Adsorption and flocculation by polymers and polymer mixtures

Polymers of various types are in widespread use as flocculants in several industries. In most cases, polymer adsorption is an essential prerequisite for flocculation and kinetic aspects are very important. The rates of polymer adsorption and of re-conformation (relaxation) of adsorbed chains are key factors that influence the performance of flocculants and their mode of action. Polyelectrolytes often tend to adopt a rather flat adsorbed configuration and in this state their action is mainly through charge effects, including ‘electrostatic patch’ attraction. When the relaxation rate is quite low, particle collisions may occur while the adsorbed chains are still in an extended state and flocculation by polymer bridging may occur. These effects are now well understood and supported by much experimental evidence. In recent years there has been considerable interest in the use of multi-component flocculants, especially dual-polymer systems. In the latter case, there can be significant advantages over the use of single polymers. Despite some complications, there is a broad understanding of the action of dual polymer systems. In many cases the sequence of addition of the polymers is important and the pre-adsorbed polymer can have two important effects: providing adsorption sites for the second polymer or causing a more extended adsorbed conformation as a result of ‘site blocking’.     

Characterization of polymer molecular mass distribution from rheological measurements

Various methods for the determination of molecular mass distribution from rheological measurements of polymer melts are introduced. Shear viscosity, entrance pressure loss, recoverable shear, and in particular the dynamic viscoelasticity data G' and G” are discussed as analytical tools to evaluate the molecular mass distribution. Well characterized samples and homologous series of the polymers PS, PE-HD, PP, and PTFE were measured to check the methods. Precise and reliable results can be obtained by calculating the molecular mass distribution from the frequency dependence of the storage modulus.     

Size-based separation of synthetic polyelectrolytes in entangled polymer solution capillary electrophoresis: the effect of binary mixtures of separating polymers differing in molecular mass

The influence on the electrophoretic behavior of polystyrenesulfonates of the percentage of high-molecular-mass chains in an entangled poly(ethylene oxide) solution having a bimodal molecular mass distribution has been investigated and compared with the results obtained for similar solutions of unimodal molecular mass distribution. The comparisons between the different separating polymer solutions were made at a constant total mass concentration, so as to keep constant the mesh size and to highlight the sole effect of the network dynamics. The use of binary polymer mixtures of two different molecular masses but of same nature can be a convenient alternative to modulate the dynamics of the network and the viscosity of the separating medium. A 20-30% content of high-molecular-mass chains in an entangled poly(ethylene oxide) solution having a binary molecular mass distribution appears to be a good compromise for a moderate viscosity and a good separation selectivity in comparison with a solution containing only chains of high molecular mass at the same concentration.     

Further EPR studies of molecular motions in polymer/plasticizer mixtures

Molecular motions in mixtures of the side chain polymer—poly(vinyl acetate) and dibuthyl phthalate were studied as a functionof polymer concentration and temperature using the technique of paramagnetic resonance (EPR). When the small spherical probe tempol (TPL) was used, we were able to approximate the observed EPR spectrum with a simulation using a single rotational correlation time τ. The peviously developed Grest–Cohen all-temperature model matched the Arrhenius polts. The EPR spectra from a cigar-shaped cholestane (COL) probe could not be adequately matched by single τ simulation when the polymer was at temperatures somewhat above the glass to rubber transition temperature (T_g). Points corresponding to these temperatures were left of the Arrhenius plot and a discontinuity was observed where the gap in the data occurred. As the concentration of plasticizer was increased, we found that the discontinuity became less steep, but the τ at which the gap occurs was always ≈ 10^?8. The spectra observed at the temperature region of the gap were approximately 50–50 composites of experimental spectra observed at ± K. In both the TPL and COL cases, there was evidence of the existence of multiple correlation times. Preliminary studies of other polymers, both with and without side chains, also indicated the existence of the gap when COL is used as the probe. © 1993 John Wiley & Sons, Inc.     

Removal of trace organic compounds from multicomponent liquid mixtures. I. Adsorption of surfactant mixtures on activated carbon

This study shows how trace amounts of surfactants are adsorbed by activated carbon under competitive conditions in aqueous solution. Surfactants used as adsorbates are sodium dodecyl sulfate (SDS) and eicosaneoxyethylene hexadecyl ether (POE). Activated carbon used as an adsorbent is Pittsburgh activated carbon. Adsorption isotherms on the activated carbon were all Freundlich-type, both in the multi-solute system and in the mono-solute systems. The total adsorbed amount in the multi-solute system increases linearly with increasing molar fraction of SDS in the initial concentration. Thus, the total adsorbed amount in the multi-solute system can be estimated by the Freundlich constants, which can be determined from the single-solute equilibrium adsorptions, and molar fractions of adsorbates in the initial concentration.     

