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1.
In order to elucidate the mechanisms of flocculation by polymer mixtures, the effect of adsorption of non-ionic poly(ethylene oxide) — PEO, two samples of strongly (SNF FO 4800) and medium charged (SNF FO 4350) cationic and two samples of medium (SNF AN 935) and weakly charged (SNF AN 905) anionic polyelectrolytes (PE) as well as their binary mixtures on the electrokinetic potential of bentonite and kaolin particles has been studied. It is shown that in the presence of PEO-anionic/cationic polymer mixture, the electrokinetic potential of particles is determined by the adsorption of the polyelectrolyte; neither cationic nor anionic segments can be displaced by the non-ionic polymer. In mixtures of cationic and anionic polyelectrolytes, the ζ-potential of particles is determined by the adsorbed amount of anionic polymer independently of the charge density of PE and way of addition of the mixture components to the suspension, i.e. (1) first adding the cationic polymer, then the anionic one, or (2) first adding the anionic polymer then the cationic one, or (3) adding an increasing amount of pre-prepared 1: 1 mixture. The highest absolute ζ-potential values are observed for pH 7.5 when the surface of bentonite or kaolin particles is “purely” negatively charged and the anionic PE layer is most extended because of few contacts to the surface. With decreasing the pH, the (negative) ζ-potential of particles decreases due to appearance of a small amount of positive charges on the surface that bond an increasing amount of negative segments and results in shrinking of the adsorbed layer of the anionic PE. It is shown also that the electrokinetic potential of particles in anionic and cationic PE mixtures at all studied pH (4, 5, and 7.5) depends on the spatial distribution of negatively charged segments near the surface. The regularities observed are explained by formation of long loops and tails of anionic segments on the surface because of the small number of contacts to the surface; the cationic polyelectrolyte forms on the surface a thin layer with a big number of contacts and which is hidden behind the more extended anionic polymer layer.  相似文献   

2.
The effect of cationic and anionic surfactants, as well as cationic and anionic polyelectrolytes (PE), their binary mixtures on the electrokinetic potential of monodisperse carboxylated polystyrene (PS) particles as a function of the reagents dose, pH, the charge density (CD) of polymers, the surfactant/PE and binary PE mixture composition, and sequence of components addition to the suspension has been studied. It has been shown that addition of increasing amount of anionic surfactant/polyelectrolytes increases the absolute value of the negative zeta-potential of PS particles; this increase is stronger the CD of the PE and pH of the system are higher. Adsorption of cationic surfactant/polyelectrolytes leads to a significant decrease in the negative ζ-potential and to overcharging the particles; changes in the ζ-potential are more pronounced for PE samples with higher CD and for suspensions with lower pH values. In mixtures of cationic and anionic PE, in a wide range of mixture composition, the ζ-potential of particles is determined by the adsorbed amount of the anionic polymer independently of the CD of PEs and the sequence of addition of the mixture components. The isoelectric point of the surface is reached at the adsorbed amount of positive charges of PE that is approximately equal to the surface CD of particles. The laws observed were explained by features of macromolecules conformation in adsorbed mixed PE layers. Considerations about the role of coulombic and non-coulombic forces in the mechanism of anionic/cationic PE adsorption are presented.  相似文献   

3.
This paper demonstrates the use of polyelectrolytes to modify and manipulate the adsorption of ionic surfactants onto the hydrophilic surface of silica. We have demonstrated that the cationic polyelectrolyte poly(dimethyl diallylammonium chloride), poly-dmdaac, modifies the adsorption of cationic and anionic surfactants to the hydrophilic surface of silica. A thin robust polymer layer is adsorbed from a dilute polymer/surfactant solution. The resulting surface layer is cationic and changes the relative affinity of the cationic surfactant hexadecyl trimethylammonium bromide, C16TAB, and the anionic surfactant sodium dodecyl sulfate, SDS, to adsorb. The adsorption of C16TAB is dramatically reduced. In contrast, strong adsorption of SDS was observed, in situations where SDS would normally have a low affinity for the surface of silica. We have further shown that subsequent adsorption of the anionic polyelectrolyte sodium poly(styrene sulfonate), Na-PSS, onto the poly-dmdaac coated surface results in a change back to an anionic surface and a further change in the relative affinities of the cationic and anionic surfactants for the surface. The relative amounts of C16TAB and SDS adsorption depend on the coverage of the polyelectrolyte, and these preliminary measurements show that this can be manipulated.  相似文献   

