Some Surface Properties of Polysorbates and Cetyl Trimethyl Ammonium Bromine Mixed Systems

Mixed surfactant solutions consisting of cationic/nonionic surfactants were prepared in different compositions of the components in aqueous solution in order to determine the surface properties. The critical micelle concentration (CMC) of aqueous solutions of the individual surfactants cetyl trimethyl ammonium bromide (CTAB) and polysorbate nonionics, and their mixtures are determined at different proportions. The results show that there is synergistic behavior in mixtures at higher mole fraction of nonionic surfactant. The effect of the alkyl chain on the CMC is also determined.     

Surface Properties and Solubility Enhancement of Anionic/Nonionic Surfactant Mixtures Based on Sulfonate Gemini Surfactants

As a class of novel surfactants, Gemini surfactants usually exhibit fairly excellent interfacial properties in aqueous solutions on account of the unique structure. They have significant application and development potential for industrial production. However, the mixing properties of Gemini surfactants with conventional surfactants are the key to their application. The equilibrium surface tension curves of anionic/nonionic surfactant mixtures based on the sulfonate Gemini surfactant (SGS-12) were measured using the Wilhelmy Plate method. The parameters of surface adsorption, the interaction parameters between anionic and nonionic surfactants, and the thermodynamic parameters of micelle formation were calculated from the corresponding equations. In addition, the dynamic surface tension (DST) curves of anionic/nonionic surfactant mixtures were examined through bubble profile analysis, and the diffusion performance parameters were acquired from empirical formulas. The solubilization of pyrene in micelle solutions was studied using UV–vis absorption spectroscopy. The results show that the interaction parameters of all anionic/nonionic surfactants are negative, indicating that there is a synergistic effect on reducing the surface tension. For the SGS-12/OP-10, SGS-12/Tween 80, SGS-12/AEO9, and SGS-12/APG0810 mixtures, the optimum mixing ratios are 6:4, 7:3, 7:3, and 8:2, respectively. The thermodynamic data of micelles show that the formation of mixed micelles for SGS-12/APG0810 mixtures is an enthalpy-driven process. The tendency of DST curves of the SGS-12/APG0810 mixture is similar to that of SGS-12. In comparison with single-surfactant solutions, the anionic/nonionic surfactant mixtures show stronger solubilization capacity toward pyrene.     

Wettability alteration and reducing water blockage in tight gas sandstone reservoirs using mixed cationic Gemini/nonionic fluorosurfactant mixtures

The unrecovered hydraulic fracturing fluid will invade the matrix and induce water blockage, creating formation damage and hindering the oil or gas production rate. First, the synergistic effect of cationic Gemini surfactant (MQAS) and nonionic fluorosurfactant (N-2821) mixtures on reducing the surface tension and wettability alteration was investigated in this paper. The critical micelle concentration (CMC) of the surfactant mixture is one or two orders of magnitude lower than that of N-2821 and MQAS, indicating that the MQAS/N-2821 mixtures exhibit an apparent synergistic effect in reducing surface tension. Moreover, the maximal contact angle of MQAS/N-2821 mixtures reached 83.55° at α_N-2821 = 0.5, and the total surfactant concentration of 1 × 10⁻⁴ mol/L due to the adsorption of surfactant. The adsorption mechanism of surfactants on the surface of quartz sand was then examined. The adsorption kinetics is consistent with the pseudo-second-order model at different surfactant concentrations, while the Freundlich model is suitable for describing the adsorption behavior of surfactants on the sandstone surface. This finding indicates that surfactant adsorption is multilayered. The MQAS/N-2821 surfactant mixtures have excellent surfactant activity due to the relationship of the capillary pressure to the surface tension, pore radius, and contact angle; thus, the addition of surfactant mixtures can reduce the liquid saturation effectively. Furthermore, the sequential imbibition experiments indicate that MQAS/N-2821 mixtures alter the wettability of the core plug, which results from the adsorption of surfactants. Compared with brine water, the MQAS/N-2821 mixtures decreased the liquid saturation and increased the permeability recovery ratios of the core plug.     

