Field-cycling NMR realaxation spectroscopy of poly(di-n-alkylsiloxanes in solid, mesomorphic, and isotropic liquid phases

The frequency dependence of the proton spin-lattice relaxation times T1 and T1., in the laboratory and rotating frames, respectively, is reported for solid and liquid phases of poly(diethylsiloxane) (PDES) and in melts of poly(dimethylsiloxane) (PDMS). The total frequency range is 5 X 102 -3 X 108 Hz and is mainly covered by field-cycling NMR relaxation spectroscopy. The relaxation behavior of PDES in the liquid but ordered mesophase is compared to that of isotropic melts of PDES and PDMS and also to that of nematic main-chain liquid-crystal polymers. The frequency dependences of PDES and PDMS liquids can be represented at low and high frequencies by power laws, section by section. The relaxation behavior in the isotropic melts is entirely equivalent to that previously reported for other polymer species. In the PDES mesophase, the exponents of the power laws are significantly larger and the crossover frequency between the two regimes is reduced. The dynamics in this phase are discussed with respect to the influence of chain modes and order director fluctuations. The main conclusion is, on the whole, that data of the liquid phases are determined by chain modes rather than by local segment fluctuations. The chain dynamics in the PDES mesophase resemble the chain modes in isotropic melts modified for a microstructure with reduced randomness, whereas the influence of order director fluctuations can neither be confirmed nor ruled out

Investigation of the olive mill solid wastes pellets combustion in a counter-current fixed bed reactor

Combustion tests and gaseous emissions of olive mill solid wastes pellets (olive pomace (OP), and olive pits (OPi)) were carried out in an updraft counter-current fixed bed reactor. Along the combustion chamber axis and under a constant primary air flow rate, the bed temperatures and the mass loss rate were measured as functions of time. Moreover, the gas mixture components such as O2, organic carbon (Corg), CO, CO2, H2O, H2, SO2, and NOx (NO + NO2) were analyzed and measured. The reaction front positions were determined as well as the ignition rate and the reaction front velocity. We have found that the exhaust gases are emitted in acceptable concentrations compared to the combustion of standard wood pellets reported in the literature (EN 303-5). It is shown that the bed temperature increased from the ambient value to a maximum value ranging from 750 to 1000 °C as previously reported in the literature. The results demonstrate the promise of using olive mill solid waste pellets as an alternative biofuel for heat and/or electricity production

Molecular exchange processes in partially filled porous glass as seen with NMR diffusometry

The self-diffusion properties of hexane confined in porous glass with different filling fractions were studied by means of pulsed field-gradient spin echo diffusometry. The spin echo attenuation curves were analyzed over a range of 3.5 orders of magnitude. Only for the partially filled sample was the shape of the echo attenuation curves found to depend on diffusion time. This observation indicates a vapor phase contribution to the total diffusional displacements and is interpreted by molecular exchange between the liquid and vapor phases. The distribution of molecular residence times in the liquid phase is evaluated from experimental data. A thorough analysis of this distribution function yields information about the nature of inhomogeneities of the liquid's spatial distribution inside the porous matrix, including typical sizes of the inhomogeneous regions and characteristics of exchange processes at the liquid/vapor interface. The model is further substantiated by additional computer simulations

Proton and deuteron field-cycling NMR relaxometry of liquids confined in porous glasses

Polar and non-polar liquids in porous glasses have been studied by proton and deuteron field-cycling NMR relaxometry. The mean pore diameters were 4 nm, 30 nm and 208 nm. The frequency dependence of the spin-lattice relaxation time T1 is strongly influenced by the polarity of the adsorbate. Non-polar liquids show a flat T1 dispersion compared with polar species. We designate the two cases as 'weak' and 'strong' adsorption respectively. Molecules of liquids at surfaces are known to adopt a preferential orientation, whereas they retain a high diffusivity. Therefore, reorientations mediated by translational displacements (RMTD) must contribute to the correlation function which decays on a timescale of up to eight orders of magnitude greater than in the bulk. The high diffusivity at the surface is made plausible by a mechanism called bulk-mediated surface diffusion recently proposed by Bychuk and O'Shaughnessy [O.V. Bychuk and B. O'Shaughnessy, J. Chem. Phys., 101 (1994) 772]. These authors found that the displacements effective on the surface can be described as the result of Levy walks. They therefore obey a Cauchy distribution. This work employs the Cauchy distribution for a numerical derivation of a surface correlation function, g(r/c), which correctly reproduces the typical correlation lengths of the substrate and thus renders the notion of the liquid molecules performing Levy walks reasonable. The difference in T1 dispersion behaviours of polar and non-polar adsorbates disappears when the free liquid is frozen while the approximately two monolayers thick surface film remains liquid. The T1 dispersions are then equally steep irrespective of the polarity. This indicates that a non-polar liquid confined to a thin, topologically two-dimensional layer on a polar surface undergoes the same relaxation mechanism as a strongly adsorbed polar liquid which is dominated by RMTD processes. | Polar and non-polar liquids in porous glasses have been studied by proton and deuteron field-cycling NMR relaxometry. The frequency dependence of the spin-lattice relaxation time T1 is strongly influenced by the polarity of the adsorbate. Non-polar liquids show a flat T1 dispersion compared with polar species. The difference in T1 dispersion behaviors of polar and non-polar adsorbates disappears when the free liquid is frozen while the approximately two monolayers thick surface film remains liquid. The T1 dispersions are then equally steep irrespective of the polarity. This indicates that a non-polar confined to a thin, topologically two-dimensional layer on a polar undergoes the same relaxation mechanism as a strongly adsorbed polar liquid dominated by RMTD processes

