Interaction behavior in ultrafiltration of nonionic surfactant micelles by adsorption

Adsorption of nonionic surfactant micelles onto ultrafiltration (UF), membranes was studied. Two homologous series of nonionic surfactants, namely, Tritons (alkylphenol ethoxylates) and Neodols (alcohol ethoxylates), were used to characterize surface properties of two polymeric ultrafiltration membranes with 20,000 nominal cutoff. Particularly, a cellulose acetate and a polysulfone membrane were investigated. Static adsorption experiments were carried out using surfactant solutions at concentrations above their critical micelle concentration. The characterization of surface properties of UF membranes was based on the adsorption behavior of surfactant species. The adsorption extent on UF membranes was affected by the hydrophobicity-to-hydrophilicity ratio mainly determining the interactions developed at the membrane-surfactant species interface. Adsorption experimental data seem generally to fit the Langmuir isotherm model. Atomic force microscopy was used to examine the alteration of the top membrane surface morphology.     

Removal of aromatic compounds in the aqueous solution via micellar enhanced ultrafiltration: Part 1. Behavior of nonionic surfactants

The effects of nonionic surfactants having different hydrophilicity and membranes having different hydrophobicity and molecular weight cut-off on the performance of micellar-enhanced ultrafiltration (MEUF) process were examined. A homologous series of polyethyleneglycol (PEG) alkylether having different numbers of methylene groups and ethylene oxide groups was used for nonionic surfactants. Polysulfone membranes and cellulose acetate membranes having different molecular cut-off were used for hydrophobic membranes and hydrophilic membranes, respectively. The concentration of surfactant added to pure water was fixed at the value of 100 times of critical micelle concentration (CMC). The flux through polysulfone membranes decreased remarkably due to adsorption mainly caused by hydrophobic interactions between surfactant and membrane material. The decline of solution flux for cellulose acetate membranes was not as serious as that for polysulfone membranes because of hydrophilic properties of cellulose acetate membranes. The surfactant rejections for the cellulose acetate membranes increased with decreasing membrane pore size and with increasing the hydrophobicity of surfactant. On the other hand the surfactant rejections for polysulfone membranes showed totally different rejection trends with those for cellulose acetate membranes. The surfactant rejections for the polysulfone membranes depend on the strength of hydrophobic interactions between surfactant and membrane material and molecular weight of surfactants.     

A concentration polarization model for the ultrafiltration of nonionic surfactants

A theoretical model has been developed that describes ultrafiltration of nonionic surfactants. The model takes into account the fact that surfactants start to aggregate and form micelles at the critical micelle concentration. The model can be used to predict the performance of the membrane if the transport properties inside and at the membrane surface as well as the surfactant association behavior, are known. Three hydrophilic ultrafiltration membranes, made of regenerated cellulose, were used in the investigation. The cut-offs of the membranes were 10,000, 20,000, and 30,000 Da. The surfactant used in the investigation was the nonionic surfactant Triton X-100. The influence of the concentration of surfactant, transmembrane pressure and pure water flux were studied theoretically and experimentally. From the results presented in this work it can be concluded that the calculated values are in good agreement with experimental data.     

Micellar-enhanced ultrafiltration of cadmium ions with anionic–nonionic surfactants

Micellar-enhanced ultrafiltration (MEUF), a surfactant-based separation process, is promising in removing multivalent metal ions from aqueous solutions. The micellar-enhanced ultrafiltration of cadmium from aqueous solution was studied in systems of anionic surfactant and mixed anionic/nonionic surfactants. The micelle sizes and zeta potentials were investigated by dynamic light scattering measurements. The effects of feed surfactant concentration, cadmium concentration and the molar ratio of nonionic surfactants to sodium dodecyl sulfate (SDS) on the cadmium removal efficiency, the rejection of SDS and nonionic surfactants and the permeate flux were investigated. The rejection efficiencies of cadmium in the MEUF operation were enhanced with higher SDS concentration and moderate Cd concentration. When SDS concentration was fixed at 3 mM, the optimal ranges of the molar ratios of nonionic surfactants to SDS for the removal of cadmium were 0.4–0.7 for Brij 35 and 0.5–0.7 for Triton X-100, respectively. With the addition of nonionic surfactants, the SDS dosage and the SDS concentration in the permeate were reduced efficiently.     

