Characterization of the Structure and Dynamics of Biomimetic Peptides by Solid-State NMR

Thesis (Ph.D.)--University of Washington, 2016-05

Microstructure and grain boundary microanalysis of X70 pipeline steel

Grain boundaries (GBs), particularly ferrite: ferrite GBs, of X70 pipeline steel were characterized using analytical electron microscopy (AEM) in order to understand its intergranular stress corrosion cracking (IGSCC) mechanism(s). The microstructure consisted of ferrite (alpha), carbides at ferrite GBs, some pearlite and some small precipitates inside the ferrite grains. The precipitates containing Ti, Nb, V and N were identified as complex carbo-nitrides and designated as (Ti, Nb, WC, N). The GB carbides occurred (1) as carbides along ferrite GBs, (2) at triple points, and (3) at triple points and extending along the three ferrite GBs. The GB carbides were Mn rich, were sometimes also Si rich, contained no micro-alloying elements (Ti, Nb, V) and also contained no N. It was not possible to measure the GB carbon concentration due to surface hydrocarbon contamination despite plasma cleaning and glove bag transfer from the plasma cleaner to the electron microscope. Furthermore, there may not be enough X-ray signal from the small amount of carbon at the GBs to enable measurement using AEM. However, the microstructure does indicate that carbon does segregate to alpha : alpha GBs during microstructure development. This is particularly significant in relation to the strong evidence in the literature linking the segregation of carbon at GBs to IGSCC. It was possible to measure all other elements of interest. There was no segregation at alpha : alpha GBs, in particular no S, P and N, and also no segregation of the micro-alloying elements, Ti, Nb and V. (C) 2003 Kluwer Academic Publishers.

Morphology and crystallography of Mg24Y5 precipitate in Mg-Y alloy

Orientation relationships between Mg24Y5 precipitates and matrix in a Mg-Y alloy were accurately determined using Kikuchi line diffraction. The Burgers relationship with habit planes of {10 (1) over bar0}(H) and {31 (4) over bar0}(H) were observed for all precipitates. Compared with the Mg17Al12 precipitate in AZ91, the precipitation hardening effect in this alloy was significantly increased. (C) 2002 Acta Materialia Inc. Published by Elsevier Science Ltd. All rights reserved.

Effect of Si additions and heat treatment on the mechanical behaviour of an Al-5Mg casting alloy

Adding 1%Si to binary Al-5Mg alloy slightly increases the yield stress in comparison with the Si free alloy but dramatically reduces the ductility and tensile strength due to the formation of brittle eutectic Mg2Si and pi-Al8FeMg3Si6 particles. Adding 3%Si slightly reduces the yield stress, presumably due to some of the Mg being tied up in the Mg2Si, and further reduces the ductility due to the increased volume fraction of intermetallics. Solution heat treatment at 436degreesC decreases the yield stress of both Si containing alloys, and slightly increases the ductility in the alloy with 3%Si. Subsequent ageing at 180degreesC has no further effects on the strength or ductility. The loss in strength of the heat treated alloys seems to be due to overageing Of Mg2Si precipitates dispersed in the bulk of the alloy. (C) 2004 W. S. Maney Son Ltd.

Effect of iron on grain refinement of high-purity MG-Al alloys

The effect of iron on the grain refinement of high-purity Mg-3%Al and Mg-91%Al alloys has been investigated using anhydrous FeCl3 as an iron additive at 750degreesC in carbon-free aluminium titanite crucibles. It was shown that grain refinement was readily achievable for both alloys. Fe- and Al-rich intermetallic particles were observed in many magnesium grains. (C) 2004 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Ultrastructure, aggregation-state, and crystal growth of biogenic nanocrystalline sphalerite and wurtzite

