Subsurface containment of CO2 is predicated on effective caprock sealing. Many previous studies have relied on macroscopic measurements of capillary breakthrough pressure and other petrophysical properties without direct examination of solid phases that line pore networks and directly contact fluids. However, pore-lining phases strongly contribute to sealing behavior through interfacial interactions among CO2, brine, and the mineral or non-mineral phases. Our high resolution (i.e., sub-micron) examination of the composition of pore-lining phases of several continental and marine mudstones indicates that sealing efficiency (i.e., breakthrough pressure) is governed by pore shapes and pore-lining phases that are not identifiable except through direct characterization of pores. Bulk X-ray diffraction data does not indicate which phases line the pores and may be especially lacking for mudstones with organic material. Organics can line pores and may represent once-mobile phases that modify the wettability of an originally clay-lined pore network. For shallow formations (i.e., < {approx}800 m depth), interfacial tension and contact angles result in breakthrough pressures that may be as high as those needed to fracture the rock - thus, in the absence of fractures, capillary sealing efficiency is indicated. Deeper seals have poorer capillary sealing if mica-like wetting dominates the wettability. We thank the U.S. Department of Energy's National Energy Technology Laboratory and the Office of Basic Energy Sciences, and the Southeast and Southwest Carbon Sequestration Partnerships for supporting this work.
Metallic materials in sliding contact typically undergo dislocation-mediated plasticity, which results in stick-slip frictional behavior associated with high coefficients of friction ({mu} > 0.8). Our recent work on two electroplated nanocrystalline Ni alloys reveal that under combined conditions of low stress and low sliding velocity, these metals have very low friction ({mu} < 0.3). The observed frictional behavior is consistent with the transition from dislocation-mediated plasticity to an alternative mechanism such as grain boundary sliding. Focused ion beam cross-sections viewed in the TEM reveal the formation of a subsurface tribological bilayer at the contact surface, where the parent nanocrystalline material has evolved in structure to accommodate the frictional contact. Grain growth at a critical distance below the contact surface appears to promote a shear-accomodation layer. We will discuss these results in the context of a grain-size dependent transition from conventional microcrystalline wear behavior to this unusual wear behavior in nanocrystalline FCC metals.
We will present a study of the structure-property relations in Reststrahlen materials that possess a band of negative permittivities in the infrared. It will be shown that sub-micron defects strongly affect the optical response, resulting in significantly diminished permittivities. This work has implications on the use of ionic materials in IR-metamaterials.
Thermal decomposition of poly dimethyl siloxane compounds, Sylgard{reg_sign} 184 and 186, were examined using thermal desorption coupled gas chromatography-mass spectrometry (TD/GC-MS) and multivariate analysis. This work describes a method of producing multiway data using a stepped thermal desorption. The technique involves sequentially heating a sample of the material of interest with subsequent analysis in a commercial GC/MS system. The decomposition chromatograms were analyzed using multivariate analysis tools including principal component analysis (PCA), factor rotation employing the varimax criterion, and multivariate curve resolution. The results of the analysis show seven components related to offgassing of various fractions of siloxanes that vary as a function of temperature. Thermal desorption coupled with gas chromatography-mass spectrometry (TD/GC-MS) is a powerful analytical technique for analyzing chemical mixtures. It has great potential in numerous analytic areas including materials analysis, sports medicine, in the detection of designer drugs; and biological research for metabolomics. Data analysis is complicated, far from automated and can result in high false positive or false negative rates. We have demonstrated a step-wise TD/GC-MS technique that removes more volatile compounds from a sample before extracting the less volatile compounds. This creates an additional dimension of separation before the GC column, while simultaneously generating three-way data. Sandia's proven multivariate analysis methods, when applied to these data, have several advantages over current commercial options. It also has demonstrated potential for success in finding and enabling identification of trace compounds. Several challenges remain, however, including understanding the sources of noise in the data, outlier detection, improving the data pretreatment and analysis methods, developing a software tool for ease of use by the chemist, and demonstrating our belief that this multivariate analysis will enable superior differentiation capabilities. In addition, noise and system artifacts challenge the analysis of GC-MS data collected on lower cost equipment, ubiquitous in commercial laboratories. This research has the potential to affect many areas of analytical chemistry including materials analysis, medical testing, and environmental surveillance. It could also provide a method to measure adsorption parameters for chemical interactions on various surfaces by measuring desorption as a function of temperature for mixtures. We have presented results of a novel method for examining offgas products of a common PDMS material. Our method involves utilizing a stepped TD/GC-MS data acquisition scheme that may be almost totally automated, coupled with multivariate analysis schemes. This method of data generation and analysis can be applied to a number of materials aging and thermal degradation studies.
Subsurface containment of CO2 is predicated on effective caprock sealing. Many previous studies have relied on macroscopic measurements of capillary breakthrough pressure and other petrophysical properties without direct examination of solid phases that line pore networks and directly contact fluids. However, pore-lining phases strongly contribute to sealing behavior through interfacial interactions among CO2, brine, and the mineral or non-mineral phases. Our high resolution (i.e., sub-micron) examination of the composition of pore-lining phases of several continental and marine mudstones indicates that sealing efficiency (i.e., breakthrough pressure) is governed by pore shapes and pore-lining phases that are not identifiable except through direct characterization of pores. Bulk X-ray diffraction data does not indicate which phases line the pores and may be especially lacking for mudstones with organic material. Organics can line pores and may represent once-mobile phases that modify the wettability of an originally clay-lined pore network. For shallow formations (i.e., < {approx}800 m depth), interfacial tension and contact angles result in breakthrough pressures that may be as high as those needed to fracture the rock - thus, in the absence of fractures, capillary sealing efficiency is indicated. Deeper seals have poorer capillary sealing if mica-like wetting dominates the wettability.
