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At least 145 records · Page 8

Magnetic circuit for Abrikosov vortices: Vortex motion in a periodic labyrinth of magnetic T and I-shaped elements under a superconducting film

Here we explore tailored labyrinth-like vortex motion in a niobium film placed on top of periodic arrays of T and I -shaped permalloy elements by imaging the vortex distribution in magnetic fields applied perpendicular to the superconducting layer under different in-plane polarizations of the TI structure. At low temperatures, we observe pronounced meandering of vortex motion around the TI elements. Remarkably, vortices can easily penetrate the sample along the TI columns even though the average vortex pinning in the patterned area is larger than in a bare niobium film. Accordingly, at temperatures close to the superconducting transition temperature, T c , the voltagecurrent curves in the patterned area show an earlier departure from the zero-resistivity state at small currents, followed by slower growth with increasing current as compared to the un-patterned film. We present a model based on magnetostatic interactions between magnetic charges at the edges of the polarized TI-elements and single magnetic charges of induced vortices to account for this behavior. We expect that similar magnetic structures imposing labyrinth-like vortex motion could be used for collective entanglement of vortices envisioned in quantum circuit operations.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Bio‐Imaging quorum sensing signal molecules in a soil‐mimic gel

Rhizosphere, the narrow region surrounding plant roots directly influenced by root exudates and the root associated microbiome, plays an important role in plant productivity and the rhizosphere is well known for stimulating microbial metabolic activities. How microbial communities interact to form stable, metabolically interconnected functional communities is an area of intense interest. The question remains on how microbially produced secreted molecules that function as intercellular communication signals shape the structure and function of microbial communities. Our goal is to detect and quantify signal molecules produced by microbes or plants in the root‐soil environment, spatially and temporarily. As a proof‐of‐concept, we are imaging diffusible extracellular microbial metabolites involved in a bacteria‐bacteria communication process called quorum‐sensing. Quorum‐sensing relies on the accumulation of high concentrations of signal molecules in the environment to control bacterial gene expression, influencing rhizosphere colonization and plant health. Local concentration of quorum sensing molecules are determined using aptamer based sensors. Aptamers that can specifically bind the desired signal molecules are selected through SELEX and immobilized on the surface of nano‐porous membranes. Binding of the signal molecules and aptamer covered surface results in changes in surface charge distribution and steric hinderance and thus modifying the transmembrane ionic transport. Changes in transmembrane impedance can be measured through electrochemical impedance spectroscopy methods to monitor local concentrations of signal molecules. Sensor responses were determined for different concentrations of signal molecules and results showed detection of C4‐HSL in a soil‐mimic solution with K D of 10 nM. We demonstrate that the quorum‐sensing signal molecule C4‐homoserine lactone and (C4‐HSL) can rapidly diffuse in a soil‐mimic gel, providing evidence for our use of a soil‐mimic for further aptasensor development and validation. The sensors were then inserted into soil mimic gel for monitoring C4‐HSL diffusion and the resulted impedance changes were used to determine the C4‐HSL concentration at different positions in the gel. Measurements of local C4‐HSL concentrations variation and numerical solution of diffusion equation were used to create 4D images of C4‐HSL molecule diffusion in the soil‐mimic gel.

Jiang, Nianyu↗

Dust on Mars: An Aeolian Threat to Human Exploration?

