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.     

Organization of amphiphiles: XII. Evidence in favor of formation of hydrophobic complexes in aqueous solution

The effects of nonionic surfactants OP-10 and OP-30 (polyoxyethylated octyl phenols with 10 and 30 oxyethylene groups, respectively) in surfactant mixtures with ionic surfactants hexadecyltrimethylammonium bromide (CTAB) and sodium dodecyl sulphate (SDS) have been investigated by a conductometric method in conjunction with fluorescence, surface tension, zeta potential, and DLS measurements. The interactions are found to be antagonistic in nature for each of the systems; i.e., micellization of CTAB as well as SDS is hindered on addition of the nonionic surfactants. The antagonism is found to be more prominent in the presence of OP-10 compared to that of OP-30. Two types of mechanistic paths, path A operating below the critical micellar concentration and path B operating beyond the critical micellar concentration of nonionic surfactants, have been suggested. In path A, the retardation in micellization has been attributed to a decrease in monomeric concentration of the ionic surfactants from solution as a result of the formation of a hydrophobic complex between nonionic and ionic surfactants. In path B, the decrease in monomer concentration is due to the solubilization of the ionic surfactant in micelles of the nonionic surfactants in a 1:1 stoichiometric ratio. A theoretical treatment to the interaction in each ionic-nonionic pair yields a positive value of the interaction parameter supporting the concept of antagonism. The formation of the hydrophobic complex is supported by fluorescence and surface tension measurements. A schematic representation of the stabilization of these hydrophobic complexes has been suggested. The association of ionic surfactants by nonionic micelles is suggested by zeta potential and DLS studies.     

Effects of emulsifier charge and concentration on pancreatic lipolysis. 1. In the absence of bile salts

An in vitro study is performed with sunflower oil-in-water emulsions to clarify the effects of type of used emulsifier, its concentration, and reaction time on the degree of oil lipolysis, α. Anionic, nonionic, and cationic surfactants are studied as emulsifiers. For all systems, three regions are observed when surfactant concentration is scaled with the critical micelle concentration, C(S)/cmc: (1) At C(S) < cmc, α ≈ 0.5 after 30 min and increases up to 0.9 after 4 h. (2) At C(S) ≈ 3 × cmc, α ≈ 0.15 after 30 min and increases steeply up to 0.9 after 2 h for the cationic and nonionic surfactants, whereas it remains around 0.2 for the anionic surfactants. (3) At C(S) above certain threshold value, α = 0 for all studied surfactants, for reaction time up to 8 h. Additional experiments show that the lipase hydrolyzes molecularly soluble substrate (tributirin) at C(S) > cmc, which is a proof that these surfactants do not denature or block the enzyme active center. Thus, we conclude that the mechanism of enzyme inhibition by these surfactants is the formation of a dense adsorption layer on an oil drop surface, which displaces the lipase from direct contact with the triglycerides.     

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.     

Electrophoretic behaviour and viscosities of metal oxides in mixed surfactant systems

 The electrokinetic behavior and viscosity of anatase and alumina in mixed-surfactant solutions were investigated. Sodium dodecylsulfate and nonionic polyoxyethylene ethers were investigated as model surfactants. Pure nonionic surfactants adsorbed on anatase and coated the particles, so that the zeta potential was nearly zero near the critical micelle concentration of surfactant. At higher surfactant concentrations, an increase in the zeta potentials was observed, suggesting a change in the microstructure of the adsorbed layer. Addition of nonionic surfactant to positively charged anatase and alumina with some preadsorbed sodium dodecylsulfate reversed the surface charge of the oxide to negative, indicating enhanced coadsorption of the anionic surfactant. At higher concentrations of the nonionic surfactant, the charge reversed back to positive. Nonionic surfactants did not reverse the surface charge of these oxides in the absence of the anionic surfactant. Coenhanced adsorption of nonionic and anionic surfactants was used to stabilize alumina at the isoelectric point, where neither surfactant adsorbed appreciably on its own. These results suggest a dramatic change in conformation of the surfactant chains in mixed systems. Further explanation and justification of the proposed changes in adsorbed surfactant conformation require spectroscopic evidence. Received: 12 March 1997 Accepted: 22 July 1997     

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.     

