Small-angle neutron scattering micelles

Cetyltrimethylammonium 4-vinylbenzoate (33) forms rod-like micelles that can be stabilized by radical polymerization. The resulting structure, was observed by small-angle neutron scattering to retain its original rod-like architecture and showed enhanced thermal stability and did not dissociate upon dilution. 

Time-resolved in situ Small Angle Neutron Scattering (SANS) investigations have provided direct experimental evidence for the initial steps in the formation of the SBA-15 mesoporous material, prepared using the non-ionic tri-block copolymer Pluronic 123 and TEOS as silica precursor. Upon time, three steps take place during the cooperative self-assembly of the Pluronic micelles and the silica species. First, the hydrolysis of TEOS is completed, without modifications of the Pluronic spherical micelles. Then, when silica species begin to interact with the micelles, a transformation from spherical to cylindrical micelles takes place before the precipitation of the ordered SBA-15 material. Lastly, the precipitation occurs and hybrid cylindrical micelles assemble into the two-dimensional hexagonal structure of SBA-15. 

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-... 

Thurn, A., Burchard, W., Niki, R. (1987a). Structure of casein micelles. I. Small-angle neutron scattering and light scattering from p- and K-casein. Colloid and Polymer Science, 265, 653-666. 

Bewersdorff HW, Frings B, Lindner P, Oberthuer RC (1986) The conformation of drag reducing micelles from small-angle-neutron-scattering experiments Rheol Acta 25 642... 

Fig. 3.2 Small-angle neutron scattering intensity as a function of wave vector magnitude for a rfPS-PB diblock forming micelles in PB, c = 5x l(T2gcm 3. Symbols, experimental results line, theoretical scattering profile for a uniform sphere (Selb et al. 1983).

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).

Whitmore and Noolandi (1985b) developed the self-consistent field theory to examine micellization in AB diblocks in a blend of AB diblock and A homopolymer solvent . The model was applied specifically to the case of PS-PB diblocks in PB homopolymer for comparison with the results of small-angle neutron scattering (SANS) experiment by Selb et al. (1983). This model is discussed in more detail in Section 3.4.2. 

The micelle formation process and structure can be described by thermodynamic functions (AG°mjc, AH°mjc, AS°mic), physical parameters (surface tension, conductivity, refractive index) or by using techniques such NMR spectroscopy, fluorescence spectroscopy, small-angle neutron scattering and positron annihilation. Experimental data show that the dependence of the aggregate nature, whether normal or reverse micelle is formed, depends on the dielectric constant of the medium (Das et al., 1992 Gon and Kumar, 1996 Kertes and Gutman, 1976 Ward and du Reau, 1993). The thermodynamic functions for micellization of some surfactants are presented in Table 1.1. 

Fig. 9 Density profiles of PEE-PSSH micelles for varying salt concentrations. The profiles were obtained by a combination of static and dynamic light scattering, small-angle neutron scattering and cryo-TEM [49]...

Measurement of characteristics of the emulsion droplets in concentrated media is indeed a difficult task. Some indirect methods have been used. The interfacial area and therefore the droplet size were determined by measuring the critical micelle concentration of miniemulsions [43]. Erdem et al. determined droplet sizes of concentrated miniemulsions via soap titration, which could be confirmed by CHDF measurements [44]. Droplet sizes without diluting the system can much better be estimated by small angle neutron scattering (SANS) measurements [23]. 

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