413 research outputs found
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Relaxation nuclear magnetic resonance imaging (R-NMRI) of desiccation in M9787 silicone pads.
The production and aging of silicone materials remains an important issue in the weapons stockpile due to their utilization in a wide variety of components and systems within the stockpile. Changes in the physical characteristics of silicone materials due to long term desiccation has been identified as one of the major aging effects observed in silicone pad components. Here we report relaxation nuclear magnetic resonance imaging (R-NMRI) spectroscopy characterization of the silica-filled and unfilled polydimethylsiloxane (PDMS) and polydiphenylsiloxane (PDPS) copolymer (M9787) silicone pads within desiccating environments. These studies were directed at providing additional details about the heterogeneity of the desiccation process. Uniform NMR spin-spin relaxation time (T2) images were observed across the pad thickness indicating that the drying process is approximately uniform, and that the desiccation of the M9787 silicone pad is not a H2O diffusion limited process. In a P2O5 desiccation environment, significant reduction of T2 was observed for the silica-filled and unfilled M9787 silicone pad for desiccation up to 225 days. A very small reduction in T2 was observed for the unfilled copolymer between 225 and 487 days. The increase in relative stiffness with desiccation was found to be higher for the unfilled copolymer. These R-NMRI results are correlated to local changes in the modulus of the materia
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Dynamics of Uranyl Peroxide Nanocapsules
Discrete aqueous metal oxide polyionic clusters that include aluminum polycations, transition-metal polyoxometalates, and the actinyl peroxide clusters have captivated the interest of scientists in the realm of both their fundamental and applied chemistries. Yet the counterions for these polycations or polyanions are often ignored, even though they are imperative for solubility, crystallization, purification, and even templating cluster formation. The actinyl peroxide clusters have counterions not only external, but internal to the hollow peroxide capsules. In this study, we reveal the dynamic behavior of these internal alkali counterions via solid-state and liquid NMR experiments. These studies on two select cluster geometries, those containing 24 and 28 uranyl polyhedra, respectively, show that the capsules-like clusters are not rigid entities. Rather, the internal alkalis both have mobility inside the capsules, as well as exchange with species in the media in which they are dissolved. The alkali mobilities are affected by both what is inside the clusters as well as the composition of the dissolving medium
Proceedings of the 23rd annual Central Plains irrigation conference
Presented at Proceedings of the 23rd annual Central Plains irrigation conference held in Burlington, Colorado on February 22-23, 2011.Includes bibliographical references
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Insight into Hydrogen Bonding of Uranyl Hydroxide Layers and Capsules by Use of ÂčH Magic-Angle Spinning NMR Spectroscopy
Solid-state ÂčH magic-angle spinning (MAS) NMR was used to investigate local proton environments in anhydrous [UOâ(OH)â] (α-UOH) and hydrated uranyl hydroxide [(UOâ)âO(OHâ 6·5HâO (metaschoepite). For the metaschoepite material, proton resonances of the ÎŒâ-OH hydroxyl and interlayer waters were resolved, with two-dimensional (2D) double-quantum (DQ) ÂčHâÂčH NMR correlation experiments revealing strong dipolar interactions between these different proton species. The experimental NMR results were combined with first-principles CASTEP GIPAW (gauge including projector-augmented wave) chemical shift calculations to develop correlations between hydrogen-bond strength and observed ÂčH NMR chemical shifts. These NMR correlations allowed characterization of local hydrogen-bond environments in uranyl Uââ capsules and of changes in hydrogen bonding that occurred during thermal dehydration of metaschoepite.This is the publisherâs final pdf. The published article is copyrighted by the American Chemical Society and can be found at: http://pubs.acs.org/journal/jpccck/about.htm
Synthesis of Allylnickel Aryloxides and Arenethiolates: Study of Their Dynamic Isomerization and 1,3-Diene Polymerization Activity
