Quantitative analysis on swelling behavior of HSMA/PVA IPN ionic gels under electric field

In order to explain the electric response of HSMA/PVA IPN ionic gel, polyion concentration (0 and/or interaction parameter (x_ij) between gel and water are used, which were previouslydetermined elsewhere by comparing swelling behaviours in the mixed solvents with Tanaka’s theory [1], Ionic polymer gel separated from the electrodes exhibits exponential responses when the electric field is applied or stopped, where the characteristic times for swelling and shrinking and equilibrium swelling ratio are successfully correlated with polyion concentration or interaction parameter. In addition, the strength of field is also an important factor to determine the overall responses. The direction of gel with respect to the electric field is also considered and optimum size was apparent to show maximum swelling.     

Estimation of viscosities of mixed polymer solutions

A semiempirical model for estimation of viscosities of concentrated polymer solutions¹ can be applied to mixtures of polymers in a common solvent. The data required for estimation of mixture viscosity are: solvent viscosity, polymer molecular weight, density, concentration, and intrinsic viscosity in the particular solvent. Calculated and experimental viscosities agree to within a few per cent for the relatively nonpolar systems for which comparative data are available. The model does not appear to be adequate for mixtures in which there are extensive hydrogen-bonding interactions. Results of the new model are equivalent to those of an empirical equation² reported to be effective for fairly concentrated binary polymer mixtures. Specific interactions between polymeric solutes can be conveniently assessed by comparing measured mixture viscosity to that calculated from the model presented. It is not clear, however, that such assessments have any fundamental significance, since the interactions which are calculated depend on the assumptions inherent in the estimation of the “ideal” mixture viscosity. The same reservations apply to other models which have been proposed for this purpose.     

Determination of intrinsic viscosity of polyelectrolyte solutions

Intramolecular hydrodynamic contribution η_intra/C to the reduced viscosity η_SP/C of polyelectrolyte solutions is derived as a function of polymer concentration C by separating the theoretically calculated intermolecular electrostatic contribution η_inter/C from the observed reduced viscosity, assuming an additivity, η_SP/C=η_intra/C+η_inter/C. The resulting intramolecular part η_intra/C reflects nearly the net effect of the polyion conformation; it increases monotonously with decreasing polymer concentration and levels off to a constant in sufficiently dilute concentrations. The leveling-off value of η_intra/C corresponds to the intrinsic viscosity [η]. From the estimated values of [η], the ionic strength I dependence of the polyion conformation has been visualized, resulting in a similarity between two relations, η_intra/C vs. C and [η] vs. I.     

Colloid‐Enhanced Ultrafiltration of Chlorophenols in Wastewater: Part V. Simultaneous Removal of a Chlorophenol and a Metal Ion

Abstract

Polyelectrolyte micellar‐enhanced ultrafiltration (PE‐MEUF) is a separation process to remove target solutes from water using a mixture of a surfactant and an oppositely charged polyelectrolyte as a colloid. An organic solute and a metal cation can simultaneously associate with the colloid, which is subsequently ultrafiltered from solution. An organic solute solubilizes in the surfactant micelle‐like aggregates whereas an inorganic cation binds onto the oppositely charged polyion chains. The solution is then passed through the membrane having pore sizes small enough to block the passage of the surfactant‐polymer aggregates. In this work, PE‐MEUF has been applied to mixtures containing dichlorophenol (DCP) and magnesium ion (Mg²⁺), using cetylpyridinium chloride (CPC) and sodium poly(styrenesulfonate) (PSS) mixtures. It was observed that the presence of Mg²⁺ does not affect DCP rejection. The [CPC] to [PSS] ratio and colloid concentration have a significant effect on both DCP and Mg²⁺ rejections. Increased ionic strength from added salt increases the gel point (colloid concentration at which flux is zero). The viscosity of the colloid solution is inversely related to the gel point.     

