Effect of ionic surfactants on the iridescent color in lamellar liquid crystalline phase of a nonionic surfactant

A nonionic surfactant, n-dodecyl glyceryl itaconate (DGI), self-assembles into bilayer membranes in water having a spacing distance of sub-micrometer in the presence of small amounts of ionic surfactants, and shows beautiful iridescent color. Ionic surfactants have strong effects on this iridescent system. We have interestingly found that the iridescent color changes with time after mixing DGI and ionic surfactants and the color in equilibrium state changes greatly with concentration of the ionic surfactants. The time-dependent color change results from the transformation of DGI aggregate structure after being mixed with ionic surfactant. It is first found that the iridescent color of this nonionic system can be changed from red to deep blue by altering the concentration of ionic surfactants added even though the total concentration of surfactant is almost constant. Such large blue shift of the iridescent color in equilibrium state cannot be fully explained by the ordinary undulation theory applied so far for this phenomenon. The flat lamellar sheets tend to curve by increasing the concentration of ionic surfactants to form separated onion-like and/or myelin-like structures. These separated structures of lamellar system result in the decrease of spacing distance between bilayer membranes because some vacant spaces necessarily appear among these structures.     

Self-organization of double-chained and pseudodouble-chained surfactants: counterion and geometry effects

Self-organization in aqueous systems based on ionic surfactants, and their mixtures, can be broadly understood by a balance between the packing properties of the surfactants and double-layer electrostatic interactions. While the equilibrium properties of micellar systems have been extensively studied and are understood, those of bilayer systems are less well characterized. Double-chained and pseudodouble-chained (or catanionic) surfactants are among the amphiphiles which typically form bilayer structures, such as lamellar liquid–crystalline phases and vesicles. In the past 10–15 years, an experimental effort has been made to get deeper insight into their aggregation patterns. With the double-chained amphiphiles, by changing counterion, adding salt or adding anionic surfactant, there are possibilities to depart from the bilayer aggregate in a controlled manner. This is demonstrated by several studies on the didodecyldimethylammonium bromide surfactant. Mixtures of cationic and anionic surfactants yield the catanionics, surfactants of the swelling type, and also show a rich phase behavior per se. A variety of liquid–crystalline phases and, in dilute regimes, equilibrium vesicles and different micellar shapes are often encountered. Phase diagrams and detailed structural studies, based on several techniques (NMR, microscopy and scattering methods), have been reported, as well as theoretical studies. The main features and conclusions emerging from such investigations are presented.     

Phenomenon observed at the onset of micellization using static light scattering

A phenomenon was observed near the critical micelle concentration (cmc) of surfactants using static light scattering. This consists of an unexpected peak in light scattering as the concentration varies between zero and above the cmc. This work studied three different surfactants: the two ionic surfactants hexadecyltrimethylammonium bromide (CTABr) and sodium dodecyl sulfate (SDS) and the nonionic surfactant Triton X-100. Peaks were observed for all three under different conditions such as varying ionic strengths and different concentration paths. These peaks are real, are reproducible, and appear to have static properties.     

Study of Cryostructuring of Polymer Systems: 25. The Influence of Surfactants on the Properties and Structure of Gas-Filled (Foamed) Poly(vinyl alcohol) Cryogels