4.
The effect of molecular mass on the formation of a bilayer structure upon the layer-to-layer adsorption of a cationic polyelectrolyte (poly(dimethyldiallylammonium chloride), molecular mass M = 500000 and 100000-200000 Da) and an anionic polyelectrolyte sodium (poly(acrylate), M = 30000 and 2100 Da) on the surface of fused quartz is studied by the capillary electrokinetic method. The time required to reach constant adsorption values and the structure of bilayer systems depend on the ratio between molecular masses of the cationic and anionic polyelectrolytes. The deformability of the bilayer system significantly exceeds that of the first layer in the case when the second layer is formed from an anionic polyelectrolyte with a lower molecular mass, thus suggesting the loosening of the first adsorption layer of the cationic polyelectrolyte. The adsorption of the anionic polyelectrolyte with higher molecular mass insignificantly affects the density of the first layer. Variation in the deformability of the layer with time (its aging) depends on the ratio between molecular masses of the polyelectrolytes.  相似文献   

5.
The adsorption of cationic and amphoteric copolymers onto controlled pore glass (CPG) powders has been studied by measurement of the powder particle zeta (zeta) potential, by determination of the adsorption isotherm, and by FT Raman measurements of the polymer-coated powder. The cationic polymers consisted chiefly of homopolymers of dimethyldiallylammonium chloride (DMDAAC) or copolymers of DMDAAC and acrylamide. The amphoteric polymers studied included copolymers of DMDAAC and acrylic acid. The comonomer ratio was varied to explore the dependence of cationic charge density on the extent and effect of adsorption. Both types of polymers adsorb onto the anionic glass surface via an ion-exchange mechanism. Consequently, a correspondingly higher mass of a low-charge-density copolymer adsorbs than of a cationic homopolymer. The presence of the anionic portion in the amphoteric polymers does not significantly alter this picture. The zeta potential, however, reflects the overall nature of the polymer. Cationic polymers effectively neutralize the glass surface, while amphoteric polymers leave the zeta potential net negative. Adsorption isotherms, determined via the depletion technique using colloidal titration, were used to "calibrate" a FT Raman method. The latter was used to determined the amount of adsorbed polymer under solution conditions in which colloidal titration could not be performed.  相似文献   

6.
The effect pH, ionic strength (KCl concentration), weakly and medium charged anionic and cationic polyelectrolytes (PEs) as well as their binary mixtures on the electrokinetic potential of silica particles as a function of the polyelectrolyte/mixture dose, its composition, charge density (CD) of the PE, and way of adding the polymers to the suspension has been studied. It has been shown that addition of increasing amount of anionic PEs increases the absolute value of the negative zeta-potential of particles at pH > pH isoelectric point (IEP = 2.5); this increase is stronger the charge density of the polyelectrolyte is higher. Adsorption of cationic polyelectrolytes at these pH values gives a significant decrease in the negative ζ-potential and overcharging the particles; changes in the ζ-potential are more pronounced for PE samples with higher CD. In mixtures of cationic and anionic PE at pH > pHIEP, the ζ-potential of particles is determined by the adsorbed amount of the anionic polymer independently of the CD of PEs, the mixture composition and the sequence of addition of the mixture components. Unexpectedly, the ζ-potential of silica at pH = 2.1, i.e. < pHIEP, turned out to be positive in the presence of both anionic PE and cationic + anionic PE mixtures. This is explained by formation (and adsorption onto positively charged silica surface) of pseudo-cationic PEs from anionic ones due to transfer of protons from the solution to the amino-group of the anionic polymer. Considerations about the role of coulombic and non-coulombic forces in the mechanism of PE adsorption are presented.  相似文献   

