Polyelectrolyte Networks: Elasticity, Swelling, and the Violation of the Flory - Rehner Hypothesis

This paper discusses the elastic behavior of polyelectrolyte networks. The deformation behavior of single polyelectrolyte chains is discussed. It is shown that a strong coupling between interactions and chain elasticity exists. The theory of the complete crosslinked networks shows that the Flory - Rehner - Hypothesis (FRH) does not hold. The modulus contains contributions from the classical rubber elasticity and from the electrostatic interactions. The equilibrium degree of swelling is estimated by the assumption of a $c^{*}$-network.Comment: submitted to Computational and Theoretical Polymer Scienc

Stimuli response of polysoap hydrogels in aqueous solution and DC electric fields

Novel types of polysoap hydrogels based on hydrophobically-modified polyelectrolytes crosslinked with N,N-methylenebisacrylamide have been prepared by free radical polymerization at 70–80°C in aqueous solution with ammonium persulfate as initiator. Poly(diallylamine-co-N,N-dodecylmethyldiallylammonium bromide) (PDA-C12), poly(N-methyldiallyl-co-N,N-dodecylmethyldiallylammonium bromide) (PMDA-C12) both contain hydrophobic side chains with 12 carbon atoms. The swelling behavior of these polysoap hydrogels was studied by immersion of the gels in buffered solutions at various pHs and ionic strengths. It was found that the structure of the polysoap backbone influenced the pH-dependent swelling and deswelling. The swelling process is reversible after repeating cycles of swelling and deswelling induced by a change of pH in appropriate buffer solutions. SEM micrographs of polysoap gels indicate that the network structures are characterized by the presence of large open pores or small closed pores. The stimuli response of the polysoap gels in electric fields was also investigated. In a contact electric field, deswelling was observed at the anode side of the gels. In a non-contact electric field, the gels bend towards the anode. The gels can turn back to the original shape and bend toward the cathode with time when higher electric potentials are applied. These properties of the gels are related to both the change of osmotic pressure caused by mobile ions and by hydrophobic interactions.

Experimental kinetic study of transesterification of ethyl acetate with methanol catalyzed by gel and macroporous acidic ion exchange resins

The reaction kinetics of the liquid-phase transesterification of ethyl acetate with methanol have been investigated over a series of commercially available ion-exchange resins. Two morphology types of cross-linked polymer resins have been considered, i.e., a gel type (Lewatit K1221) and a macroporous type (Lewatit K2640, Lewatit K2629 and Amberlyst 15). The effect of the swelling of the resin, the initial reactant molar ratio (1:1 – 10:1) and the temperature (303.15 – 333.15 K) on the reaction kinetics was experimentally assessed. Lewatit K1221, the gel-type resin, outperformed the macroporous-type resins, despite its similar number of sulfonic acid sites. The resin’s swelling behavior, which can be related to its degree of cross-linking with divinylbenzene, was identified as the key parameter to explain differences in acid site accessibility between the considered resins and, hence, the observed transesterification kinetics. A fundamental kinetic model, accounting for the chemical elementary steps as well as for the physical swelling due to solvent absorption, was constructed to quantitatively assess the experimental observations. According to this model (1) all active sites are occupied by methanol in protonated form, (2) the esters undergo a proton exchange with the protonated methanol and (3) the reaction occurs through an Eley-Rideal mechanism with the surface reaction of protonated ethyl acetate with methanol from the bulk as the rate-determining step. The kinetic model was able to adequately describe the entire experimental data set. An activation energy amounting to 49 kJ mol-1 was obtained, irrespective of the resin. Also the affinity of each of the resins for the esters was found to be similar. The differences in catalytic activity between the considered resins are found back in the values for the rate coefficients and, hence, can be brought into relation with the active site accessibility. The latter is a factor 3 to 4 higher for gel-type resins compared to macroporous-type resins. An independent experimental assessment of the resins’ swelling behavior confirmed the more pronounced swelling of the gel-type compared to the macroporous-type resins

SWELLING AND COMPRESSIBILITY CHARACTERISTICS OF SOIL - BENTONITE MIXTURES

Understanding characteristics of soil mixtures lead to increasing the confidence level before applying such materials in the field. The outcomes of this study can provide insight into the swelling and the compressibility behavior of soil – bentonite mixtures, between non-swelling materials and swelling materials. A simple swell and compression laboratory test has been conducted for the purposes of this study. The result of this study indicated that the existence of bentonite in the soil mixtures influence the swelling behavior, which follows a hyperbolic curve model. Amount and size of nonswelling fraction affected the swelling and compressibility

Swelling and shrinking kinetics of a lamellar gel phase

We investigate the swelling and shrinking of L_beta lamellar gel phases composed of surfactant and fatty alcohol after contact with aqueous poly(ethylene-glycol) solutions. The height change $\Delta h(t)$ is diffusion-like with a swelling coefficient, S: $\Delta h = S \sqrt{t}$. On increasing polymer concentration we observe sequentially slower swelling, absence of swelling, and finally shrinking of the lamellar phase. This behavior is summarized in a non-equilibrium diagram and the composition dependence of S quantitatively described by a generic model. We find a diffusion coefficient, the only free parameter, consistent with previous measurements.Comment: 3 pages, 4 figures to appear in Applied Physics Letter

Sterols sense swelling in lipid bilayers

In the mimetic membrane system of phosphatidylcholine bilayers, thickening (pre-critical behavior, anomalous swelling) of the bilayers is observed, in the vicinity of the main transition, which is non-linear with temperature. The sterols cholesterol and androsten are used as sensors in a time-resolved simultaneous small- and wide angle x-ray diffraction study to investigate the cause of the thickening. We observe precritical behavior in the pure lipid system, as well as with sterol concentrations less than 15%. To describe the precritical behavior we introduce a theory of precritical phenomena.The good temperature resolution of the data shows that a theory of the influence of fluctuations needs modification. The main cause of the critical behavior appears to be a changing hydration of the bilayer.Comment: 11 pages, 7 ps figures included, to appear in Phys.Rev.

Film extrusion of sunflower protein isolate

Film extrusion of sunflower protein isolate (SFPI) was studied. The influence of die temperature (85 to 160°C), water and glycerol contents were investigated through appearance, mechanical and thermo-mechanical properties and swelling behavior in water of films. It was demonstrated that highest temperature, well above SFPI denaturation temperature in the compound, highest glycerol content (70 parts for 100 parts of SFPI) and medium water content (20 parts for 100 parts of SFPI) gave the most regular and smoothest film (as seen on SEM micrographs). Its ultimate tensile strength, Young’s modulus and strain at break were respectively: 3.2 MPa, 17.7 MPa and 73%. Soaked in water, its swelling was about 186% w/w but the film was quiet insoluble. Effect of temperature and plasticizer content were discussed in relation to the kinetic of SFPI denaturation. These first results are very promising for the development of biodegradable protein-based films