In this study, we investigated the size, submicrometer-scale structure, and aggregation state of ZnS formed by sulfate-reducing bacteria (SRB) in a SRB-dominated biofilm growing on degraded wood in cold (Tsimilar to8degreesC), circumneutral-pH (7.2-8.5) waters draining from an abandoned, carbonate-hosted Pb-Zn mine. High-resolution transmission electron microscope (HRTEM) data reveal that the earliest biologically induced precipitates are crystalline ZnS nanoparticles 1-5 nm in diameter. Although most nanocrystals have the sphalerite structure, nanocrystals of wurtzite are also present, consistent with a predicted size dependence for ZnS phase stability. Nearly all the nanocrystals are concentrated into 1-5 mum diameter spheroidal aggregates that display concentric banding patterns indicative of episodic precipitation and flocculation. Abundant disordered stacking sequences and faceted, porous crystal-aggregate morphologies are consistent with aggregation-driven growth of ZnS nanocrystals prior to and/or during spheroid formation. Spheroids are typically coated by organic polymers or associated with microbial cellular surfaces, and are concentrated roughly into layers within the biofilm. Size, shape, structure, degree of crystallinity, and polymer associations will all impact ZnS solubility, aggregation and coarsening behavior, transport in groundwater, and potential for deposition by sedimentation. Results presented here reveal nanometer- to micrometer-scale attributes of biologically induced ZnS formation likely to be relevant to sequestration via bacterial sulfate reduction (BSR) of other potential contaminant metal(loid)s, such as Pb2+, Cd2+, As3+ and Hg2+, into metal sulfides. The results highlight the importance of basic mineralogical information for accurate prediction and monitoring of long-term contaminant metal mobility and bioavailability in natural and constructed bioremediation systems. Our observations also provoke interesting questions regarding the role of size-dependent phase stability in biomineralization and provide new insights into the origin of submicrometer- to millimeter-scale petrographic features observed in low-temperature sedimentary sulfide ore deposits.

Geochemistry of late Archaean stromatolites from Zimbabwe: evidence for microbial life in restricted epicontinental seas

We report comprehensive trace element and Sr-isotope data for microbial carbonates from the Archaean Mushandike limestone, Masvingo Greenstone Belt, Zimbabwe. The stromatolites have very coherent REE + Y patterns and share the essential shale-normalised characteristics of other Archaean marine precipitates (positive La and Gd anomalies, absence of a negative Cc anomaly and a strongly superchondritic Y/Ho ratio). Mixing models constrain the maximum amount of shale contamination to 0.25-1% and calculated detritus-free carbonate REE + Y systematics require precipitation from seawater. In terms of light-REE over heavy-REE depletion, however, the studied samples are very different from all other known Archaean marine precipitates. In shale-normalised plots, the Mushandike samples yield a negative slope. A very restricted, regional input source of the dissolved load is indicated because normalisation with locally occurring tonalite gneiss REE + Y data yields a pattern closely resembling typical shale-normalised Archaean marine chemical sediments. The disappearance of a negative Eu anomaly when patterns are normalised with local tonalite gneiss strengthens this interpretation. Sr-isotope ratios are strongly correlated with trace element contents and ratios, which explains the modest scatter in Sr-isotope ratios as representing (minor) clastic contamination. Importantly, even the least contaminated samples have very radiogenic initial Sr-87/Sr-86 ratios (0.7184) implying Sr input from an ancient high Rb/Sr source, such as the early Archaean gneisses of south-central Zimbabwe. A local ancient (3.5-3.8 Ga) source is also indicated by previously published Pb-isotope datasets for the Mushandike stromatolites. This is entirely compatible with the occurrence of 3.7-3.8 Ga zircons in quartzites and metapelites from comparably old greenstone belts within less than 150 km of the studied locality. Comparison of the Pb-isotope ratios of the Mushandike stromatolites with 2.7 and 2.6 Ga old stromatolites from the neighbouring, Belingwe Greenstone Belt demonstrates differences in initial isotope composition that relate to the extent of exchange with the open ocean. The development of numerous basins on old continental crust, with water masses variably restricted from the open ocean. suggests a lack of strong vertical topography on this late Archaean craton. (C) 2004 Elsevier B.V. All rights reserved.

