Structure of sodium carboxymethyl cellulose aqueous solutions: A SANS and rheology study

We report a small angle neutron scattering (SANS) and rheology study of cellulose derivative polyelectrolyte sodium carboxymethyl cellulose with a degree of substitution of 1.2. Using SANS, we establish that this polymer is molecularly dissolved in water with a locally stiff conformation with a stretching parameter . We determine the cross sectional radius of the chain ( 3.4 Å) and the scaling of the correlation length with concentration (ξ = 296 c^?1∕2Å for c in g/L) is found to remain unchanged from the semidilute to concentrated crossover as identified by rheology. Viscosity measurements are found to be in qualitative agreement with scaling theory predictions for flexible polyelectrolytes exhibiting semidilute unentangled and entangled regimes, followed by what appears to be a crossover to neutral polymer concentration dependence of viscosity at high concentrations. Yet those higher concentrations, in the concentrated regime defined by rheology, still exhibit a peak in the scattering function that indicates a correlation length that continues to scale as . © 2014 The Authors. Journal of Polymer Science Part B: Polymer Physics Published by Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 492–501     

Structure,rheology and electrospinning of zein and poly(ethylene oxide) in aqueous ethanol solutions

This study provided a clear correlation of the structure and rheology of solutions with the morphologies of EFM made up of proteins and polymers.     

Nonlinear rheology of aqueous solutions of hydrophobically modified hydroxyethyl cellulose with nonionic surfactant

Shear thickening and strain hardening behavior of hydrophobically modified hydroxyethyl cellulose (HMHEC) aqueous solutions was experimentally examined. We focused on the effects of polymer concentration, temperature, and addition of nonionic surfactant. It is found that HMHEC shows stronger shear thickening at intermediate shear rates in a certain concentration range. In this range, the zero-shear viscosity scales with polymer concentration as eta(0) approximately c(5.7), showing a stronger concentration dependence than for more concentrated solutions. The critical shear stress for complete disruption of the transient network follows tau(c) approximately c(1.62) in the concentrated regime. Dynamic tests of the transient network on addition of surfactants show that the enhanced zero-shear viscosity is due to an increase in network junction strength, rather than their number, which in fact decreases. The reduction in the junction number could partly explain the weak variation of strain hardening extent for low surfactant concentrations, because of longer and looser bridging chain segments, and hence lesser nonlinear chain stretching.     

Aggregation and adsorption behavior of low concentration aqueous solutions of hexadecyltrimethylammonium ortho, meta, and parafluorobenzoate

The aggregation properties of 2-, 3-, and 4-fluorobenzoic acids (2FBA, 3FBA, and 4FBA, respectively) and their salts with hexadecyltrimethylammonium cations (HTA2FB, HTA3FB, and HTA4FB) in water were studied with a battery of techniques. Their activity at the air/solution interface has been also studied. The position of the fluorine atom in the acid affected the solubility, adsorption, and aggregation in the pure acids solutions. The 4FBA is less water soluble, more hydrophobic, and has the lower critical aggregation concentration of the three isomers. The behavior of the HTA2FB compound in aqueous solution is different from that of HTA3FB and HTA4FB. The critical micelle concentration, critical concentration for sphere-to-rod-like micelle transition, and Krafft point of HTA3FB and HTA4FB are lower than those of the other surfactant but their surface activities are higher. The differences between the HTA2FB and the other two surfactants have been explained on the basis of the regular solution theory of mixed micelles and in light of the analysis of the hydration shell of the acids through molecular dynamic simulations. The results of the present work suggest that the different behaviors are due to a combination of different dehydration tendencies and the steric possibility of inclusion of the counterions in the micelle palisade layer. The formation of rod-like micelles by HTA2FB, while the tetradecyltrimethylammonium 2-fluorobenzoate only forms spherical aggregates, is explained on the basis of the packing parameter. The mentioned factors are complementary to others presented in literature. These conditions may be used in the rational design of micelles by means of molecular dynamics simulations, reducing the trial-and-error approach used to date.     

Anion adsorption of lanthanides from aqueous organic nitric acid solutions

Conclusion The equilibrium parameters of the anion exchange of lanthanides in aqueous organic complexing media are related to the acceptor properties of the organic solvents.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 924–927, April, 1987.     