Foamed poly(vinyl alcohol) (PVA) cryogels are studied. Such heterogeneous gel composites are formed as a result of the cryogenic treatment (freezing—storage in a frozen state—thawing) of water— PVA liquid foams in the absence and presence of surfactants. It is shown that the addition of ionic and nonionic surfactants to an aqueous PVA solution and its subsequent foaming result in the formation of liquid foam whose stability is lower than that of the foam prepared from an aqueous PVA solution in the absence of surfactant, i.e., surfactants cause a destabilizing effect on the foams containing PVA. Gas-filled PVA cryogels formed as a result of freezing—thawing of such foams contain large (up to ～180 μm) pores (air bubbles incorporated into the matrix of heterogeneous gel). Mechanical and thermal properties of cryogels depend on the nature and concentration of surfactants, as well as on the regime of cryogenic treatment. The rigidity of foamed PVA cryogels prepared in the presence of sodium dodecyl sulfate and cetyltrimethylammonium bromide ionic surfactants is lower and that in the presence of nonionic decaoxyethylene cetyl ether is higher than for equiconcentrated (by the polymer) foamed PVA cryogel containing no surfactant. Microscopic studies and the analysis of obtained images of cryogel structure demonstrate that the effect of surfactant on the morphology of freezing foam can be different, depending on the type of surfactant added to the initial system. This leads to foam-destabilizing effects such as the collapse, deformation, and coalescence of air bubbles; the failure of gel phase structure near the bubble surface; etc. However, the complete disintegration of the foamed structure is prevented by a very high viscosity of the unfrozen liquid microphase of a macroscopically solid sample and by the cryotropic PVA gelation that fixes the structure of partially destroyed foam.     

Effects of Various Additives on the Cloud Point of Dodecyl Polyoxyethylene Polyoxypropylene Ether

Effects of various additives, including electrolytes, alcohols and organic acids, polymers, and ionic and nonionic surfactants, on the cloud point of dodecyl polyoxyethylene (5) polyoxypropylene (4) ether nonionic surfactant aqueous solutions are investigated. The salting-out electrolytes decrease the cloud point while salting-in electrolytes increase it. Most alcohols and organic acids can lower the cloud point except for methanol and ethanol. The polymers form complexes with the surfactant and decrease the cloud point. The added surfactants can be inserted into the micelles of the nonionic surfactant and form mixed micelles, thus raising the cloud point.     

Surfactant head group and concentration influence on structure and dynamics of gellan gum hydrogels: Crossover from stretched to compressed exponential

In the present study, we have investigated the effects of surfactant addition on the structure and dynamics of gellan gum hydrogels. A strong interaction is seen between gellan gum and oppositely charged cationic surfactant, hexadecyltrimethylammonium bromide (CTAB) whereas rather weak or minimal interactions are observed when either anionic surfactant, sodium dodecylsulfate (SDS), or nonionic surfactant, Triton X-100 is added to the system. The dynamics of the hydrogels was studied, using dynamic light scattering measurements and the heterodyne method was used for data evaluation. The correlation function of parent hydrogel was fitted with a stretched exponential function, while a single plus stretched exponential function was employed to study the dynamics of hydrogel with surfactants and the corresponding relaxation times were appropriately analyzed. An interesting crossover from stretched to compressed exponential was seen when CTAB was added beyond critical micellar concentration to the system, which was not evidenced for the other two surfactants. Ensemble averaged intensity was also analyzed and the general picture that emerges is that the oppositely charged surfactant has the strongest ability to form large associations as oppose to nonionic and like-charged surfactants. The rheological measurements were carried out to determine the elastic response of the gels over a wide range of frequencies. It was seen that the elastic modulus was dependent on both the surfactant concentration and type. Cationic surfactant increased the elastic modulus markedly as opposed to the nonionic and anionic surfactants. These results may have implications for the use of polymer surfactant systems as potential products.     

Intercalation of a nonionic surfactant (C10E3) bilayer into a Na-montmorillonite clay

A nonionic surfactant, triethylene glycol mono-n-decyl ether (C(10)E(3)), characterized by its lamellar phase state, was introduced in the interlayer of a Na-montmorillonite clay at several concentrations. The synthesized organoclays were characterized by small-angle X-ray scattering in conjunction with Fourier transform infrared spectroscopy and adsorption isotherms. Experiments showed that a bilayer of C(10)E(3) was intercalated into the interlayer space of the naturally exchanged Na-montmorillonite, resulting in the aggregation of the lyotropic liquid crystal state in the lamellar phase. This behavior strongly differs from previous observations of confinement of nonionic surfactants in clays where the expansion of the interlayer space was limited to two monolayers parallel to the silicate surface and cationic surfactants in clays where the intercalation of organic compounds is introduced into the clay galleries through ion exchange. The confinement of a bilayer of C(10)E(3) nonionic surfactant in clays offers new perspectives for the realization of hybrid nanomaterials, since the synthesized organoclays preserve the electrostatic characteristics of the clays, thus allowing further ion exchange while presenting at the same time a hydrophobic surface and a maximum opening of the interlayer space for the adsorption of neutral organic molecules of important size with functional properties.     