The role of crystal coherence length on the infrared optical response of MgO thin films was investigated with regard to Reststrahlen band photon-phonon coupling. Preferentially (001)-oriented sputtered and evaporated ion-beam assisted deposited thin films were prepared on silicon and annealed to vary film microstructure. Film crystalline coherence was characterized by x-ray diffraction line broadening and transmission electron microscopy. The infrared dielectric response revealed a strong dependence of dielectric resonance magnitude on crystalline coherence. Shifts to lower transverse optical phonon frequencies were observed with increased crystalline coherence. Increased optical phonon damping is attributed to increasing granularity and intergrain misorientation.
In ductile metals, sliding contact is often accompanied by severe plastic deformation localized to a small volume of material adjacent to the wear surface. During the initial run-in period, hardness, grain structure and crystallographic texture of the surfaces that come into sliding contact undergo significant changes, culminating in the evolution of subsurface layers with their own characteristic features. Here, a brief overview of our ongoing research on the fundamental phenomena governing the friction-induced recrystallization in single crystal metals, and how these recrystallized structures with nanometer-size grains would in turn influence metallic friction will be presented. We have employed a novel combination of experimental tools (FIB, EBSD and TEM) and an analysis of the critical resolved shear stress (RSS) on the twelve slip systems of the FCC lattice to understand the evolution of these friction-induced structures in single crystal nickel. The later part of the talk deals with the mechanisms of friction in nanocrystalline Ni films. Analyses of friction-induced subsurfaces seem to confirm that the formation of stable ultrafine nanocrystalline layers with 2-10 nm grains changes the deformation mechanism from the traditional dislocation mediated one to that is predominantly controlled by grain boundaries, resulting in significant reductions in the coefficient friction.
2-Chloroethyl phenyl sulfide (CEPS), a surrogate compound of the chemical warfare agent sulfur mustard, was examined using thermal desorption coupled gas chromatography-mass spectrometry (TD/GC-MS) and multivariate analysis. This work describes a novel method of producing multiway data using a stepped thermal desorption. Various multivariate analysis schemes were employed to analyze the data. These methods may be able to discern different sources of CEPS. In addition, CEPS was applied to cotton, nylon, polyester, and silk swatches. These swatches were placed in controlled humidity chambers maintained at 23%, 56%, and 85% relative humidity. At regular intervals, samples were removed from each test swatch, and the samples analyzed using TD/GC-MS. The results were compared across fabric substrate and humidity.
Er(D,T){sub 2-x} {sup 3}He{sub x}, erbium di-tritide, films of thicknesses 500 nm, 400 nm, 300 nm, 200 nm, and 100 nm were grown and analyzed by Transmission Electron Microscopy, X-Ray Diffraction, and Ion Beam Analysis to determine variations in film microstructure as a function of film thickness and age, due to the time-dependent build-up of {sup 3}He in the film from the radioactive decay of tritium. Several interesting features were observed: One, the amount of helium released as a function of film thickness is relatively constant. This suggests that the helium is being released only from the near surface region and that the helium is not diffusing to the surface from the bulk of the film. Two, lenticular helium bubbles are observed as a result of the radioactive decay of tritium into {sup 3}He. These bubbles grow along the [111] crystallographic direction. Three, a helium bubble free zone, or 'denuded zone' is observed near the surface. The size of this region is independent of film thickness. Four, an analysis of secondary diffraction spots in the Transmission Electron Microscopy study indicate that small erbium oxide precipitates, 5-10 nm in size, exist throughout the film. Further, all of the films had large erbium oxide inclusions, in many cases these inclusions span the depth of the film.
Obtaining particulate compositional maps from scanned PIXE (proton-induced X-ray emission) measurements is extremely difficult due to the complexity of analyzing spectroscopic data collected with low signal-to-noise at each scan point (pixel). Multivariate spectral analysis has the potential to analyze such data sets by reducing the PIXE data to a limited number of physically realizable and easily interpretable components (that include both spectral and image information). We have adapted the AXSIA (automated expert spectral image analysis) program, originally developed by Sandia National Laboratories to quantify electron-excited X-ray spectroscopy data, for this purpose. Samples consisting of particulates with known compositions and sizes were loaded onto Mylar and paper filter substrates and analyzed by scanned micro-PIXE. The data sets were processed by AXSIA and the associated principal component spectral data were quantified by converting the weighting images into concentration maps. The results indicate automated, nonbiased, multivariate statistical analysis is useful for converting very large amounts of data into a smaller, more manageable number of compositional components needed for locating individual particles-of-interest on large area collection media.
Spectrum imaging combined with multivariate statistics is an approach to microanalysis that makes the maximum use of the large amount of data potentially collected in forensics analysis. Here, this study examines the efficacy of using spectrum imaging-enabled microscopies to identify chemical signatures in simulated bioagent materials. This approach allowed for the ready discrimination between all samples in the test. In particular, the spectrum imaging approach allowed for the identification of particles with trace elements that would have been missed with a more traditional approach to forensic microanalysis. Finally, the importance of combining signals from multiple length scales and analytical sensitivities is discussed.