Surface activity of mixtures of narrow-range distributed alcohol oxyethylates and sodium dodecylbenzenesulfonate

Surface and interfacial tension, emulsion inversion temperature, and detergency were determined for mixtures of sodium dodecylbenzenesulfonate and narrow-range distributed alcohol C₁₂−C₁₄ oxyethylates of different hydrophilicity. The mixtures of ionic and nonionic surfactants behave similarly to nonionic and ionic surfactants at the air/water and hydrocarbon/water interfaces, respectively. The air/water interface is mainly occupied by nonionic surfactant molecules. However, the interfacial tensions for mixtures of nonionic and ionic surfactants are similar to those of sodium dodecylbenzenesulfonate. Mixtures of narrow-range distributed oxyethylates and sodium dodecylbenzenesulfonate have a higher detergency at 40°C than individual components.     

Kinetics of the self-assembly of gemini surfactants

A stopped-flow technique combined with pulsed-field-gradient spin-echo nuclear magnetic resonance (NMR) measurements was used to study the kinetics of exchange, size, and shapes in micellar systems of cationic surfactant dimers of the alkanediyl-α-ω-bis(dodecyldimethylammonium bromide) type, with alkanediyl being 1,2-ethylene, 1,3-propylene, and 1,4-butylene. By measuring the slow relaxation time for micelles, τ₂, the micelle lifetime as a function of spacer length was obtained and was further confirmed by micelle exchange measurements by NMR diffusometry. The micelle lifetimes for the gemini surfactants were found to be in orders of magnitude longer than for the corresponding conventional surfactants. All three cationic surfactant dimers showed an increase in micelle size in one direction, i.e., became prolates, as the concentration was increased. The growth of the micelles was most pronounced for the gemini surfactants with the shortest linker unit, i.e., ethylene.     

Interaction between bisphenol A and micelles of ionic surfactants

Interactions between bisphenol A (BPA) and ionic surfactants—cationic hexadecyltrimethylammonium bromide (HTAB) and anionic sodium dodecylsulfate (SDS)—were studied by measuring interfacial tensions and the intensities of pyrene fluorescence. The critical micellar concentrations (CMC) decreased with an increase in the BPA concentration, and the degree of that decrease was greater in HTAB than in SDS. In those micelles, BPA interacted more strongly with HTAB than with SDS. Conversely, BPA adsorbed on the air-water interface cooperatively with the surfactants, even though almost no adsorption of BPA itself was observed. This cooperative adsorption was more enhanced with HTAB than with SDS. Thus, BPA worked on the surfactants to stabilize the micelles and interfacial adsorption. The stability gained by the addition of BPA was greater on the interface than in the micelle. This was evidence of decreased hydrophilicity of the head group of the ionic surfactant, which interacted with BPA, because this decrease acted on the surface activities of the surfactants more directly than on the micelle stabilities. Pyrene fluorescence measurements yielded identical results for the effect on micelle stabilities. It is noteworthy that the fluorescence intensity of peak 1, l ₁, decreased with an increase in BPA concentrations at constant concentrations of surfactant greater than the CMC, but the peak ratio, l ₁/l ₃, remained almost unchanged. This fact was also related to the interaction of BPA with the hydrophilic head groups in the surfactant micelle.     

The effect of micellar lifetime on the rate of solubilization and detergency in sodium dodecyl sulfate solutions

The slow relaxation time (τ₂) of sodium dodecyl sulfate (SDS) micelles, measured by the pressure-jump technique, was maximum at 200 mM concentration at 25°C, indicating that the most stable micelles are formed at this concentration. This is presumably related to the optimum molecular packing in the micelle. The rate of solubilization of benzene and Orange OT dye into SDS solutions was also maximum at 200 mM concentration. The results are explained as follows: The distance between micelles (i.e., intermicellar distance) decreases as the surfactant concentration (or the number of micelles) increases, resulting in a stronger electric repulsion between micelles. Therefore, the micelles become more rigid, due to the compressive force of intermicellar repulsion, as the concentration increases up to 200 mM SDS. With further increase in the SDS concentration, the micellar shape changes from spherical to cylindrical to accommodate more surfactant molecules in the solution and to minimize the free energy of the system. The interior of the tightly packed micelles is more hydrophobic than that of loosely packed micelles and, therefore, the tightly packed micelles induce rapid solubilization of nonpolar molecules (e.g., benzene, Orange OT) into these micelles.     