Stabilization of High Ionic Strength Slurries Using the Synergistic Effects of a Mixed Surfactant System

The stability of colloidal slurries is an important parameter in many industries due to problems that can arise as a result of particle settling. Particle settling is often caused by the shielding of surface charges on the particles which otherwise would prevent coagulation and subsequent settling. This is particularly a problem in high ionic strength slurries, where large amounts of ions serve to enhance the charge shielding and compression of the electrical double layer around the particles. This phenomenon has been investigated for industrially significant slurries used for tungsten and copper chemical mechanical polishing (CMP). It has been found that the effects of addition of conventional stabilizing agents (e.g., ionic surfactants, polymers) to these high ionic strength slurries are neutralized by the electrolytes in solution. However, the synergistic combination of a properly chosen ionic and nonionic surfactant has been found to be a suitable stabilizing agent for this type of system. For the CMP slurries investigated, the synergistic effect has been shown to be maximum for combinations of sodium dodecyl sulfate anionic surfactant and a variety of polymeric nonionic surfactants. The stabilization observed for these mixed surfactant systems has been explained in terms of adsorption of ionic surfactant on particle surfaces and nonionic surfactant molecules penetrating the film of the ionic surfactant due to hydrocarbon chain interactions. This brings about the steric stabilization of the slurry. Copyright 2000 Academic Press.     

Microemulsion formed by alkyl polyglucoside and an alkyl glycerol ether with weakly charged films

We have studied the effects on phase equilibria of a nonionic surfactant mixture-water-oil system when replacing small amount of surfactant molecules by ionic surfactant, sodium dodecyl sulfate (SDS). The nonionic surfactant system contains dodecyl-beta-D-maltoside (C(12)AG2) and iso-octyl glyceryl ether (i-C(8)GE) as cosurfactant, water and cyclohexane at constant water to oil ratio of 60/40 (w/w). Adding a small amount of SDS has large impact on the phase behavior. Clear liquid crystalline phase and upper microemulsion phase are added to the phase sequence at high i-C(8)GE/(C(12)AG2+i-C(8)GE) ratio. We also compare the phase equilibria of pure dodecyl maltoside system with polyglucosides mixture system.     

The microstructure of di-alkyl chain cationic/nonionic surfactant mixtures: observation of coexisting lamellar and micellar phases and depletion induced phase separation

The evolution of the microstructure and composition occurring in the aqueous solutions of di-alkyl chain cationic/nonionic surfactant mixtures has been studied in detail using small angle neutron scattering, SANS. For all the systems studied we observe an evolution from a predominantly lamellar phase, for solutions rich in di-alkyl chain cationic surfactant, to mixed cationic/nonionic micelles, for solutions rich in the nonionic surfactant. At intermediate solution compositions there is a region of coexistence of lamellar and micellar phases, where the relative amounts change with solution composition. A number of different di-alkyl chain cationic surfactants, DHDAB, 2HT, DHTAC, DHTA methyl sulfate, and DISDA methyl sulfate, and nonionic surfactants, C12E12 and C12E23, are investigated. For these systems the differences in phase behavior is discussed, and for the mixture DHDAB/C12E12 a direct comparison with theoretical predictions of phase behavior is made. It is shown that the phase separation that can occur in these mixed systems is induced by a depletion force arising from the micellar component, and that the size and volume fraction of the micelles are critical factors.     

