Hydrolysis of cationic polyacrylamides

The alkaline hydrolysis of two acrylamide-based polyelectrolytes has been investigated. The experiments were carried out in buffered aqueous solutions in the pH range of 3.5–8.5 and in the temperature range of 22–50°C. ¹³C-NMR analysis of the hydrolysis product showed that choline chloride was the substance released upon hydrolysis. The decrease in charge density of the copolymer due to the hydrolysis was studied by polyelectrolyte titration and nitrogen analysis. The results show that the rate of hydrolysis increased with increasing pH or increasing temperature. In the hydrolysis of C-PAM 1 at 22°C and pH 6, the half-life of the cationic groups was 10 days. At pH 7 the half-life was shorter, 24 h, and at pH 8.5 the reaction was very fast with a half-life of about 0.25 h. The charged groups on C-PAM 2, the polymer with the higher charge density of the two polymers studied, have somewhat longer half lives than those on C-PAM 1. This can be explained by the structure of the polymers.     

Synthetic polyelectrolytes of varying charge densities but similar molar mass based on acrylamide and their applications on palm oil mill effluent treatment

Cationic polyacrylamides of varying charge densities but similar molar mass were synthesized using free radical polymerization and Mannich reaction, characterized by different methods and applied as flocculants for palm oil mill effluents (POME). Flocculant performance was assessed by determining the polymer dosage, pH of POME and the removal efficiency of the resulting supernatants using turbidity, suspended solids and chemical oxygen demand as indicators. The pH of POME was adjusted to 3 prior to flocculation. It was found that varying the charge density of the polymer from 48.2-485 C/g affects flocculant performance significantly. Polymer adsorption increased as the charge density of the polymers increased. High charge density cationic polyacrylamide (485 C/g) is the most effective polymer as it obtains 98% turbidity removal, 98.7% suspended solids removal and 54% chemical oxygen demand removal with a dosage as low as 32 mg/l at pH 3 of POME.     

Partitioning of anionic/nonionic polysaccharides in a segregative system of anionic polyelectrolyte mixtures in aqueous solution: Effects of polymer charge density and ionic strength of solution

The partitioning of three polysaccharides, Dextran sulfate (DxS), λ‐Carrageenan (CAR), and Dextran (Dx), and its dependence on polymer charge density and ionic strength have been investigated in the segregative mixture of poly(sodium styrene sulfonate) (NaPSS) and sodium polyacrylate‐acrylamide copolymers, NaP(AA/AM), of variable charge density, in aqueous solutions. It is shown that the solubility of all the three may be zero or finite in one or both phases, but the preferred phase is determined by the charge density on the copolymer. When charge densities are equal on the phase forming polymers, the saccharides CAR and Dx favor the phase rich in PSS, but they have greater affinity for the polymer of lower charge density when the charge densities on phase polymers are unequal. The partitioning behavior of DxS is the opposite of the other two polysachharides with respect to which phase it has the greatest affinity for. The values of the partitioning coefficients show that the system may be potentially useful for the purification of polysaccharides and other macromolecules, if appropriate conditions are selected. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1728–1734, 2006     

Monitoring the stability of nanosized silica dispersions in presence of polycations by a novel centrifugal sedimentation method

The stability of Aerosil‐silica dispersions is analyzed in dependence on the addition of polycations with different charge density and hydrophobic modification using the analytical centrifuge LUMiSizer. This novel centrifugal sedimentation method allows the direct calculation of the stability parameters like sedimentation velocity and prediction of the shelf life. The highly charged polycation poly (diallyl‐dimethylammonium chloride) (PDADMAC) is compared with tailored cationic polyelectrolytes of equal degree of polymerization but lower and different charge density as well as various hydrophobic substitutions. The used technique allows to accelerate demixing and to quantify the stability of dispersions in a direct way. All polymers under study are able to stabilize aerosil dispersions, but the shelf life strongly depends on the polymer concentration. Typically for polycations, the stability increases with the polymer concentration whereas at low‐polymer content flocculation can be detected. In this context, the behavior of PDADMAC and three cationic PVB derivatives is similar, but, whereas the stability of PDADMAC containing dispersions decreases at higher polymer concentrations, PVB derivatives are effective stabilizers at higher concentrations too. The highest increase of the stability with increasing polymer concentration is obtained with the ampholytic terpolymer TP that has the lowest cationic charge. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis of copolymers containing opposite charged comonomers and their interactions with metal ions