Dynamic light scattering and rheology studies of aqueous solutions of amphiphilic sodium maleate containing copolymers

Light scattering techniques, video particle‐tracking microrheology, and bulk rheology were employed to examine the structure and dynamics of a series of alternating sodium maleate copolymers with moderately hydrophobic comonomers (diisobutylene, styrene, and isobutylene) in aqueous solutions. The scaling dependence of the specific viscosity (η_sp) on the polyelectrolyte concentration (c) was studied with and without added salt; similar trends were found in both conventional rheology and particle‐tracking microrheology measurements, showing good performance of the technique with flexible polyelectrolytes. Furthermore, with dynamic light scattering performed in high added salt conditions, we examined the behavior of the amplitude of the fast mode, which is in agreement with scaling predictions. In contrast, the slow modes are not understood and display three separate behaviors for the wavevector q dependence of the decay rate (Γ), depending on the comonomer; superdiffusive (Γ ～ q^2.7, isobutylene) possibly because of sticky aggregates, wavevector independent (Γ ～ q⁰, styrene) most likely because of coupled polyion‐ion diffusion and diffusive (Γ ～ q^2.0, diisobutylene) presumably because these aggregates are not sticky. The hydrophobicity of the comonomer appears to switch the aggregation process between “open,” “closed,” and “non” association for isobutylene, diisobutylene, and styrene respectively. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 774–785, 2007     

The state and adsorption behaviour of traces of cadmium in aqueous solutions

The state of trace cadmium in aqueous nitrate solutions has been analysed by dialysis, centrifugation and electromigration. It has been found that Cd²⁺ ions prevail in solutions of pH <5, whereas colloidal forms are present at higher pH, together with the ionic or molecular products of cadmium hydrolysis. The nature and abundance of the colloids depends on the concentration of cadmium. Mostly pseudocolloids are formed in ≤5 × 10⁻⁷ M solutions due to adsorption of Cd(OH)₂ and CdOH⁺ on foreign colloidal impurities. At 5 × 10⁻⁶ M polymerisation of the hydrolytic products probably takes place with formation of colloidal cadmium hydroxide or basic salts. Adsorption of traces of cadmium has been studied on glass and plexiglass as a function of pH, age and composition of the solution and concentration of cadmium. Probable mechanisms of adsorption have been proposed.     

Lead ion adsorption from aqueous solutions in modified Algerian montmorillonites

The adsorption of lead (II) ions on three Algerian montmorillonites (sodium, non-sodium, and acidic-activated) was studied. Transmission electron microscopy coupled with energy dispersive X-ray analysis, X-ray fluorescence and physical adsorption of gases were used to characterize the clays. This characterization has shown than the activation with acid increases the surface area as a consequence of the rupture of the laminar structure. The effect of the pH in the lead adsorption capacity was analyzed. The results show that adsorption is strongly depended on the pH. At low pH values, the mechanism that governs the adsorption behavior of clays is the competition of the metal ions with protons. Between pH 2 and 6, the main mechanism is an ion exchange process. The kinetics of the adsorption is tested with respect to pseudo-first-order and second-order models. The adsorption process, gives a better fit with the Langmuir isotherm, being the monolayer capacity ranging between 18.2 and 24.4?mg?g^?1. The adsorption of lead decreased in the order Acidic-M₂?>?M₂?>?M₁. Thermodynamic parameters such as ??H, ??S, and ??G were calculated. The adsorption process was found to be endothermic and spontaneous. The enthalpy change for Pb(II) by M₁ adsorption has been estimated as 60?kJ?mol^?1, indicating that the adsorption of Pb(II) by all montmorillonites used corresponds to a physical reaction. The adsorption capacity of washed Acidic-M₂ was very high compared to M₂ and M₁.     

