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At least 1,261 records · Page 70

Molecular-Weight-Dependent Infiltration and Adsorption of Polymers into Nanochannels

The mesoporous silica shell coating hydrogenolysis nano-catalysts alters the molecular weight distributions of cleaved polymer chains compared to catalysts without a shell. The shell, composed of radially aligned narrow cylindrical nanopores, reduces the formation of low-valued gaseous products and increases the median molecular weight of the product, thus enhancing the value of the products for polymer upcycling. Here, to understand the role of the mesoporous shell, we have studied the spatial distribution of polystyrene chains, used as a model polymer, in the nanochannels in both the melt phase and solution phase. In the melt, we observed from small-angle X-ray scattering experiments that the infiltration rate of the polymer into the nanochannels is inversely proportional to the molecular weight, which is consistent with theory. In theta solution experiments using UV–vis spectroscopy, we found that the shell significantly enhances polymer adsorption compared to nanoparticles without pores. In addition, the degree of polymer adsorption is not a monotonic function of molecular weight but initially increases with the molecular weight before eventually decreasing. The molecular weight for the peak adsorption increases with the pore diameter. This adsorption behavior is rationalized as resulting from a balance between the mixing entropy gain by surface adsorption and the conformational entropy penalty incurred by chains confined in the nanochannels. The spatial distribution of polymer chains in the nanochannels is visualized by energy-dispersive X-ray spectroscopy (EDX), and inverse Abel-transformed data reveals a less uniform polymer distribution along the primary pore axis for longer chains.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Remote sensing in the mixing zone

Characteristics of dispersion and diffusion as the mechanisms by which pollutants are transported in natural river courses were studied with the view of providing additional data for the establishment of water quality guidelines and effluent outfall design protocols. Work has been divided into four basic categories which are directed at the basic goal of developing relationships which will permit the estimation of the nature and extent of the mixing zone as a function of those variables which characterize the outfall structure, the effluent, and the river, as well as climatological conditions. The four basic categories of effort are: (1) the development of mathematical models; (2) laboratory studies of physical models; (3) field surveys involving ground and aerial sensing; and (4) correlation between aerial photographic imagery and mixing zone characteristics.

Villemonte, J. R.↗

Surface contamination on LDEF exposed materials

X-ray photoelectron spectroscopy (XPS) has been used to study the surface composition and chemistry of Long Duration Exposure Facility (LDEF) exposed materials including silvered Teflon (Ag/FEP), Kapton, S13GLO paint, quartz crystal monitors (QCM's), carbon fiber/organic matrix composites, and carbon fiber/Al Alloy composites. In each set of samples, silicones were the major contributors to the molecular film accumulated on the LDEF exposed surfaces. All surfaces analyzed have been contaminated with Si, O, and C; most have low levels (less than 1 atom percent) of N, S, and F. Occasionally observed contaminants included Cl, Na, K, P, and various metals. Orange/brown discoloration observed near vent slots in some Ag/FEP blankets were higher in carbon, sulfur, and nitrogen relative to other contamination types. The source of contamination has not been identified, but amine/amide functionalities were detected. It is probable that this same source of contamination account for the low levels of sulfur and nitrogen observed on most LDEF exposed surfaces. XPS, which probes 50 to 100 A in depth, detected the major sample components underneath the contaminant film in every analysis. This probably indicates that the contaminant overlayer is patchy, with significant areas covered by less that 100 A of molecular film. Energy dispersive x-ray spectroscopy (EDS) of LDEF exposed surfaces during secondary electron microscopy (SEM) of the samples confirmed contamination of the surfaces with Si and O. In general, particulates were not observed to develop from the contaminant overlayer on the exposed LDEF material surfaces. However, many SiO2 submicron particles were seen on a masked edge of an Ag/FEP blanket. In some cases such as the carbon fiber/organic matrix composites, interpretation of the contamination data was hindered by the lack of good laboratory controls. Examination of laboratory controls for the carbon fiber/Al alloy composites showed that preflight contamination was the most significant factor for all the contaminants generally detected at less than 1 atom percent, or detected only occasionally (i.e., all but Si, O, and C). Flight control surfaces, including sample backsides not exposed to space radiation or atomic oxygen flux, have accumulated some contamination on flight (compared to laboratory controls), but experimentally, the LDEF exposed surface contamination levels are generally higher for the contaminants Si and O. For most materials analyzed, Si contamination levels were higher on the leading edge surfaces than on the trailing edge surfaces. This was true even for the composite samples where considerable atomic oxygen erosion of the leading edge surfaces was observed by SEM. It is probable that the return flux associated with atmospheric backscatter resulted in enhanced deposition of silicones and other contaminants on the leading edge flight surfaces relative to the trailing edge. Although the Si concentration data suggested greater on-flight deposition of contaminants on the leading edge surfaces, the XPS analyses did not conclusively show different relative total thicknesses of flight deposited contamination for leading and trailing edge surfaces. It is possible that atomic oxygen reactions on the leading edge resulted in greater volatilization of the carbon component of the deposited silicones, effectively 'thinning' the leading edge deposited overlayer. Unlike other materials, exposed polymers such as Kapton and FEP-type Teflon had very low contamination on the leading edge surfaces. SEM evidence showed that undercutting of the contaminant overlayer and damaged polymer layers occurred during atomic oxygen erosion, which would enhance loss of material from the exposed surface.