Phase diagrams and microstructure of aggregates in mixed ionic surfactant/foam booster systems

The phase behavior and microstructure of surfactant systems containing a new alkanolamide-type foam booster, dodecanoyl N-methyl ethanolamide (NMEA-12), were investigated by means of phase study and small angle X-ray scattering. Different from other similar alkanolamides, NMEA-12 possesses a low melting point and forms a lyotropic liquid-crystalline phase (L(alpha) phase) at room temperature. This is attributed to the attached methyl group, which increases the fluidity of the molecule. In the SDS/NMEA-12/water system, hexagonal and lamellar (L(alpha)) liquid-crystalline phases are obtained at significantly low surfactant concentrations. The stability of these phases decreases when SDS is replaced with a nonionic surfactant (C12EO8). However, for both ionic and nonionic surfactants, the effective area per surfactant molecule at the interface shrinks upon addition of NMEA-12, indicating that the surfactant layer is getting more compact. The possible implications of these results on the potential applications of NMEA-12 as foam stabilizer are discussed.     

Phase behavior and microstructure of microemulsions with a room-temperature ionic liquid as the polar phase

Microemulsions of nonionic alkyl oligoethyleneoxide (CiEj) surfactants, alkanes, and ethylammonium nitrate (EAN), a room-temperature ionic liquid, have been prepared and characterized. Studies of phase behavior reveal that EAN microemulsions have many features in common with corresponding aqueous systems, the primary difference being that higher surfactant concentrations and longer surfactant tailgroups are required to offset the decreased solvophobicity the surfactant molecules in EAN compared with water. The response of the EAN microemulsions to variation in the length of the alkane, surfactant headgroup, and surfactant tailgroup has been found to parallel that observed in aqueous systems in most instances. EAN microemulsions exhibit a single broad small-angle X-ray scattering peak, like aqueous systems. These are well described by the Teubner-Strey model. A lamellar phase was also observed for surfactants with longer tails at lower temperatures. The scattering peaks of both microemulsion and lamellar phases move to lower wave vector on increasing temperature. This is ascribed to a decrease in the interfacial area of the surfactant layer. Phase behavior, small-angle X-ray scattering, and conductivity experiments have allowed the weakly to strongly structured transition to be identified for EAN systems.     

A disjoining pressure study of foam films stabilized by mixtures of nonionic and ionic surfactants

Studying the disjoining pressure Pi as a function of the film thickness h (Pi-h curves) of foam films stabilized by ionic and nonionic surfactants, one finds that the surface charge density q0 of films stabilized by ionic surfactants increases with increasing surfactant concentration, while the opposite holds true for nonionic surfactants. Thus, it should be possible to tune the surface charge density with mixtures of nonionic and ionic surfactants. To address this question, we studied foam films stabilized by aqueous solutions of surfactant mixtures. The mixtures consisted of the nonionic beta-dodecylmaltoside (beta-C12G2) and the cationic dodecyl trimethylammonium bromide (C12TAB) with mixing ratios of beta-C12G2/C12TAB = 1:0, 50:1, 1:1, 1:50, 0:1. The addition of small amounts of C12TAB to beta-C12G2 first neutralizes the negative surface charge of the beta-C12G2 films and finally leads to a charge reversal from negatively to positively charged surfaces. On the other hand, by adding small amounts of beta-C12G2 to C12TAB, one observes the formation of stable CBFs which was also observed for the pure C12TAB. However, in contrast to the pure C12TAB, the resulting Pi-h curves for the mixtures cannot be described with the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory; the slope of the curves is too steep, and it barely changes with changing electrolyte concentration. A possible explanation for this observation will be given and discussed.     

Unusual micelle and surface adsorption behavior in mixtures of surfactants with an ethylene oxide-propylene oxide triblock copolymer

