Photon correlation

The scattering techniques, dynamic light scattering or photon correlation spectroscopy involve measurement of the fluctuations in light intensity due to density fluctuations in the sample, in this case from the capillary wave motion. The light scattered from thermal capillary waves contains two observables. The Doppler-shifted peak propagates at a rate such that its frequency follows Eq. IV-28 and... 

Dunn C M, Robinson B FI and Leng F J 1990 Photon-correlation spectroscopy applied to the size characterization of water-in-oil microemulstion systems stabilized by aerosol-OT effect of change in the counterion Spectrochim. Acta. A 46 1017... 

Zulauf M and Eicke FI 1979 Inverted micelles and microemulsions in the ternary system Fl20/aerosol-OT-isoctane as studied by photon correlation spectroscopy J. Phys. Chem. 83 480... 

Photon Correlation Spectroscopy. Photon correlation spectroscopy (pcs), also commonly referred to as quasi-elastic light scattering (qels) or dynamic light scattering (dls), is a technique in which the size of submicrometer particles dispersed in a Hquid medium is deduced from the random movement caused by Brownian diffusion motion. This technique has been used for a wide variety of materials (60—62). 

R. Pecora, ed.. Dynamic Eight S cattering Applications of Photon Correlation Spectroscopy, Plenum Press, New York, 1985. 

Zeta potential Photon correlation Spectroscopy Zeta Plus, Micromeretics, Zeta sizer Malvern, Nicomp, Brookhaven, Goulter, Photol 0.001-30 im 0.1-1 lm... 

A very similar effect of the surface concentration on the conformation of adsorbed macromolecules was observed by Cohen Stuart et al. [25] who studied the diffusion of the polystyrene latex particles in aqueous solutions of PEO by photon-correlation spectroscopy. The thickness of the hydrodynamic layer 8 (nm) calculated from the loss of the particle diffusivity was low at low coverage but showed a steep increase as the adsorbed amount exceeded a certain threshold. Concretely, 8 increased from 40 to 170 nm when the surface concentration of PEO rose from 1.0 to 1.5 mg/m2. This character of the dependence is consistent with the calculations made by the authors [25] according to the theory developed by Scheutjens and Fleer [10,12] which predicts a similar variation of the hydrodynamic layer thickness of adsorbed polymer with coverage. The dominant contribution to this thickness comes from long tails which extend far into the solution. 

Photochemical cage 80, 82 Photon-correlation spectroscopy 141 Photoresponsive polyelectrolytes 54... 

Another largely unexplored area is the change of dynamics due to the influence of the surface. The dynamic behavior of a latex suspension as a model system for Brownian particles is determined by photon correlation spectroscopy in evanescent wave geometry [130] and reported to differ strongly from the bulk. Little information is available on surface motion and relaxation phenomena of polymers [10, 131]. The softening at the surface of polymer thin films is measured by a mechanical nano-indentation technique [132], where the applied force and the path during the penetration of a thin needle into the surface is carefully determined. Thus the structure, conformation and dynamics of polymer molecules at the free surface is still very much unexplored and only few specific examples have been reported in the literature. 

Up to now it has been tacitly assumed that each molecular motion can be described by a single correlation time. On the other hand, it is well-known, e.g., from dielectric and mechanical relaxation studies as well as from photon correlation spectroscopy and NMR relaxation times that in polymers one often deals with a distribution of correlation times60 65), in particular in glassy systems. Although the phenomenon as such is well established, little is known about the nature of this distribution. In particular, most techniques employed in this area do not allow a distinction of a heterogeneous distribution, where spatially separed groups move with different time constants and a homogeneous distribution, where each monomer unit shows essentially the same non-exponential relaxation. Even worse, relaxation... 

Patterson, G. D. Photon Correlation Spectroscopy of Bulk Polymers. Vol. 48, pp. 125-159. 

Figure 12.10 Typical time traces of (a) emission intensityand (b) lifetime, measured from a single DMPBI nanocrystal, (c) Photon correlation histogram obtained from the time trace of the emission intensity (a). The lifetimes were obtained by fitting a single exponential function to the decay curves constructed for every 2000...