Hemminger, Carol S.↗

The spectral world coordinate systems in IRAF/NOAO

The world coordinate system (WCS) for dispersion calibrated spectra used in the IRAF/NOAO spectroscopy packages is described. In particular, the image header keywords which define the coordinates in an 'image' pixel array. These keywords appear both as part of the IRAF image structure and map directly to FITS format. The types of spectra include multidimensional images with spectral dispersion as one axis, one dimensional images, and a special 'multispec' format consisting of multiple, semi-independent, one dimensional spectra in two or three dimensional images. The types of coordinate systems include multidimensional linear coordinates with individual keywords and one dimensional linear and nonlinear coordinates for the 'multispec' images stored in IRAF WCS attributes. The nonlinear world coordinate systems include polynomial, spline, sampled table, and look-up table function representations.

Valdes, F.↗

Enhancing functionalities in carbon fiber composites by titanium dioxide nanoparticles

Carbon fiber composite's high specific strength makes it incredibly useful for structural applications. However, their low strain-to-failure can be problematic in structural applications that can potentially see high strain conditions or high fatigue cycles resulting in sudden, catastrophic failure. This is further complicated by damage manifesting within the composite thus not showing damage indicators on the surface. Therefore, monitoring the structural integrity and strain history of the composite in application by itself—while maintaining positive composite performance—is vital to ensure safe operation. In this study, a homogeneous dispersion of TiO 2 nanoparticles on carbon fiber is demonstrated to generate a piezoresistive carbon fiber polymer matrix composite with enhanced self-sensing capabilities. The nanoparticle-embedded composites also exhibited superior strength and damping potential compared to the nanoparticle-free composites. The apparent interlaminar shear strength increased by up to 15% and the damping loss factor increased by an average of 150% while the piezoresistive sensitivity increased by up to 180% with the addition of a small weight fraction of nanoparticles to the fiber surface. These results demonstrate an approach to simultaneously improve the sensing capabilities, damping behavior and mechanical strength of carbon fiber composites by simply adding nanoparticles in the fiber sizing using a commercially scalable deposition method.

36 MATERIALS SCIENCE↗

Polyurethanes Based on Unmodified and Refined Technical Lignins: Correlation between Molecular Structure and Material Properties

