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Plastic deformation mechanism of calcium-silicate hydrates determined by deviatoric-stress Raman spectroscopy

Highlights: • C-(A-)S-H samples under stress were characterized at the bond and grain level. • Small angle scattering showed that 720 MPa reduced grain thickness by 30%. • In-situ Raman showed that cross-linked C-A-S-H slips along its intralayer. • However, in-situ Raman showed that C-S-H slips along the interlayer. • In-situ Raman also showed a growth in CaCO{sub 3}, indicating fracture in both samples. Creep of the cement matrix affects the structural stability of concrete. In Portland cements, the creep is largely controlled by the binding phase calcium-(aluminum-)silicate-hydrate, or C-(A-)S-H. This phase has a lamellar structure and under deviatoric stress aligns its c-axis with the principal stress. However, the limiting resistance to this reorientation is unknown at the nanocrystalline level. Small-angle X-ray scattering shows that the lamellae thickness decreases under 100's MPa deviatoric stress. Deviatoric stress Raman spectroscopy shows that there are two ways that this break-up can occur. If the material's silicate chains are cross-linked, then strain in SiO bonds does not increase above certain stresses, indicating a relaxation adjacent to the SiO bond. If the chains are not cross-linked, then the silicate chains are broken up by rastering against each other, introducing defects. These results show that the plastic deformation of C-(A-)S-H is relevant for Portland cement creep.

36 MATERIALS SCIENCE↗

Analytical Determination of Radioactive Strontium and Cesium by Thermal Ionization Mass Spectrometry

Thermal ionization mass spectrometry (TIMS) has been evaluated for the detection of the radioactive isotopes of strontium and cesium. The instrument was investigated for the analysis of isotopic ratios of 89Sr to 90Sr and 135Cs to 137Cs in the presence of atomic isobars (Y and Zr for Sr analysis and Ba for Cs analysis). Signicant discrimination using TIMS was found for both Sr and Cs through evaluation using stable isotopes. Fusion procedures with different flux were evaluated for preparation of sample matrices. Chemical separations were developed and used after fusion to isolate the Sr and Cs from a prepared background matrix (i.e., Montana Soil). A graded approach, increasing in stable background isotopes, was performed to monitor the chemistry and instrument response. A thermal neutron irradiation was performed to produce a sample that contained the radioisotopes of Sr and Cs. Even though the irradiated sample was not a certified standard it does provide accurate expectation values via published, well understood cumulative fission yield data. The results presented in this work correlate extremely well with the published data. Furthermore, a significant decrease in uncertainty (by a factor of 5 { 10) was found for the isotopic ratios measured with TIMS compared to the published values.

TIMS, environmental contamination, radiostrontium,↗

Interactions between microbial diversity and substrate chemistry determine the fate of carbon in soil.

Microbial decomposition drives the transformation of plant-derived substrates into microbial products that form stable soil organic matter (SOM). Recent theories have posited that decomposition depends on an interaction between SOM chemistry with microbial diversity and resulting function. Here, we explicitly test these theories by coupling quantitative stable isotope probing and metabolomics to track the fate of 13C enriched substrates that vary in chemical composition as they are assimilated by microbes and transformed into new metabolic products in soil. We found that mycorrhizal-driven differences in forest nutrient economies (e.g., nutrient cycling, microbial competition) led to arbuscular mycorrhizal (AM) soils harboring greater micro8ial diversity than ectomycorrhizal (ECM) soils. When incubated with 13C enriched substrates, substrate type drove shifts in the identity of active decomposers and their metabolic products in the highly diverse AM soils. The decomposition pathways were more static in the less diverse, ECM soil. Importantly, the majority of these shifts were driven by taxa only present in the AM soil suggesting a strong link between microbial identity and specialized function. Collectively, these results highlight an important interaction between ecosystem-level processes and microbial diversity; whereby the identity and function of active decomposers impacts the composition of decomposition products that can form stable SOM.

Raczka, Nanette↗

Determining plasmonic hot-carrier energy distributions via single-molecule transport measurements

Hot carriers in plasmonic nanostructures, generated via plasmon decay, play key roles in applications such as photocatalysis and in photodetectors that circumvent bandgap limitations. However, direct experimental quantification of steady-state energy distributions of hot carriers in nanostructures has so far been lacking. We present transport measurements from single-molecule junctions, created by trapping suitably chosen single molecules between an ultrathin gold film supporting surface plasmon polaritons and a scanning probe tip, that can provide quantification of plasmonic hot-carrier distributions. Our results show that Landau damping is the dominant physical mechanism of hot-carrier generation in nanoscale systems with strong confinement. The technique developed in this work will enable quantification of plasmonic hot-carrier distributions in nanophotonic and plasmonic devices.

