A 1D- and 2D-NMR Study of an Anionic Surfactant/Neutral Polymer Complex

NMR chemical shifts and linewidth measurements were examined for mixtures of sodium 10-phenyldecanoate (Na ω-PhDec) in deuterated aqueous solutions in the presence of varying compositions of poly(ethylene oxide) (PEO) polymers of 2000 and 4000 molecular weight. In addition, variable temperature NMR spectra and NMR spin lattice relaxation times (T ₁) were obtained for the PEO-4000/Na ω-PhDec system as a function of varying polymer concentrations. As expected, the polymer/surfactant systems exhibit the behaviour typical of that of an anionic surfactant/neutral polymer system with well defined critical aggregation concentrations (CMC) corresponding to the formation of polymer/surfactant complexes below the CMC of the free surfactant. The ¹H-NMR linewidths acquired for the Na ω-PhDec/PEO-4000 system before and after the CMC region of the surfactant indicate that the maximum in the linewidth of the PEO proton peak is reached at approximately twice the CMC of the free surfactant. 2D-NMR NOESY measurements on this system exhibit cross peaks between the PEO protons and the protons on the surfactant backbone, consistent with the location of the phenyl group in the micellar interior. All these NMR experiments are interpreted in terms of the structure of the polymer/surfactant complexes as a function of the system composition.

Removal of Direct Yellow 27 Dye by Ionic Flocculation: The Use of an Environmentally Friendly Surfactant

The presence of dyes is one of the main contributors to the organic load in textile effluents. In this study a mixture of surfactants, produced from animal/vegetable fats, was used to remove the Direct Yellow 27 dye from a synthetic wastewater through an ionic flocculation process. It was evaluated the effect of contact time, temperature, and surfactant concentration on dye removal efficiency. It was also evaluated the kinetics, equilibrium, and diffusion mechanism of the process. The kinetics of the process was well described by both Pseudo-second order and Elovich models. The transport of dye molecules to the surfactant flocs is controlled by the external layer. Equilibrium data showed a good fit to the Langmuir model. A removal rate of 93% was achieved in a single stage, after 5 h of contact time.     

Effects of Divalent Salts on the Interfacial Activity of the Mixed Surfactants at the Water/Model Oil Interface

In our previous report, the mixed cationic/anionic surfactant system consisting of N-dodecyl-N-methylpyrrolidinium bromide (L12) and sodium dodecyl sulfate (SDS) showed good interfacial tension (IFT) reduction of water/model oil (V_toluene:V _n-decane = 1:1). In the present study, the effects of divalent salts (MgCl₂ or CaCl₂) on the interfacial activity were systematically evaluated. The additional Mg²⁺ ions greatly reduced the IFT to an ultralow value, whereas Ca²⁺ ions caused the generation of the precipitates and resulted in increased IFT values. The precipitates disappeared in binary divalent salt solutions, and the IFT values remained at a low level. Based on the valence, polarizability, and hydrated radius of the ions, we proposed a model to explain the abnormal changes. The effects of NaCl and temperature were investigated to further verify our proposed mechanism. Moreover, the additional divalent salts obviously enhanced the stability of L12/SDS stabilized emulsions.     

Interaction Between an Anionic and an Amphoteric Surfactant. Part II: Precipitation

Use of amphoteric and anionic surfactants is very common in practical formulations such as shampoos and hand dishwashing products. Precipitation of mixtures of dimethyldodecylamine oxide (DDAO) as an amphoteric surfactant and sodium dodecyl sulfate (SDS) as an anionic surfactant were studied at different pH levels. The DDAO is a pH-sensitive surfactant and its protonation can be expressed in terms of a pK _a similar to an acid dissociation constant. The protonated form of DDAO carries a positive charge and precipitates with the oppositely charged SDS. Therefore, precipitation phase boundaries are pH dependent due to the varying degree of DDAO protonation. By combining the use of regular solution theory and the pseudophase separation model to describe micellar mixing nonidealities with the precipitate solubility product constant and the protonation dissociation constant, a model to predict the precipitation phase boundary is presented here. The model agrees well with experimental phase boundaries at different pH levels.

