Collapsing-swelling behavior

The swelling behavior of hydrogels in solutions of multivalent ions capable to associate with the network-fixed charges, e.g., Cu2+, substantially differs from that described above, viz. the collapse of gels takes place [107]. As a result of this... 

Some gels were synthesized which underwent the phase transition twice as the solvent composition was monotonically varied from 0% to 100%. Figure 30 shows the swelling behaviors of NIPA (open circles) and acrylamide (solid circles) gels in a mixture of dimethylsulfoxide (DMSO) and water [24]. When the DMSO concentration was lower than 33%, the NIPA gel was slightly swollen. Above 33% DMSO, a discrete transition to a collapsed state occurred. However, the gel showed a discontinuous re-swelling at 90%. Such reentrant behavior has also been observed when temperature or pH were used as variables. 

We present a review of theoretical and experimental results on the swelling behavior and collapse transition in polymer gels obtained by our group at Moscow State University. The main attention is paid to polyelectrolyte networks where the most important factor is additional osmotic pressure created by mobile counter ions. The influence of other factors such as condensation of counter ions, external mechanical force, the mixed nature of low-molecular solvents, interaction of network chains with linear macromolecules and surfactants etc. is also taken into account Experimental results demonstrate a good correlation with theoretical analysis. 

The first quantitative theory of the reentrant collapse was developed in Ref. [49], The theory explained the phenomenon of the simple reentrant collapse which was observed in Refs. [14, 41]. A more general theory of swelling and collapse of charged networks in the binary solvent was developed in Ref. [31] and described in Sect. 2.4.1. We have seen that one of the most essential features of the swelling behavior in mixed solvents is a redistribution of solvent molecules within the network giving a different solvent composition in the gel and the external solution. This redistribution is more pronounced for the collapsed gel, because the probability of contacts of the molecules of the solvent with polymer links in the collapsed gel is higher than in the swollen gel. 

The swelling behavior of poly(N-isopropylacrylamide) has been studied extensively [18,19]. It has been shown that this gel has a lower critical point due to the hydrophobic interaction. Such a swelling curve is schematically illustrated in Fig. 9. The gel is swollen at a lower temperature and collapses at a higher temperature if the sample gel is allowed to swell freely in water. The volume of the gel changes discontinuously at 33.6°C. The swelling curves obtained in this way correspond to the isobar at zero osmotic pressure. On the other hand, the friction coefficient is measured along the isochore, which is given in Fig. 9,... 

To determine the feasibility of this gel process, we studied various gels to elucidate their swelling behavior. We were concerned about the swelling kinetics, the conditions for swelling or collapse, the effect of gel composition on swelling, and the size of molecules which are excluded from the gel. There investigations are the focus of the following sections. 

Fig. 9 The polymer-tethered lipid monolayer (a) can swell by the up-take of significant amounts of water (b) surface-plasmon optical evidence of the swelling behavior of a polymer-cushioned monolayer by the exposure to air of different humidity (% relative humidity as indicated). Upon exposure to dry air the tethered monolayer collapses to its water-free thickness (however, can swell again if exposed to humid air (not shown))...

The temperature-dependent swelling behavior of the pol mier layers can also be measured by optical microscopy. Spin-coated and photo cross-linked polymer films on a Si wafer are swollen in cold water, and then the layer thickness is observed while successively increasing the bath temperature. The swelling ratio at a certain temperature is determined by the ratio of the layer thickness in the swollen/collapsed state at that temperature and the thickness in the dry state [31]. 

Another promising class of hydrogels that exhibit responsive behavior is complexing hydrogels. Osada studied complex formation in PMAA hydrogels (Osada, 1980). In acidic media, the PMAA membranes collapsed in the presence of linear PEG chains due to the formation of interpolymer complexes between the PMAA and PEG. The gels swelled when placed in... 

The properties of both organic matter and clay minerals may affect the release of contaminants from adsorbed surfaces. Zhang et al. (1990) report that desorption (in aqueous solution) of acetonitrille solvent from homoionic montmorillonite clays is reversible, and hysteresis appears to exist except for K+-montmorillonite. This behavior suggests that desorption may be affected by the fundamental difference in the swelling of the various homoionic montmorillonites, when acetonitrile is present in the water solution. During adsorption, it was observed that the presence of acetonitrile affects the swelling of different homoionic clays. At a concentration of 0.5 M acetonitrile in solution, the layers of K+-montmorillonite do not expand as they would in pure water, while the layers of Ca +- and Mg +-montmorillonite expand beyond a partially collapsed state. The behaviors of K+-, Ca +-, and Mg +-montmorillonite are different from the behavior of the these clays in pure water. Na+-montmorillonite is not affected by acetonitrile presence in an aqueous solution. 

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