Huve, P., Verrecchia, T., Bazile, D., Vauthier, C., and Couvreur, C., Simultaneous use of size exclusion chromatography and photon correlation spectroscopy for the characterization of poly(lactic acid) nanoparticles, /. Chromatogr. A, 675, 129, 1994. 

Various techniques and equipment are available for the measurement of particle size, shape, and volume. These include for microscopy, sieve analysis, sedimentation methods, photon correlation spectroscopy, and the Coulter counter or other electrical sensing devices. The specific surface area of original drug powders can also be assessed using gas adsorption or gas permeability techniques. It should be noted that most particle size measurements are not truly direct. Because the type of equipment used yields different equivalent spherical diameter, which are based on totally different principles, the particle size obtained from one method may or may not be compared with those obtained from other methods. 

K Thode, RH Muller, M Kresse. Two-time window and multiangle photon correlation spectroscopy size and zeta potential analysis—highly sensitive rapid assay for dispersion stability. J Pharm Sci 89 1317-1324, 2000. 

Zulauf, M and Eicke, H.F. "Inverted Micelles and Microemulsions in the Ternary System H20/Aerosol OT/Isooctane as Studied by Photon Correlation Spectroscopy," J. Phvs. Chem.. 1979, 82(4), 480 486. 

Obviously, in the case of PS these discrepancies are more and more reduced if the probed dimensions, characterized by 2ti/Q, are enlarged from microscopic to macroscopic scales. Using extremely high molecular masses the internal modes can also be studied by photon correlation spectroscopy [111,112], Corresponding measurements show that - at two orders of magnitude smaller Q-values than those tested with NSE - the line shape of the spectra is also well described by the dynamic structure factor of the Zimm model (see Table 1). The characteristic frequencies QZ(Q) also vary with Q3. Flowever, their absolute values are only 10-15% below the prediction. 

Figure 17 Molar mass distributions of polystyrene in ethyl acetate obtained by dynamic light scattering (photon correlation spectroscopy, PCS) and TDFRS with short and long exposure time tp. The dashed curves represent the distribution as determined by SEC. Reproduced with permission from Rossmanith and Kohler [107]. Copyright 1996 American Chemical Society.

PVA and TaM -for the 88%-hydrolyzed PVA. The same dependence was found for the adsorbed layer thickness measured by viscosity and photon correlation spectroscopy. Extension of the adsorption isotherms to higher concentrations gave a second rise in surface concentration, which was attributed to multilayer adsorption and incipient phase separation at the interface. The latex particle size had no effect on the adsorption density however, the thickness of the adsorbed layer increased with increasing particle size, which was attributed to changes in the configuration of the adsorbed polymer molecules. The electrolyte stability of the bare and PVA-covered particles showed that the bare particles coagulated in the primary minimum and the PVA-covered particles flocculated in the secondary minimum and the larger particles were less stable than the smaller particles. 

Thickness of the Adsorbed PVA Layer. The thickness of the adsorbed PVA layer (6) was measured using two independent methods capillary viscometry and photon correlation spectroscopy. 

Effect of PVA Molecular Weight on Adsorbed Layer Thickness. Figure 4 shows the variation of reduced viscosity with volume fraction for the bare and PVA-covered 190nm-size PS latex particles. For the bare particles, nre(j/ is independent of and the value of the Einstein coefficient is ca. 3.0. For the covered particles, rired/ t increases linearly with tp. Table IV gives the adsorbed layer thicknesses calculated from the differences in the intercepts for the bare and covered particles and determined by photon correlation spectroscopy, as well as the root-mean-square radii of gyration of the free polymer coil in solution. The agreement of the adsorbed layer thicknesses determined by two independent methods is remarkable. The increase in adsorbed layer thickness follows the same dependence on molecular weight as the adsorption density, i.e., for the fully hydrolyzed PVA s and... 

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