The Effects of Dynamic Noncovalent Interaction between Surfactants and Additional Salt on the pH-Switchable Interfacial Tension Variations

The dynamic noncovalent interaction between the anionic surfactant sodium dodecyl benzene sulfonate (SDBS) and 1,3-diphenylguanidine (DPG) was employed to control the interfacial activity of the surfactant. At high HCl concentration (1000 mg L⁻¹), the SDBS/DPGⁿ⁺ system could reduce the water/oil interfacial tension (IFT) to 10⁻⁴ mN m⁻¹ order of magnitude, which was much lower than the IFT values in the SDBS/DPG⁺ system with a low HCl concentration (100 mg L⁻¹) and the individual SDBS system by three and four orders of magnitude, respectively. The pH-switchable protonation of amido groups in DPG molecules determines the SDBS/DPG molecular interaction and the amplitude of IFT reduction, which was confirmed by control experiments using two other surfactants (sodium dodecyl sulfate [SDS] and dodecyl trimethylammonium bromide [DTAB]). Moreover, the investigation of the NaCl and temperature effects on the IFT indicated the intensity of mixed SDBS/DPGⁿ⁺ adsorption layers at the water/oil interface.     

Surfactant Enhanced Oil Recovery in a High Temperature and High Salinity Carbonate Reservoir

The goal of this work was to find an effective surfactant system for enhanced oil recovery after water injection substituting for oil at a vuggy fractured reservoir with a high temperature and high salinity (220,000 mg/L). Four types of surfactants with concentrations (less than 0.2 %) were screened. Washing oil experiments were conducted in Amott cells. A surfactant system was established by mixing a surfactant with best ultimate recovery and one with best recovery rate. The optimized surfactant system could recover 50 % of remaining oil. To study the mechanism of enhanced oil recovery after water injection substituting oil, interfacial tension (IFT) and contact angle were measured. Experimental results showed that surfactants with good washing ability had low IFT, but surfactants with low IFT may not have a good washing ability. IFT had no obvious relationship with the increased oil recovery or washing ability. The optimized system could not alter carbonate to decrease the oil‐wetting capability. Though octadecyl trimethyl ammonium chloride had a good ability wet the carbonate with water, it could not recover much oil. Therefore, except for interfacial tension and wettability alteration, there must be other parameters dominating oil recovery after water injection substituting for oil.     

Investigation of Interfacial Tension Reduction,Wettability Alteration,and Oil Recovery Using a New Non-ionic Oil-Based Surfactant from Gemini Surfactants Family Coupled with Low-Salinity Water: Experimental Study on Oil-Wet Carbonate Rock

Low-salinity surfactant (LSS) flooding is a combined enhanced oil recovery (EOR) technique that increases oil recovery (OR) by altering the rock surface wettability and reducing oil–water interfacial tension (IFT). In this study, optimum concentrations of several types of salt in distilled water were obtained on the basis of IFT experiments for the preparation of low-salinity water (LSW). Then, a new oil-based natural surfactant (Gemini surfactant, GS) was combined with LSW to investigate their effects on IFT, wettability, and OR. Experimental results showed that LSW is capable of reducing IFT and contact angle, but the synergy of GS and the active ions Mg²⁺, Ca²⁺, and SO₄²⁻ in LSW was more effective on IFT reduction and wettability alteration. The combination of 1000 ppm MgSO₄ and 3000 ppm GS led to a decrease in contact angle from 134.82° to 36.98° (oil-wet to water-wet). Based on core flooding tests, LSW injection can increase OR up to 71.46% (for LSW with 1000 ppm MgSO₄), while the combination of GS and LSW, as LSS flooding, can improve OR up to 84.23% (for LSS with 1000 ppm MgSO₄ and 3000 ppm GS). Therefore GS has great potential to be used as a surfactant for EOR.     

Preparation of Modified Reduced Graphene Oxide nanosheet with Cationic Surfactant and its Dye Adsorption Ability from Colored Wastewater

In this paper, reduced graphene oxide (rGO) nanosheet from graphite was synthesized using the top-down approach. The surface of rGO was modified by cetyltrimethylammonium bromide (CTAB) to prepare rGO/CTAB adsorbent for anionic dye removal. The prepared rGO/CTAB was characterized by XRD, FTIR, FE-SEM and TGA. The operation parameters (surfactant concentration, adsorbent dosage, pH and initial concentration of dye solution) affecting the batch adsorption process to remove direct red 80 (DR80) and direct red 23 (DR23) were studied in detail. The dye adsorption capacity of rGO/CTAB was 213 and 79 mg/g for DR80 and DR23, respectively. In addition, dye removal followed the Langmuir isotherm with pseudo-second order reaction kinetics.     