Morphological features of interfacial intermetallics and interfacial reaction rate in Al-11Si-2.5Cu-(0.15/0.60)Fe cast alloy/die steel couples

Soldering reactions are commonly observed during high pressure die casting of aluminium alloys, and involve the formation and growth of interfacial intermetallics between the die and the cast alloy. It is generally believed that close to 1% Fe is necessary in the aluminium alloy to reduce soldering. However, the role of iron in the interfacial reaction has not been studied in detail. In this investigation, reaction couples were formed between H13 tool steel substrates and an Al-11Si-2.5Cu melt containing either 0.15 or 0.60% Fe. Examination revealed distinctly different intermetallic layer morphology. The overall growth and chemistry of the reaction layer and the reaction rate measured by the consumption of the substrate were compared for the two alloy melts. It was demonstrated that a higher iron content reduces the rate of interfacial reaction, consistent with an observed thicker compact ( solid) intermetallic layer. Hence, the difference in reaction rate can be explained by a significant reduction in the diffusion flux due to a thicker compact layer. Finally, the mechanism of the growth of a thicker compact layer in the higher iron melt is proposed, based on the phase relations and diffusion both within and near the interfacial reaction zone. (C) 2004 Kluwer Academic Publishers.

Corrosion behaviour of a pressure die cast magnesium alloy

High pressure die casting is the most important production method for casting magnesium alloy components, and uniformity of appearance is an important criterion for acceptance of a component by customers. This paper investigates the influence of uniformity in surface appearance of diecast AZ91D plates on their corrosion behaviour. Through immersion, hydrogen collection and weight loss measurements it was found that corrosion is more likely to occur on the areas of the plate that appear to be darker, leading to a non-uniformly corroded surface. Microstructural analysis showed that the non-uniformity in appearance is related to a difference in the morphology and distribution of porosity across the surface of a diecast AZ91D plate. The darker areas of the surface are high in porosity which breaks the continuity of the beta-phase network and provides shortcut paths for corrosion from the surface to the interior of the casting. The brighter shiny areas of the surface are much less porous, with isolated pores being confined by corrosion resistant beta-precipitates thus reducing the corrosion rate.

Age hardening of a sintered Al-Cu-Mg-Si-(Sn) alloy

The age hardening response of a sintered Al-3.8 wt% Cu-1.0 wt% Mg-0.70 wt% Si alloy with and without 0.1 wt% Sn was investigated. The sequence of precipitation was characterised using transmission electron microscopy. The ageing response of the sintered Al-Cu-Mg-Si-(Sn) alloy is similar to that of cognate wrought 2xxx series alloys. Peak hardness was associated with a fine, uniform dispersion of lath shaped precipitates, believed to be either the betaor Q phase, oriented along < 010 >. directions and theta' plates lying on {001}(alpha). planes. Natural ageing also resulted in comparable behaviour to that observed in wrought alloys. Porosity in the powder metallurgy alloys did not significantly affect the kinetics of precipitation during artificial ageing. Trace levels of tin, used to aid sintering, slightly reduced the hardening response of the alloy. However, this was compensated for by significant improvements in density and hardness. (c) 2005 Elsevier B.V. All rights reserved.

As-cast morphology of iron-intermetallics in Al-Si foundry alloys

The as-cast three-dimensional morphologies of alpha-Al-15(Fe,Mn)(3)Si-2 and beta-Al5FeSi intermetallics were investigated by serial sectioning. Large beta-Al5FeSi intermetallics were observed to grow around pre-existing dendrite arms. The alpha-Al-15(Fe,Mn)(3)Si-2 intermetallic particle was observed to have a central polyhedral particle and an external highly convoluted three-dimensional structure. (c) 2005 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Farnesoid X receptor agonism - a new approach to the treatment of cholesterol gallstone disease