Micellization and adsorption at the air-solution interface of binary mixtures of the triblock copolymer of ethylene oxide and propylene oxide, EO23PO52EO23 (EPE), and the surfactants sodium dodecyl sulfate (SDS), dodecyl trimethylammonium chloride (DTAC), and tetraethylene glycol monooctyl ether (C8EO4) have been studied by neutron reflectivity and surface tension. The synergistic attractive interaction between the polymer and the ionic surfactants has been analyzed in the framework of the pseudo phase approximation and gives rise to a stronger interaction for EPE/SDS than EPE/DTAC. In contrast, the interaction of the nonionic surfactant C8EO4 with the copolymer EPE shows an unexpected and rather different behavior, resulting in a strongly repulsive interaction, characterized by a positive interaction parameter. The neutron reflectivity measurements of the surface excess, where the predicted and measured surface excesses are directly compared, provide evidence that challenges the applicability of the pseudo phase approximation for describing the surface mixing behavior. Structural information on the mixed adsorbed layer provides evidence which in part explains the observed discrepancies between the measured surface excesses and the behavior predicted from the pseudo phase approximation. Furthermore the structural evidence can be use to rationalize the differences in behavior observed between the ionic and nonionic surfactants.     

Influence of ionic charges on the bilayers of lamellar phases

The influence of ionic charges on the mesophases in the ternary system of C(12-16)E(6) (LA 070), ethylhexylglycerid (EHG), and water was studied. The charge was introduced by adding the ionic surfactant SDS (sodium dodecyl sulfate). The single lamellar phase (5 wt % LA 070 and 240 mM EHG in water) yields a bluish homogeneous solution. With the addition of SDS, the samples become more and more clear. Rheology measurements indicate that increased charge density increases the storage modulus G', and the lamellar phases show typical behavior of a viscoelastic fluid with a yield stress at higher SDS concentration. SAXS measurements show that the interlamellar distance D decreases with SDS concentration. The addition of ionic surfactants suppresses the Helfrich undulations, flattens the bilayers, and decreases interbilayer spacing due to electrostatic repulsions of the ionic surfactant head groups. Furthermore, the L(alpha) phase transforms into vesicle phases as the SDS concentration is increased. Second, it is shown that with added NaCl electrolyte the phase with charged surfactant behaves again in the same way as the initial uncharged system. The addition of salt screens the electrostatic interaction, which leads to a higher flexibility of the bilayers and a decrease of the storage modulus G'. Theoretical calculations show that the shear moduli of the L(alpha) phases are much smaller than the osmotic pressure of the systems. Several models are proposed for the explanation of the shear moduli. The model due to Lekkerkerker for the electric contribution of the bending constant of the bilayer seems to yield good results for the transition to vesicles.     

How does cross-linking affect the stability of block copolymer vesicles in the presence of surfactant?

Block copolymer vesicles are conveniently prepared directly in water at relatively high solids by polymerization-induced self-assembly using an aqueous dispersion polymerization formulation based on 2-hydroxypropyl methacrylate. However, dynamic light scattering studies clearly demonstrate that addition of small molecule surfactants to such linear copolymer vesicles disrupts the vesicular membrane. This causes rapid vesicle dissolution in the case of ionic surfactants, with nonionic surfactants proving somewhat less destructive. To address this problem, glycidyl methacrylate can be copolymerized with 2-hydroxypropyl methacrylate and the resulting epoxy-functional block copolymer vesicles are readily cross-linked in aqueous solution using cheap commercially available polymeric diamines. Such epoxy-amine chemistry confers exceptional surfactant tolerance on the cross-linked vesicles and also leads to a distinctive change in their morphology, as judged by transmission electron microscopy. Moreover, pendent unreacted amine groups confer cationic character on these cross-linked vesicles and offer further opportunities for functionalization.     

Microstructure of un-neutralized hydrophobically modified alkali-soluble emulsion latex in different surfactant solutions

