Polymers, gels solutions

Polymers in Solution. Polyacrylamide is soluble in water at all concentrations, temperatures, and pH values. An extrapolated theta temperature in water is approximately —40° C (17). Insoluble gel fractions are sometimes obtained owing to cross-link formation between chains or to the formation of imide groups along the polymer chains (18). In very dilute solution, polyacrylamide exists as unassociated coils which can have an eUipsoidal or beanlike stmcture (19). Large aggregates of polymer chains have been observed in hydrolyzed polyacrylamides (20) and in copolymers containing a small amount of hydrophobic groups (21). 

The enzyme can be immobilized on the electrode by several techniques (53). The simplest method, first used in 1962, is to trap an enzyme solution between the electrode surface and a semipermeable membrane. Another technique is to immobilize the enzyme in a polymer gel such as polyacrylamide which is coated on the electrode surface. Very thin-membrane films can be obtained by electropolymerization techniques (49,54,55) using polypyrrole, polyindole, or polyphenylenediamine films, among others. These thin films (qv) offer the advantage of improved diffusion of substrate and product that... 

Dissociation equilibriums in both electrolyte and polymer gels and the ionic concentration partition (Donnand potential) between solutions and polymer gels allow189 the relaxation-oxidation current to be obtained as a function of the perchlorate concentration ... 

Diffusion of flexible macromolecules in solutions and gel media has also been studied extensively [35,97]. The Zimm model for diffusion of flexible chains in polymer melts predicts that the diffusion coefficient of a flexible polymer in solution depends on polymer length to the 1/2 power, D N. This theoretical result has also been confirmed by experimental data [97,122]. The reptation theory for diffusion of flexible polymers in highly restricted environments predicts a dependence D [97,122,127]. Results of various... 

Perrin model and the Johansson and Elvingston model fall above the experimental data. Also shown in this figure is the prediction from the Stokes-Einstein-Smoluchowski expression, whereby the Stokes-Einstein expression is modified with the inclusion of the Ein-stein-Smoluchowski expression for the effect of solute on viscosity. Penke et al. [290] found that the Mackie-Meares equation fit the water diffusion data however, upon consideration of water interactions with the polymer gel, through measurements of longitudinal relaxation, adsorption interactions incorporated within the volume averaging theory also well described the experimental results. The volume averaging theory had the advantage that it could describe the effect of Bis on the relaxation within the same framework as the description of the diffusion coefficient. 

Altenberger, AR TirreU, M Dahler, JS, Hydrodynamic Screening and Particle Dynamics in Porous Media, SemidUute Polymer Solutions and Polymer Gels, Journal of Chemical Physics 84,5122, 1986. 

A derivatized hydroxyethylcellulose polymer gel exhibited excellent fluid-loss control over a wide range of conditions in most common completion fluids. This particular grated gel was compatible with the formation material and caused little or no damage to original permeability [1341]. Detailed measurements of fluid loss, injection, and regained permeability were taken to determine the polymer particulate s effectiveness in controlling fluid loss and to assess its ease of removal. Hydroxyethylcellulose can be etherified or esterified with long chain alcohols or esters. An ether bond is more stable in aqueous solution than is an ester bond [96]. 

Polymer gels and ionomers. Another class of polymer electrolytes are those in which the ion transport is conditioned by the presence of a low-molecular-weight solvent in the polymer. The most simple case is the so-called gel polymer electrolyte, in which the intrinsically insulating polymer (agar, poly(vinylchloride), poly(vinylidene fluoride), etc.) is swollen with an aqueous or aprotic liquid electrolyte solution. The polymer host acts here only as a passive support of the liquid electrolyte solution, i.e. ions are transported essentially in a liquid medium. Swelling of the polymer by the solvent is described by the volume fraction of the pure polymer in the gel (Fp). The diffusion coefficient of ions in the gel (Dp) is related to that in the pure solvent (D0) according to the equation ... 

T Momii, T Nose. Concentration-dependent collapse of polymer gels in solution of incompatible polymers. Macromolecules 22 1384-1389, 1989. 

All copolymers were prepared by solution polymerization, under adiabatic conditions, giving at least 99.9% conversions. The polymer gels were granulated and then dried at 90 °C to a residual water content of 10 to 12%. The active polymer content of each sample was calculated from the initial weight of the comonomers and the weight of the dried gel. Hydrolysis of the polymers was determined by conductometric titration to be less than 0.2% of the acrylamide charge. The molecular weight of the polymers was 8-10 million as determined by intrinsic viscosity measurements. 

The functionalized polymers have catalytic properties similar to those of their soluble analogues.1 A solution-like character is characteristic of polymer gels. As polymers become more highly cross-linked, they lose the solution-like character and their properties approach of those of inorganic solids. 

Concerning drug delivery, electrically erodible polymer gels for controlled release of drugs have been prepared, and a measured release rate of insulin has been observed under electrical stimulus [69]. A suspension of zinc insulin in a mixed solution of poly(ethyloxazoline) and PMAA was formed into a gel by decreasing the pH of the suspension. The obtained complex gel with 0.5 wt% of insulin was attached to a woven platinum wire cathode which was 1 cm away from the anode and immersed in 0.9% saline solution. When a stepped function of electrical current of 5 mA was applied to the insulin-loaded gel matrix, insulin was released in a stepwise manner up to a release of 70%. The insulin rate measured was 0.10 mg/h. 

The model of electric field-controlled artificial muscles has been described in 1972 [5], Fragala et al. fabricated an electrically activated artificial muscle system which uses a weakly acidic contractile polymer gel sensitive to pH changes. The pH changes are produced through electrodialysis of a solution. The response of the muscle as a function of pH, solution concentration, compartment size, certain cations, and gel fabrication has been studied. The relative change in length was about 10%, and the tensile force was 1 g/0.0025 cm2 under an applied electric field of 1.8 V and 10 mA/cm2. It took 10 min for the gel to shrink. 

Jeong and coworkers have reported peptide-based thermo-gelling systems using PEG-b-polyAla as an injectable cellular scaffold [315]. The polymer aqueous solution undergoes sol-gel transition as temperature increases. The fraction of the p-sheet structure of the poly Ala dictated the population and thickness of fibrous nanostructure in the hydrogel, which affected the proliferation and protein... 

There are three situations that appear to be relevant here. First, we may think of a solid polymer formed from the melt second, the much more compliant elastomers that initially come to mind when we think of rubber elasticity and third, polymer gels formed in polymer solutions. In each case the details of the physical chemistry of the macromolecules is crucial to the understanding of the structure that is formed. In this section we will concentrate on organic macromolecules because the rheology of these molecular systems is often the reason for their use. 

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