Unexpected adsorption behavior of nonionic surfactants from glycol solvents

Adsorption and interfacial properties of model methyl-capped nonionic surfactants C8E4OMe [C8H17O(C2H4O)4CH3] and C10E4OMe [C10H21O(C2H4O)4CH3] were studied in water and water/ethylene glycol mixtures as well as pure ethylene glycol. Critical micellar concentrations (cmc's), surface tensions, and surface excess were determined using surface tension (ST) and neutron reflection (NR) as a function of solvent type and surfactant tail length. The ST results show a strong dependence on solvent type in terms of cmc. The NR data were analyzed using a single-layer model for the adsorbed surfactant films. Surprisingly, the adsorption parameters obtained in both water and pure ethylene glycol were very similar, and variations in film thickness or area per molecule are negligible in respect of the uncertainties. Similarly, for C10E4OMe, estimates for the free energies of adsorption and micellization show only a weak solvent dependence. These results suggest that for such model nonionic surfactants dilute solution properties are dictated by solvophobicity, which is quite similar for this class of water, glycol, and water-glycol mixtures. More specifically, the nature of the adsorption layer appears to be hardly affected by the type of solvent subphase. The findings highlight the significance of solvophobicity and show that model nonionic surfactants can behave very similarly in hydrogen-bonding glycol solvents and water.     

Mixed adsorption of ionic and nonionic surfactants on active carbon

Summary Adsorption depends mainly on the relative amounts of anionic and nonionic surfactants present, the equilibrium concentration and the duration of exposure. In the case of similar hydrophobic chain lengths nonionic surfactants will be adsorbed more strongly than anionic compounds, thus displacing the latter from the carbon surface.The difference in the attraction to the carbon surface can be such, that significant adsorption of anionics is only observed where anionics are present in considerable excess.Under such conditions, anionics will diffuse more rapidly into the pore system of the adsorbant than nonionics. Therefore, the surface coverage with anionics will be higher after short exposure than after a longer period of time, when replacement by nonionics has started.At very low equilibrium concentrations (corresponding to low surface coverage), adsorption of anionics will be even increased by the presence of nonionics. This is due to the formation of mixed layers and the fact that in such layers the repulsion between the charged hydrophilic groups of the anionic surfactants will decrease.

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Zusammenfassung Die Adsorption hängt entscheidend von dem Mischungsverhältnis Aniontensid/ nichtionogenes Tensid, der Gleichgewichtskonzentration und der Adsorptionszeit ab. Bei annähernd gleicher hydrophober Kette werden nichtionogene Tenside stärker adsorbiert als Aniontenside und verdrängen diese von der Kohlenstoffoberfläche. Der Unterschied in der Attraktion zur Kohlenstoffoberfläche ist so groß, daß eine signifikante Adsorption von Aniontensiden erst bei hohem Überschuß in der Mischung im Vergleich zum nichtionogenen Tensid beobachtet werden kann. Unter diesen Verhältnissen diffundieren Aniontenside schneller in das Porensystem des Adsorbens, so daß im Bereich kurzer Zeiten, bevor die Verdrängung durch das nichtionogene Tensid einsetzt, an der Oberfläche Aniontenside stärker adsorbiert sind. Im Bereich sehr geringer Gleichgewichtskonzentrationen und dementsprechend geringen Oberflächenbelegungen wird jedoch wegen der Bildung von Mischfilmen beider Tensidarten und Verminderung der gegenseitigen Abstoßung der gleichsinnig geladenen hydrophilen Gruppen des Aniontensides durch das nichtionogene Tensid die Adsorption des Aniontensids sogar gesteigert.

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With 7 figures

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Presented at IUPAC-International Conference on Colloid and Surface Science, Budapest 15–20 September 1975.     