Experimental Study on Foam Properties of Mixed Systems of Silicone and Hydrocarbon Surfactants

Silicone surfactants are inevitably involved in industrial applications in combination with hydrocarbon surfactants, but properties of the mixtures of silicone and hydrocarbon surfactants have received little attention, especially foam properties of the mixtures. In this study, aqueous solutions of respective binary mixtures of a nonionic silicone surfactant with anionic, cationic, and nonionic hydrocarbon surfactants were prepared for evaluation of their foam properties. Surface tension of aqueous solutions of the mixtures were measured with the maximum bubble pressure method. Foaming ability and foam stability of the mixtures were then evaluated with the standard Ross–Miles method. The findings show that the addition of the silicone surfactant results in a decrease in surface tension for aqueous solutions of the hydrocarbon surfactants. The critical micelle concentration (CMC) of the hydrocarbon surfactants is also changed by the additive silicone surfactant. Additionally, clear foam synergistic effects were observed in the mixtures of silicone and hydrocarbon surfactants, regardless of the ionic types of the hydrocarbon surfactant. The foam stability of the hydrocarbon surfactant was shown to generally improve with the increasing concentration of the silicone surfactant. Even so, aqueous solutions of different ionic hydrocarbon surfactants in the presence of the silicone surfactant will give different foam stabilities. The results of the present study are meant to provide guidance for the practical application of foams generated by the mixtures of the silicone and hydrocarbon surfactants.     

The adsorption behavior of dialkyl dimethyl ammonium chloride-nonionic surfactant binary systems

From the practical standpoint of fabric softener formulation, a comparative study was made on adsorption behavior toward fabrics of binary systems consisting of di(hydrogenated tallow) dimethyl ammonium chloride (purified Arquad 2HT) and typical polyoxyethylenated nonionic surfactants which are commonly used as auxiliary agents for softeners. Soxhlet extraction of treated fabrics and quantitative analysis by high-performance liquid chromatography (HPLC) gave significant results indicating many of these nonionic surfactants, assumed to be inherently unadsorbable in rinse-cycle treatment, were highly adsorbable even at a high bath ratio by being applied with the water-insoluble cationic surfactant. Moreover, it was also disclosed that the hydrophobic structure of nonionic surfactants is another factor, other than hydrophobicity, determining adsorption. Furthermore, the mechanism of this nonionic adsorption was elucidated on the basis of results of structural analyses of binary dispersions by differential scanning calorimetry (DSC), X-ray diffraction, electron spin resonance spectroscopy (ESR) and transmission electromicroscopy (TEM) in addition to partition measurements of the surfactants into the dispersed and the continuous aqueous phases. It was concluded that the primary driving force for this nonionic adsorption is an association with the lamellar of Arquad 2HT and that the cationic vesicles act as “anchors” in adsorption.     

Mixed Micelles of Trisiloxane Based Silicone and Hydrocarbon Surfactants Systems in Aqueous Media: Dilute Aqueous Solution Phase Diagrams, Surface Tension Isotherms, Dilute Solution Viscosities, Critical Micelle Concentrations and Application of Regular Solution Theory

Mixtures of trisiloxane type nonionic silicone surfactant (SS) with sodium dodecylsulfate, tetradecyltrimethylammonium bromide or tert-octylphenol ethoxylated with 9.5 ethylene oxide groups were studied in water at 30 °C by dilute aqueous solution phase diagrams, surface tension and dilute solution viscosity methods. The cloud points for the silicone surfactant aqueous solutions increased upon addition of hydrocarbon surfactants indicating the formation of hydrophilic complexes in mixture solutions. The scrutiny of the surface tension isotherms plotted as a function of SS concentration revealed that competitive adsorption effects are the characteristic features in these mixtures depending upon the SS concentration. Otherwise the isotherms exhibited two break points and the difference of concentration between the two break points increased with the increase in SS concentration indicating the cooperative nature of interactions. The micellar mole fractions of individual surfactants were determined by Rublingh's regular solution theory; interaction parameters and activity coefficients were evaluated and interpreted in terms of synergistic type interactions in these mixtures. The surface active parameters in mixture solutions were estimated and their analysis shows that the molecular species in the mixture solutions have a preferential tendency for adsorption at the air/water interface than in association form in the bulk solution. The effect of hydrocarbon surfactants on the intrinsic viscosity of SS micelles was monitored and related to the enhanced hydration in mixed micelles.     

Adsorption of cationic/nonionic surfactant mixtures on polyester

Experiments were performed to characterize the adsorption of the cationic surfactant benzalkonium chloride (BZK) on polyester as well as measure the effect of the cationic surfactant on polyester surface charge. Additional studies were performed to examine the effect of adding nonionic surfactants on surface charge. In studies of adsorption of BZK on polyester, different behaviors were observed at pH values 6 and 10, with adsorption reaching a maximum at pH 10 but not at pH 6. In probing the zeta potential and isoelectric point (IEP) of polyester exposed to solutions composed of BZK (cationic surfactant) and an ethoxylated alcohol (nonionic surfactant), it was seen that the IEP could be shifted to higher pH levels by increasing the mole fraction of nonionic surfactant in a cationic/nonionic surfactant solution. A maximum in the IEP was obtained at a certain mole fraction for most cases. The shift in the IEP was hypothesized to be driven by increased deposition of the cationic, since the nonionic itself did not significantly change the IEP. The cooperative interactions between cationic and nonionic species were theorized to be driven not so much by attractive interactions, but other interactions, such as minimization of cationic charge repulsion.     