Surface properties of mixtures of surface-active sugar derivatives with ionic surfactants: theoretical and experimental investigations

Surface properties of systems that are mixtures of ionic surfactants and sugar derivatives-anionic surfactant sodium dodecyl sulfate and n-dodecyl-beta-D-maltoside (SDS/DM) and cationic surfactant dodecyltrimethylammonium bromide and n-dodecyl-beta-D-glucoside (DTABr/DG)-were investigated. The experimental results obtained from measurements of surface tension of mixtures with various ratio of ionic to nonionic components were analyzed by two independent theories. First is Motomura theory, derived from the Gibbs-Duhem equation, allowing for indirect evaluation of the composition of mixed monolayers and the Gibbs energies of adsorption, corresponding to mutual interaction between surfactants in mixed adsorbed film. As second theory we used our newly developed theoretical model of adsorption of ionic-nonionic surfactant mixtures. Using this approach, we were able to describe the experimental surface tension isotherms for mixtures of surface-active sugar derivatives and ionic surfactants. We obtained a good agreement with experimental data using the same set of model parameters for a whole range of studied compositions of a given surfactant mixture. The values of surface excess calculated from both theories agreed with each other with a reasonable accuracy. However, the newly developed model of adsorption of ionic-nonionic surfactant mixtures has the advantage of straightforward determination of surface layer composition. By the solution of equations of adsorption, one can obtain directly the values of surface excess of all components (surfactant ions, counterions, and nonionic surfactants molecules), which are present in the investigated system.     

Bending elasticity of charged surfactant layers: the effect of mixing

Expressions have been derived from which the spontaneous curvature (H(0)), bending rigidity (k(c)), and saddle-splay constant (k(c)) of mixed monolayers and bilayers may be calculated from molecular and solution properties as well as experimentally available quantities such as the macroscopic hydrophobic-hydrophilic interfacial tension. Three different cases of binary surfactant mixtures have been treated in detail: (i) mixtures of an ionic and a nonionic surfactant, (ii) mixtures of two oppositely charged surfactants, and (iii) mixtures of two ionic surfactants with identical headgroups but different tail volumes. It is demonstrated that k(c)H(0), k(c), and k(c) for mixtures of surfactants with flexible tails may be subdivided into one contribution that is due to bending properties of an infinitely thin surface as calculated from the Poisson-Boltzmann mean field theory and one contribution appearing as a result of the surfactant film having a finite thickness with the surface of charge located somewhat outside the hydrophobic-hydrophilic interface. As a matter of fact, the picture becomes completely different as finite layer thickness effects are taken into account, and as a result, the spontaneous curvature is extensively lowered whereas the bending rigidity is raised. Furthermore, an additional contribution to k(c) is present for surfactant mixtures but is absent for k(c)H(0) and k(c). This contribution appears as a consequence of the minimization of the free energy with respect to the composition of a surfactant layer that is open in the thermodynamic sense and must always be negative (i.e., k(c) is generally found to be brought down by the process of mixing two or more surfactants). The magnitude of the reduction of k(c) increases with increasing asymmetry between two surfactants with respect to headgroup charge number and tail volume. As a consequence, the bending rigidity assumes the lowest values for layers formed in mixtures of two oppositely charged surfactants, and k(c) is further reduced in anionic/cationic surfactant mixtures where the surfactant in excess has the smaller tail volume. Likewise, the reduction of k(c) is enhanced in mixtures of an ionic and a nonionic surfactant where the ionic surfactant has the smaller tail. The effective bilayer bending constant (k(bi)) is also found to be reduced by mixing, and as a result, k(bi) is seen to go through a minimum at some intermediate composition. The reduction of k(bi) is expected to be most pronounced in mixtures of two oppositely charged surfactants where the surfactant in excess has the smaller tail in agreement with experimental observations.     

Use of surfactants to remove water-based inks from plastic film: effect of calcium ion concentration and length of surfactant hydrophobe