Synthesis,Characterization, and Evaluation of Ethoxylated Lauryl-Myrisityl Alcohol Nonionic Surfactants as Wetting Agents,Anti-Foamers,and Minimum Film Forming Temperature Reducers in Emulsion Polymer Lattices

Two nonionic FAEO (fatty alcohol ethoxylated) surfactants with varying solubility were obtained by the reaction of lauryl-myrisityl alcohol (LMA) with ethylene oxide to yield lauryl-myristyl/alcohol ethoxylated with 3 and 31 mol of ethylene oxide by changing the length of polyethylene glycol segment. The prepared surfactants, designated as LMAEO-3 and LMAEO-31, were characterized for their structures using spectroscopic measurements; in addition, their surface properties were investigated. The results indicated that LMAEO-31 exhibits excellent surface activity. Evaluation of the surfactants as wetting agents, anti-foamers, and minimum film forming temperature (MFFT) reducer in emulsion polymer lattices achieved promising results indicating high performance in the mentioned industrial applications.     

The Effect of Counterions of Linear Alkylbenzene Sulfonate on Skin Compatibility

Interactions of a widely used commercial anionic surfactant, linear alkylbenzene sulfonate, with zein protein, a water insoluble protein, was studied to better understand the effects of the counterion on skin irritation of anionic surfactants. The neutralizing ions used were inorganics: Li⁺, Na⁺, K⁺, Mg²⁺, and NH₄⁺ and organics: monoethanolamine, diethanolamine, and triethanolamine. According to the results obtained, the influence of counterions of anionic surfactants on zein solubilization is significant; with magnesium counterions showing lower zein solubilization. In aqueous solutions, zein solubilization by anionic surfactant is related to the effect of the counterion on the critical micelle concentration of the surfactant for the inorganic counter‐ions; for the organic counter‐ions, effects of tighter anionic binding in the micelle also contribute to zein solubilization trends.     

Counterion Effect on Krafft Temperature and Related Properties of Octadecyltrimethylammonium Bromide

In the present work, we have investigated the effect of some counterions on the Krafft temperature (T _K) and the micelle formation of octadecyltrimethylammonium bromide (OTAB) in aqueous solution. The results showed that the ions with more chaotropic nature increase the T _K while those with a kosmotropic, hydrotropic and less chaotropic nature lower the T _K of the surfactant. More chaotropic SCN^? and I^?, being weakly hydrated, form contact ion pairs with the octadecyltrimethylammonium ion and reduce the electrostatic repulsion between the surfactant molecules. As a result, these ions exhibit salting out behavior and raise the T _K of the surfactant. On the other hand, less chaotropic Cl^? and NO₃ ^?, kosmotropic SO₄ ^2? and F^? and hydrotropic benzoate and salicylate ions increase the solubility of the surfactant, with a consequent decrease in the T _K. SO₄ ^2?, F^?, benzoate and salicylate cannot form contact ion pairs with the weakly hydrated cationic part of OTAB. Rather, being extensively hydrated and kosmotropic in nature, these ions do not show any tendency to shed their hydrated water molecules to form contact ion pairs with the weakly hydrated octadecyltrimethylammonium ion and therefore, stay apart. As a result, the T _K of the surfactant decreases significantly in the presence of these ions. The critical micelle concentration (CMC) of the surfactant decreases significantly in the presence of these ions due to screening of the micelle surface charge by the added counterions. Consequently, the surfactant molecules attain better packing because of substantial reduction in the electrostatic repulsion between the charged head-groups, showing a significant decrease in the CMC.     

A Novel Study on the Gel Phase Formed in a Catanionic Surfactant System

A novel gel phase was constructed in a catanionic surfactant system with the compositions of 1-tetradecyl-3-methylimidazolium chloride (C₁₄mimCl) and sodium dodecyl sulfate (SDS). The gel phases were studied through visual observations, differential scanning calorimetry (DSC), rheological measurements, and scanning electron microscopy (SEM). The visual observation and DSC confirmed the formation of gels and phase transitions from gel to sol. The dynamic rheological results showed the viscoelastic properties of gels. The SEM technique was used to further indicate the microstructure of gels. Finally, the formation mechanisms of gels are proposed based on the critical packing parameter. We expect to develop a new route to construct the gels.     

Ionic Behavior Assessment of Surface-Active Compounds from Corn Steep Liquor by Exchange Resins

Depending on their ionic nature, biosurfactants can be classified as nonionic, anionic, cationic, or amphoteric. The ionic behavior of biosurfactants is an important characteristic that dictates their use in industrial applications. In this work, a biosurfactant extract obtained from corn steep liquor was subjected to anionic or cationic resins, in order to study the ionic behavior under different operational conditions using response surface methodology. The independent variables included in the study are the dilution of biosurfactant solution, the amount of cationic or anionic resin, and the extraction time, whereas the dependent variables studied consisted of the surface tension of biosurfactant aqueous solution, after contacting with anionic or cationic resin. The results showed that biosurfactant extracted from corn steep liquor is amphoteric, since both resins were able to entrap this biosurfactant, making it particularly suited for use in personal care preparations for sensitive skin.     