The NASA HEDS Program is duly concerned for human explorers regarding the potential hazard posed by the ubiquitous dust mantle on Mars. To evaluate properties of dust that could be hazardous to humans, the MPS 2001 Lander payload will include the Mars Environmental Compatibility Assessment (MECA) experiment. This includes optical and atomic-force microscopy to evaluate soil grains for shape and size, wet chemistry to evaluate toxic substances, electrometry to evaluate triboelectric charging, and test-material palets to evaluate electrostatic and magnetic adhesion, and the hardness/abrasiveness of soil grains; these experimental subcomponents are delivered samples by the camera-equipped robotic arm of the lander which will acquire material from depths of 0.5 to 1.0 m in the soil. Data returned by MECA will be of value to both the BEDS and planetary/astrobiology communities. Dust poses a threat to human exploration because the martian system does not hydrologically or chemically remove fine particles that are being continuously generated by thermal, aeolian, and colluvial weathering, and by volcanism and impact over billions of years. The dust is extremely fine-grained, in copious quantities, ubiquitous in distribution, continually mobile, and a source of poorly-grounded static charges -- a suite of characteristics posing a particulate and electrical threat to explorers and their equipment. Dust is mobilized on global and regional scales, but probably also unpredictably and violently at local scales by dust devils. The latter might be expected in great abundance owing to near surface atmospheric instability (dust devils were detected by Pathfinder during its brief lifetime). Preliminary laboratory experiments suggest that space-suit materials subjected to windblown dust may acquire a uniform, highly adhesive dust layer that is also highly cohesive laterally owing to electrostatic forces. This layer will obscure visibility through the helmet visor, penetrate joints and fabrics, change the thermal properties of the suit, and possibly affect electronic/electrical suit functions. It is paramount that future missions address the issue of interparticle forces, and in particular, the role played by ionizing radiation in affecting these forces on Mars.

Marshall, J.↗

Dust on Mars: An Aeolian Threat to Human Exploration?

The NASA HEDS Program is duly concerned for human explorers regarding the potential hazard posed by the ubiquitous dust mantle on Mars. To evaluate properties of dust that could be hazardous to humans, the NMS 2001 Lander payload will include the Mars Environmental Compatibility Assessment (MECA) experiment. This includes optical and atomic-force microscopy to evaluate soil grains for shape and size, wet chemistry to evaluate toxic substances, electrometry to evaluate triboelectric charging, and test-material palets to evaluate electrostatic and magnetic adhesion, and the hardness/abrasiveness of soil grains; these experimental subcomponents are delivered samples by the camera-equipped robotic arm of the lander which will acquire material from depths of 0.5 to 1.0 m in the soil. Data returned by MECA will be of value to both the hEDS and planetary/astrobiology communities. Dust poses a threat to human exploration because the martian system does not hydrologically or chemically remove fine particles that are being continuously generated by thermal, aeolian, and colluvial weathering, and by volcanism and impact over billions of years. The dust is extremely fine-grained, in copious quantities, ubiquitous in distribution, continually mobile, and a source of poorly-grounded static charges -- a suite of characteristics posing a particulate and electrical threat to explorers and their equipment. Dust is mobilized on global and regional scales, but probably also unpredictably and violently at local scales by dust devils. The latter might be expected in great abundance owing to near surface atmospheric instability (dust devils were detected by Pathfinder during its brief lifetime). Preliminary laboratory experiments suggest that space-suit materials subjected to windblown dust may acquire a uniform, highly adhesive dust layer that is also highly cohesive laterally owing to electrostatic forces. This layer will obscure visibility through the helmet visor, penetrate joints and fabrics, change the thermal properties of the suit, and possibly affect electronic/electrical suit functions. It is paramount that future missions address the issue of interparticle forces, and in particular, the role played by ionizing radiation in affecting these forces on Mars.