Radical polymerization was used to synthesize three copolymers of [3‐(methacryloylamino)propyl]trimethylammonium chloride and methacrylic acid [P(MPTA‐co‐MA)]; three copolymers of MPTA and 2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid [P(MPTA‐co‐APSA)], which had different feed monomer mole ratios but a constant total number of moles (0.03 mol); and the homopolymers poly(MPTA), poly(MA), and poly(APSA). The yields for all homopolymers and copolymers were over 70 and 90%, respectively. All products were dissolved in water, purified, and fractioned by an ultrafiltration membrane with different exclusion limits of the molecular weight (3,000, 10,000, 30,000, and 100,000 g mol^?1). All fractions were lyophilized. The polymeric materials were characterized by FTIR and ¹H‐NMR spectroscopy. The metal ion interaction with the hydrophilic polymers was determined as a function of the pH and the filtration factor. It was dependent on the pH, type of ligand group, and charge of the metal ion. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1715–1721, 2003     

Double stimuli-responsive behavior of linear and star-shaped poly(N,N-diethylaminoethyl methacrylate) in aqueous solution

We report on the synthesis and characterization of linear and star-shaped poly(N,N-diethylaminoethyl methacrylate) (PDEA). The synthesis was accomplished by Atom Transfer Radical Polymerization (ATRP) via a core-first approach using sugar-based multifunctional initiators. The investigation of the solution properties in water shows that PDEA is both pH- and temperature-responsive, analogous to the behavior of poly(N,N-dimethylaminoethyl methacrylate) (PDMA). In literature, PDEA is frequently referred to as being only pH-sensitive. The critical pH values for the aggregation are close to the apparent pK_a values in all cases, i.e. a high charge density is necessary to keep the polymers soluble. The cloud points show a strong dependence on the pH value of the solution but no dependence on either molecular weight or architecture. Thus, the two polymers differ only quantitatively, as PDEA has cloud points about 40 K lower than PDMA and critical pH values which are 1.5-2 units lower than PDMA.     

Effect of the type of polymer functional groups on the structure of its film formed on the alumina surface – Suspension stability

The effects of polymer functional group and solution pH on stability of colloidal Al₂O₃ water suspension were studied. Both the nonionic polymers: polyethylene glycol (PEG), polyethylene oxide (PEO) and the ionic ones: polyacrylic acid (PAA), polyacrylamide (PAM), polyvinyl alcohol (PVA) were used in the experiments. The following methods were applied: turbidimetry (stability measurements), spectrophotometry (determination of polymer adsorption), viscosimetry (thickness of polymer adsorption layer), potentiometric titration (solid surface charge density) and microelectrophoresis (potential zeta). It was shown that anionic polyacrylic acid is both the most effective stabilizer (at pH 9) and flocculant (at pH 3) of the alumina suspension. Its carboxyl groups have the greatest affinity for the surface active sites (the largest adsorption) of all functional groups present in the other examined polymers. The latter, i.e. hydroxyl (PEG, PEO, and PVA) and acetate (PVA) show a much lower affinity for the Al₂O₃ surface (negligible adsorption) and minimally affect the stability of the alumina-solution system.     

Electrochemical polymerisation of phenol in aqueous solution on a Ta/PbO<Subscript>2</Subscript> anode

This paper deals with the treatment of aqueous phenol solutions using an electrochemical technique. Phenol can be partly eliminated from aqueous solution by electrochemically initiated polymerisation. Galvanostatic electrolyses of phenol solutions at concentration up to 0.1 mol dm⁻³ were carried out on a Ta/PbO₂ anode. The polymers formed are insoluble in acidic medium but soluble in alkaline. These polymers were filtered and then dissolved in aqueous solution of sodium hydroxide (1 mol dm⁻³). The polymers formed were quantified by total organic carbon (TOC) measurement. It was found that the conversion of phenol into polymers increases as a function of initial concentration, anodic current density, temperature, and solution pH. The percentage of phenol polymerised can reach 15%.     

