Small-angle neutron scattering solutions Micelles

Finally, we have designed and synthesized a series of block copolymer surfactants for C02 applications. It was anticipated that these materials would self-assemble in a C02 continuous phase to form micelles with a C02-phobic core and a C02-philic corona. For example, fluorocarbon-hydrocarbon block copolymers of PFOA and PS were synthesized utilizing controlled free radical methods [104]. Small angle neutron scattering studies have demonstrated that block copolymers of this type do indeed self-assemble in solution to form multimolecular micelles [117]. Figure 5 depicts a schematic representation of the micelles formed by these amphiphilic diblock copolymers in C02. Another block copolymer which has proven useful in the stabilization of colloidal particles is the siloxane based stabilizer PS-fr-PDMS [118,119]. Chemical... 

Regioselective crosslinking of the core domain of cylindrically shaped, wormlike micelles composed of poly[(butadiene)45-b-(ethylene oxide)55] and assembled in aqueous solution at < 5% block copolymer concentrations, was performed using radical coupling of the double bonds throughout the poly(butadiene) phase [27] (Figure 6.3b). This resulted in a 13% reduction in the core diameter, from 14.2 to 12.4 nm, as measured by small-angle neutron scatter-... 

Fig. 4.1 Top schematic illustration of micellar phases formed by the Pluronic copolymer P85 (PE 026PP0i9 PEO,6) with increasing temperature. Bottom small-angle neutron scattering patterns from sheared solutions in D20 of this copolymer (25wt%). The three columns (left-right) correspond to a liquid spherical micelle phase at 25 °C, a cubic phase of spherical micelles at 27 °C and a hexagonal phase of rod-like micelles at 68 °C (Mortensen 1993a).

The pH-induced micellization of a DMAEMA-6-DEAEMA diblock copolymer has been studied in detail using dynamic light scattering, small-angle neutron scattering, and fluorescence spectroscopy [166], The DMAEMA constitutes the corona of the micelle, whereas the DEAEMA forms the core. Pyrene was used as a probe to determine the nature of the DEAEMA blocks. It was shown that the hydrophobicity of the micellar cores increased progressively as the solution pH was adjusted from pH 7 to 9. In the presence of an electrolyte, it was possible to observe both individual chains (unimers) and micelles under certain conditions. The critical micellization pH depended on both the copolymer concentration and also the background electrolyte concentration. 

Both small-angle X-ray scattering (SAXS) and small-angle neutron scattering (SANS) have been used for obtaining detailed structural information about macromolecular species such as micelles or polymers in supercritical solutions. A variety of different microstructures have been identified in SCFs. In addition, changes in the fluid density have been shown to not only affect the primary structure, but also the secondary structure involving the spatial distribution of micelles or polymers in the continuous-phase solvent. This can have dramatic effects on reaction rates and pathways. 

Structural characterization of block copolymer aggregates by dynamic and static light scattering (DLS and SLS) in combination with small angle neutron scattering (SANS) at variable ionic strength and pH in the solution enables one to discriminate between frozen and dynamic (equilibrium) micelles. In particular, SANS provides direct information about the core size and shape because of relatively low scattering density of the corona. 

Even in dilute solutions they associate (49, 50). Published sizes of the micelles vary from 2 to 4 run. Sophisticated analytical techniques such as small-angle X-ray diffraction (SAXS), small-angle neutron scattering (SANS), and NMR were used to study the asphaltene particle or micelle sizes (51). MacKay (15) reported that a MWtof 10,000 g/mol would correspond to a 2 to 4-nm cluster. This is very much smaller than a 1-pm water droplet, and considered to be 1/100 to 1/1000 the droplet diameter. This topic is worthy of a review on its own. However, the colloidal properties of asphaltenes, micelles, and... 

In Table 1 we present the Zp values determined in THF and two different THE/DME mixtures. These values, on the order of 1 rm, are comparable to those reported by Discher and coworkers [38,70] and by Bates and coworkers [71,72] for PEO-PI cylindrical micelles with a core diameter of 20 nm in water. Here PEG denotes poly(ethylene oxide). Bates and coworkers deduced their values of Zp from small-angle neutron scattering experiments, whereas Discher and coworkers determined the Zp values using fluorescence microscopy. The fact that the Zp values that we determined from viscometry are comparable to those of the PEO-PI cyUndrical micelles with similar core diameters again suggests the validity of the YFY theory in treating the nanofiber viscosity data. This study demonstrates that block copolymer nanofibers have dilute solution properties similar to those of semi-flexible polymer chains. 

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