Effect of Inorganic Additives on a Conventional Anionic–Nonionic Mixed Surfactants System in Aqueous Solution

The interaction between an anionic surfactant (sodium dodecyl sulfate) and a nonionic surfactant [polyoxyethylene (9.5) octyl phenyl ether] in aqueous salt solution was investigated using the surface tension method. The critical micelle concentration values were determined for the individual surfactants and their corresponding mixtures. The interaction parameter between the surfactants in the mixed micelles, the activity and activity coefficients in the mixed micelles, and the thermodynamic parameters were calculated using various approaches, viz., Clint, Rubingh, and Maeda models. It was observed that the critical micelle concentration of the mixed surfactants system reveals little deviation from ideality.     

Mechanistic Studies of Particulate Soil Detergency: I. Hydrophobic Soil Removal

The mechanism of particulate soil detergency using aqueous surfactant systems is not well understood. In this research, carbon black (model hydrophobic soil) removal from a hydrophilic (cotton) and hydrophobic (polyester) fabric is studied using anionic, nonionic, and cationic surfactants. The zeta potential, solid/liquid spreading pressure, contact angle and surfactant adsorption of both soil and fabric are correlated to detergency over a range of surfactant concentrations and pH levels. Electrostatic repulsion between fabric and soil is generally found to be the dominant mechanism responsible for soil removal for all surfactants and fabrics. Steric effects due to surfactant adsorption are also important for nonionic surfactants for soil detachment and antiredeposition. Solid/liquid interfacial tension reduction due to surfactant adsorption also aids in detergency in cationic surfactant systems. Wettability is not seen as being an important factor and SEM photos show that entrapment of soil in the fabric weave is not significant; the particles are only attached to the fabric surface. Anionic surfactants perform best, then nonionic surfactants. Cationic surfactants exhibit poor detergency which is attributed to low surfactant rinseability.     

Synergistic Effect of Mixed Surfactant Systems on Foam Behavior and Surface Tension

Foam and surface tension behaviors of different ionic/nonionic surfactant solutions along with their different combinations have been investigated. Among different surfactants, sodium dodecyl sulfate showed the highest foamability over other surfactants. Mixed surfactant systems were always found to have higher foamability than the individual surfactant. It was also noticeable that nonionic surfactants show good foamability when they combine with anionic and cationic surfactants. In the case of mixed surfactant systems, nonionic/cationic surfactant mixtures showed lower surface tension than nonionic/anionic surfactant mixture due to a synergistic effect.     

Properties of aqueous solution of a fluorocarbon surfactant and a nonionic surfactant,and their mixtures

The surface tensions of aqueous solutions of lithium perfluorooctane sulfonate (LiFOS) and hexaethyleneglycoln-dodecylether (6ED), and of their mixtures, were measured. The effect of each surfactant additives on the adsorption and the micelle formation was discussed on the basis of the surface tension values using the Langmuir adsorption equation for the mixture of both surfactants and the modified Szyszkowski equation. From these results, in the range of low concentrations of 6ED or LiFOS, some of the 6ED molecules which had already adsorbed on the solution surface were found to be replaced by LiFOS molecules in an addition of LiFOS surfactant and vice-versa. In the ranges of higher concentration above critical micelle concentration (CMC) of each surfactant, it was concluded that the mixed micelle could be formed in the mixed system of both surfactants as well as in the mixed system of two kinds of ordinary hydrocarbon surfactants.     

Adsorption characteristics of ionic and nonionic surfactants on hydrophobic pigment in aqueous medium

The current study is based on the investigation of the adsorption properties of ionic and nonionic surfactants on an organic hydrophobic pigment powder, namely, β‐copper phthalocyanine, in aqueous medium. The nonionic surfactants, selected systematically to represent varying degrees of ethoxylation, are nonylphenol ethoxylates, whereas the ionic surfactant is sodium oleate, a carboxylate‐type anionic reagent. The adsorption of surfactants was assessed qualitatively by surface analysis of powders, before and after the adsorption of the surfactants. The experimental results were explained by the structural and other properties of the surfactants and the surface properties of the pigment. The specific adsorption of surfactants on pigments was verified by zeta potential measurements, as they altered the zeta potential values to a great extent. Nonionic surfactants decreased the absolute value of the zeta potential of the powder; whereas anionic surfactant sodium oleate shifted the zeta potential to more negative values. On the one hand, Fourier Transform–infrared and X‐ray diffraction examinations of the pigments did not show any noticeable evidence for surfactant untreated or treated copper phthalocyanine. On the other hand, thermal analysis (both thermogravimetric and differential thermal analysis) showed clear evidence of the surfactants on both pigments, as substantial changes in thermogravimetric curves were assessed.     