Effective plastic film deinking could permit the reuse of recycled polymer to produce clear film, reduce solid waste for landfills, reduce raw material demand for polymer production, and aid process economics. In this study, the deinking of a commercial polyethylene film printed with water-based ink was studied using surfactants in the presence of hardness ions (calcium ions) at various pH levels. The electrostatic properties of ink particles in a washing bath were also investigated. Synthetic anionic surfactant or fatty acid soap in the presence of calcium ions at alkaline pH levels was found to be nearly as effective at deinking as cationic, nonionic, or amphoteric surfactants alone. However, adding calcium ions decreases the deinking effectiveness of cationic, nonionic, and amphoteric surfactants. Increasing the length of the ionic surfactant hydrophobe enhances deinking. Zeta potential measurements showed that water-based ink particles in water reach the point of zero charge (PZC) at a pH of about 3.6, above which ink particles are negatively charged, so cationic surfactant tends to adsorb better on the ink than anionic surfactant above the PZC in the absence of calcium. As the cationic surfactant concentration is varied between 0.005 and 25 mM, the zeta potential of the ink particles reverses from negative to positive owing to adsorption of cationic surfactant. For anionic surfactants, added calcium probably forms a bridge between the negatively charged ink and the negatively charged surfactant head groups, which synergizes adsorption of the surfactant and aids deinking. In contrast, calcium competes for adsorption sites with cationic and nonionic surfactants, which inhibits deinking. All the surfactants studied here disperse ink particles effectively in the washing bath above pH 3 except for the ethoxylated amine surfactant.     

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.     

Effect of interactions between the adsorbed species on the properties of single and mixed-surfactant monolayers at the air/water interface

Experimental data on surface tension available from the literature and generated in the present study are analyzed to estimate the applicability of adsorption models, based on the Frumkin equation, to nonionic and ionic surfactants and their mixtures. Optimization programs based on the least-squares method in media of Delphi V and Pascal VII are used. The effect of interactions between the adsorbed species on surface tension is considered in all cases. The results are compared to those obtained with the simpler Szyszkowski equation, employed in numerous studies of nonionic surfactants, when interactions are neglected. Cases where the Frumkin model can be successfully employed with ionic surfactants and mixtures are presented and the conditions of its applicability are analyzed. Related characteristic quantities (maximum adsorption, standard free energy of surfactant adsorption, energy of interaction between adsorbed species, standard free energy of counterion adsorption, degree of coverage by surfactant/counterion associates) are established as a function of: The properties of an adsorption layer from a mixture of nonionic and ionic surface-active species are compared to those of the single surfactants.     

Interaction of Nonionic Surfactant Triton-X-100 with Ionic Surfactants

The interaction in two mixtures of a nonionic surfactant Triton-X-100 (TX-100) and different ionic surfactants was investigated. The two mixtures were TX-100/sodium dodecyl sulfate (SDS) and TX-100/cetyltrimethylammonium bromide (CTAB) at molar fraction of TX-100, α_TX-100 = 0.6. The surface properties of the surfactants, critical micelle concentration (CMC), effectiveness of surface tension reduction (γ_CMC), maximum surface excess concentration (Γ_max), and minimum area per molecule at the air/solution interface (A _min) were determined for both individual surfactants and their mixtures. The significant deviations from ideal behavior (attractive interactions) of the nonionic/ionic surfactant mixtures were also determined. Mixtures of both TX-100/SDS and TX-100/CTAB exhibited synergism in surface tension reduction efficiency and mixed micelle formation, but neither exhibited synergism in surface tension reduction effectiveness.     

Micellar solutions of ionic surfactants and their mixtures with nonionic surfactants: Theoretical modeling vs. Experiment

Here, we review two recent theoretical models in the field of ionic surfactant micelles and discuss the comparison of their predictions with experimental data. The first approach is based on the analysis of the stepwise thinning (stratification) of liquid films formed from micellar solutions. From the experimental step-wise dependence of the film thickness on time, it is possible to determine the micelle aggregation number and charge. The second approach is based on a complete system of equations (a generalized phase separation model), which describes the chemical and mechanical equilibrium of ionic micelles, including the effects of electrostatic and non-electrostatic interactions, and counterion binding. The parameters of this model can be determined by fitting a given set of experimental data, for example, the dependence of the critical micellization concentration on the salt concentration. The model is generalized to mixed solutions of ionic and nonionic surfactants. It quantitatively describes the dependencies of the critical micellization concentration on the composition of the surfactant mixture and on the electrolyte concentration, and predicts the concentrations of the monomers that are in equilibrium with the micelles, as well as the solution’s electrolytic conductivity; the micelle composition, aggregation number, ionization degree and surface electric potential. These predictions are in very good agreement with experimental data, including data from stratifying films. The model can find applications for the analysis and quantitative interpretation of the properties of various micellar solutions of ionic surfactants and mixed solutions of ionic and nonionic surfactants.     