Surface adsorption and micelle formation of aqueous solutions of polyethyleneglycol and sugar surfactants

The surface tension of aqueous solutions of tetraethyleneglycol octyl ether (C8E4) and octyl-β-d-maltopyranoside (OM) mixture was measured as a function of the total molality of surfactants and the composition of OM under atmospheric pressure at 298.15 K by drop volume technique. The results of surface tension measurements were analyzed by originally developed thermodynamic equations, then phase diagrams of adsorption and micelle formation were constructed. From the analysis of the surface tension data, it was found that the C8E4 and OM molecules interact attractively in the adsorbed film and the excess Gibbs energy of adsorption can be compared with those observed in typical cationic–nonionic surfactant systems; nevertheless, they are mixed almost ideally in the mixed micelle. Judging from a negative excess surface area calculated by differentiating the excess Gibbs energy by the surface tension, we concluded that the attraction between C8E4 and OM molecules is a short-range one originated in the hydrogen bonding between them which favors the planar configuration.     

Removal of lead from aqueous solutions by adsorption with surface precipitation

An activated carbon from Coconut (Cocos nucifera) shells was prepared by physical activation with carbon dioxide and water vapor. The activated carbon obtained has a surface area of 1058 m² g^?1 and such a high micropore volume of 0.49 cm³ g^?1. This carbon was studied for the removal of lead from water. Sorption studies were performed at 30 °C, at different pH and adsorbent doses, in batch mode. Lead precipitation was observed on the surface of the activated carbon. Maximum adsorption occurred at pH 9 for an adsorbent dose of 2 g L^?1. Kinetic studies, at the initial concentration of 150 mg L^?1 of lead, pH 5 and an adsorbent dose of 1 g L^?1, yielded an equilibrium time of 50 h for this activated carbon. The kinetic data were modeled with the pseudo first order, the pseudo second order and the Bangham models. The pseudo second order model fitted the data well. The sorption rate constant (7 × 10^?4 mol^?1 Kg s^?1) and the maximum amount of lead adsorbed (0.23 mol kg^?1) are quite good compared to the data found in literature. Sorption equilibrium studies were conducted in a concentration range of lead from 0 to 150 mg L^?1. In an aqueous lead solution with an initial concentration of 30 mg L^?1, at pH 5, adsorbent dose 1 g L^?1, activated Coconut shell carbon removed at equilibrium 100 % of the heavy metal. The equilibrium data were modeled with the Langmuir and Freundlich equations, of which the former gave the best fit. The Langmuir constants Q_{max eq} (0.23 mol kg^?1) and K_L (487667 L mol^?1) are in good agreement with literature. XPS studies identified adsorbed species as lead carbonates and/or lead oxalates and precipitates as lead oxide and/or lead hydroxide on the activated carbon surface. The Coconut shell activated carbon is a very efficient carbon due to its high surface area, to the presence of many micropores on its surface and to the presence surface groups like hydroxyls promoting adsorption in the porous system and lead crystal precipitation on the activated carbon surface.     

Removal of copper from aqueous solutions by adsorption on activated carbons

The adsorption isotherms of Cu(II) ions from aqueous solutions in the concentration range 40–1000 mg l⁻¹ on two samples of granulated and two samples of activated carbon fibres containing varying amounts of associated oxygen have been reported. The adsorption isotherms are type I of BET classification showing initially a rapid adsorption tending to be asymptotic at higher concentrations. The amounts of oxygen associated with the carbon surface has been enhanced by oxidation with nitric acid and ammonium persulphate in the solution phase and with oxygen gas at 350°C and decreased by degassing of the oxidized carbon samples at 400, 650 and 950°C. The adsorption of Cu(II) ions increases on oxidation and decreases on degassing. The increase in adsorption on oxidation depends on the nature of the oxidative treatment while the decrease in adsorption on degassing depends on the temperature of degassing. This has been attributed to the increase in the carbon–oxygen acidic surface groups on oxidation and their decrease on degassing. Suitable mechanisms consistent with the results have been proposed.     