7.
Masadome T 《Talanta》2003,59(4):659-666
The reaction of the cationic dye, crystal violet (CV) with the anionic polyelectrolytes such as potassium poly (vinyl sulfate) (PVSK) results in a decrease of the absorbance of CV at the maximum absorption wavelength (590 nm). This change of the absorption spectra of the CV has been already applied to the determination of anionic polyelectrolytes using flow injection analysis method. In this paper, CV was applied to the indicator for the determination of cationic polyelectrolytes such as poly (diallyldimethylammonium chloride) (Cat-floc) by photometric titration, using a PVSK solution as a titrant. The end-point of the titration is detected as the break point of the titration curve. A linear relationship between the concentration of cationic polyelectrolyte and the end-point volume of the titrant exists in the concentration range from 0 to 5×10−5 eq. mol dm−3 for Cat-floc, glycol chitosan and methylglycol chitosan. The effects of the concentration of CV and coexisting electrolytes in the sample solution and the effect of pH of the sample solution on the degree of the change of absorbance at the end-point were also examined.  相似文献   

8.
We have experimentally studied the adsorption of polyelectrolytes at oppositely charged surfaces. A weak flexible polyelectrolyte, poly(acrylic acid), was adsorbed from dilute solutions on a Langmuir film of a cationic amphiphile, dimethyldioctadecylammonium bromide. The polymer surface coverage, Gamma, at equilibrium was measured by two reflectivity techniques-ellipsometry and polarization modulated infrared reflection absorption spectroscopy (PM-IRRAS)-as a function of the surface charge density, sigma, and of the polymer ionization degree, alpha. Different adsorption regimes were evidenced. For weakly charged surfaces, sigma < sigma sat, Gamma increases with sigma and with 1/alpha, as expected for a neutralization of the surface by the adsorbed polymers. For highly charged surfaces, sigma > sigma sat, the adsorption of polyelectrolytes saturates. The mean orientation of the adsorbed chains also depends on the value of sigma: it is parallel to the surface for sigma < sigma (< sigma sat) and orthogonal to the surface for sigma > sigma. We have measured the values of sigma sat and sigma as a function of alpha and compared the results with existing theories.  相似文献   

9.
The adsorption of three sodium lignosulfonates on hematite was studied as a function of pH in the range from 4 to 10.5, and in the presence or absence of calcium ions (10?3 mol/L calcium choride). Intrinsic viscosity measurements demonstrated that the effective size of the macromolecules was not significantly affected under the experimental conditions. The adsorption results showed that electrostatic forces between the anionic polyelectrolytes and the hematite surface controlled the adsorption process although substantial non-electrostatic interactions were also clearly observed. The adsorption density inversely correlated with the anionicity of the tested lignosulfonates, especially with the content of sulfonic groups, with the least anionic polyelectrolyte producing the highest adsorption level. It was suggested that lateral repulsive electrostatic forces between the adsorbed macromolecules prevented dense adsorption of more anionic lignosulfonates. From this point of view, the effect of calcium on adsorption was attributed not only to its specific adsorption and surface charge reversal, but also to screening the anionic groups of lignosulfonates and minimizing the lateral repulsive interactions especially at high pH.  相似文献   

10.
Methacrylic acid (MA) and [3-(methacryloylamino)propyl]trimethylammonium chloride (MAPTAC) were polymerized to give amphoteric copolymers with various compositions. The structure and H-bonding of water in an aqueous solution of the copolymer were analyzed using the contours of the O-H stretching in the polarized Raman spectra. For comparison, the H-bonded network structure of aqueous solutions of homopolymers (polyMA and polyMAPTAC) was also examined. From the relative intensity of the collective band (C value) corresponding to a long range coupling of the O-H stretching in the aqueous polymer solutions, the number of H-bonds disrupted due to the presence of one monomer residue of the polymers (Ncorr) was determined. The Ncorr value for polyMA was largely positive, and with an increase in the content of the MAPTAC residue, the Ncorr value became smaller, and after passing a minimum (which was still slightly positive) at a roughly equivalent molar ratio, the Ncorr value increased again. This is in significant contrast with the larger positive Ncorr values for the homopolymers (both polyMA and polyMAPTAC), and other ordinary polyelectrolytes such as sodium polyethylenesulfonate, poly-L-lysine hydrobromide and sodium polyacrylate. Furthermore, the Ncorr value for the copolymer (MA ratio MAPTAC = 56:44) became much smaller by the neutralization of MA residues in the copolymer with sodium hydroxide, and comparable to those for neutral polymers such as poly(ethylene glycol) and poly(N-vinylpyrrolidone) and zwitterionic polymers such as poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC) and poly[3-sulfo-N,N-dimethyl-N-(3'-methacryloylaminopropyl)propanaminium inner salt]. The present results clearly indicate that the amphoteric polymers with comparative contents of cationic and anionic groups do not significantly disturb the H-bonded network structure of water, probably due to the counteraction of the electrostatic hydration effect by the proximity between the anionic and cationic side groups.  相似文献   