Experimental Study of CMC Evaluation in Single and Mixed Surfactant Systems, Using the UV–Vis Spectroscopic Method

In this study, the critical micellar concentration (CMC) of anionic, cationic and nonionic surfactants was determined using the UV–Vis spectroscopic method. Sodium lauryl sulfate (SDS) as anionic, hexadecyl-trimethyl-ammonium bromide as cationic, tert-octylphenol ethoxylates TOPEON (with N = 9.5, 7.5 and 35) and lauryl alcohol ethoxylate (23EO) as nonionic surfactants have been used. Concentration of surfactants varies both from below and above the CMC value in the pyrene solution. In addition, the amount of the CMC was determined using the values from the data obtained from the graph of absorbance versus concentration of surfactants. A comparative study was conducted between the results of the present study and the literature which shows a good agreement, in particular for TOPEO9.5 and LAEO23. Furthermore, the CMC value of SDS (as an ionic surfactant) in the presence of nonionic surfactants was also examined. The result reveals that with addition of small amount of nonionic surfactant to the anionic SDS surfactant, a decline in the CMC value of the anionic–nonionic system relative to the CMC of pure anionic surfactant was observed. In addition and for the first time, the effect of UV irradiation on the size of the micelle formations was studied. It was found that UV irradiation causes the formation of smaller micelles which is of prime concern in membrane technology.     

Influence of breakup and reformation of micelles on surfactant diffusion in pure and mixed micellar systems

Pulsed field gradient (PFG) NMR technique was used to study diffusion of surfactant ions in the following two micellar systems: (i) aqueous solution of an anionic surfactant sodium dodecyl sulfate (SDS), and (ii) aqueous solution of a mixture of SDS and a small amount of the cationic surfactant N-dodecyltrimethylammonium bromide (C₁₂TAB). PFG NMR measurements provided separate sets of data on diffusion of SDS and C₁₂TAB surfactant ions for a broad range of diffusion times. For each type of surfactants at least two components with different effective diffusivities were observed at sufficiently small diffusion times. The faster component was assigned to the surfactants that experience breakup or reformation of micelles during the diffusion time of the PFG NMR measurement, while the slower component was assigned to the surfactants that did not participate in such events during the diffusion time. The observed changes of the fractions and diffusivities of these components with increasing diffusion time were found to be in a qualitative agreement with such assignment. Fundamental understanding of surfactant diffusion in micellar system is important due to an increasing use of such systems for synthesis of porous materials where micelles are used as templates as well as for many other applications.     

Solubilization of selected polycyclic aromatic compounds by nonionic surfactants

Solubilization of selected polycyclic aromatic compounds (PAC) by biodegradable nonionic surfactants, Tergitol 15-S-X (X=7 or 9) and Neodol 25–7, was investigated and correlated with micellar properties of these surfactants. These PAC include dibenzofuran, phenanthrene, acenaphthene, fluoranthene, and 9-chloroanthracene. Tergitol surfactants are mixtures of secondary ethoxylated alcohols, and Neodol 25–7 is a mixture of similar species but has the alcohol group in the primary position. These surfactants have the same chain length of hydrophobic tails and similar numbers of ethylene oxides. The results show that the Neodol surfactant yields micelles having larger hydrophobic core volume and renders a higher solubilization capacity for the PAC solubilizates in comparison with Tergitol surfactants. In general, aggregation numbers and micellar sizes both increase at elevated temperatures still below the cloud point. The micellewater partition coefficients of these PAC by the nonionic surfactants were well correlated to their octanol-water partition coefficients. Moreover, an estimated log K _ow value of 9-chloanthracene is 4.78.     

Colloidal flocculation of micellar solutions of anionic surfactants

Micellar solutions of anionic surfactants usually precipitate in the presence of cations, following a mechanism by which initially cations bind themselves to the micellar surface until saturation is achieved. At higher cation concentrations, unbound cations precipitate with surfactant monomers. In a few cases cations, and especially Al³⁺, cause surfactant micelles to flocculate. These flocs have properties as adsorbents of acidic organic compounds, which might be used in water treatment processes. Both α-olefinsulfonates C₁₄−C₁₆, and laurylsulfate micellar solutions are fast flocculation colloidal systems in the presence of Al³⁺.     

