Preparation, characterization, solution properties and rheological behaviour of polyacrylamide

In this report a survey is given on structure and properties of polyacrylamide homopolymers (PAAm) in solution. However the review is restricted to all those papers, where a molecular characterization of the polymers has been achieved as a basis to correlate this fundamental information with applicational properties. Different polymerization methods are summarised in brief, the preparation and solution structure of long chain branched polyacrylamides as well as chemical modification reactions of linear PAAm are also mentioned. A number of experimental characterization methods (GPC, ultracentrifugation, intrinsic viscosity, and light scattering measurements) are described with special emphasis on the difficulties of the different procedures including some proposals for properly designed experimental techniques. The state of solution is discussed in view of experimental data obtained with different solvents. Moreover viscosity constant o is calculated for aqueous solution and the unperturbed dimensions are estimated. All available data on cross correlations (e.g. [η] - M, S0 - M, 12 - M) are collected with the intention to give a survey of established relations and, comparing the given relationships, to suggest the reliable ones of them. The phenomenon of long-term viscosity decrease of aqueous PAAm solutions has been investigated and discussed with regard to its molecular origin. The viscoelastic properties are discussed in dependence on molecular weight, concentration, solvent quality, and shear rate (⩽106 · s−1). Based on these data a simple equation was developed oped for the η0-c-M relationship, which can be applied to other polymer systems as well. It is further described that the elastic nature (first normal stress difference) may overwhelm the viscous nature (shear stress) at relatively low shear rates. This high elasticity can cause deviation from laminar flow conditions. Moreover, it can be demonstrated — based on instationary measurements as well as the comparison of steady shear flow with dynamic rheology — that energetic interactions (H-bonds) strongly influence the rheological behaviour.

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