11.
Anionic and cationic polyelectrolytes were grafted on a bleached kraft pulp. Grafting an anionic polyelectrolyte (sodium poly-acrylate-polyacrylamide copolymer) resulted in modified fibers possessing outstanding affinity for water and saline solutions in the pH range where the polymer is ionized. Swelling is the result of both the grafting operation itself and of the presence of the ionized polyelectrolyte.

The swollen grafted fibers could be disintegrated under intense shear to give a colloidal solution exhibiting pseudoplastic thixo-tropic behavior. Electron microscopic examination revealed that during the shearing process the fiber had been disintegrated into its constitutive elements, long rodlike protofibrils, which are believed to be mainly responsible for the high viscosities observed.

Grafting a cationic polyelectrolyte (polydimethylamino ethyl methacrylate hydrochloride) produced fibers with lower but significant water swelling. The influence of pH on swelling was similar, although reversed, to that observed with the anionic grafted fibers. The presence of a large number of cationic groups in the porous cellulose fiber gel points to applications in ion-exchange and adsorption processes.  相似文献   


12.
The swelling behavior in the solutions of sodium chloride, linear polyelectrolytes and ionic surfactants of the composites based on clay mineral bentonite (BENT) embedded in neutral and slightly charged poly(acrylamide) (PAAm) gels is studied. Negatively charged flat clay particles incorporated into polymer gel adsorb oppositely charged surfactant and linear polyelectrolyte and attract the charged chains of cationic polymer matrix. The results of SAXS study manifest the formation of lamella structure of the cationic surfactant adsorbed by the clay plates. The gels loaded with the clay show a strong response to changes in the nature and the composition of the ionic environment.  相似文献   

13.
The use of 4-(dimethylamino)pyridine to form an adhesion layer for the adsorption of anionic polyelectrolytes on gold surfaces is investigated. In situ surface plasmon resonance spectroscopy is used to monitor the changes in thickness of the adsorbed layers as a function of pH changes. Weak (poly(acrylate)) and strong (poly(styrenesulfonate)) polyelectrolytes have been studied. Although 4-(dimethylamino)pyridine is weakly bound to gold, it is not displaced by these polyelectrolytes and acts as an adhesion layer. The relationship of the interaction of anionic polyelectrolytes with 4-(dimethylamino)pyridine-modified planar gold and gold nanoparticles is discussed.  相似文献   

14.
A plasticized poly (vinyl chloride) (PVC) membrane electrode sensitive to dodecylbenzenesulfonate (DBS) ion is applied to the determination of anionic polyelectrolytes such as potassium poly (vinyl sulfate) (PVSK) by potentiometric titration, using a poly (diallyldimethylammonium chloride) (Cat-floc) solution as a titrant. The end-point of the titration is detected as the potential jump of the plasticized PVC membrane electrode caused by decrease in the concentration of DBS ion added to the sample solution as a marker ion, due to the ion association reaction between the DBS ion and Cat-floc. The effects of the concentration of DBS ion, coexisting surfactants and electrolytes in the sample solution and pH of the sample on the degree of the potential jump at the end-point were examined. A linear relationship between the concentration of anionic polyelectrolyte and the end-point volume of the titrant exists in the concentration range from 2 × 10–5 to 4 × 10–4 N for PVSK, alginate, and carrageenan.  相似文献   