On the stiffness of the welan chain

Welan, purified as its sodium salt from unpasteurised culture broth, was analyzed by dilute aqueous viscometry. Measurements in water and at low ionic strength were carried out to evaluate the charge effect on intrinsic viscosity. The value of intrinsic viscosity at low ionic strength, determined by the isoionic dilution method, is close to that obtained at higher salt concentrations. A comparison is made among the stiffness parameters determined by different treatment of experimental data. The results agree with previous reports on the weak polyelectrolyte character and high stiffness of the welan chain. Received: 11 July 1996/Revised version: 21 October 1996/Accepted: 22 October 1996     

Water-soluble copolymers. VI. Dilute solution viscosity studies of random copolymers of acrylamide with sulfonated comonomers

Dilute solution viscosity of a series of random copolymers of acrylamide (AM) with sodium-2-acrylamido-2-methylpropane sulfonate (NaAMPS) and with sodium-2-sulfoethylmethacrylate (NaSEM) has been studied using a four-bulb shear dilution capillary viscometer. The hydrodynamic volume of the copolymers in aqueous media was determined as a function of salt concentration, temperature, shear rate, and time. A linear relationship was observed between the intrinsic viscosity [η]₀ and the reciprocal of the square root of ionic strength in sodium chloride solutions, with salt concentrations varying from 0.043M to 0.257M. Negative temperature coefficients for [η]₀ indicate a decrease in the hydrodynamic volume of the ionic polymer molecules with increasing temperature. The relative zero-shear-intrinsic-viscosity change in distilled water to 0.257M sodium chloride aqueous media is used to elucidate viscosity–structure relationships. A maximum value is reached for this parameter at a composition of about 30 mol % of ionic comonomers for AM–NaAMPS and AM–NaSEM copolymer series.     

Solution properties of polyelectrolytes. III. Effect of sodium polystyrene sulfonate concentration on viscometric and size exclusion chromatographic behavior at different ionic strengths

The effect of sodium polystyrene sulfonate concentration on the shape of its molecules in aqueous solution at different NaNO₃ ionic strengths has been analyzed by viscometry and size-exclusion chromatography (s.e.c). An equation has been developed which predicts the intrinsic viscosity, [η] _p.cp.cs, at finite concentration of both polyion (c_p) and electrolyte (c_s). The experimental results obtained by both techniques can be accounted for in terms of the theory. Several factors involved in the elution mechanism have been considered and the variation of the slopes of s.e.c. calibration curves with c_p and c_s has been discussed in terms of polyion conformation changes.     

Polyelectrolytes as secondary calibration standards for aqueous size-exclusion chromatography

The effect of the ionic strength of the solvent on the size-exclusion chromatography of narrow molecular weight dextrans and monodisperse sodium polystyrene sulfonates has been investigated. In both NaOH and NaCl solutions the elution volume of the sodium polystyrene sulfonates increased as the ionic strength was increased, while the elution volume of the dextrans decreased slightly as the ionic strength was increased. The elution data for various ionic strength solvents could not be described by the traditional universal calibration procedure of plotting the product of the intrinsic viscosity and the molecular weight vs. the elution volume. By using a modified calibration procedure which includes excluded volume effects, the elution data can be described for NaOH solution of moderate and high ionic strength. This modified calibration technique was unable to describe the elution data for very low ionic strength NaOH solutions and for the NaCl solutions. Possible explanations of the inability of straightforward size exclusion chromatographic calibration techniques to quantitatively described all the observed elution behavior are discussed.     

Electro-optical and viscometric behaviour of sodium polystyrene sulphonate in formamide

Unusual electro-optical signals have been recorded on sodium polystyrene sulphonate in formamide. It was shown that such signals largely arise from the positive birefringence of the solvent being superimposed on the negative birefringence of the polyion. On the basis of conductimetric experiments, the residual content of ammonium formate caused by hydrolysis of formamide was estimated. Commercial formamide of analytical grade was shown to contain rather large amounts (0.02 M) of ammonium formate, sufficient to very strongly decrease the polyelectrolyte effect. The persistence length in these conditions is equal to 80Å, quite similar to that determined in 2 × 10^?2 M NcCl aqueous solution. At a lower ammonium formate content (7 × 10^?4 M), the degree of extension of the polyion at infinite dilution, calculated from the relaxation time of the birefringence, is identical to that measured in 6 × 10^?4 M NaCl. The influence of the nature of the solvent and the ionic strength on the electric polarizability and the optical anisotropy factor was also analysed and compared with the results obtained in water. The latter parameter was discussed in terms of the so-called form anisotropy of the solvent and the intrinsic optical anisotropy of the polyion.     