Marshall, J.↗

NASA's Earth Observing System (EOS): Delivering on the Dream, Today and Tomorrow

This paper describes the successful operations of NASA's Earth Observing System (EOS) satellites over the past 10 years and the plans for the future. Excellent operations performance has been a key factor in the overall success of EOS. The EOS Program was conceived in the 1980s and began to take shape in the early 1990s. EOS consists of a series of satellites that study the Earth as an interrelated system. It began with the launch of Terra in December 1999, followed by Aqua in May 2002, and Aura in July 2004. A key EOS goal is to provide a long-term continuous data set to enable the science community to develop a better understanding of land, ocean, and atmospheric processes and their interactions. EOS has produced unprecedented amounts of data which are used all over the world free of charge. Mission operations have resulted in data recovery for Terra, Aqua, and Aura that have consistently exceeded mission requirements. The paper describes the ground systems and organizations that control the EOS satellites, capture the raw data, and distribute the processed science data sets. The paper further describes how operations have evolved since 1999. Examples of this evolution include (a) the implementation of new mission safety requirements for orbital debris monitoring; (b) technology upgrades to keep facilities at the state of the art; (c) enhancements to meet changing security requirements; and (d) operations management of the 2 international Earth Observing Constellations of 11 satellites known as the "Morning Constellation" and the "A-Train". The paper concludes with a view into the future based on the latest spacecraft status, lifetime projections, and mission plans.

Kelly, Angelita C.↗

From Detector Layout to Signal Analysis: Geometry Optimization and Neutron-Gamma Tagging in Plastic Scintillator Detectors

Neutrinos are elementary particles with many properties still unknown. Their masses so far have only upper and lower limits. Still, due to neutrino oscillations, it is clear that they are not massless, as stated by the Standard Model of Elementary Particles. Neutrinos are also present in the Universe in vast amounts, but they rarely interact with the surrounding matter. Their abundance makes them very interesting for many theories beyond the Standard Model, e.g., dark matter searches and CP symmetry violation in the leptonic sector, which could be (partially) responsible for the observed matter-antimatter asymmetry in today's Universe.\\ The Deep Underground Neutrino Experiment (DUNE) is a next-generation accelerator-based neutrino oscillation experiment that will study neutrinos with unprecedented precision and may answer many open questions. DUNE uses a powerful neutrino beam from Fermilab. It consists of a Near Detector (ND) complex to measure neutrinos before oscillat ion, and a Far Detector (FD) complex $1300\ \mathrm{km}$ away to measure them after oscillation. As part of the ND complex, measurements are also possible with different angles to the neutrino beam. This enables excellent control of systematic uncertainties of e.g., neutrino cross section measurements.\\ One detector in the near detector complex is The Muon Spectrometer (TMS), an extension of a Liquid Argon (LAr) detector that measures the charge and momentum of muons produced in neutrino interactions within the LAr. The design of this detector, which consists of alternating layers of steel and plastic scintillator bars, must be optimized for the expected muon energies.\\ In this thesis, a study of the optimal module orientation plan is presented, which is necessary for the physics performance of the near detector complex and, by extension, DUNE. As part of this study, the event reconstruction was also developed and improved. Simulated muons are then reconstructed, and the performan ce of different module orientation plans is tested.\\ As a second part, a study of neutron and gamma tagging using a Pulse Shape Discriminating (PSD) plastic scintillator is presented. The properties of this material allow particle differentiation based on the temporal distribution of emitted light. A novel approach to using the individual light signals was successfully tested using data from a small, local test setup.

Nehm, Asa [Mainz U.]↗

Measurement of the liquid argon scintillation pulse shape using differentiable simulation in the coherent CAPTAIN-Mills experiment

The coherent CAPTAIN-Mills (CCM) experiment is a liquid argon (LAr) light collection detector searching for MeV-scale neutrino and beyond Standard Model physics signatures. Two hundred eight-inch photomultiplier tubes instrument the seven-ton fiducial volume with 50% photocathode coverage to detect light produced by charged particles. CCM’s light-based approach reduces requirements of LAr purity, compared to other detection technologies, such that sub-MeV particles can be reliably detected without additional LAr filtration and with 𝒪⁡(1) parts per million of common contaminants. We present a measurement of LAr light production and propagation parameters, with uncertainties, obtained from a sample of MeV-scale electromagnetic events. The optimization of this high-dimensional parameter space was facilitated by a differentiable optical photon Monte Carlo simulation and detailed photomultiplier tube response characterization. This result accurately predicts the timing and spatial distribution of light due to scintillation and Cherenkov emission in the detector. This is the first description of photon propagation in LAr to include several effects, including anomalous dispersion of the index of refraction near the ultraviolet resonance, Mie scattering from impurities, and Cherenkov light production.

