Scattering copolymers

PEO formed a surface while the hydrophobic carbosilane dendritic block was incorporated into the micelle core. Micellar characteristics were determined using fluorescence techniques and dynamic light scattering. Copolymers with a third-generation dendritic block could not be dispersed in water. 

Micellar structure has been a subject of much discussion [104]. Early proposals for spherical [159] and lamellar [160] micelles may both have merit. A schematic of a spherical micelle and a unilamellar vesicle is shown in Fig. Xni-11. In addition to the most common spherical micelles, scattering and microscopy experiments have shown the existence of rodlike [161, 162], disklike [163], threadlike [132] and even quadmple-helix [164] structures. Lattice models (see Fig. XIII-12) by Leermakers and Scheutjens have confirmed and characterized the properties of spherical and membrane like micelles [165]. Similar analyses exist for micelles formed by diblock copolymers in a selective solvent [166]. Other shapes proposed include ellipsoidal [167] and a sphere-to-cylinder transition [168]. Fluorescence depolarization and NMR studies both point to a rather fluid micellar core consistent with the disorder implied by Fig. Xm-12. 

Mortensen K 1996 Structural studies of PEO-PPO-PEO triblock copolymers, their micellar aggregates and mesophases a small-angle neutron scattering study J. Phys. Condens Matters A103-A104... 

Copolymers of vinyUdene chloride and methyl acrylate have been studied by x-ray techniques (75). For example, the long period (lamellar thickness) for an 8.5 wt % methyl acrylate copolymer was found to be 9.2 nm by smaH-angle x-ray scattering. The unit cell is monoclinic, with a = 0.686 and c = 1.247 nm by wide-angle x-ray scattering. 

The main experimental techniques used to study the failure processes at the scale of a chain have involved the use of deuterated polymers, particularly copolymers, at the interface and the measurement of the amounts of the deuterated copolymers at each of the fracture surfaces. The presence and quantity of the deuterated copolymer has typically been measured using forward recoil ion scattering (FRES) or secondary ion mass spectroscopy (SIMS). The technique was originally used in a study of the effects of placing polystyrene-polymethyl methacrylate (PS-PMMA) block copolymers of total molecular weight of 200,000 Da at an interface between polyphenylene ether (PPE or PPO) and PMMA copolymers [1]. The PS block is miscible in the PPE. The use of copolymers where just the PS block was deuterated and copolymers where just the PMMA block was deuterated showed that, when the interface was fractured, the copolymer molecules all broke close to their junction points The basic idea of this technique is shown in Fig, I. 

Another example of OTHdC application is the study of the association/ dissociation of copolymer micelles. Using the light-scattering technique, the... 

In this case, the elements of the crosslinked structure exhibit higher mobility, the permeability of the crosslinked structure depends on the degree of hydration. It should be noted that the pore size in hydrated crosslinked copolymers is determined by small-angle X-ray scattering or with the aid of electron microscopy using special methods of preparation for the CP samples [15],... 

Richards, R. W. Small Angle Neutron Scattering from Block Copolymers. Vol. 71, pp. 1 to 40. 

Experimentally, the stretching of block copolymer chains has been addressed in two ways by measuring L as a function of N, and by measuring the components of Rg of the block chains both parallel and perpendicular to the interface. The domain dimensions have been studied most extensively for styrene-isoprene and styrene-butadiene block copolymers X-ray and neutron scattering are the methods of choice. The predicted SSL scaling of L N2/3 has been reported for spheres, cylinders and lamellae [99,102-106], but not in all cases. For example, Bates et al. found N0 37 for styrene-butadiene spheres [100], and Hadziioannou and Skoulios observed N0 79 for styrene-isoprene lamellae [107], In the sphere case, kinetic limitations to equilibration were felt to be an important factor [100],... 

Brown, W Schillen, K Hvidt, S, Triblock Copolymers in Aqueous Solution Studied by Static and Dynamic Light Scattering and Oscillatory Shear Measurements. Influence of Relative Block Sizes, Journal of Physical Chemistry 96, 038, 1992. 

However, even homopolymer molecular weight aver calculated from GPC frequently do not agree with those from osmometry and li t scattering or for that matter with those from another set of GPC operating conchtions Copolymers... 

Branching in the polymer chain affects the relationship between retention and molecular weight.83 Universal calibration has been used with some success in branched polymers, but there are also pitfalls. Viscosimetry84-91 and other instrumental methods have proved to be useful. A computer simulation of the effects of branching on hydrodynamic volume and the detailed effects observable in GPC is available in the literature.92 93 In copolymer analysis, retention may be different for block and random copolymers, so universal calibration may be difficult. However, a UV-VIS detector, followed by a low-angle light-scattering (LALLS) detector and a differential... 

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