A new family of allylnickel(I1) complexes, [Ni(η^3-+allyl)(”-X)]_2 (X = ArO, ArS), have been synthesized by anion metathesis of the sodium or lithium salts of aryloxides or arenethiolates with [Ni(η^3-allyl)(”-Br)]_2. The complexes are proposed to be dimeric and to consist of a mixture of cis and trans isomers. A dynamic process rapidly equilibrates the cis and trans isomers of the pentafluorophenoxide, 2,6-difluorophenoxide, and 3,5-bis(trifluoromethyl)phenoxide complexes on the ^1H NMR time scale. The 2,6-dimethylphenoxide, 2,6-diisopropylphenoxide, 2,4,6-
tris(trifluoromethyl)phenoxide, and pentafluorothiophenoxide complexes are static at room temperature. A variable-temperature NMR study of the 3,5-bis(trifluoromethyl)phenoxide complex provided activation enthalpy and entropy values of 12.9 kcal/mol and -6.6 cal/ (K mol), respectively. Allyl rotation or cleavage of one of the ”-X bridges is proposed as the mechanism for the isomerization. The pentafluorophenoxide, 3,5-bis(trifluoromethyl)phenoxide, and 2,4,6-tris(trifluoromethy1)phenoxide complexes initiate the rapid polymerization of 1,3-cyclohexadiene and 1,3-butadiene to form high-molecular weight, 1,4-linked polymers
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Solid-State Dynamics of Uranyl Polyoxometalates
Understanding fundamental uranyl polyoxometalate
(POM) chemistry in solution and the solid state is
the first step to defining its future role in the development
of new actinide materials and separation processes
that are vital to every step of the nuclear fuel cycle. Many
solid-state geometries of uranyl POMs have been described,
but we are only beginning to understand their
chemical behavior, which thus far includes the role of templates
in their self-assembly, and the dynamics of encapsulated
species in solution. This study provides unprecedented
detail into the exchange dynamics of the encapsulated
species in the solid state through Magic Angle Spinning
Nuclear Magnetic Resonance (MAS NMR) spectroscopy. Although
it was previously recognized that capsule-like molybdate
and uranyl POMs exchange encapsulated species
when dissolved in water, analogous exchange in the solid
state has not been documented, or even considered.
Here, we observe the extremely high rate of transport of
Liâș and aqua species across the uranyl shell in the solid
state, a process that is affected by both temperature and
pore blocking by larger species. These results highlight
the untapped potential of emergent f-block element materials
and vesicle-like POMs.Keywords: polyoxometalate, solid-state NMR, uranyl, proton MAS NMR, ion-exchang
Share of afghanistan populace in hepatitis B and hepatitis C infection's pool: is it worthwhile?
There is a notable dearth of data about Hepatitis B Virus (HBV) and Hepatitis C Virus(HCV) prevalence in Afghanistan. Awareness program and research capacity in the field of hepatitis are very limited in Afghanistan. Number of vulnerabilities and patterns of risk behaviors signal the need to take action now
Non-Newtonian Couette-Poiseuille flow of a dilute gas
The steady state of a dilute gas enclosed between two infinite parallel
plates in relative motion and under the action of a uniform body force parallel
to the plates is considered. The Bhatnagar-Gross-Krook model kinetic equation
is analytically solved for this Couette-Poiseuille flow to first order in the
force and for arbitrary values of the Knudsen number associated with the shear
rate. This allows us to investigate the influence of the external force on the
non-Newtonian properties of the Couette flow. Moreover, the Couette-Poiseuille
flow is analyzed when the shear-rate Knudsen number and the scaled force are of
the same order and terms up to second order are retained. In this way, the
transition from the bimodal temperature profile characteristic of the pure
force-driven Poiseuille flow to the parabolic profile characteristic of the
pure Couette flow through several intermediate stages in the Couette-Poiseuille
flow are described. A critical comparison with the Navier-Stokes solution of
the problem is carried out.Comment: 24 pages, 5 figures; v2: discussion on boundary conditions added; 10
additional references. Published in a special issue of the journal "Kinetic
and Related Models" dedicated to the memory of Carlo Cercignan
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