Cherenkov detectors↗

Immunofluorescent Detection of DNA Double Strand Breaks induced by High-LET Radiation

Within cell nuclei, traversing charged heavy ion particles lead to the accumulation of proteins related to DNA lesions and repair along the ion trajectories. Irradiation using a standard geometric setup with the beam path perpendicular to the cell monolayer generates discrete foci of several proteins known to localize at sites of DNA double strand breaks (DSBs). One such molecule is the histone protein H2AX (gamma-H2AX), which gets rapidly phosphorylated in response to ionizing radiation. Here we present data obtained with a modified irradiation geometry characterized by a beam path parallel to a monolayer of human fibroblast cells. This new irradiation geometry leads to the formation of gamma-H2AX aggregates in the shape of streaks stretching over several micrometers in the x/y plane, thus enabling the analysis of the fluorescence distributions along the particle trajectories. Qualitative analysis of these distributions presented insights into the DNA repair kinetics along the primary track structure and visualization of possible chromatin movement. We also present evidence of colocalization of gamma-H2AX with several other proteins in responses to ionizing radiation exposure. Analysis of gamma-H2AX has the potential to provide useful information on human cell responses to high LET radiation after exposure to space-like radiation.

Cucinotta, Francis A.↗

Finding the magnetopause location using soft X-ray observations and a statistical inverse method

Variability in the location and shape of the dayside magnetopause is attributed to magnetic reconnection, a fundamental process that enables the transfer of mass, energy, and momentum from the solar wind into the magnetosphere. The spatial and temporal properties of the magnetopause, under varying solar and magnetospheric conditions, remain largely unknown because empirical studies using in-situ observations are challenging to interpret. Global wide field-of-view (FOV) imaging is the only means to simultaneously observe the spatial distribution of the plasma properties over the vast dayside magnetospheric region and, subsequently, quantify the energy transport from the interplanetary medium into the terrestrial magnetosphere. Two upcoming missions, ESA/CAS SMILE and NASA’s LEXI will provide wide-field imagery of the dayside magnetosheath in soft X-rays, an emission generated by charge exchange interactions between high charge-state heavy ions of solar wind origin and exospheric neutral atoms. High-cadence two-dimensional observations of the magnetosheath will allow the estimation of dynamic properties of its inner boundary, the magnetopause, and enable studies of its response to changes in the solar wind dynamic pressure and interplanetary magnetic field orientation. This work introduces a statistically-based estimation approach based on inverse theory to estimate the spatial distribution of magnetosheath soft X-ray emissivities and, with this, identify the location of the magnetopause over the Sun−Earth line. To do so, we simulate the magnetosheath structure using the MHD-based OpenGGCM model and generate synthetic soft X-ray images using LEXI’s orbit and attitude information. Our results show that 3-D estimations using the described statistically-based technique are robust against Poisson-distributed shot noise inherent to soft X-ray images. Also, our proposed methodology shows that the accuracy of both three-dimensional (3-D) estimation and the magnetopause standoff distance calculation highly depends on the observational point.

Gonzalo Cucho-Padin↗

Effects of Kinetic Processes in Shaping Io's Global Plasma Environment: A 3D Hybrid Model

The global dynamics of the ionized and neutral components in the environment of Io plays an important role in the interaction of Jupiter's corotating magnetospheric plasma with Io. The stationary simulation of this problem was done in the MHD and the electrodynamics approaches. One of the main significant results from the simplified two-fluid model simulations was a production of the structure of the double-peak in the magnetic field signature of the I0 flyby that could not be explained by standard MHD models. In this paper, we develop a method of kinetic ion simulation. This method employs the fluid description for electrons and neutrals whereas for ions multilevel, drift-kinetic and particle, approaches are used. We also take into account charge-exchange and photoionization processes. Our model provides much more accurate description for ion dynamics and allows us to take into account the realistic anisotropic ion distribution that cannot be done in fluid simulations. The first results of such simulation of the dynamics of ions in the Io's environment are discussed in this paper.