Importance of micellar kinetics in relation to technological processes

The association of many classes of surface-active molecules into micellar aggregates is a well-known phenomenon. Micelles are in dynamic equilibrium, constantly disintegrating and reforming. This relaxation process is characterized by the slow micellar relaxation time constant, tau(2), which is directly related to the micellar stability. Theories of the kinetics of micelle formation and disintegration have been discussed to identify the gaps in our complete understanding of this kinetic process. The micellar stability of sodium dodecyl sulfate micelles has been shown to significantly influence technological processes involving a rapid increase in interfacial area, such as foaming, wetting, emulsification, solubilization, and detergency. First, the available monomers adsorb onto the freshly created interface. Then, additional monomers must be provided by the breakup of micelles. Especially when the free monomer concentration is low, which is the case for many nonionic surfactant solutions, the micellar breakup time is a rate-limiting step in the supply of monomers. The Center for Surface Science & Engineering at the University of Florida has developed methods using stopped flow and pressure jump with optical detection to determine the slow relaxation time of micelles of nonionic surfactants. The results showed that the ionic surfactants such as SDS exhibit slow relaxation times in the range from milliseconds to seconds, whereas nonionic surfactants exhibit slow relaxation times in the range from seconds (for Triton X-100) to minutes (for polyoxyethylene alkyl ethers). The slow relaxation times are much longer for nonionic surfactants than for ionic surfactants, because of the absence of ionic repulsion between the head groups. The observed relaxation times showed a direct correlation with dynamic surface tension and foaming experiments. In conclusion, relaxation time data of surfactant solutions correlate with the dynamic properties of the micellar solutions. Moreover, the results suggest that appropriate micelles with specific stability or tau(2) can be designed by controlling the surfactant structure, concentration, and physicochemical conditions (e.g., salt concentration, temperature, and pressure). One can also tailor micelles by mixing anionic/cationic or ionic/nonionic surfactants for a desired stability to control various technological processes.     

Aggregation work at polydisperse micellization: ideal solution and "dressed micelle" models comparing to molecular dynamics simulations

General thermodynamic relations for the work of polydisperse micelle formation in the model of ideal solution of molecular aggregates in nonionic surfactant solution and the model of "dressed micelles" in ionic solution have been considered. In particular, the dependence of the aggregation work on the total concentration of nonionic surfactant has been analyzed. The analogous dependence for the work of formation of ionic aggregates has been examined with regard to existence of two variables of a state of an ionic aggregate, the aggregation numbers of surface active ions and counterions. To verify the thermodynamic models, the molecular dynamics simulations of micellization in nonionic and ionic surfactant solutions at two total surfactant concentrations have been performed. It was shown that for nonionic surfactants, even at relatively high total surfactant concentrations, the shape and behavior of the work of polydisperse micelle formation found within the model of the ideal solution at different total surfactant concentrations agrees fairly well with the numerical experiment. For ionic surfactant solutions, the numerical results indicate a strong screening of ionic aggregates by the bound counterions. This fact as well as independence of the coefficient in the law of mass action for ionic aggregates on total surfactant concentration and predictable behavior of the "waterfall" lines of surfaces of the aggregation work upholds the model of "dressed" ionic aggregates.     

Aggregation of ionic surfactants to block copolymer assemblies: a simple fluorescence spectral study

A simple and elegant method based on steady-state fluorescence spectral measurement is demonstrated to study the interaction mechanism of copolymers and ionic surfactants with a suitable selection of fluorescent probe and also its general applicability in studying other systems. Three different concentration regions have been indicated from the changes in full width at half-maximum of the emission spectra and fluorescence intensity of coumarin 153 with the molar ratio of ionic surfactant to triblock copolymer (n). At low n values, copolymer-surfactant complexes are basically copolymer-rich micelles with few surfactant molecules, and at very high n values, copolymer-rich micelles are destroyed and surfactant-rich micelles with free copolymer monomers are formed. It has been observed that, in the intermediate surfactant concentration region, the transformation of a dominantly copolymer-rich complex to a mainly surfactant-rich complex can be either gradual incorporation of surfactants into the copolymer-rich micelles with freeing of copolymer units until surfactant-rich micelles are formed (type I) or simultaneous buildup of surfactant-rich micelles together with the destruction of copolymer-rich micelles (type II). The interaction mechanism for nonionic copolymers (P123 and F127) with ionic surfactants (SDS and CTAC) is mainly type II, but at higher copolymer concentrations interaction via the type I mechanism also operates. However, it is dominantly the type I mechanism that operates for common nonionic (TX100) and ionic surfactants.     