The stabilization effect of mixed-surfactants in the emulsion polymerization of styrene

Summary The emulsion polymerization of styrene was performed at 50°C with a mixture of anionic and nonionic surfactants using different surfactant concentrations. In the single-surfactant systems, a proportional relationship was observed between the total particle surface area per cm³ of aqueous solution at 90% conversion (TS) and the amount of surfactant used for each polymerization. For mixed-surfactant systems an additivity was established between the TS value and surfactant composition. The study of the particle size data from low to high conversion showed that the particle number changed with conversion.     

Synergistic effect of polymer-surfactant mixtures on the stability of aqueous silica suspensions

The aim of the present work was to investigate the effect of cationic/nonionic surfactant mixtures on the dispersion and flocculation behavior of aqueous silica suspensions. In the study dodecylamine (DDA) was used as the cationic surfactant and polyethylene oxide-polypropylene oxide-polyethylene oxide (PEO–PPO–PEO) triblock copolymers were employed as the nonionic surfactant. The dispersion and flocculation behavior of aqueous silica suspensions were studied mainly by turbidity measurements at low solids loading (0.05 vol.%) to observe the stability of the system for a given time period. Rheological measurements were performed at higher solids loadings to determine the viscosity as a function of shear rate. Adsorption behavior of single and mixed surfactants onto silica surface was studied using a total organic carbon analyzer.Results of the study showed that dispersion and flocculation behavior of aqueous silica suspensions depends on the type and concentration of surfactant, cationic/nonionic surfactant ratio and surfactant addition sequence to the system.     

The stabilization effect of mixed-surfactants in the emulsion polymerization of methyl methacrylate

Summary The emulsion polymerization of methyl methacrylate (MMA) was conducted at 50°C using either anionic or nonionic surfactants, or a mixture of the two at different surfactant concentrations. In the singlesurfactant systems a proportional relationship was observed between the total particle surface area per cm³ of aqueous solution at 90% conversion (TS) and the amount of surfactant used. For mixed-surfactant systems, a relationship close to an additive one was found between the TS value and the amount of each surfactant used. The particle number did not remain constant during the polymerization, while the TS value continuously increased. It was also found that MMA formed a paste easily at higher (M/W) ratios, which could be alleviated by using higher surfactant concentrations.     

Wettability of Polymeric Solids by Aqueous Solutions of Anionic and Nonionic Surfactant Mixtures

Measurements of the surface tension (γ _LV) and advancing contact angle () on poly(tetrafluoroethylene) (PTFE) and poly(methyl methacrylate) (PMMA) were carried out for aqueous solutions of sodium decyl sulfate (SDS) and p-(1,1,3,3-tetramethylbutyl)phenoxypoly(ethylene glycol) (TX100) and their mixtures. The results obtained indicate that the values of the surface tension and contact angles of solutions of surfactants on PTFE and PMMA surfaces depend on the concentration and composition of the surfactant mixtures. Calculations based on the Lucassen-Reynders equation indicate that for single surfactants and their mixtures at a given concentration in the bulk phase the values of surface excess concentration of surfactants at water–air and PTFE–water interfaces are nearly the same, so the adsorption of the surfactants at water–air and PTFE–water interfaces should also be the same. However, the adsorption of TX100 and its mixtures with SDS at water–air interface is higher than that at PMMA–water interface, which is confirmed by the ratio of absolute values of molecular interaction parameters at these interfaces calculated on the basis of Rosen approach. If we take into account the hydration of the poly(ethylene oxide) chains of TX100 and acid and base parameters of the surface tension of water it appears that the PMMA surface is covered by the 'pure' water molecules from the solution or molecules connected with the chain of nonionic surfactant. On the other hand, the lack of SDS molecules at the PMMA–water interface may result from the formations of its micelles which are connected with the TX100 chain.     