Mixed Surfactant-Based Reverse Micellar Extraction Studies of Bovine Lactoperoxidase

The suitability of reverse micellar extraction for recovery of bovine lactoperoxidase (LP) from aqueous solution was evaluated using systems formed by ionic and nonionic surfactant mixtures. The influence of ionic surfactant concentration, organic solvent, and pH on the extraction of LP into the reverse micellar phase was studied. The Tween® series surfactants with Aerosol-OT (bis-(2-ethylhexyl) sulfosuccinate) showed better extraction of LP in the reverse micelles (RM) compared to the Triton® and Span® series of surfactants. Complete extraction of LP from an aqueous phase of initial concentration 25 mg L⁻¹ occurred with the RM formed by 90 mM Aerosol-OT/8 mM Tween® 80 in isooctane. The optimal pH, ionic strength, and positively charged ionic surfactant concentration for back extraction were also studied and a maximum of 95.5% back extraction efficiency and 66% LP activity recovery was obtained for a pH of 10.5,1 M KCl and 60 mM cetyltrimethylammonium bromide system.     

Packing of polyethylene oxide chains in a mixed micelle

The effects of an anionic surfactant, sodium dodecyl sulfate (SDS), on the micellar properties of a nonionic surfactant such as homogeneous heptaethylene glycol n-dodecyl ether (7ED) have been studied by the charge transfer solubilization of 7,7,8,8-tetracyanoquinodimethane, pNa, and electric conductivity measurements. Attention has been paid to changes in packing of polyethylene oxide chains in the mixed micelle and to binding of the counterions onto the micelle surface. All measurements were made on solutions ranging in 7ED concentration from 1 × 10⁻⁶ to 1×10⁻¹ M, while the SDS concentration was maintained constant. It has been shown that the binding of Na⁺ ions to the mixed micelle occurs in the 7ED concentration region where the packing of polyethylene oxide chains in the micelle is loose, while release of Na⁺ ions is observed when the packing is compact. The results of electric conductivity correspond well with those mentioned above. However, in the region of high 7ED concentration, the decreasing mobility of the mixed micelles affects the electric conductivity more than the increasing degree of ionic dissociation of the micelle.     

Solution properties of mixed surfactant system sodium dodecyl sulfate and alkyl polyoxyethylene ether system

The effect of oxyethylene groups in a nonionic surfactant on the solution properties of anionicnonionic systems is described; these systems are sodium dodecyl sulfate (SDS)—hexadecyl polyoxyethylene ethers (C₁₆POE_n, where n=10, 20, 30 and 40). The degree of ionic dissociation of the mixed micelles decreases with increasing numbers of oxyethylene groups in the nonionic surfactant. As polyoxyethylene chain lengths increase, the electrical conductivities of the mixed surfactant solutions decrease, in spite of the decrease in activation energy for conduction. The radius of the mixed micelle with the electric double layer is larger for a nonionic surfactant having a shorter polyoxyethylene chain length than for one having a long polyoxyethylene chain. This may be attributed to the fact that the mixed micelle is formed more easily by a nonionic surfactant with a shorter polyoxyethylene chain length than by one with a longer chain.     

Laundry Detergency of Solid Nonparticulate Soil or Waxy Solids: Part II. Effect of the Surfactant Type

In this work, methyl palmitate with a melting point around 30°C was used as a model of waxy soil. Its detergency was evaluated with a hydrophilic surface (cotton) or a hydrophobic surface (polyester) using different surfactants: alcohol ethoxylate (EO9), sodium dodecyl sulfate (SDS), methyl ester sulfonate (MES), methyl ester ethoxylate (MEE), and two extended surfactants (C_12,14-10PO-2EO-SO₄Na and C_12,14-16PO-2EO-SO₄Na). The detergency efficiency at a 0.2 wt.% surfactant and 5 wt.% NaCl gradually increased while redeposition gradually decreased with increasing washing temperature in most studied surfactant solutions; this was observed both above and below the melting point of methyl palmitate on both studied fabrics. If the methyl palmitate was heated above the melting point when deposited on the fabric, it was better able to penetrate into the fabric matrix as compared to deposition below the melting point, resulting in poorer detergency for heated deposition, particularly for washing temperatures lower than the melting point. Among the surfactants studied, the nonionic surfactant (EO9) showed the highest detergency efficiency (73–94%) at any washing temperature especially on the polyester fabric. For washing temperatures below the melting point, detergency performance correlated well with the contact angle of surfactant solution on the solid methyl palmitate surface for all studied surfactants when salinity was varied. In this work, conditions resulting in the highest detergency below the melting point corresponded to the highest detergency above the melting point, suggesting this as a systematic approach to formulating below the melting point of the soil. Charge of particles or fabric was not observed to be important to the detergency mechanism, but steric factors resulting from surfactant adsorption were observed to be important mechanistic factors in waxy solid detergency.     

