Reactions of Atomic Oxygen (O(3P)) with Polybutadienes and Related Polymers

Thin films of the following polymers were exposed at ambient temperature to ground-state oxygen atoms (O(3P)), generated by a radio-frequency glow discharge in O2: cis- and trans-1,4-polybutadienes (CB and TB), amorphous 1,2-polybutadiene (VB), polybutadienes with different 1,4/1,2 contents, trans polypentenamer (TP), cis and trans polyoctenamers (CO and TO), and ethylene-propylene rubber (EPM). Transmission infrared spectra of CB and TB films revealed extensive surface recession, or etching, unaccompanied by any microstructural changes within the films, demonstrating that the reactions were confined to the surface layers. Contrary to the report by Rabek, Lucki, and Ranby (1979), there was no O(3P)-induced cis-trans isomerization in CB or TB. From weight-loss measurements, etch rates for polybutadienes were found to be markedly dependent on vinyl content, decreasing by two orders of magnitude from CB (2% 1,2) to structures with 30 to 40% 1,2 double bonds, thereafter increasing by half an order of magnitude to VB (97% 1,2). Relative etch rates for EMP and the polyalkenamers were in the order: EMP is greater than CO (or TO) is greater than TP is greater than CB. The sole non-elastomer examined, TB, had an etch rate about six times that of CB, ascribable to a morphology difference. Cis/trans content had a negligible effect on the etch rate of the polyalkenamers. Mechanisms involving crosslinking through units are proposed for the unexpected protection imparted to polybutadienes by the 1,2 double bonds

A conformal oxidation-resistant, plasma-polymerized coating

A comparative study was made of the surface recession (etching) of thin films of plasma polymerized tetrafluoro ethylene (PPTFE), polytetrafluoro ethylene (PTFE), and ion-beam sputter deposited polytetrafluoro ethylene (SPTFE) exposed to ground-state atomic oxygen downstream from a nonequilibrium radio-frequency O2 plasma. At 22 C, the etch rates for PTFE, SPTFE, and PPTFE were in the ratio of 8.7:1.8:1.0. A thin, conformal coating of PPTFE (etch rate of 0.3 nm/h at 22 C) was found to protect an underlying cast film of a reactive polymer, cis-1,4 polybutadiene, against ground-state atomic oxygen attack for the time required to fully etch away the PPTFE coating. From ESCA analysis, PTFE exhibited only minor surface oxidation (uptake of 0.5 atom percent O) upon etching, its F/C ratio decreasing slightly from 2.00 to 1.97; PPTFE exhibited considerable surface oxidation (uptake of 5.9 atom percent O) intermediate between those of PTFE and PPTFE, with a decrease in F/C ratio from 1.73 to 1.67. A plasma-polymerized fluorocarbon coating such as PPTFE might be useful for space applications to protect polymers that are vulnerable to oxidation or degradation by oxygen atoms

Emission of volatile halogenated organic compounds over various Dead Sea landscapes