The structural complexity and robust intermolecular interactions have challenged the incorporation of technical lignin into value-added polymeric materials for decades. To study the correlation between lignin molecular structure and material properties of lignin-based polyurethanes, we applied co-solvent enhanced lignocellulosic fractionation pretreatment followed by sequential precipitation to produce three distinct lignin preparations with narrowly distributed (molecular weight dispersity <2) and comparatively low molecular weight (<1500 g/mol) from poplar biomass. Structural characterization indicated that these lignin preparations differed in average molecular chain length and stiffness as well as hydroxyl group distribution. Secondary hydroxyl group providers such as aliphatic diols and polyethers were incorporated as building blocks into the lignin-based polyurethanes to provide additional hydrogen capacity to improve the dispersion of lignin in the polyurethane network. The selected aliphatic diols and polyethers interacted with lignin molecules at different levels of strength depending on their molecular structure, and their impacts were ultimately reflected in the mechanical and thermal properties of the resulting lignin-based polyurethanes. The copolymerization of technical lignin with tailored structure and secondary hydroxyl providers could provide new strategies in formulating lignin-based/containing polyurethanes for various functional applications.

36 MATERIALS SCIENCE↗

PbS/CdS Quantum Dot Room-Temperature Single-Emitter Spectroscopy Reaches the Telecom O and S Bands via an Engineered Stability

We synthesized PbS/CdS core/shell quantum dots (QDs) to have functional single-emitter properties for room-temperature, solid-state operation in the telecom O and S bands. Two shell-growth methods–cation exchange and successive ionic layer adsorption and reaction (SILAR)–were employed to prepare QD heterostructures with shells of 2–16 monolayers. PbS/CdS QDs were sufficiently bright and stable to resolve photoluminescence (PL) spectra representing both bands from single nanocrystals using standard detection methods, and for a QD emitting in the O-band a second-order correlation function showed strong photon antibunching, important steps toward demonstrating the utility of lead chalcogenide QDs as single-photon emitters (SPEs). Irrespective of type, few telecom-SPEs exist that are capable of such room-temperature operation. Access to single-QD spectra enabled a direct assessment of spectral line width, which was ~70–90 meV compared to much broader ensemble spectra (~300 meV). We show inhomogeneous broadening results from dispersity in PbS core sizes that increases dramatically with extended cation exchange. Quantum yields (QYs) are negatively impacted at thick shells (>6 monolayers) and, especially, by SILAR-growth conditions. Time-resolved PL measurements revealed that, with SILAR, initially single-exponential PL-decays transition to biexponential, with opening of nonradiative carrier-recombination channels. Radiative decay times are, overall, longer for core/shell QDs compared to PbS cores, which we demonstrate can be partially attributed to some core/shell sizes occupying a quasi-type II electron–hole localization regime. Finally, we demonstrate that shell engineering and the use of lower laser-excitation powers can afford significantly suppressed blinking and photobleaching. However, dependence on shell thickness comes at a cost of less-than-optimal brightness, with implications for both materials and experimental design

36 MATERIALS SCIENCE↗

Evolution of micro-pores in Ni–Cr alloys via molten salt dealloying

Porous materials with high specific surface area, high porosity, and high electrical conductivity are promising materials for functional applications, including catalysis, sensing, and energy storage. Molten salt dealloying was recently demonstrated in microwires as an alternative method to fabricate porous structures. The method takes advantage of the selective dissolution process introduced by impurities often observed in molten salt corrosion. This work further investigates molten salt dealloying in bulk Ni–20Cr alloy in both KCl–MgCl 2 and KCl–NaCl salts at 700 °C, using scanning electron microscopy, energy dispersive spectroscopy, and X-ray diffraction (XRD), as well as synchrotron X-ray nano-tomography. Micro-sized pores with irregular shapes and sizes ranging from sub-micron to several microns and ligaments formed during the process, while the molten salt dealloying was found to progress several microns into the bulk materials within 1–16 h, a relatively short reaction time, enhancing the practicality of using the method for synthesis. The ligament size increased from ~ 0.7 μm to ~ 1.3 μm in KCl–MgCl 2 from 1 to 16 h due to coarsening, while remaining ~ 0.4 μm in KCl–NaCl during 16 h of exposure. The XRD analysis shows that the corrosion occurred primarily near the surface of the bulk sample, and Cr 2 O 3 was identified as a corrosion product when the reaction was conducted in an air environment (controlled amount sealed in capillaries); thus surface oxides are likely to slow the morphological coarsening rate by hindering the surface diffusion in the dealloyed structure. 3D-connected pores and grain boundary corrosion were visualized by synchrotron X-ray nano-tomography. This study provides insights into the morphological and chemical evolution of molten salt dealloying in bulk materials, with a connection to molten salt corrosion concerns in the design of next-generation nuclear and solar energy power plants.

