Macroscale morphologies

Self-organization of amphiphilic (co)polymers has resulted in assemblies such as micelles, vesicles, fibers, helical superstructures, and macroscopic tubes [174, 175]. These nanoscale to macroscale morphologies are of interest in areas ranging from material science to biology [176]. Stimuli-responsive versions of these assemblies are likely to further enhance their scope as smart materials. Thermo- or pH-sensitive polymer micelles [177] and vesicles [178] have been reported in which the nature of the functionality at the corona changes in response to the stimulus. Some attention has been also paid to realize an environment-dependent switch from a micelle-type assembly with a hydrophilic corona to an inverted micelle-type assembly with a lipophilic corona [179]. 

Self-assembly is essentially chemical fabrication. Like macroscale fabrication techniques, self-assembly allows a great deal of design flexibility in that it affords the opportunity to prepare materials with custom shapes or morphologies. The advantages of self-assembly include an increased level of architecture control and access to types of functionality unobtainable by most other types of liquid-phase techniques. For example, it has been demonstrated that materials with nonlinear optical properties (e.g., second harmonic generation), which require noncen-trosymmetric structures, can be self-assembled from achiral molecules. 

Recently reported meso- and macroscale self-assembly approaches conducted, respectively, in the presence of surfactant mesophases [134-136] and colloidal sphere arrays [137] are highly promising for the molecular engineering of novel catalytic mixed metal oxides. These novel methods offer the possibility to control surface and bulk chemistry (e.g. the V oxidation state and P/V ratios), wall nature (i.e. amorphous or nanocrystalline), morphology, pore structures and surface areas of mixed metal oxides. Furthermore, these novel catalysts represent well-defined model systems that are expected to lead to new insights into the nature of the active and selective surface sites and the mechanism of n-butane oxidation. In this section, we describe several promising synthesis approaches to VPO catalysts, such as the self-assembly of mesostructured VPO phases, the synthesis of macroporous VPO phases, intercalation and pillaring of layered VPO phases and other methods. 

Looking back, the only unequivocal membrane improvement, in spite of all these efforts, has been the reduction of thickness from 200 jjim in 1995 to <50 (jun in 2005. In terms of chemical or morphological modifications at the microstructural level, no definite recommendations could be discerned so far. The focus of the works reviewed herein has been exploring the fundamental relations between micromorphology and transport from micro- to macroscales for prototypical polymer electrolyte membranes and the understanding of their major principles of operation. 

As the properties of materials are cJosely related to their structures, the realization of a material with certain properties can be achieved through stmcture control. The stmcture of ceramic materials, however, consists of many types of microstructural elements sucdi as particJes, grains, pores, defects, fibers, layers, and interfaces. These microstmctural elements can be classified by size into four scale levels (i) atomic-molecular scale (ii) nanoscale (iii) microscale, and (iv) macroscale, as shown in Figure 8.1. Besides their physical and chemical nature, other features of these elements including their morphology, configuration, distribution, and orientation are also important. It is obvious, therefore, that there are many factors which can control the structure of materials - not only the types of the elements, but also their features. 

Voitko, K.V., Whitby, R.L.D., Gun ko, VM. et al. 2011. Morphological and structural features of nano- and macroscale carbons affecting hydrogen peroxide decomposition in aqueous medium. J. Colloid Interface Sci. 361 129-136. 

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