Gallstone disease is very common among native Americans and Hispanics, and similar to 20 million patients are treated for this disease annually in the US. The nuclear farnesoid X receptor (FXR) is the receptor for bile acids, and GW4064 is a synthetic agonist at the FXR. FXR-/- mice fed a lithogenic diet (high fat, cholesterol and cholic acid) are more susceptible to gallstone disease than wild-type mice with the same mixed background, thus establishing that the ablation of FXR is associated with this disease. The C57L mouse is susceptible to gallstone formation. When C57L mice are fed a lithogenic diet for a week, the bile contains large aggregates of cholesterol precipitates, and two of five C57L mice had macroscopic cholesterol crystals. in contrast, when C57L mice were fed the lithogenic diet and administered GW4064 100 mg/kg/day by oral gavage, there was no precipitation of cholesterol. Treatment with this agent also increased bile salt and phospholipid concentration, and prevented gallbladder epithelium damage. As FXR agonism with GW4064 has been shown to be useful in a mouse model of cholesterol gallstone disease, it should undergo further development for the treatment of this condition.

Edge-to-edge matching and its applications - Part II. Application to Mg-Al, Mg-Y and Mg-Mn alloys

A model for the crystallography and morphology of diffusion-controlled phase transformations - edge-to-edge matching - has been used to predict the orientation relationships (OR) and habit planes of precipitates Mg17Al12 in Mg-Al alloy, Mg24Y5 in Mg-Y alloy and alpha-Mn in Mg-Mn alloy. Based on the crystal structures and lattice parameters only, the model predicts that the possible ORs between Mg17Al12 and Mg matrix are the near Burgers OR, the Potter OR, the Gjonnes-Ostmoe OR and the Crawley OR. In the Mg-Y alloy, the OR between Mg24Y5 precipitates and the Mg matrix is predicted to be the Burgers OR only. The model also predicts that there are no reproducible ORs between alpha-Mn and Mg in the Mg-Mn alloy. Combining the edge-to-edge matching model and W. Zhang's Deltag approach, the habit plane and side facets of the precipitate for each OR can be determined. All the predicted ORs and the corresponding habit planes in Mg-Al and Mg-Y alloys agree very well with the experimental results. (C) 2004 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

The effect of manganese on the grain size of commercial AZ31 alloy

The effect of manganese on gain refinement of a commercial AZ31 alloy has been investigated using an Al-60%Mn master alloy splatter as an alloying additive at 730 degrees C in aluminium titanite crucibles. It is shown that grain refinement by manganese is readily achievable in AZ31. Electron microprobe analyses reveal that prior to the addition of extra manganese the majority of the intermetallic particles found in AZ31 are of the AL(8)Mn(5) type. However, after the addition of extra manganese in the range from 0.1% to 0.8%, the predominant group of intermetallic particles changes to the metastable AlMn type. This leads to a hypothesis that the metastable AlMn intermetallic particles are more effective than Al8Mn5 as nucleation sites for magnesium grains. The hypothesis is supported by the observation that a long period of holding at 730 degrees C leads to an increase in grain size, due probably to the transformation of the metastable AlMn to the stable Al8Mn5. The hypothesis has also been used to understand the mechanism of grain refinement by superheating.

Influence of calcium on the microstructure and properties of an Al-7Si-0.3Mg-xFe alloy

The effect of Ca addition on the microstructure, physical characteristics (density/porosity), and mechanical properties (tensile and impact strength) has been investigated in an Al-7Si-0.3Mg-xFe (x = 0.2, 0.4, and 0.7) alloy. The size of Al-Fe intermetallic platelets (beta-Al5FeSi) increased with increasing Fe content. The addition of Ca modified the eutectic microstructure and also reduced the size of intermetallic Fe-platelets, causing improved elongation and impact strengths. A low level of Ca addition (39 ppm) reduced the porosity of the alloys. The tensile strength was decreased marginally with Ca addition. However, Ca addition improved the ductility of the alloy by 18.3, 16.7, and 44 pet and the impact strength by 44, 48, and 15.8 pct for Fe contents of 0.2, 0.4, and 0.7 pct, respectively.