The influence of the adsorbent amount on the changes in molecular mass distribution of polymers under adsorption from mixtures

Changes in the molecular mass distribution (MMD) for polymer as a result of adsorption from binary and ternary solutions have been studied by the exclusion chromatography method. It was found that the affinity of polymer components to a surface has a crucial influence on the changes in MMD of polymers. The diminution of polydispersity in solutions after adsorption was observed for two polymers. In the case of the polar polymer poly(butyl methacrylate) (PBMA) the diminution of polydispersity is caused mainly by the preferential adsorption of low-molecular-mass fractions, whereas in the case of the nonpolar polymer polystyrene (PS) it is caused by the transition of the high-molecular-mass fractions onto the adsorbent surface. The analysis of experimental results indicates that the quantity of the adsorbent affects the composition of the adsorption layer formed by polymers of different chemical nature.     

Adsorption and desorption of polymer/surfactant mixtures at solid-liquid interfaces: substitution experiments

The adsorption of mixtures of aqueous solutions of cationic hydroxyethylcellulose polymer JR400 and anionic surfactant, sodium dodecyl sulfate, using atomic force microscopy (AFM) has been studied. Samples with various compositions from different regions of the ternary phase diagram presented in our previous work were imaged by atomic force microscopy on freshly cleaved mica, and hydrophobically modified mica and silica in soft-contact mode. A series of "washing" (subsequent injection of compositions with gradually decreasing polymer/surfactant ratio) and "scratching" (mechanical agitation of the surface material with an AFM tip) experiments were performed. It was revealed that the morphology of the adsorbed layer altered in a manner following the changes in morphology in the bulk solution. These changes were evidenced in cluster formation in the layer. The results suggest that the influence of the surface was limited to the formation of the adsorbed layer where the local concentrations of polymer and surfactant were higher than those in the bulk. All further modifications were driven by changes in the mixture composition in bulk. Force measurements upon retraction reveal the formation of network structures within the surface aggregates that will greatly slow structural reequilibration.     

Charge-transfer complexing in polymer mixtures. IV. Acceptor polymers from nitrophthalic acids and their mixtures with donor polymers from aryliminodiethanols

A series of electron acceptor polyesters was prepared from 5-nitroisophthalic, nitroterephthalic, and 4,6-dinitroisophthalic acids. Those polymers prepared at high molecular weight were tough, soluble, linear materials of well-defined structure. These materials were mixed with electron-donor polymers based on aryliminodiethanols where the aryl group was phenyl, p-anisyl, 2,5-dimethoxyphenyl, and 3,4,5-trimethoxyphenyl. The effects of the mixtures on the mechanical, spectral, viscometric, and conductive properties were studied and compared to the component polymers.     

The effect of polymer chain length on the thermodynamics of acrylate/cyanobiphenyl mixtures

The effect of polymer molecular mass on the phase behaviour and solubility limits of polymer/liquid crystal mixtures is studied for blends of poly(methyl methacrylate) (PMMA) and the small-molecule liquid crystal, 4'-octyl-4-biphenylcarbonitrile (8CB). The phase diagrams from optical microscopy show a limit to the effect of increasing polymer molecular mass. The Flory-Huggins theory (FH) for polymer solutions is used to extract the interaction parameter, χ, from the phase diagrams. The initial FH fits are performed with the assumption that χ is independent of polymer molecular mass, but result in poor correlation to the microscopy data. When χ is allowed to scale with M _w, however, the FH fits are consistent with the limiting molecular mass behaviour. This result represents, to our knowledge, the first time that this scaling behaviour has been observed in polymer/liquid crystal blends. The solubility limit, β, of 8CB in PMMA for each polymer molecular mass is also determined and, when compared with the results of previous studies, support the concept that β is independent of both polymer composition and molecular masses when the polymer molecular mass exceeds ca. 5×10⁵ g mol^-1.     

Solvation of tetraalkylammonium chlorides in acetonitrile-water mixtures: mass spectrometry and molecular dynamics simulations.