Effect of cotton substrate characteristics upon surfactant adsorption

It is shown that the reported differences in anionic surfactant adsorption on cotton can be largely attributed to the presence of variable amounts of natural wax on the fiber surface. High adsorption values with peaks near critical micelle concentration (cmc) result from surfactant adsorption on the wax surface. Wax-free surfaces fail either to show the same high maxima or the same relative magnitude of adsorption. At surfactant cmc the adsorption relationship for waxy cotton (millimoles/g. of cotton) cationic: nonionic: anionic was roughly 66 to 17 to 74. For dewaxed cotton, this became 40 to 10 to nil. Confirming the findings of others, no adsorption by cotton of sodium tripolyphosphate occurs either with waxy or wax-free cotton. Also addition of tripolyphosphate decreased the adsorption of several anionic surfactants. At concentrations greater than cmc and at sufficiently-high solution temperature, anionic surfactants can solubilize cotton wax, leaving a less waxy substrate upon which adsorption is then reduced.     

Adsorption study of nonionic surfactants on polyester fibers

An adsorption study of a series of nonionic surfactants on polyester fiber was performed to determine the relative importance of sub-strate affinity in the detergency process. The fiber used in this study was a multifilament polyester yarn. Because of the relatively low surface area/g of the yarn, analytical methods for detecting the depletion of surfactant due to adsorption have to be extremely sensitive. One qualitative technique used was streaming potential measurements. The electrokinetic effect, which the streaming poten-tial measures, depends on the nature of the electrical double layer at the fiber/solution interface. The modification of the streaming potential indicates that the extent of surfactant adsorption onto the fiber surface is very similar for the nonionic surfactants studied. A very sensitive, quantitative analytical technique, which can only be used for surfactants with an appropriate chromophore, is ultraviolet (UV) spectroscopy. The UV study showed that the adsorption of the nonylphenol ethoxylate onto the polyester is Langmuirian with the adsorption plateau occurring at the critical micelle concentra-tion. For alcohol ethoxylates without a UV chromophore, con-venient quantification at the ppm level represents a difficult analyt-ical problem. In this work, total carbon analysis was developed as a sensitive analytical tool for surfactant determination. Agreement between the UV and total carbon data for the nonylphenol ethox-ylate was quite good. The relevance of the data to the detergency process is discussed.     

Adsorption mechanism of surfactants on nonwoven fabrics

For improved surface properties, nonwoven fabrics of polypropylene and poly(ethylene terephthalate) were treated with several kinds of surfactants, including anionic, cationic, and nonionic types. The adsorption isotherms of the anionic, cationic, and nonionic surfactants on the nonwoven fabrics were different. The adsorption isotherm of the cationic surfactant (dodecyl dimethylbenzyl/ammonium chloride) exhibited a maximum. The adsorption isotherm of the anionic surfactant (sodium dodecylbenzene sulfonate) was in the shape of the fifth Brunauer adsorption isotherm, and that of the nonionic surfactant (alkylphenol/ethylene oxide condensate) was similar to the fourth Brunauer adsorption isotherm. The time of the adsorption equilibrium was constant for the same types of adsorbate and adsorbent, and it was not related to the initial concentration. The specific surface resistance of the nonwoven fabrics decreased substantially after the adsorption of ionic surfactants. The nonwoven fabrics with the surfactants were characterized with scanning electron microscopy and X‐ray photoelectron spectroscopy. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3210–3215, 2003     

Aggregation and Phase Separation Phenomenon of Amitriptyline Hydrochloride Under the Influence of Pharmaceutical Excipients

The interaction between the amphiphilic drug amitriptyline hydrochloride (AMT) and the nonionic surfactants used in drug delivery has been investigated. Herein, we report the micellization behavior of AMT in presence of ethoxylated alkyl phenols in aqueous medium and the clouding phenomenon in the absence and presence of different nonionic surfactants in buffer solution. The values of critical micelle concentration (CMC) of AMT obtained using the conductivity method, decrease as nonionic surfactant concentration increases. With an increase in temperature, the CMC first increases and then decreases. At 303.15 K, the maximum CMC values were obtained with or without nonionic surfactant. The results obtained indicate attractive interactions (synergism) between the two mixing amphiphiles in solution. The experimentally obtained critical micelle concentration (CMC) values are always lower than ideal CMC values. Micellar mole fraction (X₁) values, calculated by different proposed models, show the contribution of nonionic surfactant concentration. At a fixed drug concentration (50 mmol kg^?1) and pH (=6.7) nonionic surfactants show continuous increase in cloud point (CP). Increase in drug concentration and pH, in the presence of fixed amounts of nonionic surfactant, increases and decreases the CP, respectively.