15.
Capillary electrophoresis and electrokinetic chromatography are typically carried out in unmodified fused‐silica capillaries under conditions that result in a strong negative zeta potential at the capillary wall and a robust cathodic electroosmotic flow. Modification of the capillary wall to reverse the zeta potential and mask silanol sites can improve separation performance by reducing or eliminating analyte adsorption, and is essential when conducting electrokinetic chromatography separations with cationic latex nanoparticle pseudo‐stationary phases. Semipermanent modification of the capillary walls by coating with cationic polymers has proven to be facile and effective. In this study, poly([2‐(acryloyloxy)ethyl]trimethylammonium chloride) polymers were synthesized by reversible addition‐fragmentation chain transfer polymerization and used as physically adsorbed semipermanent coatings for capillary electrophoresis and electrokinetic chromatography separations. An initial synthesis of poly([2‐(acryloyloxy)ethyl]trimethylammonium chloride) polymer coating produced strong and stable anodic electroosmotic flow of –5.7 to –5.4 × 10−4 cm2/V⋅s over the pH range of 4–7. Significant differences in the magnitude of the electroosmotic flow and effectiveness were observed between synthetic batches, however. For electrokinetic chromatography separations, the best performing batches of poly([2‐(acryloyloxy)ethyl]trimethylammonium chloride) polymer performed as well as the commercially available cationic polymer polyethyleneimine, whereas polydiallylammonium chloride and hexadimethrine bromide did not perform well.  相似文献   

16.
Water‐soluble crosslinked hollow nanoparticles were prepared using pH‐responsive anionic polymer micelles as templates. The template micelles were formed from pH‐responsive diblock copolymers (PAMPS‐PAaH) composed of the poly(sodium 2‐(acrylamido)‐2‐methylpropanesulfonate) and poly(6‐(acrylamido)hexanoic acid) blocks in an aqueous acidic solution. The PAMPS and PAaH blocks form a hydrophilic anionic shell and hydrophobic core of the core‐shell polymer micelle, respectively. A cationic diblock copolymer (PEG‐P(APTAC/CEA)) with the poly(ethylene glycol) block and random copolymer block composed of poly((3‐acrylamidopropyl)trimethylammonium chloride) containing a small amount of the 2‐(cinnamoyl)ethylacrylate photo‐crosslinkable unit can be adsorbed to the anionic shell of the template micelle due to electrostatic interaction, which form a core‐shell‐corona three‐layered micelle. The shell of the core‐shell‐corona micelle is formed from a polyion complex with anionic PAMPS and cationic P(APTAC/CEA) chains. The P(APTAC/CEA) chains in the shell of the core‐shell‐corona micelle can be photo‐crosslinked with UV irradiation. The template micelle can be dissociated using NaOH, because the PAaH blocks are ionized. Furthermore, electrostatic interactions between PAMPS and PAPTAC in the shell are screened by adding excess NaCl in water. The template micelles can be completely removed by dialysis against water containing NaOH and NaCl to prepare the crosslinked hollow nanoparticles. Transmission electron microscopy observations confirmed the hollow structure. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012  相似文献   

17.
Studies of the adsorption of high molecular weight polymers on colloidal latex and silica particles and their subsequent flocculation were carried out. Neutral polyethylene oxide samples with both a narrow and a broad molecular weight distribution were used together with low charged cationic copolymers. The influence of the particle concentration and polymer dose on the flocculation were systematically investigated under quiescent conditions.Equilibrium bridging only occurred with polyelectrolyte, even in very dilute suspensions, at high particle coverage. In contrast to this, non-equilibrium bridging occurred with both neutral polymer and polyelectrolytes but only for more concentrated suspensions and small amounts of adsorbed polymer. Polymer adsorption in dilute suspensions, which did not show particle aggregation was measured an electrophoretic technique. In more concentrated suspensions, where flocculation takes place, we found that aggregation prevents further polymer adsorption and induces both an excluded volume and a surface effect. The consequences on the shape of the isotherms differ according to the aggregation mechanism.A significant decrease of the amount, , of adsorbed polymer is observed with non-equilibrium bridging. When both mechanisms simultaneously contribute to the aggregation, the value of depends on their relative importance. In the intermediate range of copolymer dose their respective contributions are critically sensitive to the details of the mixing step and stirring, leading to non reproducible experimental results.  相似文献   