Volatile halogenated organic compounds (VHOCs), such as methyl halides (CH3X; X is Br, Cl and I) and very short-lived halogenated substances (VSLSs; bromoform-CHBr3, dibromomethane-CH2Br2, bromodichloromethane-CHBrCl2, trichloroethylene-C2HCl3, chloroform-CHCl3- A nd dibromochloromethane-CHBr2Cl) are well known for their significant influence on ozone concentrations and oxidation capacity of the troposphere and stratosphere and for their key role in aerosol formation. Insufficient characterization of the sources and the emission rate of VHOCs limits our ability to understand and assess their impact in both the troposphere and stratosphere. Over the last two decades, several natural terrestrial sources for VHOCs, including soil and vegetation, have been identified, but our knowledge of emission rates from these sources and their responses to changes in ambient conditions remains limited. Here we report measurements of the mixing ratios and fluxes of several chlorinated and brominated VHOCs from different landscapes and natural and agricultural vegetated sites at the Dead Sea during different seasons. Fluxes were generally positive (emission into the atmosphere), corresponding to elevated mixing ratios, but were highly variable. Fluxes (and mixing ratios) for the investigated VHOCs ranged as follows: CHBr3 from 79 to 187 nmolm2 d1 (1.9 to 22.6 pptv), CH2Br2 from 55 to 71 nmolm2 d1 (0.7 to 19 pptv), CHBr2Cl from 408 to 768 nmolm2 d1 (0.4 to 11 pptv), CHBrCl2 from 29 to 45 nmolm2 d1 (0.5 to 9.6 pptv), CHCl3 from 577 to 883 nmolm2 d1 (15 to 57 pptv), C2HCl3 from 74 to 884 nmolm2 d1 (0.4 to 11 pptv), methyl chloride (CH3Cl) from-5300 to 10,800 nmolm2 d1 (530 to 730 pptv), methyl bromide (CH3Br) from 111 to 118 nmolm2 d1 (7.5 to 14 pptv) and methyl iodide (CH3I) from 25 to 17 nmolm2 d1 (0.4 to 2.8 pptv). Taking into account statistical uncertainties, the coastal sites (particularly those where soil is mixed with salt deposits) were identified as sources of all VHOCs, but this was not statistically significant for CHCl3. Further away from the coastal area, the bare soil sites were sources for CHBrCl2, CHBr2Cl, CHCl3, and probably also for CH2Br2 and CH3I, and the agricultural sites were sources for CHBr3, CHBr2Cl and CHBrCl2. In contrast to previous reports, we also observed emissions of brominated trihalomethanes, with net molar fluxes ordered as follows: CHBr2Cl > CHCl3 > CHBr3 > CHBrCl2 and lowest positive flux incidence for CHCl3 among all trihalomethanes; this finding can be explained by the soil's enrichment with Br. Correlation analysis, in agreement with recent studies, indicated common controls for the emission of CHBr2Cl and CHBrCl2 and likely also for CHBr3. There were no indications for correlation of the brominated trihalomethanes with CHCl3. Also in line with previous reports, we observed elevated emissions of CHCl3 and C2HCl3 from mixtures of soil and different salt-deposited structures; the flux correlations between these compounds and methyl halides (particularly CH3I) suggested that at least CH3I is also emitted via similar mechanisms or is subjected to similar controls. Overall, our results indicate elevated emission of VHOCs from bare soil under semiarid conditions. Along with other recent studies, our findings point to the strong emission potential of a suite of VHOCs from saline soils and salt lakes and call for additional studies of emission rates and mechanisms of VHOCs from saline soils and salt lakes

Decohering d-dimensional quantum resistance

The Landauer scattering approach to 4-probe resistance is revisited for the case of a d-dimensional disordered resistor in the presence of decoherence. Our treatment is based on an invariant-embedding equation for the evolution of the coherent reflection amplitude coefficient in the length of a 1-dimensional disordered conductor, where decoherence is introduced at par with the disorder through an outcoupling, or stochastic absorption, of the wave amplitude into side (transverse) channels, and its subsequent incoherent re-injection into the conductor. This is essentially in the spirit of B{\"u}ttiker's reservoir-induced decoherence. The resulting evolution equation for the probability density of the 4-probe resistance in the presence of decoherence is then generalised from the 1-dimensional to the d-dimensional case following an anisotropic Migdal-Kadanoff-type procedure and analysed. The anisotropy, namely that the disorder evolves in one arbitrarily chosen direction only, is the main approximation here that makes the analytical treatment possible. A qualitatively new result is that arbitrarily small decoherence reduces the localisation-delocalisation transition to a crossover making resistance moments of all orders finite.Comment: 14 pages, 1 figure, revised version, to appear in Phys. Rev.

