1,721,181 research outputs found
Kinetics of decomposition in ionic solids II : neutron scattering study of the system AgCl-NaCl
No full textThe kinetic of decomposition in the quasi-binary ionic system AgCl-NaCl has been studied by means of time-resolved neutron diffraction and small-angle neutron scattering. The coherent critical point is estimated as 447 +/- 3 K, 24 K below the upper critical binodal temperature. The chemical decomposition is almost completed in the first 200 s irrespective of the temperature. The mechanical relaxation of the lattice, however, takes place on a much longer timescale and is dominated by coherency strains leading to metastable intermediate states
The role of the binding salt sodium salicylate in semidilute ionic cetylpyridinium chloride micellar solutions: a rheological and scattering study
No full textThe micellar system based on cetylpyridinium chloride (CPyCl) and sodium salicylate (NaSal) in brine solution is investigated on both macro- and micro-length scales through rheology and scattering measurements. The linear viscoelasticity of the system and its structural parameters are explored by systematically changing the amount of NaSal over an extremely wide range of concentrations, thus producing salt-to-surfactant molar ratios from zero to about 8.5. As a result, the well-known non-monotonic behaviour of the zero-shear rate viscosity as a function of salinity can be connected to micellar morphological changes, whose driving force is represented by the simultaneous binding and screening actions of NaSal. The viscosity behaviour can be seen as a direct consequence of consecutive lengthening/shortening of the contour length, where the micelles attempt to minimize the electrostatic charge density on their surface. Along similar lines, the scattering measurements of the semidilute solutions show that the local stiffness of the micellar chain changes with increasing salt content influencing the elasticity of the resulting network. Within this general view, the branching of the micelles can be seen as a side effect attributable to the main character of the play, namely, the binding salt NaSal, whereas the overall dynamics of the system is driven by the considerable changes in the entanglement density of the micellar network
Segregation of hydrogen at internal Ag/MgO (metal/oxide)-interfaces as observed by small angle neutron scattering
No full textThe chemical composition of metal/oxide (M/O)-interfaces was studied for an internally oxidized Ag-lat.%Mg-alloy with small MgO nanoprecipitates in a dilute Ag matrix. This composition was varied by exposing the sample to oxygen (p(O-2) = 2 x 10(4) Pa), hydrogen (p(H-2) = 10(5) Pa) or vacuum (p < 10(-4) Pa). By means of small angle neutron scattering (SANS) we were able to show that hydrogen segregates at the internal Ag/MgO-interfaces. The average hydrogen occupancy at the Ag/MgO-phase boundary can be determined to be Theta(H) = (7.1 +/- 0.5) x 10(14) H/cm(2). In addition it could be shown that for each segregated hydrogen atom one Ag atom is displaced from the M/O-interface. The amount of hydrogen at the interfaces is in agreement with a model of structural vacancies at densely packed interface planes. To the best of our knowledge these are the first SANS-measurements that provide information about the segregation of hydrogen and deuterium at internal interfaces. (C) 2004 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved
Interaction of hydrogen and deuterium with dislocations in palladium as observed by small angle neutron scattering
No full textSmall angle neutron scattering (SANS) measurements on Pd samples containing dislocations with a density of a few 10(11) cm(-2) reveal an additional intensity for a scattering vector of 0.02 Angstrom (1) to 0.2 Angstrom (1) after loading with hydrogen (H) or deuterium (D). The corresponding net cross section is inversely proportional to the scattering vector as expected for line type scattering objects with a superimposed exponential decrease stemming from scattering within the Guinier-regime. This experimental finding is in accordance with a model where extended segregation of H or D within the dilated regions of edge dislocations occurs. In a first order approximation this corresponds to a precipitation of cylindrically shaped hydrides along the dislocation line and can be treated quantitatively yielding radii in agreement with SANS data. Whereas gas volumetric measurements at the same total concentration reveal no difference for the amount of H- and D-segregation, there is a pronounced effective difference in SANS intensities which cannot be explained by the different scattering lengths alone. However, the different sign of the latter quantity in combinations with an expected volume expansion within the hydride/deuteride region provides a reasonable explanation of the intensity difference observed. Knowing the amount of segregated H or D from gas volumetry and the dislocation density from electron microscopy the SANS results can be explained in a self consistent way. (C) 2001 Acta Materialia Inc. Published by Elsevier Science Ltd. All rights reserved