Effects of nonionic surfactant on the rheological property of associative polymers in complex formulations

The rheological properties of hydrophobically modified ethoxylated urethane (HEUR) were investigated in the presence of a nonionic surfactant, polyoxyethylene stearyl ether (C₁₈(EO)₂₀). The presence of nonionic surfactants played an important role in tuning the rheological properties of HEUR aqueous solutions. Observing both plateau modulus and viscoelastic relaxation time of HEUR aqueous solutions with varying the concentration of C₁₈(EO)₂₀ allowed us to demonstrate that C₁₈(EO)₂₀ readily interacts with the hydrophobic segments of HEUR polymers, which eventually formed a strong micellar network. Moreover, the micellar network formed at a critical concentration of C₁₈(EO)₂₀, ∼0.6% w/v, was indeed stable against both ionic strength and pH in the aqueous medium and complex formulations, such as a colloid suspension and an oil-in-water emulsion, thus providing more practical applications as thickeners for a wide variety of complex formulations.     

Mixed Micellization and Interfacial Properties of Polyoxyethylene Sorbitan Esters with Cetylpyridinium Chloride: A Tensiometric Study

In this work a surface tensiometric method was used to study the effect of the chain length of non-ionic surfactants, viz. ethoxylated sorbitan esters, on micellar composition, critical micellar concentration, mutual interaction parameter (β ₁₂), and activity coefficients of the mixed micelles formed with the cationic surfactant cetylpyridinium chloride at 25 °C. The micellar characteristics evaluated using the Clint, Rubingh, and Blankschtein models deviated significantly from ideality, and were used to ascertain the validity of these theories. Thermodynamic stability in terms of Maeda’s approach and interfacial properties is also discussed.     

Activity of horseradish peroxidase in aqueous and reverse micelles and back‐extraction from reverse‐micellar phases

Studies on the activity of the enzyme horseradish peroxidase (HRP) have been carried out in micellar as well as reverse‐micellar media. The activity of the enzyme was studied in the presence of different classes of surfactants – ionic as well as non‐ionic. In aqueous media, the activity of the enzyme varied depending on whether the concentration of the surfactant used was above or below the critical micellar concentration (CMC). The enzyme was also studied in reverse‐micellar systems. HRP was introduced into the reverse micellar phase by the injection method and its activity within the reverse micelles was determined. The effect of water to surfactant ratio (W_o) on activity within reverse micelles was studied, and an almost two‐fold increase in activity was seen when the enzyme was encapsulated within reverse micelles of aqueous phase fractional hold‐up (?) of 0.0072 (v/v) consisting of sodium bis‐(2‐ethylhexyl) sulfosuccinate (AOT) in isooctane at a W_o of 20. The activity of HRP was measured over a wide range of AOT concentrations having different W_o values. Back‐extraction of HRP from these reverse micelles was carried out at varying ionic strengths of phosphate buffer. Back extraction was found to be highest at pH 7.0 in 40 mol m^?3 phosphate buffer and 100 mol m^?3 sodium chloride. © 2001 Society of Chemical Industry     

Hydrotropic and surfactant properties of novel diisopropyl naphthalene sulfonates

A novel surfactant and hydrotrope, sodium diisopropylnaphthalene sulfonate (SDIPNS) has been developed. It contains about 92% diisopropylnaphthalene sulfonate, compared to other materials which are less than 50% diisopropylnaphthalene sulfonate. Aqueous solutions of 34–36% active SDIPNS have dual functionality. They have excellent surface properties and are compatible with conventional anionic, nonionic, and amphoteric surfactants. They demonstrate good laundering detergency in combination with sodium lauryl ethoxy sulfate, with or without builder. They maintain surface activity in 150 ppm hard water (Ca²⁺/Mg²⁺=2∶1), 5% NaCl, pH 2, and pH 12. They are effective hydrotropes. They enhance surfactant solubility, raise the cloud point of nonionic surfactants, and modify the viscosity of surfactant formulations. They are light in color and are low-foaming. Presented as a Poster Session at the American Oil Chemists' Society Annual Meeting, May 9–12, 1999, Orlando, Florida.     