Lipatov, Alexander S.↗

Towards a reliable assessment of charging effects during surface analysis: Accurate spectral shapes of ZrO 2 and Pd/ZrO 2 via X-ray Photoelectron Spectroscopy

X-ray Photoelectron Spectroscopy of large bandgap or insulating material surfaces relies on an effective mechanism that compensates for the emission (loss) of electrons by maintaining the material surface at a steady-state uniform potential. While a steady-state may be attained by utilizing an active compensation, such as low power electron emitting filament, there is the possibility that the surface potential is not uniform over the area analyzed, leading to peak shifts and incorrect spectral interpretation. Here, in this work, a spectral data processing method based on mapping the ZrO 2 and Pd/ZrO 2 surfaces utilizing photoemission peak binding energy is proposed, which provides information about the response of specific material surfaces to charge compensation. Spectromicroscopy of ZrO 2 and Pd/ZrO 2 surfaces without spatial information is used to monitor the efficacy of charge compensation. Exploiting counts distributed over many bins require the use of procedures and algorithms essential to practical mapping peak positions. Iterative singular value decomposition is therefore introduced and utilized as a means of efficiently delivering spatially resolved spectra from which binding energy for peaks is computed. The concepts developed in this work result in robust and accurate peak models of ZrO 2 and Pd/ZrO 2 that can be applied in XPS analysis of not only ZrO 2 but other large bandgap or insulating material surfaces. Supporting arguments for a peak model representing signal from Zr 3p and Pd 3d are developed within this work are presented.

36 MATERIALS SCIENCE↗

The electrospray: Fundamentals and combustion applications

Liquid fuel dispersion in practical systems is typically achieved by spraying the fuel into a polydisperse distribution of droplets evaporating and burning in a turbulent gaseous environment. In view of the nearly unsurmountable difficulties of this two-phase flow, it would be useful to use an experimental arrangement that allow a systematic study of spray evolution and burning in configurations of gradually increasing levels of complexity, starting from laminar sprays to fully turbulent ones. An Electrostatic Spray (ES) of charged droplets lends itself to this type of combustion experiments under well-defined conditions and can be used to synthesize gradually more complex spray environments. In its simplest configuration, a liquid is fed into a small metal tube maintained at several kilovolts relative to a ground electrode few centimeters away. Under the action of the electric field, the liquid meniscus at the outlet of the capillary takes a conical shape, with a thin jet emerging from the cone tip. This jet breaks up farther downstream into a fine spray of charged droplets. Several advantages distinguish the electrospray from alternative atomization techniques: the self-dispersion property of the spray due to coulombic repulsion; the absence of droplet coalescence; the potential control of the trajectories of charged droplets by suitable disposition of electrostatic fields; and the decoupling of atomization, which is strictly electrostatic, from gas flow processes. Furthermore, as recently shown in our laboratory, the electrospray can produce quasi-monodisperse droplets over a very broad size range (1-100 microns). The ultimate objective of this research project is to study the formation and burning of electrosprays of liquid fuels first in laminar regimes and then in turbulent ones. Combustion will eventually be investigated in conditions of three-dimensional droplet-droplet interaction, for which experimental studies have been limited to either qualitative observations in sprays or more quantitative observations on simplified systems consisting of a small number of droplets or droplet arrays. The compactness and potential controllability of this spray generaiton system makes it appealing for studies to be undertaken in the next two years on electrospray combustion in reduced-gravity environments such as those achievable at NASA microgravity test facilities.