Hydrophobically modified acrylamide‐based polybetaines. I. Synthesis,characterization, and stimuli‐responsive solution behavior

Acrylamide‐based, hydrophobically modified (HM) polybetaines containing N‐butylphenylacrylamide (BPAM) and varying amounts of the sulfobetaine monomer 3‐(2‐acrylamido‐2‐methylpropanedimethylammonio)‐1‐propanesulfonate (AMPDAPS) or the carboxybetaine monomer 4‐(2‐acrylamido‐2‐methylpropyldimethylammonio)butanoate (AMPDAB) were synthesized by micellar copolymerization. The corresponding control (co)polymers lacking BPAM or betaine comonomers were also prepared. The terpolymers were characterized by ¹³C‐NMR and UV spectroscopy, classical light scattering, and potentiometric titration. Low charge density polymers contained 3.9–8.6 mol % betaine, whereas the high charge density systems contained 17–25 mol % betaine; the HM polymers contained up to 1.0 mol % BPAM as the hydrophobe. The weight‐average molecular weights of the polymers ranged from 4.19 × 10⁵ to 1.29 × 10⁶ g/mol, and most HM polymers exhibited negative second virial coefficients. The pK_a of the carboxybetaine moieties was found to increase with increasing levels of hydrophobic and betaine comonomer incorporation. The response of aqueous polymer solutions to various external stimuli, including changes in solution pH and electrolyte concentration, was investigated using rheological analysis. The solution behavior of the polymers was characteristic of HM polyacrylamides and acrylamide‐based polyzwitterions. The high charge density HM polycarboxybetaine exhibited unusual solution behavior that can be explained in terms of electrostatic, hydrophobic, and hydrogen‐bonding associations. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 647–657, 2004     

Parameters affecting the performance of polyelectrolytes as aids to water clarification

An investigation of the flocculation of silica and alumina suspensions by a series of synthetic flocculants of a wide range of charge density both anionic and cationic in nature has been carried out. The extent of flocculation was determined by measurements of settling rate, sediment volume and supernatant clarity. The effect of the pH of the suspension on the performance of a number of selected polymers has been investigated. In the systems examined, flocculation was largely controlled by the charge carried by the suspended particles and polymer molecules. The dosage/settling rate characteristics of kaolin suspensions flocculated with non-ionic polymers of varying molecular weight are reported. The dosages of non-ionic polymers required for optimum flocculation of kaolin suspensions of varying solids content have been measured. At low particle concentrations bridging is less effective, and is probably reduced due to the adsorption of polymer molecules on to single particles.     

Flocculation of kaolin suspension with cationic polymer

Flocculation experiments have been carried out using cationic polymers and kaolin suspensions. The effects of polymer dosage, kaolin concentration, pH, agitation, molecular weight and charge density of polymer, concentration of polymer solution, and addition of inorganic salt were systematically examined. It was found that two optimal points of polymer dosage exist between 0 to 8 × 10^?3 kg/kg-kaolin. The flocs formed at each optimal dosage are different from each other in shape and in size. It is concluded that these two kinds of flocculation are respectively caused by the neutralization of the surface charge of the particles due to the adsorption of free polymer and by the incomplete neutralization owing to the presence of polymer droplets.     

Electrochemical and structural characterization of copper recycled from anodes of spent Li-ion batteries

In this study, the charge efficiency, nucleation growth, and morphology of electrodeposited copper from spent Li-batteries were studied. The charge efficiency for these deposits shows a maximum value of 99.41%, under a charge density of 5.0 C cm^?2. Studies with the SEM technique at pH 2.0 show well-formed nuclei. At pH 4.5, the deposits take the form of dendrites. XRD analysis shows that, in both cases, a Cu₂O structure is present, but with a large amount at pH 4.5, evidenced by peaks of [002] and [110] directions.     