36 MATERIALS SCIENCE↗

A theoretical investigation of the hydrolysis of uranium hexafluoride: the initiation mechanism and vibrational spectroscopy

Depleted uranium hexafluoride (UF 6 ), a stockpiled byproduct of the nuclear fuel cycle, reacts readily with atmospheric humidity, but the mechanism is poorly understood. Here we compare several potential initiation steps at a consistent level of theory, generating underlying structures and vibrational modes using hybrid density functional theory (DFT) and computing relative energies of stationary points with double-hybrid (DH) DFT. A benchmark comparison is performed to assess the quality of DH-DFT data using reference energy differences obtained using a complete-basis-limit coupled-cluster (CC) composite method. The associated large-basis CC computations were enabled by a new general-purpose pseudopotential capability implemented as part of this work. Dispersion-corrected parameter-free DH-DFT methods, namely PBE0-DH-D3(BJ) and PBE-QIDH-D3(BJ), provided mean unsigned errors within chemical accuracy (1 kcal mol -1 ) for a set of barrier heights corresponding to the most energetically favorable initiation steps. The hydrolysis mechanism is found to proceed via intermolecular hydrogen transfer within van der Waals complexes involving UF 6 , UF 5 OH, and UOF 4 , in agreement with previous studies, followed by the formation of a previously unappreciated dihydroxide intermediate, UF 4 (OH) 2 . The dihydroxide is predicted to form under both kinetic and thermodynamic control, and, unlike the alternate pathway leading to the UO 2 F 2 monomer, its reaction energy is exothermic, in agreement with observation. Finally, harmonic and anharmonic vibrational simulations are performed to reinterpret literature infrared spectroscopy in light of this newly identified species.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Three-step colloidal gelation revealed by time-resolved x-ray photon correlation spectroscopy

The gelation of PEGylated gold nanoparticles dispersed in a glycerol–water mixture is probed in situ by x-ray photon correlation spectroscopy. Following the evolution of structure and dynamics over 10 4 s, a three-step gelation process is found. First, a simultaneous increase of the Ornstein–Zernike length ξ and slowdown of dynamics is characterized by an anomalous q-dependence of the relaxation times of τ ∝q -6 and strongly stretched intermediate scattering functions. After the structure of the gel network has been established, evidenced by a constant ξ, the dynamics show aging during the second gelation step accompanied by a change toward ballistic dynamics with τ ∝ q -1 and compressed correlation functions. In the third step, aging continues after the arrest of particle motion. Our observations further suggest that gelation is characterized by stress release as evidenced by anisotropic dynamics once gelation sets in.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Impact resistance of fiber composite blades used in aircraft turbine engines

Resistance of advanced fiber reinforced epoxy matrix composite materials to ballistic impact was investigated as a function of impacting projectile characteristics, and composite material properties. Ballistic impact damage due to normal impacts, was classified as transverse (stress wave delamination and splitting), penetrative, or structural (gross failure). Steel projectiles were found to be gelatin ice projectiles in causing penetrative damage leading to reduced tensile strength. Gelatin and ice projectiles caused either transverse or structural damage, depending upon projectile mass and velocity. Improved composite transverse tensile strength, use of dispersed ply lay-ups, and inclusion of PRD-49-1 or S-glass fibers correlated with improved resistance of composite materials to transverse damage. In non-normal impacts against simulated blade shapes, the normal velocity component of the impact was used to correlate damage results with normal impact results. Stiffening the leading edge of simulated blade specimens led to reduced ballistic damage, while addition of a metallic leading edge provided nearly complete protection against 0.64 cm diameter steel, and 1.27 cm diameter ice and gelatin projectiles, and partial protection against 2.54 cm diameter projectiles of ice and gelatin.