Thermodynamic study of triclosan adsorption from aqueous solutions on activated carbon

The change in the thermodynamic properties of triclosan adsorption on three activated carbons with the different surface chemistry was studied through immersion calorimetry and equilibrium data; the amount adsorbed of triclosan (Q) during calorimetry was determined and correlated with the energy associated with adsorbate–adsorbent interactions in the adsorption process. It was noted that triclosan adsorption capacity decreases with an increase in oxygenated surface groups. For an activated carbon oxidized with HNO₃ (OxAC), the amount adsorbed was 8.50?×?10^?3 mmol g^?1, for a activated carbon without modification (GAC) Q?=?10.3?×?10^?3 mmol g^?1 and for a activated carbon heated at 1073 K (RAC1073) Q?=?11.4?×?10^?3 mmol g^?1. The adsorbed amounts were determined by adjusting the isotherms to the Sips model. For the activated carbon RAC1073, the immersion enthalpy (ΔH_imm) was greater than those of the other two activated carbons due to the formation of interactions with the solvent (ΔH_immOxAC?=?? 27.3 J g^?1?<?ΔH_immGAC?=?? 40.0 J g^?1?<?ΔH_imm RAC1073?=???60.7 J g^?1). The changes in the interaction enthalpy and Gibbs energy are associated with adsorbate–adsorbent interactions and side interactions such as the adsorbate–adsorbate and adsorbate–solvent interactions.

     

Selective adsorption of cerium on activated charcoal from aqueous electrolyte solutions

The adsorption of cerium on activated charcoal has been studied as a function of shaking time, pH, concentration of adsorbate and temperature. The adsorption of cerium obeys Freyndlich and Langmuir isotherms. The influence of different cations and anions on cerium adsorption has been exmined. The adsorption of other metal ions on activated charcoal has been studied under specified conditions to check its selectivity for cerium adsorption. Consequently, cerium was removed from a mixture containing Ce, Ba, Sr, Ru, Cs, Cr, Nd, Pr and In. About 99% of the adsorbed cerium on activated charcoal can be recovered with 3M HNO₃ solution. A wavelelngth dispersive X-ray fluorescence spectrometer was used for measuring the cerium concentration.     

Effects of nonionic surfactant and associative thickener on the rheology of polyacrylamide in aqueous glycerol solutions

The effect of a low molecular weight nonionic surfactant and an acrylic associative thickener on the rheology of polyacrylamide in aqueous glycerol solutions under steady shear was experimentally investigated. The nonionic surfactant (Tween20), associative thickener (Acrysol TT935) and polyacrylamide (Separan AP30) underwent complex molecular interactions in solution as reflected by rheological measurements. The surfactant also interacted with the glycerol solvent. The addition of surfactant in aqueous glycerol solutions reduced the surface tension, as well as the solution viscosity, at low surfactant concentration. The solution viscosity went through a minimum at certain surfactant concentration, depending on the composition of glycerol/water mixture, before increasing again. Similar behavior was found when the surfactant was added to the polyacrylamide solution, except there was an initial increase in the viscosity before the reduction. The associative thickener, Acrysol TT935 (an anionic acrylic emulsion copolymer) exhibited a strong affinity with polyacrylamide in solution, as indicated by a sharp increase in the solution viscosity. The dilute polyacrylamide solution became highly elastic in the presence of either the nonionic surfactant on the associative thickener. A threestage model was proposed to describe the surfactant/thickener/polymer interactions.     

Thermodynamics, adsorption kinetics and rheology of mixed protein-surfactant interfacial layers

Depending on the bulk composition, adsorption layers formed from mixed protein/surfactant solutions contain different amounts of protein. Clearly, increasing amounts of surfactant should decrease the amount of adsorbed proteins successively. However, due to the much larger adsorption energy, proteins are rather strongly bound to the interface and via competitive adsorption surfactants cannot easily displace proteins. A thermodynamic theory was developed recently which describes the composition of mixed protein/surfactant adsorption layers. This theory is based on models for the single compounds and allows a prognosis of the resulting mixed layers by using the characteristic parameters of the involved components. This thermodynamic theory serves also as the respective boundary condition for the dynamics of adsorption layers formed from mixed solutions and their dilational rheological behaviour. Based on experimental studies with milk proteins (β-casein and β-lactoglobulin) mixed with non-ionic (decyl and dodecyl dimethyl phosphine oxide) and ionic (sodium dodecyl sulphate and dodecyl trimethyl ammonium bromide) surfactants at the water/air and water/hexane interfaces, the potential of the theoretical tools is demonstrated.The displacement of pre-adsorbed proteins by subsequently added surfactant can be successfully studied by a special experimental technique based on a drop volume exchange. In this way the drop profile analysis can provide tensiometry and dilational rheology data (via drop oscillation experiments) for two adsorption routes — sequential adsorption of the single compounds in addition to the traditional simultaneous adsorption from a mixed solution. Complementary measurements of the surface shear rheology and the adsorption layer thickness via ellipsometry are added in order to support the proposed mechanisms drawn from tensiometry and dilational rheology, i.e. to show that the formation of mixed adsorption layer is based on a modification of the protein molecules via electrostatic (ionic) and/or hydrophobic interactions by the surfactant molecules and a competitive adsorption of the resulting complexes with the free, unbound surfactant. Under certain conditions, the properties of the sequentially formed layers differ from those formed simultaneously, which can be explained by the different locations of complex formation.     