Modification of the molar anionic charge density of acetone–formaldehyde–sulfite dispersant to improve adsorption behavior and effectiveness in the presence of CaAMPS®‐co‐NNDMA cement fluid loss polymer

Sulfonated aldol polycondensates were synthesized from acetone, formaldehyde, and different amounts of sodium sulfite, resulting in polymers with varying degrees of sulfonation (DS). The anionic charge amount of these macromolecules measured by polyelectrolyte titration decreased with lower DS. The effectiveness of the acetone–formaldehyde–sulfite (AFS) polycondensates as cement dispersant was found to depend on the amount of polymer adsorbed on cement. AFS adsorption decreases with lower DS. Interaction and compatibility between AFS and CaAMPS®‐co‐NNDMA fluid loss additive was studied by formulating binary additive systems composed of one of the modified AFS polymers and CaAMPS‐co‐NNDMA. At high DS, AFS adsorbs strongly and prevents CaAMPS‐co‐NNDMA from adsorbing in sufficient amounts on the cement surface. The result is poor fluid loss control of the cement slurry. AFS polymers with lower DS, however, allow simultaneous adsorption of both polymers in sufficient quantities to provide good fluid loss control and low rheology at the same time. Thus, effectiveness of both additives was retained. Obviously, effectiveness of such multi‐admixture systems depends on the adjustment of the adsorption behavior of the individual components relative to each other. Molar anionic charge density of the polymers was found to be a major parameter influencing their relative adsorption behavior. The AFS polymer with DS = 0.2 possesses a molar anionic charge density comparable to CaAMPS‐co‐NNDMA. Thus, when admixtures with similar molar anionic charge densities are used, the performance of one component is not negatively influenced by the other. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Magnetic field effects on the active dissolution of iron

The impact of superimposed magnetic fields on the behavior of iron in 0.05 M H₂SO₄ at low anodic polarization was investigated by means of potentiostatic polarization measurements. Significant magnetic field effects were observed even though the active dissolution reaction in the investigated potential region is formally charge transfer controlled. The current density can be enhanced or reduced dependent on the magnetic field to electrode configuration. The results are discussed in terms of the magnetic field impact on the surface pH value during the anodic dissolution. Our findings are likely to have important consequences for the life-time prediction of ferromagnetic components in electromagnetic devices and for future studies on magneto-electrodeposition processes.     

Electrosynthesis and electrochemical characterisation of phenazine polymers for application in biosensors

A comparative investigation has been undertaken of the electrosynthesis and electrochemical properties of three different electroactive polymers on carbon film electrode substrates: poly(neutral red) from the phenazine dye neutral red, and poly(methylene green) and poly(methylene blue), from the corresponding phenothiazine dyes. The formation of the radical cation at different potentials and the chemical structures of the monomers both influence the electropolymerisation process of the three polyaromatic dyes. Of the three, poly(neutral red) is shown to have the best adhesion at carbon film electrodes. The influence of the electrolyte and pH on film growth and on electrochemical properties was investigated. The formal potential decreased linearly with increase in pH, in the pH range from 1 to 7 for all three polymers. The modified electrodes were also characterised by electrochemical impedance spectroscopy. The bulk and interfacial characteristics of the two phenothiazine polymers were similar and oxygen-dependent, but different to those of the phenazine polymer, poly(neutral red), which were not significantly influenced by the presence of oxygen in solution. Perspectives for use in electrochemical biosensors are indicated.     

Vectorial insertion of bacteriorhodopsin for directed orientation assays in various polymeric biomembranes

Here we demonstrate the rapid reconstitution and preserved functionality of vectorially-inserted bacteriorhodopsin from Halobacterium Halobium in ABA block copolymer thin films. We have utilized a triblock copolymeric membrane that simulates biological systems as a matrix to enable protein refolding to observe the activity of bacteriorhodopsin in purple membrane form as well as in individual molecules. In addition to observing protein-polymer compatibility properties using polymers of varying lengths (4 vs. 8.4 nm in height) and compositions (UV-cross-linkable methacrylate or acrylate ended), we have observed that vectorial insertion of the proteins, and hence, the directionality of proton pumping is dependent upon the pH of the medium to manipulate the asymmetric charge density of the polymer membrane during reconstitution.     