Friedrich, L. A.↗

The inner edge of the plasma sheet and the diffuse aurora

Three dimensional measurements from the ISEE-1 low energy electron spectrometer are used to map the location of the inner edge of the plasma sheet and study the anisotropies in the electron distribution function associated with this boundary. Lower energy plasma sheet electrons have inner edges closer to the Earth than higher energies with the separations at different energies being larger near dawn and after dusk than at midnight. Lowest energy inner edges are frequently located adjacent to the plasmapause in the dawn hemisphere but are often separated from it in the dusk hemisphere by a gap of at least several Re. The energy dispersion is minimal in the afternoon quadrant where the inner edge is near the magnetopause and frequently oscillating on a time scale of minutes. The location of the inner edge is probably determined primarily by the motion of electrons in the existing electric and magnetic fields rather than by strong diffusion as has sometimes been supposed.

Fairfield, D. H.↗

The inner edge of the plasma sheet and the diffuse aurora

Three dimensional measurements from the ISEE-1 low energy electron spectrometer are used to map the location of the inner edge of the plasma sheet and study the anisotropies in the electron distribution function associated with this boundary. Lower energy plasma sheet electrons have inner edges closer to the earth than higher energies with the separations at different energies being larger near dawn and after dusk than at midnight. Lowest energy inner edges are frequently located adjacent to the plasmapause in the dawn hemisphere but are often separated from it in the dusk hemisphere by a gap of at least several Re. The energy dispersion is minimal in the afternoon quadrant where the inner edge is near the magnetopause and frequently oscillating on a time scale of minutes. The location of the inner edge is probably determined primarily by the motion of electrons in the existing electric and magnetic fields rather than by strong diffusion as has sometimes been supposed. Previously announced in STAR as N83-32595

Fairfield, D. H.↗

Operational characteristics of the dispersed sensor processor mesh

The dispersed sensor processing mesh (DSPM) is part of an experimental system used to pursue a proof of concept for an advanced fault-tolerant communication strategy. The DSPM experiments incorporate sensors and effectors into an ultra-reliable nodal network in which a central bus controller performs algorithms to grow and maintain the network. The experiments demonstrate that DSPM is an achievable communication network that can sustain failures and continue to function properly. The results of the experiment give insights into the unique characteristics of the DSPM network and the network's capacity to limit physical damage propagation, limit damaged-data propagation, and to survive cyclic communication paths. This paper describes the concept, mechanization, and performance of the DSPM system in a real-time flight-critical environment.

Abbott, L. W.↗

Photoionization of the diffuse interstellar medium and galactic halo by OB associtations

Assuming smoothly varying H I distributions in te Galactic disk, we have calculated the geometry of diffuse II regions due to OB associations in the Galactic plane. Near the solar circle, OB associations with a Lyman continuum (Lyc) photon luminosity Psi(sub Lyc) = 3.3 x 10(exp 7) cm(exp -2) s(exp -1), produce H II regions that are density bounded in the vertical direction (H II chimneys) allowing Lyc to escape the gaseous disk and penetrate into the Galactic halo. We provide analytic formulae for the Lyc escape fraction as functions of S(sub 0) O-star catalog of Garmany and a new Lyc stellar stellar Lyc stellar flux calibration, we find a production rate of Lyc photons by OB associations within 2.5 kpc of Psi(sub Lyc) = 3.3 x 10(exp 7) cm(exp -2) s(exp -1). Integrating the fraction of Lyc photons that escape the disk over our adopted luminosity function of OB associations, we estimate that approximately 7% of the ionizing photons, or Phi(sub Lyc) = 2.3 x 10(exp 6) cm(exp -2) s(exp -1), escape each side of the H I disk layer and penetrate the diffuse ionized medium ('Reynolds layer'). This flux is sufficient to explain the potoionization of this, although we have not constructed a model for the observed H-alpha emission and pulsar dispersion measures that is fully consistent with the absorption rate of Lyc in the H II layer. Since our quiescent model does not account for the effects of dynamic chimneys and superbubbles, which should enhance Lyc escape, we conclude the O stars are the probable source of ionizing radiation for the Reynolds layer. For a random distribution of OB associations throughout the disk, the Lyc flux is nearly uniform for heights Z is greater than approximately 0.8 kpc above the midplane.