At low pH conditions and in the presence of anionic, cationic, and nonionic surfactants, hydrophobically modified alkali-soluble emulsions (HASE) exhibit pronounced interaction that results in the solubilization of the latex. The interaction between HASE latex and surfactant was studied using various techniques, such as light transmittance, isothermal titration calorimetry, laser light scattering, and electrophoresis. For anionic surfactant, noncooperative hydrophobic binding dominates the interaction at concentrations lower than the critical aggregation concentration (CAC) (C < CAC). However, cooperative hydrophobic binding controls the formation of mixed micelles at high surfactant concentrations (C > or = CAC), where the cloudy solution becomes clear. For cross-linked HASE latex, anionic surfactant binds only noncooperatively to the latex and causes it to swell. For cationic surfactant, electrostatic interaction occurs at very low surfactant concentrations, resulting in phase separation. With further increase in surfactant concentration, noncooperative hydrophobic and cooperative hydrophobic interactions dominate the binding at low and high surfactant concentrations, respectively. For anionic and cationic surfactant systems, the CAC is lower than the critical micelle concentration (CMC) of surfactants in water. In addition, counterion condensation plays an important role during the binding interaction between HASE latex and ionic surfactants. In the case of nonionic surfactants, free surfactant micelles are formed in solution due to their relatively low CMC values, and HASE latexes are directly solubilized into the micellar core of nonionic surfactants.     

Dependence on Oil Chain Length of the Curvature Elastic Properties of Nonionic Surfactant Films: Emulsification Failure and Phase Equilibria

We compare two ternary microemulsions, stabilized by the nonionic surfactant pentaethylene‐glycol‐dodecyl‐ether (C₁₂E₅), containing decane or hexadecane. The comparison involves phase behavior and properties of O/W droplet microemulsions investigated with SAXS, static and dynamic light scattering, and NMR. Striking differences are observed. The systems are analyzed in terms of curvature elastic properties of surfactant film. Apart from an increase of the spontaneous curvature, there also appears to be a small but significant increase in the saddle splay constant as the oil chain length is increased.     

Solution self-assembly of the sophorolipid biosurfactant and its mixture with anionic surfactant sodium dodecyl benzene sulfonate

The self-assembly in aqueous solution of the acidic (AS) and lactonic (LS) forms of the sophorolipid biosurfactant, their mixtures, and their mixtures with anionic surfactant sodium dodecyl benzene sulfonate, LAS, has been studied using predominantly small-angle neutron scattering, SANS, at relatively low surfactant concentrations of <30 mM. The more hydrophobic lactonic sophorolipid forms small unilamellar vesicles at low surfactant concentrations, in the concentration range of 0.2 to 3 mM, and transforms via a larger unilamellar vesicle structure at 7 mM to a disordered dilute phase of tubules at higher concentrations, 10 to 30 mM. In marked contrast, the acidic sophorolipid is predominantly in the form of small globular micelles in the concentration range of 0.5 to 30 mM, with a lower concentration of larger, more planar aggregates (lamellar or vesicular) in coexistence. In mixtures of AS and LS, over the same concentration range, the micellar structure associated with the AS sophorolipid dominates the mixed-phase behavior. In mixtures of anionic surfactant LAS with the AS sophorolipid, the globular micellar structure dominates over the entire composition and concentration range studied. In contrast, mixtures of LAS with the LS sophorolipid exhibit a rich evolution in phase behavior with solution composition and concentration. At low surfactant concentrations, the small unilamellar vesicle structure present for LS-rich solution compositions evolves into a globular micelle structure as the solution becomes richer in LAS. At higher surfactant concentrations, the disordered lamellar structure present for LS-rich compositions transforms to small vesicle/lamellar coexistence, to lamellar/micellar coexistence, to micellar/lamellar coexistence, and ultimately to a pure micellar phase as the solution becomes richer in LAS. The AS sophorolipid surfactant exhibits self-assembly properties similar to those of most other weakly ionic or nonionic surfactants that have relatively large headgroups. However, the more hydrophobic nature of the lactonic sophorolipid results in a more complex and unusual evolution in phase behavior with concentration and with concentration and composition when mixed with anionic surfactant LAS.     

PEP与阴离子表面活性剂复配体系泡沫性能的研究

研究了PEP型非离子表面活性剂分别与十二烷基苯磺酸钠（DBS）,十二烷基硫酸钠（SDS）形成复配体系的泡沫性能,讨论了浓度及配比的变化对泡沫性能的影响,结果表明起泡性和稳泡性皆随混合表面活性剂的浓度的上升而增强;在一定浓度下,随着PEP比例下降,起泡性和稳泡性也随着增大,并达到稳定值。