Nanoscale Motion of Soft Nanoparticles in Unentangled and Entangled Polymer Matrices
Full text linkWe have studied the motion of polyhedral oligomeric silsesquioxane (POSS) nanoparticles modified with poly(ethylene glycol) (PEG) arms immersed in PEG matrices of different molecular weight. Employing neutron spin echo spectroscopy in combination with pulsed field gradient (PFG) NMR we found the following. (i) For entangled matrices the center of mass mean square displacement (MSD) of the PEG-POSS particles is subdiffusive following a t0.56 power law. (ii) The diffusion coefficient as well as the crossover to Fickian diffusion is independent of the matrix molecular weight and takes place as soon as the center of mass has moved a distance corresponding to the particle radius—this holds also for unentangled hosts. (iii) For the entangled matrices Rubinstein’s scaling theory is validated; however, the numbers indicate that beyond Rouse friction the entanglement constraints appear to strongly increase the effective friction even on the nanoparticle length scale imposing a caveat on the interpretation of microrheological experiments. (iv) The oligomer decorated PEG-POSS particles exhibit the dynamics of a Gaussian star with an internal viscosity that rises with an increase of the host molecular weight
Effect of the salt-induced micellar microstructure on the nonlinear shear flow behavior of ionic cetylpyridinium chloride surfactant solutions
No full textThe shear flow dynamics of linear and branched wormlike micellar systems based on cetylpyridinium chloride and sodium salicylate in brine solution is investigated through rheometric and scattering techniques. In particular, the flow and the structural flow response are explored via velocimetry measurements and rheological and rheometric small-angle neutron scattering (SANS) experiments, respectively. Although all micellar solutions display a similar shear thinning behavior in the nonlinear regime, the experimental results show that shear banding sets in only when the micelle contour length L[over ̄] is sufficiently long, independent of the nature of the micellar connections (either linear or branched micelles). Using rheometric SANS, we observe that the shear banding systems both show very similar orientational ordering as a function of Weissenberg number, while the short branched micelles manifest an unexpected increase of ordering at very low Weissenberg numbers. This suggests the presence of an additional flow-induced relaxation process that is peculiar for branched systems
A Small-Angle Neutron Scattering Study of a Soft Model Nanofiller in an Athermal Melt
No full textWe present a detailed small-angle neutron scattering investigation of mixtures of poly(ethylene oxide) (PEO)/polyhedral oligomeric silsesquioxane (POSS) hybrids, a popular nanofiller, addressing the conformation of the model-grafted nanoparticles as well as their influence on the linear polymer matrix in which they are embedded. The nanofiller has a well-defined graft arm length and is monomolecular. Because of the identical chemical nature of the grafted arm and matrix chains, it can be considered as an ideal athermal mixture. We have introduced a random phase approximation approach with general application possibilities for other grafted nanofillers, combining the star-like and particle-like characteristics of the POSS nanofiller. The size of the nanofiller remained unaffected and Gaussian upon mixing with linear chains of various lengths, and no aggregation of the nanofiller was observed. This turns the POSS-based nanocomposite into an interesting model compound. The mixtures of PEO chains with the octafunctional PEO–POSS nanofiller were found to resemble those of a micellar system whereas within experimental uncertainty the radius of gyration of the embedding matrix remained basically unaltered despite some tendency toward shrinking
An interplay of small angle neutronscattering and rheological relaxation data in deformed polymer melts
No full textTube model approaches in lines and branched polymers from in situ neutron scattering experiments
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