Evaluation of adsorption of nonionic surfactants blend at water/oil interfaces

The inherent biocompatibility of Span and Tween surfactants makes them an important class of nonionic emulsifiers that are employed extensively in emulsion and foam stabilization. The adsorption of Span-Tween blend at water/oil surface of emulsion has been investigated using a population balance model for the first time. Destability of emulsion was modeled by considering sedimentation, coalescence and interfacial coalescence terms in population balance equation (PBE). The terms of coalescence efficiency and interfacial coalescence time were considered as a function of surface coverage of droplets by surfactant molecules. The surface coverage at different surfactant concentrations was determined by minimization of difference between the model predictions and experimental average droplet sizes. After optimization, the surface coverage outputs were fitted with different adsorption isotherms to evaluate the adsorption behavior of Span-Tween surfactants blend at water/oil surface. The results show that Freundlich isotherm can predict the adsorption behavior of closer to the experimental observation. Moreover, fitted parameters imply the favorable adsorption of Span-Tween blend at water/oil interface.     

Novel nonionic polymerisable surfactants based on sulfoxides. 1. Monomer synthesis and general surfactant behaviour

The synthesis, surface activity, and micellisation of a series of new nonionic polymerisable surfactants, often referred to as surfmers, are described. These monomers bear terminal vinyl groups or acrylic esters, and the nonionic sulfoxide moiety. Compared to many other nonionic hydrophilic fragments, the sulfoxide group behaves as a strongly hydrophilic fragment of small volume, that can balance up to an acryloyloxyundecyl hydrophobic chain. The incorporation of the polar acrylate moiety at the end of the hydrophobic chain seems to confer surfactant properties similar to the ones of bola amphiphiles to the monomers. Received: 22 March 2001 Accepted: 11 August 2001     

Influence of nonionic surfactants on the chromatographic behaviour of proteins in hydrophobic interaction chromatography

The chromatographic characteristics of proteins in the presence of additives of nonionic surfactants Brij-35 and Tween-80 in the conditions of descending gradient of ammonium sulfate and phenyl-coated polymeric stationary phase were investigated. It was revealed that retention factors of proteins may be regulated by use of mentioned additives. The improvement of resolution is achieved for some hardly separated pairs of proteins, viz. albumin egg/albumin bovine, aldolase/tripsin. A reversion of the elution order is observed for tripsin/chymotrypsinogen A.     

Simultaneous determination of cationic surfactants and nonionic surfactants by ion-association titration.

A simultaneous determination of cationic and nonionic surfactants has been developed using ion-association titration. Tetrabromophenolphthalein ethyl ester (TBPE) was used as an indicator. Benzalkonium reacted with TBPE to form a blue ion-associate in the organic phase. When tetrakis(4-fluorophenyl)borate was added dropwise to the solution, the color of the organic phase turned to yellow at the equivalence point. In addition, when a large amount of potassium ion was added to a solution including Triton X-100, Triton X-100 could be determined by the same technique as described above because of formation of the K+-Triton X-100 cation. The proposed method is available for the stepwise determination of cationic and nonionic surfactants in mixtures.     

Interaction of nonionic surfactants with copolymer microgel particles of NIPAM and acrylic acid

Binding of the nonionic surfactants Triton X-100 and Triton X-405 onto linear copolymers of N-isopropylacrylamide (NIPAM) and acrylic acid and to cross-linked microgel particles of similar composition but differing in their cross-link densities has been studied. The binding capacities vary for each of these polymeric systems, being smallest for the linear copolymer. The binding is also significantly less in all cases for the more hydrophilic surfactant, namely, Triton X-405. By comparing estimates of the pore or "cage" size within the microgel particles with the dimensions of the free micelles in solution, it is concluded that micelles of Triton X-100 form within the microgel particles more readily for the lower cross-linked microgel particles. However, micelles do not form as easily inside either microgel for Triton X-405. The swelling/deswelling behavior of each of the two microgels, in the presence of the surfactants, has been explained in terms of their relative binding behavior and how this contributes to the osmotic pressure difference inside and outside the microgel particles and also in terms of micelle "bridging" of the polymer network, causing shrinkage.     