The solvation of tetramethylammonium chloride (Me4NCl) and tetra-n-butylammonium chloride (Bu4NCl) in water-acetonitrile mixtures was investigated by mass spectrometry of clusters isolated from the solution. As far as the positive ions are concerned, clusters composed of alkylammonium ions and acetonitrile molecules only were observed, even for mixtures with high water content. In contrast, for the negative ions, clusters composed of chloride with both water and/or acetonitrile molecules were observed. For the smaller system (Me4NCl) we performed quantum chemical calculations and molecular dynamics simulations. It was found that even though water is present in the solvation shell of Me4N+, only acetonitrile has a strong electrostatic interaction with the cation. Water molecules around Me4N+ form hydrogen bonds with other water molecules, and they interact with Me4N+ mainly via dispersive interactions. These results indicate that Me4N+ behaves like a hydrophobic solute. On the other hand, the interaction of Cl- with water and acetonitrile is of comparable strength and, in both cases, the electrostatic interaction dominates. Herein we demonstrate experimentally and theoretically that positive and negative ions give rise to characteristic solvation structures in mixed solvents: even a relatively small organic cation, such as Me4N+, exhibits a hydrophobic-like solvation shell.     

Evaluation of molecular mass and tacticity of polyvinyl alcohol by non-equilibrium capillary electrophoresis of equilibrium mixtures of a polymer and a dye

Non-equilibrium capillary electrophoresis of equilibrium mixtures (NECEEM) has been used to characterize polyvinyl alcohol (PVA). Commercial PVA samples with different molecular masses, from M(w)=15 up to 205 kDa, were used. According to the (13)C NMR spectra, the samples also differed in tacticity (stereoregularity). Mixtures of PVA and the anionic azo-dye Congo Red (CR) were injected in the presence of a borate buffer. The electropherograms gave a band and a peak due to the residual PVA-CR complex and the excess dye, respectively, plus a superimposed exponential decay due to the partial dissociation of the complex during migration. The stoichiometry of the PVA-CR complex, q=[monomer]/[dye], reached a maximum, q(sat), which depended on both M(w) and tacticity of PVA. Thus, q(sat) decreased from a molar ratio of ca. 4.9 to 3.6 at increasing M(w) values, this variation also being largely dependent on tacticity. A similar dependence of the electrophoretic mobility of the complex on both M(w) and tacticity was also observed. A possible explanation, based on the formation of a stack of CR ions inside the PVA-CR complex, was proposed and discussed. Finally, at increasing M(w) values, the stability constant of the complex increased slightly, and the pseudo-first order dissociation rate of the complex decreased, this later parameter also showing a dependence on both M(w) and tacticity.     

Chromatographic mass of a polymer and its use for determining the molecular mass characteristics

The method has been proposed for determining the molecular characteristics of flexible-chain polymers that obey the universal calibration principle and for which there are available experimental data on the intrinsic viscosity. This method is based on studying the dependence of the hydrodynamic volume M _n[η], M _w[η], M _z[η], and M _η[η] on parameter a in the Mark-Kuhn-Houwink equation. It has been found that, for parameter a varying in the range from 0.5 to 0.8, the weight-average hydrodynamic volume M _w[η] remains almost unchanged. This allows estimation of M _w based on a single intrinsic viscosity value. The notion of the chromatographic mass of a polymer is advanced and is employed for determining other molecular mass parameters.     

Surface tension of polymer solutions. IV. Three-component mixtures

The lattice-theory equations for the surface tensions of polymer solutions based on the parallel-layer model have been tested for three-component systems. Surface tensions of solutions of some low molecular weight polyisobutylenes and polydimethylsiloxanes in n-heptane–tetralin mixtures and solutions of mixtures of the polymers in these solvents were measured at room temperature. The results are in good agreement with the theoretical calculations.     

The effect of light on the viscosity and molecular mass of nitrocellulose

The photodegradation of a series of nitrocellulose (NC) samples with nitrogen contents ranging from 11.69% to 13.55% has been investigated by observing changes in molecular mass and viscosity using, respectively, size exclusion chromatography (SEC) and a modified cone and plate rheometer. When NC in γ-butyrolactone was subjected to UV light in the range 320-390 nm its specific viscosity (η_sp) was found to decrease noticeably, a change attributed to polymer chain scission and de-aggregation. This view was supported by an observed reduction in the mass average molecular mass (M_w). In contrast, irradiation with a single wavelength at 365 nm did not significantly change either η_sp or M_w and similar behaviour was observed when NC solutions were irradiated with visible light (400-500 nm). In the solid state, the photodegradation of water-wet NC is faster than that of the dried material, which is attributed to the catalytic effect of acids formed from the reaction between water and nitrogen oxides (NO_x) arising from NC decomposition. A higher degree of crystallinity in the NC, as found by X-ray diffraction (XRD), was shown to lead to a smaller decrease in viscosity and molecular mass. This is thought to be because the photodegradation reaction is suppressed in crystalline NC by more effective radical-radical recombination.     