Gomez, Alessandro↗

Shell model analysis of the B ( E 2,2 + → 0 + ) values in the A = 70, T = 1 triplet 70 Kr, 70 Br, and 70 Se

The B(E2, 2 + → 0 + ) transition strengths of the T=1 isobaric triplet 70 Kr, 70 Br, 70 Se, recently measured at the RIKEN Radioactive Isotope Beam Factory (RIBF), are discussed in terms of state-of-the-art large scale shell model calculations using the JUN45 and JUN45 + LNPS plus Coulomb interactions. In this Letter we argue that, depending on the effective charges used, the calculations are either in line with the experimental data within statistical uncertainties, or the anomaly happens in 70 Br, rather than 70 Kr. In the latter case, we suggest that it can be due to the presence of a hitherto undetected 1 + T = 0 state below the yrast 2 + T = 1 state. Furthermore, our results do not support a shape change of 70 Kr with respect to the other members of the isobaric multiplet.

59 ≤ A ≤ 89↗

Fission Product Evaluation (Quarterly Report)

The LLNL team has developed a theoretical framework to compute the fission fragment charge and mass distributions of odd-mass nuclei, which can be formed in neutron-induced reactions on even-even nuclei. For example, n+ 238 U leads to the compound nucleus 239 U which has 147 neutrons. Odd-mass and odd-odd nuclei are spin-polarized: the spin of the nucleus is not equal to 0 as in even-even nuclei (a consequence of pairing correlations) but is in fact set by a single particle. In practice, that single particle can occupy different quantum-mechanical configurations, each with different spin. This affects the deformation properties of the nucleus and, as a result, the distribution of fission fragments. These distributions require two inputs for the calculation: a potential energy surface (= the total energy of the nucleus as a function of the deformation of the nuclear shape, often parametrized with 2 degrees of freedom) and the collective inertia tensor associated with each point of the PES. In an odd-mass or odd-odd nucleus, each quantity depends on the configuration of the single particle. We computed of the order of 20 to 30 different such configurations to extract the PES for spins K=1/2, 3/2, 5/2, 7/2, and 9/2 of 239 U. We then computed the primary yields for each such PES, as shown in Fig. 1 below. These yields were weighed with the spin distribution associated with the reaction 238 U+n and the resulting distribution used as input to FREYA to compute the independent yields shown in Fig. 2. These yields are then used as inputs to the FIER code to extract the cumulative yields and compare with LLNL-LANL measurements at TUNL.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Impingement-Current-Erosion Characteristics of Accelerator Grids on Two-Grid Ion Thrusters

Accelerator grid sputter erosion resulting from charge-exchange-ion impingement is considered to be a primary cause of failure for electrostatic ion thrusters. An experimental method was developed and implemented to measure erosion characteristics of ion-thruster accel-grids for two-grid systems as a function of beam current, accel-grid potential, and facility background pressure. Intricate accelerator grid erosion patterns, that are typically produced in a short time (a few hours), are shown. Accelerator grid volumetric and depth-erosion rates are calculated from these erosion patterns and reported for each of the parameters investigated. A simple theoretical volumetric erosion model yields results that are compared to experimental findings. Results from the model and experiments agree to within 10%, thereby verifying the testing technique. In general, the local distribution of erosion is concentrated in pits between three adjacent holes and trenches that join pits. The shapes of the pits and trenches are shown to be dependent upon operating conditions. Increases in beam current and the accel-grid voltage magnitude lead to deeper pits and trenches. Competing effects cause complex changes in depth-erosion rates as background pressure is increased. Shape factors that describe pits and trenches (i.e. ratio of the average erosion width to the maximum possible width) are also affected in relatively complex ways by changes in beam current, ac tel-grid voltage magnitude, and background pressure. In all cases, however, gross volumetric erosion rates agree with theoretical predictions.