Acrylic acid copolymer nanoparticles for drug delivery. Part II: Characterization of nanoparticles surface-modified by adsorption of ethoxylated surfactants

Copolymer nanoparticles of acrylic acid, acrylic amide, acrylic butylester, and methacrylic methylester with increasing content of acrylic acid were produced and surface-modified by adsorption of nonionic (Poloxamer 407, Poloxamine 908, Antarox CO 990) and ionic (Gafac RE 960) surfactants. The coated particles were characterized with regard to parameters relevant for the in vivo organ distribution: coating layer thickness, charge-reducing effect of the coating layer and surface hydrophobicity. Gafac was found to form highly charged surface layers leading to recognition by the reticuloendothelial system (RES). The hydrophobicity of the coating layers decreased with increasing thickness. The thickest coating layers were found on the most hydrophobic particles possessing least content of acrylic acid (1.9%). These particles coated with the nonionics were regarded as sufficiently hydrophilic to potentially reduce the uptake by the RES in vivo. The properties of coating layers can therefore be optimized by variation of the monomer ratios in copolymers.     

Ion-association compounds of anionic surfactants with iron(II)chelates: Part II. Selective determination of surfactants

Homologous anionic surfactants may be separated from each other by solvent extraction of their ion-association compounds with iron(II) chelates. Separations of components from a number of surfactant mixtures were investigated, and the effect of solution variables on extraction and separation was studied. A method is proposed for the determination of surfactants of various chain lengths. Applications of this method to synthetic mixtures and to biodegradation experiments are described.     

Effect of adsorption of nonionic surfactants on the stabilizing ability of latexes in preparation of epoxy emulsions

The effect exerted by adsorption of nonionic surfactants on the stabilizing ability of latexes in preparation of epoxy emulsions and on the structural-rheological properties of these emulsions was examined. The stabilizing effect was attributed to heterostabilization of particles of the mixed dispersed phase and to the strength of the structural framework formed.     

Binding on strong polyelectrolytes of mixed ionic and nonionic surfactants below their critical micelle concentration observed by fluorescence

The binding of mixed surfactants of cationic cetyltrimethylammonium bromide (CTAB) and nonionic octaethylene glycol monododecyl ether (C ₁₂E ₈) on anionic polyelectrolyte poly[2-acrylamido-2-methylpropanesulfonic acid (PAMPS)] and fluorophore-labeled copolymers containing about 40 mol% of AMPS was investigated at different mole fractions, Y , of CTAB in the surfactant mixture. The excimer emission of the cationic probe 1-pyrenemethylamine hydrochloride (PyMeA·HCl), nonradiative energy transfer (NRET) between pyrene and naphthalene labels and I ₁/ I ₃ of the pyrene label were determined by varying the total surfactant concentration, c _Surf. The I _E/ I _M value of PyMeA·HCl firstly increases and then decreases to 0 with c _Surf, showing a maximum on every curve. The critical aggregation concentration of the mixed surfactants determined from the I _E/ I _M maximum decreased from 5×10 ^-5 to 1×10 ^-5 mol/l as Y increased from 0.1 to 0.50, and then leveled off as Y increased up to unity. And at least 5×10 ^-6 mol/l CTAB was required for the mixed surfactants to bind on the PAMPS cooperatively. Equimolar binding of CTAB on AMPS was formed at I _E/ I _M=0 when Y =0.25, while at Y =0.1 some CTAB molecules in the mixed micelle were directed to the water phase without binding with AMPS. Both the intramolecular and the intermolecular NRET increased and then decreased with c _Surf, having a maximum on each curve corresponding to the equimolar binding of CTAB and AMPS so long as Y >0, indicating the coiling of the chain and interchain aggregation upon bound surfactants. The I _Py/ I _Np value at the maximum decreased with decreasing Y because more nonionic surfactant C ₁₂E ₈ participated into the polyelectrolyte-mixed surfactant complexes together with bound CTAB.     