Adsorption of carbon dioxide-methane mixtures in porous carbons: effect of surface chemistry

A combined experimental and molecular simulation study of the coadsorption of CO₂ and CH₄ in porous carbons is reported. We address the effect of surface chemistry by considering a numerical model of disordered porous carbons which has been modified to include heterochemistry (with a chemical composition consistent with that of the experimental sample). We discuss how realistic the numerical sample is by comparing its pore size distribution (PSD), specific surface area, porous volume, and porosity with those for the experimental sample. We also discuss the different criteria used to estimate the latter properties from a geometrical analysis. We demonstrate the ability of the MP method to estimate PSD of porous carbons from nitrogen adsorption isotherms. Both the experimental and simulated coadsorption isotherms resemble those obtained for pure gases (type I in the IUPAC classification). On the other hand, only the porous carbon including the heterogroups allows simulating quantitatively the selectivity of the experimental adsorbent for different carbon dioxide/methane mixtures. This result shows that taking into account the heterochemistry present in porous carbons is crucial to represent correctly adsorption selectivities in such hydrophobic samples. We also show that the adsorbed solution theory describes quantitatively the simulated and experimental coadsorption isotherms without any parameter adjustment.     

Self-consistent field modeling of adsorption from polymer/surfactant mixtures

We report on the development of a self-consistent field model that describes the competitive adsorption of nonionic alkyl-(ethylene oxide) surfactants and nonionic polymer poly(ethylene oxide) (PEO) from aqueous solutions onto silica. The model explicitly describes the response to the pH and the ionic strength. On an inorganic oxide surface such as silica, the dissociation of the surface depends on the pH. However, salt ions can screen charges on the surface, and hence, the number of dissociated groups also depends on the ionic strength. Furthermore, the solvent quality for the EO groups is a function of the ionic strength. Using our model, we can compute bulk parameters such as the average size of the polymer coil and the surfactant CMC. We can make predictions on the adsorption behavior of either polymers or surfactants, and we have made adsorption isotherms, i.e., calculated the relationship between the surface excess and its corresponding bulk concentration. When we add both polymer and surfactant to our mixture, we can find a surfactant concentration (or, more precisely, a surfactant chemical potential) below which only the polymer will adsorb and above which only the surfactant will adsorb. The corresponding surfactant concentration is called the CSAC. In a first-order approximation, the surfactant chemical potential has the CMC as its upper bound. We can find conditions for which CMC < CSAC . This implies that the chemical potential that the surfactant needs to adsorb is higher than its maximum chemical potential, and hence, the surfactant will not adsorb. One of the main goals of our model is to understand the experimental data from one of our previous articles. We managed to explain most, but unfortunately not all, of the experimental trends. At the end of the article we discuss the possibilities for improving the model.     

Reversed phase behaviour of high molecular mass polystyrenes in ethyl acetate solvent mixtures

Chromatographia - The reversed phase behaviour of high molecular mass polystyrenes was investigated on C18 bonded phase columns with ethyl acetate-methanol and ethyl acetateacetonitrile mobile...     

Lowering the molecular mass limit of thermal field-flow fractionation for polymer separations

Thermal field-flow fractionation (ThFFF) is capable of separating a wide molecular mass range of polymers by their molecular mass (Mr) and chemical composition. However, retention and resolution decrease significantly for polymers with Mr<20 kDa. Various approaches for increasing the retention of low Mr (<15 kDa) polymers were investigated. Our results showed that temperature conditions and single-component solvents had a limited effect on polymer retention and that certain binary solvent mixtures caused a dramatic increase in retention. The binary solvents approach has enabled the use of a ThFFF system and temperature conditions to separate 2.6 kDa PS from 4.4 kDa PS, thereby extending the applicability of ThFFF to lower molecular masses. The effect of binary solvent mixtures on polymer retention is correlated with the mixture viscosity.