The Jason II virtual control van system, data acquisition system, web-based event logger, and SeaNet

Scientific underwater remotely operated vehicles (ROVs) collect data from multiple video cameras and scientific instruments. This integrated information is often only available in an ROV control-van during operations. Although all the data is logged, it is difficult for scientists to re-create a combined display of this data and have the ability to review and access an entire cruise dataset easily. We introduce a methodology of taking continuous real-time information snapshots (infosnaps) during interesting events and at regular time intervals for complete data coverage. These infosnaps capture four simultaneous video sources, vehicle data, instrument data, and event data as entered by scientists. The infosnaps are automatically cataloged and immediately accessible and searchable via a web-browser. We developed, built, and deployed the Jason II Virtual Control Van system on seven Jason cruises. The system has captured over 50,000 control-van infosnaps, containing more than 200,000 images co-registered with vehicle telemetry and scientific instrument data. The Virtual Control Van is designed for both scientific collaboration and public/educational outreach. It has been integrated with the SeaNet system to provide remote on-shore access. The report describes the Jason II Virtual Control Van system and includes instructions for setting up the system in the field.Funding was provided by the W. M. Keck Foundation under Grant No. 991735

4DGeoBrowser : a web-based data browser and server for accessing and analyzing multi-disciplinary data

This report describes the 4DGeoBrowser software system. The GeoBrowser is a web-based application developed at the Woods Hole Oceanographic Institution by Steven Lerner and Andrew Maffei. It has been designed with the goal of creating, accessing, and analyzing repositories of oceanographic datasets that have been generated by investigators in differing scientific disciplines. Once the information is loaded onto a Geobrowser server the investigator-user is able to login to the website and use a set of data access and analysis tools to search, plot, and display this information. GeoBrowser servers are also capable of processing commands that are submitted remotely via HTTP URLs or email. Scientists are able to use this capability to make calls to the GeoBrowser server and generate click-able maps, tables of urls, and customized HTML pages. These can then be used to enhance websites associated with scientific projects. Examples of supporting scientific website functionality that includes time series plotting, data delivery by email, geo-spatial plotting of interdisciplinary data, map-based search capabilities and other functionality are presented in this report. The report includes examples of GeoBrowser application websites, a user manual, and a reference guide. In addition, the concept of Electronic Index Cards (EICs) is presented

Two-dimensional magnetoexcitons in the presence of spin-orbit coupling

We study theoretically the effect of spin-orbit coupling on quantum well excitons in a strong magnetic field. We show that, in the presence of an in-plane field component, the excitonic absorption spectrum develops a double-peak structure due to hybridization of bright and dark magnetoexcitons. If the Rashba and Dresselhaus spin-orbit constants are comparable, the magnitude of splitting can be tuned in a wide interval by varying the azimuthal angle of the in-plane field. We also show that the interplay between spin-orbit and Coulomb interactions leads to an anisotropy of exciton energy dispersion in the momentum plane. The results suggest a way for direct optical measurements of spin-orbit parameters.Comment: 9 pages, 6 figure

Boundedness of Pseudodifferential Operators on Banach Function Spaces

We show that if the Hardy-Littlewood maximal operator is bounded on a separable Banach function space $X(\mathbb{R}^n)$ and on its associate space $X'(\mathbb{R}^n)$, then a pseudodifferential operator $\operatorname{Op}(a)$ is bounded on $X(\mathbb{R}^n)$ whenever the symbol $a$ belongs to the H\"ormander class $S_{\rho,\delta}^{n(\rho-1)}$ with $0<\rho\le 1$, $0\le\delta<1$ or to the the Miyachi class $S_{\rho,\delta}^{n(\rho-1)}(\varkappa,n)$ with $0\le\delta\le\rho\le 1$, $0\le\delta0$. This result is applied to the case of variable Lebesgue spaces $L^{p(\cdot)}(\mathbb{R}^n)$.Comment: To appear in a special volume of Operator Theory: Advances and Applications dedicated to Ant\'onio Ferreira dos Santo