Microstructure studies small-angle neutron scattering

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Nafion has been the subject of extensive characterization studies [1]. Its microstructure has been exhaustively studied by scattering methods, especially small angle X-ray scattering (SAXS) and small angle neutron scattering (SANS) [19-23]. Mechanical properties of Nafion as functions of temperature have been used to identify temperature-induced transitions [2,24—27]. Transport of protons and water has also been the subject of numerous studies over the past 25 years [28-34]. However, there has been limited progress in coimecting the chemical structure of Nafion to mechanical and transport properties, especially how these properties are altered due to environmental conditions. In this chapter, we will review recent studies of mechanical and transport properties of Nafion done under controlled conditions of water activity and temperature. 

In a previous study of fumed silica by mercury porosimetry (ref. 1), we established an inverse dependence of the powder compressibility k on applied pressure P, heralded by power-law differential volume vs pressure curves. Independent small-angle neutron scattering (SANS) measurements, undertaken to establish microstructure, indicated a decreasing zero-angle intensity, I(q- 0), with increasing sample compression. 

As in binary surfactant-water systems considered previously, two constraints on the geometry of the surfactant interface are active a local constraint, which is due to the surfactant molecular architecture, and a global constraint, set by the composition. These constraints alone are sufficient to determine the microstructure of the microemulsion. They imply that the expected microstructure must vary continuously as a function of the composition of tile microemulsion. Calculations show - and small-angle X-ray and neutron scattering studies confirm - that the DDAB/water/alkane microemulsions consist of a complex network of water tubes within the hydrocarbon matrix. As water is added to the mixture, the Gaussian curvature - and topology -decreases [41]. Thus the connectivity of the water networks drops (Fig. 4.20). 

Both small angle X-ray (SAXS) cind neutron scattering (SANS) are established techniques and their experimental application is similar. However, limitations on sample size, thickness and containment are much more restricted with X-rays because of absorption of radiation. One problem which can arise with neutrons is the subtraction of the flat incoherent contribution which can be quite large in the case of hydrogenous materials. This disadvantage can be partially offset by the possibility of using isotopic substitution. SANS is particularly powerful because the penetrating power of neutrons makes it possible to study material microstructure in the wet state. Instrumentally, both SAXS and SANS require a source of radiation, collimation system, sample containment and a detection system. 

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