Partitioning and Localization of Fragrances in Surfactant Mixed Micelles

The localization and dynamics of fragrance compounds in surfactant micelles are studied systematically in dependence on the hydrophobicity and chemical structure of the molecules. A broad range of fragrance molecules varying in octanol/water partition coefficients P _ow is employed as probe molecules in an aqueous micellar solution, containing anionic and nonionic surfactants. Diffusion coefficients of surfactants and fragrances obtained by Pulsed Field Gradient (PFG)-NMR yield the micelle/water distribution equilibrium. Three distinct regions along the log(P _ow) axis are identified: hydrophilic fragrances (log(P _ow) < 2) distribute almost equally between micellar and aqueous phases whereas hydrophobic fragrances (log(P _ow) > 3.5) are fully solubilized in the micelles. A steep increase of the incorporated fraction occurs in the intermediate log(P _ow) region. Here, distinct micelle swelling is found, while the incorporation of very hydrophobic fragrances does not lead to swelling. The chemical structure of the probe molecules, in addition to hydrophobicity, influences fragrance partitioning and micelle swelling. Structural criteria causing a decrease of the aggregate curvature (flattening) are identified. ²H-NMR spin relaxation experiments of selectively deuterated fragrances are performed monitoring local mobility of fragrance and leading to conclusions about their incorporation into either micellar interface or micelle core. The tendencies of different fragrance molecules (i) to cause interfacial incorporation, (ii) to lead to a flattening of the micellar curvature and (iii) to incorporate into micelles are shown to be correlated.     

Cold Water Detergency of Triacylglycerol Semisolid Soils: The Effect of Salinity,Alcohol Type,and Surfactant Systems

Cold water detergency of triacylglycerol semisolid soils is much more challenging than liquid vegetable oils due to poorer interaction between surfactants and semisolid soil. This research seeks to improve the removal efficiency of semisolid soils below their melting points using surfactant-based formulations containing different alcohol additives. To this end, cold water detergency of solid coconut oil and solid palm kernel oil was investigated in various surfactant/alcohol systems, including single anionic extended surfactants, single nonionic alcohol ethoxylate surfactants, and a mixture of anionic surfactants. A series of alcohols (2-butanol, 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, and 1-decanol) were added to the surfactant formulations to investigate cold water detergency improvement. While cold water detergency using surfactants alone was poor, it was considerably improved when optimum salinity (S*) and 1-heptanol, 1-octanol, or 1-nonanol were introduced to the studied surfactant formulations. The maximum detergency of solid coconut oil exceeded 90% removal in the 0.1 w/v% C_14-15-8PO-SO₄Na/0.2 w/v% 1-octanol/4 w/v% NaCl system (a final optimized surfactant system) at a washing temperature of 10°C versus 22.9 ± 2.2% in the surfactant alone (not at optimum salinity and no additive). Further analysis showed that improved cold water detergency using surfactant/intermediate-chain alcohols/NaCl could be correlated with high wettability (low contact angle) as well as favorable surfactant system-soil interaction as observed by lower interfacial tension values. In contrast, the improved cold water detergency was observed to be independent of dispersion stability. This work thus demonstrates that surfactant system design, including additives, can improve cold water detergency of semisolid soils and should be further explored in future research.     

Electrical Aspects of Adsorbing Colloid Flotation. XIX. Viscosity and the Structures of Mixed Micelles

Abstract

Viscosity measurements on mixed surfactant solutions containing the nonionic surfactant Triton X-100 and a number of other cosurfactants (dodecanoic acid, dodecyl amine, sodium dodecylsulfate, dodecyltrimethylammonium chloride, dodecyl alcohol, and sodium dodecylphosphate) indicate the presence of two quite different ‘types of micelles’. Solutions containing an electrically neutral cosurfactant exhibit very large viscosities, indicating the presence of extended micellar structures. Solutions containing a charged cosurfactant exhibit much lower viscosities, indicating that the micelles in these solutions are small spherical or ellipsoidal structures. Evidently coulombic repulsions destabilize the extended structures when charged surfactants are present in the micelles. The effects of pH and ionic strength are consistent with this interpretation.