Adsorption characteristics of polyacrylamide and sulfonate-containing polyacrylamide copolymers on sodium kaolinite

Polyacrylamide and its copolymer containing 6.8 mole % 2-acrylamido-2-methylpropane sulfonic acid were prepared by an irradiation-initiated precipitation polymerization technique. The polymer was characterized by intrinsic viscosity under conditions similar to those used during adsorption measurements. Hydrolytic degradation of the polyacrylamide was found to be negligible under conditions used. The adsorption substrate, sodium kaolinite, was prepared by extensive ion exchange treatment. Equilibrium adsorption of the polymers on the sodium kaolinite was made as a function of polymer concentration, solution pH, ionic strength, and temperature.     

Dilute solution properties of naphthalene-labeled cationic poly(dimethyl sulfate quaternized acrylamide/N,N-dimethylaminopropylmaleimide copolymer)

The properties of a novel cationic, naphthalene-labeled cationic poly(dimethyl sulfate quaternized acrylamide/N,N-dimethylaminopropylmaleimide copolymer), poly-(DSQADMAPM)/NA in aqueous solution are examined in this study, measuring intrinsic viscosity, reduced viscosity, and ionic strength. This cationic poly(DSQADMAPM)/NA’s intrinsic viscosity is dependent on the type and concentration of salt added to the aqueous solution. The intrinsic viscosity behavior of the cationic poly(DSQADMAPM)/NA resulting from the electrostatic repulsive force of the polymer chain is contrasted with polyampholyte. Smaller anions such as F⁻ with a common cation (K⁺) are found to be the most difficult to be bound to the end group, indicating that a higher intrinsic viscosity of the poly(DSQADMAPM)/NA would be in KF salt aqueous solution. Smaller cations such as Li⁺ with a common anion (Cl⁻) are found to be the most difficult to be bound to the quaternary ammonium group, indicating that a higher intrinsic viscosity of the poly(DSQADMAPM)/NA would also be in LiCI salt aqueous solution. Models are proposed to account for the poly(DSQADMAPM)/NA solution viscometrics.     

An analysis of the viscous behaviour of polymeric solutions

Viscosity data of an aluminum soap solution, a polyisobutylene solution, a polyacrylamide solution, and ten polystyrene solutions have been analysed using two rheological models: the Carreau model A and the Ellis model. The model parameters were obtained by non-linear regression. The importance of the zero-shear viscosity for design purposes is illustrated by observing the appearance of a master curve in the representation of the dimensionless viscosity versus the product of the zero-shear viscosity by the shear rate. A linear relation is shown to exist between the logarithm of the zero-shear viscosity and the polymer concentration. It is asserted that either model should replace advantageously the commonly used power-law expression.     

Improved Maxwell Model Approach and its Applicability toward Lifetime Prediction of Biobased Viscoelastic Fibers

The evaluation of relaxation measurements is a well-established technique for predicting the lifetime of polymer materials, with research primarily focusing on increasing prediction accuracy and minimizing material testing time. The current study presents a novel approach toward describing the long-term behavior of viscoelastic polymers based on the Maxwell model. It assumes a mean relaxation time of the polymer chains in conjunction with a dimensionless number that accounts for averaged polymer chain inhomogeneities. This coefficient is analogous to the dimensionless number, which successfully describes the asymmetry of both the Weibull distribution and of particle size distribution according to the Rosin, Rammler, Sperling and Bennet model. In comparison to earlier models based on time-superposition principles, the current approach enables lifetime prediction using a single short-term measurement, which must be taken at a properly chosen applied strain. The applicability of the new model in predicting the long-term behavior has been demonstrated by the analysis of the relaxation behavior of semi-crystalline bio-based fibers.     

Rheological, Interfacial and Thermal Control of Polymer Adhesion. I. Isothermal Theoryf

We have developed an isothermal theory of separation in polymer-solid adhering systems. The model used is based on the (observed) drawing of filaments between a bulk polymer and a solid. In the isothermal theory, a criterion is set up, demarcating filament elongation vs. detachment of the filament base from the solid. It employs a dimensionless parameter, ω, that relates free energy of adhesion, elongational viscosity or yield strength of the polymer, and filament size, to adhesive performance. The isothermal theory can be applied directly to the separation processes that occur with pressure-sensitive adhesives. Certain observations by Aubrey and Sherriff, by Gardon and by Kaelble are explained. The validity of the demarcation is believed to extend beyond pressure-sensitive systems, to all thermoplastic adhesives and/or coatings.     