Interaction between polymer and anionic/nonionic surfactants and its mechanism of enhanced oil recovery

Various experimental methods were used to investigate interaction between polymer and anionic/nonionic surfactants and mechanisms of enhanced oil recovery by anionic/nonionic surfactants in the present paper. The complex surfactant molecules are adsorbed in the mixed micelles or aggregates formed by the hydrophobic association of hydrophobic groups of polymers, making the surfactant molecules at oil-water interface reduce and the value of interfacial tension between oil and water increase. A dense spatial network structure is formed by the interaction between the mixed aggregates and hydrophobic groups of the polymer molecular chains, making the hydrodynamic volume of the aggregates and the viscosity of the polymer solution increase. Because of the formation of the mixed adsorption layer at oil and water interface by synergistic effect, ultra-low interfacial tension (～2.0?×?10^?3 mN/m) can be achieved between the novel surfactant system and the oil samples in this paper. Because of hydrophobic interaction, wettability alteration of oil-wet surface was induced by the adsorption of the surfactant system on the solid surface. Moreover, the studied surfactant system had a certain degree of spontaneous emulsification ability (D50?=?25.04?µm) and was well emulsified with crude oil after the mechanical oscillation (D50?=?4.27?µm).     

Thermal diffusion behavior of nonionic surfactants in water

We studied the thermal diffusion behavior of hexaethylene glycol monododecyl ether (C12E6) in water by means of thermal diffusion forced Rayleigh scattering (TDFRS) and determined Soret coefficients, thermal diffusion coefficients, and diffusion constants at different temperatures and concentrations. At low surfactant concentrations, the measured Soret coefficient is positive, which implies that surfactant micelles move toward the cold region in a temperature gradient. For C12E6/water at a high surfactant concentration of w1 = 90 wt % and a temperature of T = 25 degrees C, however, a negative Soret coefficient S(T) was observed. Because the concentration part of the TDFRS diffraction signal for binary systems is expected to consist of a single mode, we were surprised to find a second, slow mode for C12E6/water system in a certain temperature and concentration range. To clarify the origin of this second mode, we investigated also, tetraethylene glycol monohexyl ether (C6E4), tetraethylene glycol monooctyl ether (C8E4), pentaethylene glycol monododecyl ether (C12E5), and octaethylene glycol monohexadecyl ether (C16E8) and compared the results with the previous results for octaethylene glycol monodecyl ether (C10E8). Except for C6E4 and C10E8, a second slow mode was observed in all systems usually for state points close to the phase boundary. The diffusion coefficient and Soret coefficient derived from the fast mode can be identified as the typical mutual diffusion and Soret coefficients of the micellar solutions and compare well with the independently determined diffusion coefficients in a dynamic light scattering experiment. Experiments with added salt show that the slow mode is suppressed by the addition of w(NaCl) = 0.02 mol/L sodium chloride. This suggests that the slow mode is related to the small amount of absorbing ionic dye, less than 10(-5) by weight, which is added in TDFRS experiments to create a temperature grating. The origin of the slow mode of the TDFRS signal will be tentatively interpreted in terms of a ternary mixture of neutral micelles, dye-charged micelles, and water.     

Adsorption of mixtures of nonionic sugar-based surfactants with other surfactants at solid/liquid interfaces II. Adsorption of n-dodecyl-beta-D-maltoside with a cationic surfactant and a nonionic ethoxylated surfactant on solids

Synergy and antagonism between sugar-based surfactants, a group of environmentally benign surfactants, and cationic surfactants and nonionic ethoxylated surfactants have been investigated in this study with solids which adsorbs only one or other when presented alone. Sugar-based n-dodecyl-beta-D-maltoside (DM) does not adsorb on silica by itself. However, in mixtures with cationic dodecyltrimethylammonium bromide (DTAB) and nonionic nonylphenol ethoxylated decyl ether (NP-10), DM adsorbs on silica through hydrophobic interactions. In contrast, although DM does adsorb on alumina, the presence of NP-10 reduces the adsorption of DM as well as that of the total surfactant adsorption. Such synergistic/antagonistic effects of sugar-based n-dodecyl-beta-D-maltoside (DM) in mixtures with other surfactants at solid/liquid interfaces were systematically investigated and some general rules on synergy/antagonism in mixed surfactant systems are identified. These results have implications for designing surfactant combinations for controlled adsorption or prevention of adsorption.