Fractional Langevin equation

We investigate fractional Brownian motion with a microscopic random-matrix model and introduce a fractional Langevin equation. We use the latter to study both sub- and superdiffusion of a free particle coupled to a fractal heat bath. We further compare fractional Brownian motion with the fractal time process. The respective mean-square displacements of these two forms of anomalous diffusion exhibit the same power-law behavior. Here we show that their lowest moments are actually all identical, except the second moment of the velocity. This provides a simple criterion which enables to distinguish these two non-Markovian processes.Comment: 4 page

Proton spin dynamics in polymer melts: New perspectives for experimental investigations of polymer dynamics

The proton spin dynamics in polymer melts is determined by intramolecular and intermolecular magnetic dipole-dipole interactions among the proton spins. During many decades it was postulated that the main contribution is a result of intramolecular magnetic dipole-dipole interactions of protons belonging to the same polymer segment. This postulate is far from reality. The relative weights of intra- and intermolecular contributions are time (or frequency) dependent and sensitive to details of polymer chain dynamics. It is shown that for isotropic models of polymer dynamics, in which already at short times the segmental displacements are not correlated with the polymer chain's initial conformation, the influence of the intermolecular dipole-dipole interactions becomes stronger with increasing evolution time (i.e. decreasing frequency) than the corresponding influence of the intramolecular counterpart. On the other hand, an inverted situation is predicted by the tube-reptation model: here the influence of the intramolecular dipole-dipole interactions increases faster with time than the contribution from intermolecular interactions. This opens a new perspective for experimental investigations of polymer dynamics by proton NMR, and first results are reported. © 2014 Elsevier B.V

Self-diffusion in fluids in porous glass: Confinement by pores and liquid adsorption layers

Diffusion coefficients of 10 different polar and nonpolar liquids filled in porous glasses with mean pore diameters of 4 or 30 nm were determined with the aid of the NMR field-gradient technique. In the time scale of these experiments (0.3 to 500 ms) diffusion coefficients were found to be time independent. Within the experimental error, no influence of the polarity of the adsorbate can be stated. The diffusion coefficients of all investigated fluids in glass with 4 and 30 nm pores were reduced by factors of 0.17 and 0.63, respectively, relative to the bulk values. This relatively weak reduction can be explained by considering the known porosities of the adsorbents. The second objective of this study was to examine the diffusion behaviour below the melting point of adsorbates in porous glass. Fluids confined in pores do not freeze at the bulk freezing temperatures. In this respect, two phases must be distinguished. A maximal two monolayer thick film adsorbed on the inner surfaces does not crystallize at all, whereas the 'free' fraction of the fluid in the pores freezes at reduced temperatures according to the Gibbs-Thompson relation. The nonfrozen surface layers form a network in which self-diffusion can be investigated. Experiments have been carried out with cyclohexane. A reduction factor of 0.06 was found relative to the extrapolated values of the entirely unfrozen fluid in porous glass with a mean pore diameter of 30 nm. It is, thus, demonstrated that molecules in adsorption layers virtually retain their translational degrees of freedom along the surfaces. The lowering of the diffusivity is mainly due to the geometric restriction rather than to the interaction with the surface

Medical management with or without interventional therapy for unruptured brain arteriovenous malformations (ARUBA): a multicentre, non-blinded, randomised trial

Background The clinical benefit of preventive eradication of unruptured brain arteriovenous malformations remains uncertain. A Randomised trial of Unruptured Brain Arteriovenous malformations (ARUBA) aims to compare the risk of death and symptomatic stroke in patients with an unruptured brain arteriovenous malformation who are allocated to either medical management alone or medical management with interventional therapy. Methods Adult patients (\u3e= 18 years) with an unruptured brain arteriovenous malformation were enrolled into this trial at 39 clinical sites in nine countries. Patients were randomised (by web-based system, in a 1: 1 ratio, with random permuted block design [block size 2, 4, or 6], stratified by clinical site) to medical management with interventional therapy (ie, neurosurgery, embolisation, or stereotactic radiotherapy, alone or in combination) or medical management alone (ie, pharmacological therapy for neurological symptoms as needed). Patients, clinicians, and investigators are aware of treatment assignment. The primary outcome is time to the composite endpoint of death or symptomatic stroke; the primary analysis is by intention to treat. This trial is registered with ClinicalTrials.gov, number NCT00389181. Findings Randomisation was started on April 4, 2007, and was stopped on April 15, 2013, when a data and safety monitoring board appointed by the National Institute of Neurological Disorders and Stroke of the National Institutes of Health recommended halting randomisation because of superiority of the medical management group (log-rank Z statistic of 4.10, exceeding the prespecified stopping boundary value of 2.87). At this point, outcome data were available for 223 patients (mean follow-up 33.3 months [SD 19.7]), 114 assigned to interventional therapy and 109 to medical management. The primary endpoint had been reached by 11 (10.1%) patients in the medical management group compared with 35 (30.7%) in the interventional therapy group. The risk of death or stroke was significantly lower in the medical management group than in the interventional therapy group (hazard ratio 0.27, 95% CI 0.14-0.54). No harms were identified, other than a higher number of strokes (45 vs 12,