高分子稀溶液中溶剂对分子特性与流变性能的影响

本文研究了不同溶剂对离子性和非离子性高分子稀溶液的分子构型和流变性能的影响.在部分水解的聚丙烯酰胺水溶液中加入无机盐,测量并计算了分子扩张因数,特征粘度与盐浓度、盐离子价数、溶液pH值的关系.同时使用不同的有机溶剂测量聚丁烯溶液的Maxwell模型松弛时间和分子扩张因数.研究表明,高分子稀溶液可藉调整溶剂性质的方法以达到期望的流变特性.     

Aqueous solution properties of poly[3-dimethyl (methacryloyloxyethyl) ammonium propane sulfonate]

The aqueous solution properties of an ampholytic poly[3-dimethyl (methacryloyloxyethyl) ammonium propane sulfonate] [poly(DMAPS)] are studied by measurements of cloud point determination, intrinsic viscosity, degree of binding, and ionic strength. The minimum salt concentration and intrinsic viscosity of this polyampholyte are related to the type and concentration of added salt. Both the polymeric and monomeric betaines in the presence of NaCl have the lower degree of binding, indicating that the proton ion (H⁺) is relatively difficult to bind the SO^?₃ at the end of sulfobetaine. An increase in ionic strength causes the pK_a to decrease at the half-neutralization point.     

Structure–property relationships for sulfonated poly(butylene terephthalate)

Structure–property relationships have been developed for sulfonated poly(butylene terephthalate) copolymers. The compositional variables investigated were sulfonate content, molecular weight, and polymer endgroup composition, and the fundamental polymer properties evaluated were melt viscosity, crystallization kinetics, and impact strength. It was found that all compositional variables significantly affect all of the polymer properties of interest. The most interesting effect is the influence of polymer endgroup composition on polymer properties. The trends indicate that the carboxylic acid endgroups form intermolecular interactions with sodium sulfonate groups, resulting in a decrease in the strength of intermolecular ionic interactions between sodium sulfonate groups. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4662–4771, 2006     

Estimation of Binding Constants of Cd(II), Ni(II) and Zn(II) with Polyethyleneimine (PEI) by Polymer Enhanced Ultrafiltration (PEUF) Technique

Abstract

Continuous and batch processes of polymer enhanced ultrafiltration for the estimation of binding constants of divalent cadmium, nickel, and zinc ions have been elaborated. Polyethyleneimine was used as a complexation agent. Effect of pH and ionic strength on the binding ability of target metal ions to polyethyleneimine were estimated by continuous mode PEUF system. A mathematical model was developed to estimate apparent complexation constants of metal ions with PEI. The development of this model, which is in good agreement with experimental data, enables to compare the data obtained in both continuous and batch system and correlate the effect of pH and ionic strength with apparent binding constants.     

Polymers in mixed solvents: application of the new representation of viscosity data as a function of molecular weight

The relation proposed between the intrinsic viscosity and the molecular weight of a polymer^1,2 (1/[η]versus 1/M^1/2), has been applied in this paper in cases when the polymer is dissolved in a binary solvent mixture. We have then shown that even in this case we can calculate in a very accurate way the molecular weight of the polymer from its intrinsic viscosity, especially in the molecular weight range where the Mark-Houwink-Sakurada equation is the least applicable (M_w < 150 000).     

Xanthan gum: A versatile biopolymer for biomedical and technological applications

Xanthan gum is an extracellular polymer produced mainly by the bacterium Xanthomonas campestris. Traditionally it plays an important role in industrial applications as thickener, emulsion stabilizer and it has been added to water‐based drilling fluids due to its pseudoplastic behavior and thermal stability. The structural properties of xanthan in solution can be tuned by the temperature and ionic strength; under high ionic strength or low temperature, xanthan chains are arranged in helical conformation, whereas under low ionic strength or high temperature, xanthan chains are coiled. Xanthan high molecular weight favors the building up of physical and chemical networks, which have been used as carriers for drugs and proteins and as scaffolds for cells. In combination with other polymers xanthan has been applied as excipient in tablets or as supporting hydrogels for drug release applications, particularly due to its acid resistance. The large versatility of xanthan gum opens the possibility for the creation of new architectures and additional applications involving this fascinating polymer. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42035.