Techniques for studying block copolymers

In this section, a brief outline is given of the major methods used to study block copolymers, whether in the melt, solid or solution state and whether in bulk or 

Pioneering contact mode AFM studies by Meiners et ai. (1995) show that chemical sensitivity at the surface of thin polymer films can be achieved by measuring the microscopic friction and stiffness for glassy block copolymers. This provides invaluable information to complement topography on the nature of the block at the surface. 

Chapters 3 and 4 respectively. A good review of methods for the examination of thermal properties of polymers is provided by Thompson (1989). 

Laplace transformation of eqn 1.1 (often using the CONTIN program (Provencher 1982)) yields the distribution of relaxation times, A(t). The decay rates of the relaxation modes provide translational diffusion coefficients. 

In polymer solutions, DLS is used to determine the hydrodynamic radius of the constituent particles using the Stokes-Einstein equation 

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Other more exotic techniques have been employed to study block copolymer micelles. For example, Price and co-workers used ultramicroscopy (Chapter 1) to determine diffusion coefficients and hydrodynamic radii of diblocks in selective solvents (Price et al. 1979). 

The second example concerns the multidisciplinary study of the micelliz-ing block copolymer polystyrene-( -poly(2-vinylpyridine)-ft-poly(ethylene oxide) (PS-PVP-PEO), which shows a high tendency to aggregation and the formation of micellar clusters [88,89]. It shows the application of SRM for studying the mobility and structural details of different domains in micelle-like polymeric nanoparticles. The fluorescence technique reveals interesting features of studied systems that are hardly accessible by other techniques. Section 3.3 is devoted to the development of the methodology of the solvent relaxation technique for studying nanostructured self-assembling systems. 

Copolymerizations of benzvalene with norhornene have been used to prepare block copolymers that are more stable and more soluble than the polybenzvalene (32). Upon conversion to (CH), some phase separation of nonconverted polynorhornene occurs. Other copolymerizations of acetylene with a variety of monomers and carrier polymers have been employed in the preparation of soluble polyacetylenes. Direct copolymeriza tion of acetylene with other monomers (33—39), and various techniques for grafting polyacetylene side chains onto solubilized carrier polymers (40—43), have been studied. In most cases, the resulting copolymers exhibit poorer electrical properties as solubiUty increases. 

ADMET is quite possibly the most flexible transition-metal-catalyzed polymerization route known to date. With the introduction of new, functionality-tolerant robust catalysts, the primary limitation of this chemistry involves the synthesis and cost of the diene monomer that is used. ADMET gives the chemist a powerful tool for the synthesis of polymers not easily accessible via other means, and in this chapter, we designate the key elements of ADMET. We detail the synthetic techniques required to perform this reaction and discuss the wide range of properties observed from the variety of polymers that can be synthesized. For example, branched and functionalized polymers produced by this route provide excellent models (after quantitative hydrogenation) for the study of many large-volume commercial copolymers, and the synthesis of reactive carbosilane polymers provides a flexible route to solvent-resistant elastomers with variable properties. Telechelic oligomers can also be made which offer an excellent means for polymer modification or incorporation into block copolymers. All of these examples illustrate the versatility of ADMET. 

Recent developments in polymer chemistry have allowed for the synthesis of a remarkable range of well-defined block copolymers with a high degree of molecular, compositional, and structural homogeneity. These developments are mainly due to the improvement of known polymerization techniques and their combination. Parallel advancements in characterization methods have been critical for the identification of optimum conditions for the synthesis of such materials. The availability of these well-defined block copolymers will facilitate studies in many fields of polymer physics and will provide the opportunity to better explore structure-property relationships which are of fundamental importance for hi-tech applications, such as high temperature separation membranes, drug delivery systems, photonics, multifunctional sensors, nanoreactors, nanopatterning, memory devices etc. 

The technique of self-nucleation can be very useful to study the nucleation and crystallization of block copolymers that are able to crystallize [29,97-103]. Previous works have shown that domain II or the exclusive self-nucleation domain disappears for systems where the crystallizable block [PE, PEO or poly(e-caprolactone), PCL] was strongly confined into small isolated MDs [29,97-101]. The need for a very large number of nuclei in order to nucleate crystals in every confined MD (e.g., of the order of 1016 nuclei cm 3 in the case of confined spheres) implies that the amount of material that needs to be left unmolten is so large that domain II disappears and annealing will always occur to a fraction of the polymer when self-nucleation is finally attained at lower Ts. This is a direct result of the extremely high number density of MDs that need to be self-nucleated when the crystallizable block is confined within small isolated MDs. Although this effect has been mainly studied in ABC triblock copolymers and will be discussed in Sect. 6.3, it has also been reported in PS-fc-PEO diblock copolymers [29,99]. 

The more recently developed cryo-TEM technique has started to be used with increasing frequency for block copolymer micelle characterization in aqueous solution, as illustrated by the reports of Esselink and coworkers [49], Lam et al. [50], and Talmon et al. [51]. It has the advantage that it allows for direct observation of micelles in a glassy water phase and accordingly determines the characteristic dimensions of both the core and swollen corona provided that a sufficient electronic contrast is observed between these two domains. Very recent studies on core-shell structure in block copolymer micelles as visualized by the cryo-TEM technique have been reported by Talmon et al. [52] and Forster and coworkers [53]. In a very recent investigation, cryo-TEM was used to characterize aqueous micelles from metallosupramolecular copolymers (see Sect. 7.5 for further details) containing PS and PEO blocks. The results were compared to the covalent PS-PEO counterpart [54]. Figure 5 shows a typical cryo-TEM picture of both types of micelles. 

Covalently connecting two incompatible polymers at their ends leads to a fascinating class of self-assembling materials [1]. Block copolymers constitute a well-studied and well-documented set of nanostructured hybrid materials [2], Many synthetic techniques are available for generating AB diblock, ABA triblock, ABC triblock and even more complicated block architectures [3,4], Furthermore, the thermodynamics governing the self-assembly... 

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