Effects of surfactant micelles on viscosity and conductivity of poly(ethylene glycol) solutions

The neutral polymer-micelle interaction is investigated for various surfactants by viscometry and electrical conductometry. In order to exclude the well-known necklace scenario, we consider aqueous solutions of low molecular weight poly(ethylene glycol) (2-20)x10(3), whose radial size is comparable to or smaller than micelles. The single-tail surfactants consist of anionic, cationic, and nonionic head groups. It is found that the viscosity of the polymer solution may be increased several times by micelles if weak attraction between a polymer segment and a surfactant exists, epsilon相似文献   

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.     

Thermosensitive amphiphilic polyphosphazenes and their interaction with ionic surfactants

Temperature-responding physical hydrogels are promising materials as injectable drug delivery carriers which could hold useful bioactive materials inside the polymer networks for further controlled releases. Aimed at desired qualities at body temperature, those gel characteristics need to be adjusted carefully. In this point of view, surfactant is one of the useful molecules to be used by simple formulations without harmful chemical reactions. In this study, thermothickening of amphiphilic nonionic polyphosphazene solution is modified by anionic and cationic surfactants with different alkyl chains and counter-ions. Specified in the thermothickening system, a maximum viscosity (η_max) and a temperature at that point (T_max) are changed independently reflecting unique intermolecular interactions. At low concentration (1–9 mM) of the added surfactant, the η_max is maximized at 3 mM surfactant regardless of the surfactant type while the T_max is increased continuously along with the surfactant concentration. From a kinetic point of view, this 3 mM surfactant at the maximized η_max reflects a polymer-dominating interaction and highly favorable polymer–surfactant interaction with a low selectivity in the surfactant type. However, the magnitude of the maximum viscosity (η_max) is dependent on the surfactant tail, which reflects the lifetime and the strength of the hydrophobic domains of the polymer network affected by the surfactants. Meanwhile, the magnitude of the T_max depended on the surfactant head group, which means the interfacial tension of the polymer solutions changed by the surfactants. At high concentration (10 and 30 mM) of the cationic surfactants added to the polymer solutions with two different viscosities, the cationic surfactants are supposed to interact either with the hydrophobic parts of the aggregated polymer with high viscosity or on the backbone of the less- or non-aggregated polymer with low viscosity.Ionic surfactants change the thermothickening of the amphiphilic nonionic polyphosphazene solution in a unique tail- or head-dependent way. Moreover, the concentration of the added surfactants and the association pattern of the pure polymer solutions are also crucial for the thermothickening phase behaviors. Temperature-responsive polyphosphazenes in this work exhibit unique and controllable interactions with ionic surfactants.     

Self-consistent field modeling of adsorption from polymer/surfactant mixtures

We report on the development of a self-consistent field model that describes the competitive adsorption of nonionic alkyl-(ethylene oxide) surfactants and nonionic polymer poly(ethylene oxide) (PEO) from aqueous solutions onto silica. The model explicitly describes the response to the pH and the ionic strength. On an inorganic oxide surface such as silica, the dissociation of the surface depends on the pH. However, salt ions can screen charges on the surface, and hence, the number of dissociated groups also depends on the ionic strength. Furthermore, the solvent quality for the EO groups is a function of the ionic strength. Using our model, we can compute bulk parameters such as the average size of the polymer coil and the surfactant CMC. We can make predictions on the adsorption behavior of either polymers or surfactants, and we have made adsorption isotherms, i.e., calculated the relationship between the surface excess and its corresponding bulk concentration. When we add both polymer and surfactant to our mixture, we can find a surfactant concentration (or, more precisely, a surfactant chemical potential) below which only the polymer will adsorb and above which only the surfactant will adsorb. The corresponding surfactant concentration is called the CSAC. In a first-order approximation, the surfactant chemical potential has the CMC as its upper bound. We can find conditions for which CMC < CSAC . This implies that the chemical potential that the surfactant needs to adsorb is higher than its maximum chemical potential, and hence, the surfactant will not adsorb. One of the main goals of our model is to understand the experimental data from one of our previous articles. We managed to explain most, but unfortunately not all, of the experimental trends. At the end of the article we discuss the possibilities for improving the model.