parameters of color, turbidity, suspended solids, pH, chemical and biochemical oxygen demand (COD and BOD). Thus, through the XRD analysis the formation of cristobalite α in all samples was observed. The best average size of pore was found to be 1.75 μm with 61.04 % apparent porosity, thus obtaining an average 97.9 % color removal and 99.8 % removal of suspended solid

Hybrid materials based on polyethylene and MCM-41 microparticles functionalized with silanes: catalytic aspects of in situ polymerization, crystalline features and mechanical properties

New nanocomposites based on polyethylene have been prepared by in situ polymerization of ethylene in presence of mesoporous MCM-41. The polymerization reactions were performed using a zirconocene catalyst either under homogenous conditions or supported onto mesoporous MCM-41 particles, which are synthesized and decorated post-synthesis with two silanes before polymerization in order to promote an enhanced interfacial adhesion. The existence of polyethylene chains able to crystallize within the mesoporous channels in the resulting nanocomposites is figured out from the small endothermic process, located at around 80 C, on heating calorimetric experiments, in addition to the main melting endotherm. These results indicate that polyethylene macrochains can grow up during polymerization either outside or inside the MCM-41 channels, these keeping their regular hexagonal arrangements. Mechanical response is observed to be dependent on the content in mesoporous MCM-41 and on the crystalline features of polyethylene. Accordingly, stiffness increases and deformability decreases in the nanocomposites as much as MCM-41 content is enlarged and polyethylene amount within channels is raised. Ultimate mechanical performance improves with MCM-41 incorporation without varying the final processing temperature.

Energy Loss Function of Solids Assessed by Ion Beam Energy-Loss Measurements: Practical Application to Ta2O5

We present a study where the energy loss function of Ta2O5, initially derived in the optical limit for a limited region of excitation energies from reflection electron energy loss spectroscopy (REELS) measurements, was improved and extended to the whole momentum and energy excitation region through a suitable theoretical analysis using the Mermin dielectric function and requiring the fulfillment of physically motivated restrictions, such as the f- and KK-sum rules. The material stopping cross section (SCS) and energy-loss straggling measured for 300–2000 keV proton and 200–6000 keV helium ion beams by means of Rutherford backscattering spectrometry (RBS) were compared to the same quantities calculated in the dielectric framework, showing an excellent agreement, which is used to judge the reliability of the Ta2O5 energy loss function. Based on this assessment, we have also predicted the inelastic mean free path and the SCS of energetic electrons in Ta2O5.

Comb-like acrylic-based polymer latexes containing nano-sized crystalline or liquid crystalline domains

306 p.