Surface Charge of Variable Porosity Al2O3(s) and SiO2(s) Adsorbents

The surface charge properties of two SiO₂ and three Al₂O₃ mineral adsorbents with varying degrees of framework porosity were investigated using discontinuous titration and ion adsorption methodologies. Points of zero net charge (p.z.n.c) for porous and non-porous SiO₂ were <2.82 and for Al₂O₃ minerals ranged from 6.47–6.87. Silica surfaces possessed very slight negative charge in the acid pH range (pH < 7) and significant dissociation of silanol groups occurred at pH > 7. Variation of surface charge density with aqueous proton concentration was nearly identical within a mineral type (i.e., SiO₂ or Al₂O₃) irrespective of the degree of framework porosity, indicating that the densities of dissociable surface sites are equivalent, when normalized to surface area. The results suggest that the use of titration methods alone may be insufficient for thorough surface charge characterization, particularly at low and high pH. Proton titrations should be coupled with concurrent ion adsorption measurements to confirm surface charge development. Discontinuous proton titration and ion adsorption data, which were in agreement in the slightly acidic through slightly basic pH range, both indicated that p.z.n.c. was equal to the point of zero net proton charge (p.z.n.p.c.) for the variable charge minerals investigated.     

Charge density effects on polyelectrolyte dynamic rheology

The dynamic rheological properties of an uncharged polymer and charged polyelectrolytes were evaluated in salt‐free water at various concentrations above the entanglement concentration. A poly(acrylic acid) homopolymer was used as the uncharged polymer and was ionized to anionic poly(acrylic acid‐co‐sodium acrylate) at five levels of ionization (0.05, 0.10, 0.15, 0.30, and 0.50). The polymers exhibited a terminal region at a low frequency and a plateau region at a high frequency. The dynamic data for the nonionic parent and all charged polymers could be reduced to a master curve, which indicated a similar distribution of relaxation times for the nonionic and charged polymers. The shear modulus, relaxation time, and zero shear viscosity properties exhibited a concentration and charge density dependence. Higher power‐law exponents for the rheological properties were noted for the nonionic polymer versus the charged derivatives. The number of mechanically active entanglements per number of chains increased with the polymer concentration and charge density. The total number of mechanically active entanglements per number of chains that occurred because of imposing a charge to the nonionic parent did not change with increased concentration, and this indicated a different entanglement mechanism for charged polymers in comparison with their nonionic parent. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Electrochemical and structural characterization of cobalt recycled from cathodes of spent Li-ion batteries

In this work, cobalt from spent Li-ion batteries of cellular phones was recycled using electrochemical techniques. The efficiency, structure and morphology of deposits were influenced by the pH solution and charge density. Maximum efficiency is obtained for pH = 5.40 for all charge densities analyzed. The presence of the cobalt hcp phase for both pH solutions (5.40 and 2.70) and charge density conditions (10.0 and 50.0 C cm⁻²) used in the electrodeposition process was detected by X-ray diffraction. The growth of the cobalt deposit is favored in the crystallographic direction [002] for pH = 5.40 and in the direction [110] for pH = 2.70 when the charge density is 10.0 C cm⁻². The [100] and [101] crystallographic directions of hcp phase were detected by X-ray diffractogram for both pH conditions when the charge density was increased to 50.0 C cm⁻². The potentiodynamic dissolution of the cobalt depends on its structural composition.     

Characteristics of water-absorbent polymer emulsions

Water-in-Oil (W/O) and Oil-in-Water (O/W) type water absorbent polymer emulsions were studied using two different polymerization methods. W/O type water absorbent polymer emulsions were prepared by the inverse emulsion polymerization of ammonium acrylate (AA), the quaternized salt of dimethyl-aminoethyl methacrylate (DMQ) and acrylamide (AM) with N,N-methylene-bisacrylamide (MBA) as a crosslinker. A pH sensitive water absorbent polymer emulsion was prepared by the conventional emulsion polymerization of diethyl-aminoethyl methacrylate (DEAEMA) with ethylene glycol dimethacrylate (EGDMA) as a crosslinker. It was confirmed that the water absorption capacity of crosslinked polymers in inverse emulsion was controlled by crosslink density and dissociative charge density, and the crosslinked polyDEAEMA particles had a phase transition property of swelling and shrinking with pH. The dispersions of these water swollen crosslinked polymer particles exhibited an increase in viscosity and thixotropic fluidity.