Barker, Timothy↗

Studies of low-energy Galactic cosmic-ray composition at 22 AU. I - Secondary/primary ratios

Data from the High Energy Telescope of the CRS experiment on Voyager 2 have been used to measure the intensity, spectra, and elemental abundances of Galactic cosmic rays from Be to Ni at about 100 MeV/n. The charge resolution of this telescope varies from sigma = 0.034 for oxygen to sigma = 0.11 for iron. The solar modulation deceleration parameter Phi relevant for these data is estimated to be around 300 MV (Phi = 150 MeV/n for particles with A/Z = 2), an unprecedently low level for such measurements. This low modulation parameter is a result of the measurements being made in the outer heliosphere at a heliocentric distance of 22 AU, and centered on the solar minimum period of cycle 21. The results on secondary/primary ratios are used to test the Leaky-Box model of cosmic ray propagation, using the most recent cross sections data in hydrogen and helium, and taking into account the effects of the ionized fraction of the interstellar medium. It is found that all the secondary/primary ratios up to P/S are completely consistent with an exponential pathlength distribution (PLD). This PLD shape also accounts for the Sc-V/Fe ratio.

Ferrando, P.↗

Extraction of Qualitative Features from Sensor Data Using Windowed Fourier Transform

In this paper, we use Matlab to model the health monitoring of a system through the information gathered from sensors. This implies assessment of the condition of the system components. Once a normal mode of operation is established any deviation from the normal behavior indicates a change. This change may be due to a malfunction of an element, a qualitative change, or a change due to a problem with another element in the network. For example, if one sensor indicates that the temperature in the tank has experienced a step change then a pressure sensor associated with the process in the tank should also experience a step change. The step up and step down as well as sensor disturbances are assumed to be exponential. An RC network is used to model the main process, which is step-up (charging), drift, and step-down (discharging). The sensor disturbances and spike are added while the system is in drift. The system is allowed to run for a period equal to three time constant of the main process before changes occur. Then each point of the signal is selected with a trailing data collected previously. Two trailing lengths of data are selected, one equal to two time constants of the main process and the other equal to two time constants of the sensor disturbance. Next, the DC is removed from each set of data and then the data are passed through a window followed by calculation of spectra for each set. In order to extract features the signal power, peak, and spectrum are plotted vs time. The results indicate distinct shapes corresponding to each process. The study is also carried out for a number of Gaussian distributed noisy cases.

Amini, Abolfazl M.↗

An NMR study of microvoids in polymers

An understanding of polymer defect structures, like microvoids in polymeric matrices, is crucial to their fabrication and application potential. In this project guest atoms are introduced into the microvoids in PMR-15 and NMR is used to determine microvoid sizes and locations. Xenon is a relatively inert probe that would normally be found naturally in polymer or in NMR probe materials. There are two NMR active xenon isotopes, Xe-129 and Xe-131. The Xe atom has a very high polarizability, which makes it sensitive to the intracrystalline environment of polymers. Interactions between the Xe atoms and the host matrix perturb the Xe electron cloud, deshielding the nuclei, and thereby expanding the range of the observed NMR chemical shifts. This chemical shift range which may be as large as 5000 ppm, permits subtle structural and chemical effects to be studied with high sensitivity. The Xe(129)-NMR line shape has been found to vary in response to changes in the pore symmetry of the framework hosts line Zeolites and Clathrasil compounds. Before exposure to Xe gas, the PMR-15 samples were dried in a vacuum oven at 150 C for 48 hours. The samples were then exposed to Xe gas at 30 psi for 72 hours and sealed in glass tubes with 1 atmosphere of xenon gas. Xenon gas at 1 atmosphere was used to tune up the spectrometer and to set up the appropriate NMR parameters. A single Xe-129 line at 83.003498 Mhz (with protons at 300 Mhz) was observed for the gas. With the xenon charged PMR-15 samples, a second broader line is observed 190 ppm downfield from the gas line (also observed). The width of the NMR line from the Xe-129 absorbed in the polymer is at least partially due to the distribution of microvoid sizes. From the chemical shift (relative to the gas line) and the line width, we estimate the average void sizes to be 2.74 +/- 0.20 angstroms. Since Xe-129 has such a large chemical shift range (approximately 5000 ppm), we expect the chemical shift anisotropy to contribute to the line width (delta upsilon = 2.5 kHz).

Toy, James↗