Uranium adsorption by non-treated and chemically modified cactus fibres in aqueous solutions

The adsorption efficiency of Opuntia ficus indica fibres regarding the removal of hexavalent uranium [U(VI)] from aqueous solutions has been investigated prior and after the chemical treatment (e.g. phosphorylation and MnO₂-coating) of the biomass. The separation/removal efficiency has been studied as a function of pH, uranium concentration, adsorbent mass, ionic strength, temperature and contact time. Evaluation of the experimental data shows that biosorption is strongly pH-depended and that the MnO₂-coated product presents the highest adsorption capacity followed by the phosphorylated and non-treated material. Experiments with varying ionic strength/salinity don’t show any significant effect on the adsorption efficiency, indicating the formation of inner-sphere surface complexes. The adsorption reactions are in all cases exothermic and relatively fast, particularly regarding the adsorption on the MnO₂-coated product. The results of the present study indicate that adsorption of uranium from waters is very effective by cactus fibres and particularly the modified treated fibres. The increased adsorption efficiency of the cactus fibres is attributed to their primary and secondary fibrillar structure, which result in a relative relative high specific surface available for sorption.     

Surface rheology of saponin adsorption layers

Extracts of the Quillaja saponaria tree contain natural surfactant molecules called saponins that very efficiently stabilize foams and emulsions. Therefore, such extracts are widely used in several technologies. In addition, saponins have demonstrated nontrivial bioactivity and are currently used as essential ingredients in vaccines, food supplements, and other health products. Previous preliminary studies showed that saponins have some peculiar surface properties, such as a very high surface modulus, that may have an important impact on the mechanisms of foam and emulsion stabilization. Here we present a detailed characterization of the main surface properties of highly purified aqueous extracts of Quillaja saponins. Surface tension isotherms showed that the purified Quillaja saponins behave as nonionic surfactants with a relatively high cmc (0.025 wt %). The saponin adsorption isotherm is described well by the Volmer equation, with an area per molecule of close to 1 nm(2). By comparing this area to the molecular dimensions, we deduce that the hydrophobic triterpenoid rings of the saponin molecules lie parallel to the air-water interface, with the hydrophilic glucoside tails protruding into the aqueous phase. Upon small deformation, the saponin adsorption layers exhibit a very high surface dilatational elasticity (280 ± 30 mN/m), a much lower shear elasticity (26 ± 15 mN/m), and a negligible true dilatational surface viscosity. The measured dilatational elasticity is in very good agreement with the theoretical predictions of the Volmer adsorption model (260 mN/m). The measured characteristic adsorption time of the saponin molecules is 4 to 5 orders of magnitude longer than that predicted theoretically for diffusion-controlled adsorption, which means that the saponin adsorption is barrier-controlled around and above the cmc. The perturbed saponin layers relax toward equilibrium in a complex manner, with several relaxation times, the longest of them being around 3 min. Molecular interpretations of the observed trends are proposed when possible. Surprisingly, in the course of our study we found experimentally that the drop shape analysis method (DSA method) shows a systematically lower surface elasticity, in comparison with the other two methods used: Langmuir trough and capillary pressure tensiometry with spherical drops. The possible reasons for the observed discrepancy are discussed, and the final conclusion is that the DSA method has specific problems and may give incorrect results when applied to study the dynamic properties of systems with high surface elasticity, such as adsorption layers of saponins, lipids, fatty acids, solid particles, and some proteins. The last conclusion is particularly important because the DSA method recently became the preferred method for the characterization of fluid interfaces because of its convenience.