Neutral Hydrogels

To determine the crosslinking density from the equilibrium elastic modulus, Eq. (3.5) or some of its modifications are used. For example, this analysis has been performed for the PA Am-based hydrogels, both neutral [18] and polyelectrolyte [19,22,42,120,121]. For gels obtained by free-radical copolymerization, the network densities determined experimentally have been correlated with values calculated from the initial concentration of crosslinker. Figure 1 shows that the experimental molecular weight between crosslinks considerably exceeds the expected value in a wide range of monomer and crosslinker concentrations. These results as well as other data [19, 22, 42] point to various imperfections of the PAAm network structure. 

The change of chemical potential due to the elastic retractive forces of the polymer chains can be determined from the theory of rubber elasticity (Flory, 1953 Treloar, 1958). Upon equaling these two contributions an expression for determining the molecular weight between two adjacent crosslinks of a neutral hydrogel prepared in the absence of... 

Peppas and Merrill (1977) modified the original Flory-Rehner theory for hydrogels prepared in the presence of water. The presence of water effectively modifies the change of chemical potential due to the elastic forces. This term must now account for the volume fraction density of the chains during crosslinking. Equation (4) predicts the molecular weight between crosslinks in a neutral hydrogel prepared in the presence of water. 

Responsive polyelectrolyte hydrogels that have been used for controlled release systems include gels which are hydrophobic in their neutral state... 

Several theories have been proposed to calculate the molecular weight between crosslinks in a hydrogel membrane. Probably the most widely used of these theories is that of Flory and Rehner [5]. This theory deals with neutral polymer networks and assumes a Gaussian distribution of polymer chains and tetrafunctional crosslinking within the polymer network. 

It must be noted that Eqs. (35) and (36) are for the case in which the crosslinks in the polymer network were introduced in solution as with the Peppas-Merrill equation for neutral hydrogels and also that a Gaussian chain distribution is assumed. The complete equilibrium expressions accounting for the mixing, elastic-retractive, and ionic contributions to the chemical potential for anionic networks in the two cases described above are then... 

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