Dove, James B.↗

Penetration of the interplanetary magnetic field B(sub y) magnetosheath plasma into the magnetosphere: Implications for the predominant magnetopause merging site

Magnetosheath plasma peertated into the magnetospere creating the particle cusp, and similarly the interplanetary magnetic field (IMF) B(sub y) component penetrates the magnetopause. We reexamine the phenomenology of such penetration to investigate implications for the magnetopause merging site. Three models are popular: (1) the 'antiparallel' model, in which merging occurs where the local magnetic shear is largest (usually high magnetic latitude); (2) a tilted merging line passing through the subsolar point but extending to very high latitudes; or (3) a tilted merging line passing through the subsolar point in which most merging occurs within a few Earth radii of the equatorial plane and local noon (subsolar merging). It is difficult to distinguish between the first two models, but the third implies some very different predictions. We show that properties of the particle cusp imply that plasma injection into the magnetosphere occurs most often at high magnetic latitudes. In particular, we note the following: (1) The altitude of the merging site inferred from midaltitude cusp ion pitch angle dispersion is typically 8-12 R(sub E). (2) The highest ion energy observable when moving poleward through the cusp drops long before the bulk of the cusp plasma is reached, implying that ions are swimming upstream against the sheath flow shortly after merging. (3) Low-energy ions are less able to enter the winter cusp than the summer cusp. (4) The local time behavior of the cusp as a function of B(sub y) and B(sub z) corroborates predictions of the high-latitude merging models. We also reconsider the penetration of the IMF B(sub y) component onto closed dayside field lines. Our approach, in which closed field lines ove to fill in flux voids created by asymmetric magnetopause flux erosion, shows that strich subsolar merging cannot account for the observations.

Newell, Patrick T.↗

Recent Progress in the Development of a Multi-Layer Green's Function Code for Ion Beam Transport

To meet the challenge of future deep space programs, an accurate and efficient engineering code for analyzing the shielding requirements against high-energy galactic heavy radiation is needed. To address this need, a new Green's function code capable of simulating high charge and energy ions with either laboratory or space boundary conditions is currently under development. The computational model consists of combinations of physical perturbation expansions based on the scales of atomic interaction, multiple scattering, and nuclear reactive processes with use of the Neumann-asymptotic expansions with non-perturbative corrections. The code contains energy loss due to straggling, nuclear attenuation, nuclear fragmentation with energy dispersion and downshifts. Previous reports show that the new code accurately models the transport of ion beams through a single slab of material. Current research efforts are focused on enabling the code to handle multiple layers of material and the present paper reports on progress made towards that end.

Tweed, John↗

A comparative analysis of different van der Waals treatments for molecular adsorption on the basal plane of 2H-MoS 2

The binding energy of hydrogen sulfide, ammonia, ethane, ethylene, butadiene, benzene, toluene, pyridine, pyrrole, and thiophene on the basal plane of the semi-conducting 2H-molybdenum sulfide (MoS 2 ) was calculated with the following flavors of Density Functional Theory (DFT): GGA-PW91, PBE-D3, vdW-DF, optPBE, optB86b, optB88, vdW-TS, and BEEF-vdW. The GGA-PW91 binding energies are negligible (<0.07 eV in magnitude) in all cases. The predictions with vdW-DF and PBE-D3 are the closest (error <0.05 eV) to the isosteric heats of adsorption calculated from reported temperature programmed desorption data for thiophene and butadiene. For all dispersion flavors examined here, the magnitude of the dispersion contribution to the binding energy increases linearly with the number of heavy atoms in the adsorbate, with each atom contributing 0.05 eV (BEEF-vdW) – 0.09 eV (optB88-vdW). Further, this implies that the calculated adsorption constants of molecules larger than acridine (i.e., comprising > 14 non-heavy atoms) can vary by more than four orders of magnitude at industrial conditions depending on the chosen method of dispersion correction. Further, dispersion effects fall off rapidly (>0.03 eV/ non-hydrogen atom/Å) as the adsorbate-surface distance increases.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