18.
Summary: Well‐defined flexible, annealed, and quenched polyelectrolytes with two cationic sites per monomeric unit are synthesized. The synthetic scheme involves the synthesis of narrowly distributed poly(ptert‐butoxystyrene) precursors by anionic polymerization high vacuum techniques, hydrolysis to poly(p‐hydroxystyrene), and subsequent quantitative functionalization by a Mannich‐type reaction, to yield annealed polyelectrolytes with two dimethylamino groups per monomer. In a last step, the dimethylamino groups are converted into quaternary ammonium salts by reaction with methyl iodide to give high‐charge‐density quenched cationic polyelectrolytes. The polymers are molecularly characterized by NMR and FT‐IR spectroscopy, while their solution behavior is studied by potentiometric titrations, turbidimetry, and fluorescence spectroscopy as a function of pH, in the case of the annealed polyelectrolytes, as well as by viscometry in the case of the quenched polyelectrolytes.

Schematic diagram of the synthesis of the polyelectrolytes.  相似文献   


19.
The cycloterpolymerizations of single‐, twin‐, and triple‐tailed hydrophobes with hydrophilic monomer N,N‐diallyl‐N‐carboethoxymethylammonium chloride and sulfur dioxide afforded a series of cationic polyelectrolytes (CPEs) in excellent yields. These CPEs, upon the acidic hydrolysis of the pendent ester groups, gave the corresponding pH‐responsive cationic acid salts, which, upon a treatment with sodium hydroxide, were converted to polybetaines (PBs), anionic polyelectrolytes (APEs), and PB/APE polymers containing various proportions of zwitterionic (PB) and anionic fractions (APE) in the polymer chain. At a shear rate of 0.36 s−1 at 30 °C, salt‐free water solutions of the CPEs (2 g/dL) containing 8, 4, and 2.67 mol % of the single‐, twin‐, and triple‐tailed hydrophobes (all having 8 mol % octyloxy tails) had apparent viscosity values of 70, 2800, and 396,000 cps, respectively. The PB/APE polymer with a ratio of 33:67 for the zwitterionic and anionic fractions in the polymer chain gave the highest viscosity value. The superior viscosity behavior of the polymers containing the triple‐tailed hydrophobe was attributed to the blocky nature of the comonomer. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5480–5494, 2006  相似文献   

20.
The regularities, kinetics and mechanisms of flocculation of Escherichia coli and B. thuringiensis var. israelensis (Bti) cellular suspensions by water-soluble polymers-and first of all cationic polyelectrolytes of different charge density and stiffness of the macromolecule chain have been investigated. The effect of the focculant dose and nature, its charge density, the hydrophobic-hydrophilic balance in macromolecule, the suspension concentration, the mode of adding the reagent, the pH and the medium composition on the degree of aggregation of cells both in perikinetic regime and in a flowing system is considered. It has been shown that the main laws of microorganism's suspension flocculation are the same as the laws of flocculation of inorganic dispersions but at the same time the first process is much more complicated because the cell-flocculant interactions are strongly affected by products of cell metabolism, components of the culture liquor, pH value, electrolyte content as well as by the changing structure of the cell surface. On the basis of complex measurements of polymer adsorption and its effect on the electrokinetic potential and degree of aggregation of cells, a conclusion is made that the aggregation of E. coli cells by flexible polyelectrolytes like polydiethylaminoethylmetacrylate and its copolymers with acrylic acid, acrylamide and vinylpyrrolidone is due to charge neutralization, while the flocculation in the presence of rigid-chain chitosan and its derivatives is caused mainly by "bridging" between cells via adsorbed macromolecules. Extraction of cells from suspension can be enhanced by combination of electroflotation and flocculation by cationic polyelectrolytes. It has been shown that dilute suspensions of Bti bacteria can be effectively flocculated and concentrated using different cationic and anionic polyelectrolytes that is necessary for its formulation and use as anti-mosquito agent.  相似文献   

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