Science & Technology - Other Topics↗

Novel Geochemistry Determined from High Pressure, High Temperature Simulation Experiments of Hydraulic Fracture Test Site 2

A standard method in unconventional oil and gas production is the process of hydraulic fracturing followed by a shut-in period, during which the fracture fluid remains pressurized in the reservoir for up to three weeks before production begins. Despite this widely used process, very little is known about what occurs in the reservoir during this shut-in process. In order to properly delineate potential reservoir reactions that may occur during shut-in that would lead to corrosion and scaling events, experiments were conducted in high pressure, high temperature reactors to simulate conditions of the Wolfcamp Formation in the Delaware Basin. Experimental design allowed the assessment of the effect of proppant, microbiology, and time on the mineralogy and fluid chemistry in the reservoir. Results suggest the biggest impact on fluid chemistry and shale mineralogy during shut-in is time. Analyses demonstrate dissolution of the shale material, with maximum dissolved ions occurring after 7 days of the shut-in period. After 21 days, results suggest precipitation occurs. The Delaware Basin is demonstrated to be high in sulfate content, which further increases in the fluid due to dissolution reactions during shut-in. The pressure vessel experiments suggest there was no significant contribution to reactions from microbiology during the shut-in period. Furthermore, early production samples demonstrate a significant selection of the microorganism Caminicella, a genus of which has previously been correlated to corrosion and sulfide production. Results suggest shut-in conditions may provide high sulfate concentrations that could later be utilized by a shifted microbial community to drive potential well infrastructure failure. This is the first study to incorporate microbiology, mineralogy, and fluid chemistry to investigate the fundamental geochemical reactions that occur during shut-in and early phase production of the Delaware Downloaded from http://onepetro.org/URTECONF/proceedings-pdf/21URTC/2-21URTC/D021S032R001/2477425/urtec-2021-5219-ms.pdf/1 by Carol Worster on 28 February 2022 Basin. Results from this study can complement observations from the Hydraulic Fracture Test Site 2 observations

58 GEOSCIENCES↗

Determination of Eros Physical Parameters for Near Earth Asteroid Rendezvous Orbit Phase Navigation

Navigation of the orbit phase of the Near Earth steroid Rendezvous (NEAR) mission will re,quire determination of certain physical parameters describing the size, shape, gravity field, attitude and inertial properties of Eros. Prior to launch, little was known about Eros except for its orbit which could be determined with high precision from ground based telescope observations. Radar bounce and light curve data provided a rough estimate of Eros shape and a fairly good estimate of the pole, prime meridian and spin rate. However, the determination of the NEAR spacecraft orbit requires a high precision model of Eros's physical parameters and the ground based data provides only marginal a priori information. Eros is the principal source of perturbations of the spacecraft's trajectory and the principal source of data for determining the orbit. The initial orbit determination strategy is therefore concerned with developing a precise model of Eros. The original plan for Eros orbital operations was to execute a series of rendezvous burns beginning on December 20,1998 and insert into a close Eros orbit in January 1999. As a result of an unplanned termination of the rendezvous burn on December 20, 1998, the NEAR spacecraft continued on its high velocity approach trajectory and passed within 3900 km of Eros on December 23, 1998. The planned rendezvous burn was delayed until January 3, 1999 which resulted in the spacecraft being placed on a trajectory that slowly returns to Eros with a subsequent delay of close Eros orbital operations until February 2001. The flyby of Eros provided a brief glimpse and allowed for a crude estimate of the pole, prime meridian and mass of Eros. More importantly for navigation, orbit determination software was executed in the landmark tracking mode to determine the spacecraft orbit and a preliminary shape and landmark data base has been obtained. The flyby also provided an opportunity to test orbit determination operational procedures that will be used in February of 2001. The initial attitude and spin rate of Eros, as well as estimates of reference landmark locations, are obtained from images of the asteroid. These initial estimates are used as a priori values for a more precise refinement of these parameters by the orbit determination software which combines optical measurements with Doppler tracking data to obtain solutions for the required parameters. As the spacecraft is maneuvered; closer to the asteroid, estimates of spacecraft state, asteroid attitude, solar pressure, landmark locations and Eros physical parameters including mass, moments of inertia and gravity harmonics are determined with increasing precision. The determination of the elements of the inertia tensor of the asteroid is critical to spacecraft orbit determination and prediction of the asteroid attitude. The moments of inertia about the principal axes are also of scientific interest since they provide some insight into the internal mass distribution. Determination of the principal axes moments of inertia will depend on observing free precession in the asteroid's attitude dynamics. Gravity harmonics are in themselves of interest to science. When compared with the asteroid shape, some insight may be obtained into Eros' internal structure. The location of the center of mass derived from the first degree harmonic coefficients give a direct indication of overall mass distribution. The second degree harmonic coefficients relate to the radial distribution of mass. Higher degree harmonics may be compared with surface features to gain additional insight into mass distribution. In this paper, estimates of Eros physical parameters obtained from the December 23,1998 flyby will be presented. This new knowledge will be applied to simplification of Eros orbital operations in February of 2001. The resulting revision to the orbit determination strategy will also be discussed.

Miller, J. K.↗