Polymers structure complexity sample sizes

The presently most popular approach to two-dimensional polymer HPLC avails partial or preferably full suppression of the molar mass effect in the Id column so that the complex polymer or complex polymer system is separated mainly or even exclusively according to chemical structure or physical architecture of macromolecules occuring in sample. Appropriate coupled methods of polymer HPLC are to be applied to this purpose (compare section 11.8). In the 2d separation column - it is usually SEC - the fractions from the Id column are further discriminated according to their molecular size. In other words, fractions obtained in the first-dimension column are separated in the self-existent second-dimension column, which applies distinct separation mechanism(s). Only exceptionally SEC... 

The significant intrinsic limitation of SEC is the dependence of retention volumes of polymer species on their molecular sizes in solution and thus only indirectly on their molar masses. As known (Sections 16.2.2 and 16.3.2), the size of macromolecnles dissolved in certain solvent depends not only on their molar masses but also on their chemical structure and physical architecture. Consequently, the Vr values of polymer species directly reflect their molar masses only for linear homopolymers and this holds only in absence of side effects within SEC column (Sections 16.4.1 and 16.4.2). In other words, macromolecnles of different molar masses, compositions and architectures may co-elute and in that case the molar mass values directly calculated from the SEC chromatograms would be wrong. This is schematically depicted in Figure 16.10. The problem of simultaneous effects of two or more molecular characteristics on the retention volumes of complex polymer systems is further amplifled by the detection problems (Section 16.9.1) the detector response may not reflect the actual sample concentration. This is the reason why the molar masses of complex polymers directly determined by SEC are only semi-quantitative, reflecting the tendencies rather than the absolute values. To obtain the quantitative molar mass data of complex polymer systems, the coupled (Section 16.5) and two (or multi-) dimensional (Section 16.7) polymer HPLC techniques must be engaged. 

In this book, an explanation of capacitive behaviour in similar and comparable systems is not directly possible with constant-phase elements because such a comparison is only possible if n values are equal, particularly in the study of surfaces covered with polymer coatings where a unification of the envisaged parameters is necessary. The impedances measured match with a relatively large amount of samples, of which the structure can be complex, showing many sources of non-idealities (e.g. variations in thickness of the membrane, pore size and pore density42 7). A good indication if such non-idealities occur can be found in the values of n. If they are not comparable, non-idealities occur. 

---