Solution Properties of Alkyl β-D-Maltosides

Alkyl β-D-maltosides are an important class of sugar-based nonionic surfactants and have been widely studied. Nevertheless, it is still necessary to investigate further their amphiphilic structure-surface property relationships. In this article, we reported a series of properties of synthetic alkyl β-D-maltosides ( 6a – 6i , n = 6–18) including their hydrophilic–lipophilic balance (HLB) number, water solubility, hygroscopicity, moisture-retention capacity, foaming ability, surface tension, thermotropic phase behavior, and skin irritation. Their HLB number and water solubility decreased with increasing alkyl chain length. Hexyl β-D-maltoside exhibited the strongest hygroscopicity and moisture-retention capacity. Decyl β-D-maltoside and dodecyl β-D-maltoside possessed excellent foaming power and foaming stability. Furthermore, the critical micelle concentration (CMC) of alkyl β-D-maltoside ( 6a – 6g , n = 6–14) and their surface tension at CMC decreased with increasing alkyl chain length. At last, alkyl β-D-maltosides ( 6a – 6g ) should be considered as safe surfactants by the skin irritation assessment.     

Surfactants as Antimicrobials: A Brief Overview of Microbial Interfacial Chemistry and Surfactant Antimicrobial Activity

In this brief overview of a large and complex subject, as presented at the 2018 Surfactants in Solution conference, the need for, and impact of, hard surface antimicrobial products is demonstrated. The composition of the interfaces of three common classes of pathological microbes, bacteria, viruses, and fungi, is discussed so that surfactant and cleaning product development scientists better understand their interfacial characteristics. Studies of antimicrobial efficacy from the four major classes of surfactants (cationic, anionic, amphoteric, and nonionic) are shown. The need for preservatives in surfactants is elucidated. The regulatory aspects of antimicrobials in cleaning products to make antimicrobial claims are stressed.     

Dynamic Analysis of the Removal of Fatty Acid from a Pet Surface Using a Quartz Crystal Microbalance

A quartz crystal microbalance (QCM) was used to study the removal of stearic acid from poly(ethylene terephthalate) (PET) substrate in aqueous alkali and surfactant solutions. The PET substrate was prepared on a QCM gold electrode by spin‐coating; its properties were examined by scanning electron microscopy, X‐ray photoelectron spectroscopy, and water contact angle measurements. As a result, the QCM electrode was found to be completely covered with a smooth PET film. To investigate the effect of soil deposition state on its removal, stearic acid (an oily soil model) was deposited onto the PET substrate with the Langmuir–Blodgett (LB) technique or by spraying. The QCM frequency was recorded during the removal of stearic acid from the PET substrate in aqueous solutions. In NaOH solution, stearic acid deposited by the LB method was more rapidly removed than when deposited by the spraying method. However, the LB films of stearic acid were difficult to be removed in surfactant solutions. With respect to removal behavior of spray‐deposited stearic acid in surfactant solutions, the results determined by the QCM method were compared with those from microscopic image analysis. The removal efficiencies in the sodium dodecyl sulfate solution were in good agreement between the two methods. However, in the alkyl ethoxylate solution, the removal efficiencies obtained by the QCM method were larger than those from microscopic image analysis. These experimental results were explained by the removal mechanism of stearic acid by the alkali and surfactant solutions.     

The Irritant Effects of Pharmaceutically Applied Surfactants

Dermal or transdermal medication may lead to irritant contact dermatitis. However, little information is available on the irritant effect of surfactants which are applied in topical formulations. Our aim was to examine the irritant effect of the most frequent compounds in topical products. A murine model was applied. The following compounds were examined: sodium lauryl sulphate (SLS), polyethoxylated (40EO) hydrogenated castor oil and sucrose laurate. SLS led to severe erythema, increase in transepidermal water loss (TEWL) and induced necrosis and accumulation of neutrophylic granulocytes and lymphocytes. Exposure to sucrose laurate resulted in an elevation of TEWL, but histology did not reveal impairment of the skin structure. Application of polyethoxylated (40EO) hydrogenated castor oil was not accompanied by tissue damage. Special attention should be paid to the irritant effect of SLS. Polyethoxylated (40EO) hydrogenated castor oil seems to be a non-irritant agent and sucrose laurate is also a promising candidate for application in topical preparations.     

Aqueous Foam Stabilized by Hydrophobic SiO2 Nanoparticles using Mixed Anionic Surfactant Systems under High-Salinity Brine Condition

A primary concern of surfactant-assisted foams in enhanced oil recovery (EOR) is the stability of the foams. In recent studies, foam stability has been successfully improved by the use of nanoparticles (NP). The adhesion energy of the NP is larger than the adsorbed surfactant molecules at the air–water interface, leading to a steric barrier to mitigate foam-film ruptures and liquid-foam coalescence. In this study, the partially hydrophobic SiO₂ nanoparticles (SiO₂-NP) were introduced to anionic mixed-surfactant systems to investigate their potential for improving the foamability and stability. An appropriate ratio of internal olefin sulfonate (C_15-18 IOS) and sodium polyethylene glycol monohexadecyl ether sulfate (C₃₂H₆₆Na₂O₅S) was selected to avoid the formation of undesirable effects such as precipitation and phase separation under high-salt conditions. The effects of the NP-stabilized foams were investigated through a static foam column experiment. The surface tension, zeta potential, bubble size, and bubble size distribution were observed. The stability of the static foam in a column test was evaluated by co-injecting the NP-surfactant mixture with air gas. The results indicate that the foam stability depends on the dispersion of NP in the bulk phase and at the water–air interface. A correlation was observed in the NP-stabilized foam that stability increased with increasing negative zeta potential values (−54.2 mv). This result also corresponds to the smallest bubble size (214 μm in diameter) and uniform size distribution pattern. The findings from this study provide insights into the viability of creating NP-surfactant interactions in surfactant-stabilized foams for oil field applications.     

Application of Acoustic Spectroscopy to the Characterization of Surfactant Solutions,Emulsions, and Microemulsions: d–Limonene–Water–C12EO7–Isopropanol System

The application of acoustic spectroscopy to the characterization of binary C₁₂EO₇—water system was studied. It was discovered that the size of micelles in aqueous surfactant solutions could not be determined, but it was possible to determine the size of water nanodomains existing in the surfactant-rich systems. It was suggested that in colloidal systems, the energy of ultrasonic waves is dissipated only by interfaces existing between condensed phases. The characterization of Winsor transitions by acoustic spectroscopy in water/d-limonene system stabilized by a mixture of nonionic surfactant and isopropyl alcohol (cosolvent) was also explored. In one study, systems with a constant d-limonene to water weight ratio obtained in the course of titration of d-limonene-in-water emulsion with increasing amounts of surfactant+alcohol were investigated. In another study, a balanced d-limonene/water microemulsion was sequentially diluted with water and d-limonene. The transition between Winsor I and Winsor IV systems was monitored in both cases. Droplet size distributions were calculated using different models for dispersed and continuous phase composition. It was demonstrated that the magnitude of acoustic scattering played a significant role in the ability to reliably determine droplet size distributions, and in particular to simultaneously observe nanometer-size and micron-size droplets in Winsor I systems. An attempt was made to account for intrinsic attenuation of surfactant and alcohol by associating them with the aqueous phase, but this approach was shown not to be applicable in the case of Winsor IV microemulsions.     

Optimization and Applicability of a Novel Sensor for Potentiometric Determination of Anionic Surfactants

Novel potentiometric sensors for anionic surfactant (AS) determination, with different percentages of tetraoctadecylammonium tetraphenylborate (TODA-TPB) as sensing materials and different electrolytes (sodium chloride, lithium chloride, sodium dodecyl sulfate (NaDS), sodium tetraphenylborate, sodium acetate, and potassium chloride) at varied concentration levels, were developed and compared. The sensor with best response characteristics was further characterized. It had a fast response time (5 s), a low signal drift (2.0 and 2.9 mV h⁻¹ in a detergent solution and NaDS, respectively), a wide pH working range (3–11), and a longer lifetime of 6 months. This novel sensor was characterized with Nernstian response toward NaDS (−58.0 mV decade⁻¹ of activity), a wide working range (1.3 · 10⁻⁷–5 · 10⁻³ M), and a low limit of detection (1.0 · 10⁻⁷ M). It proved to be an accurate and reliable sensor for AS determination in multicomponent mixtures of AS and household wastewater using a potentiometric titration method. Nonionic surfactants, which are commonly mixed with AS in commercial products to obtain better properties of products, had an insignificant impact on AS determination.