Thermo- and pH-Responsiveness of Emulsions Stabilized with Acidic Thermosentive Polymers

A temperature- and pH-responsive polymeric surfactant was prepared by copolymerizing N-isopropylacrylamide, methacrylic acid, and octadecylacrylate. Poly(N-isopropylacrylamide-co-methacrylic acid-co-octadecylacrylate) (P(NIPAM-MAA-ODA) was used as an emulsifier for the preparation of water-in-oil emulsions. The mean droplet size at room temperature was almost constant for 50 hours at pH 5.0, 7.0, and 9.0. However, the size markedly increased for 50 hours at pH 3.0, possibly because of the low hydrophilicity of the copolymer and the small interfacial area one molecule of the copolymer can stabilize at a low pH value. The droplet size markedly decreased from 4.7 to 1.8 µm, when the pH of medium increased from 5.0 to 9.0 with the temperature kept constant. This may be ascribed to that the hydrophilicity of the copolymer and the interfacial area one molecule of copolymer can stabilize will be higher at a higher pH value. When the temperature increased over 35°C with the pH kept constant, the droplet size significantly increased probably because the NIPAM segment of the copolymer becomes hydrophobic with increasing the temperature so the copolymer would poorly act as an emulsifier.     

Synthesis of AA-MMA Block Copolymer by RAFT Polymerization and Used as Emulsifier cum Macroinitiator and Its Influence on the Film Properties

Blocked copolymer of acrylic acid-methyl methacrylate with controlled molecular architecture were prepared by reversible addition chain fragmentation polymerization and were characterized by Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance (¹H NMR), and gel permeation chromatography (GPC) for structural evaluation. The neutralized copolymers were evaluated for the critical micelle concentration (CMC), hydrophilic lipophilic balance (HLB) and were utilized as polymeric emulsifier cum macro RAFT initiator for the synthesis of acrylic binder. The structure properties of the emulsifier were evaluated correlating with the film properties.     

Self-assembly and emulsification of poly{[styrene-alt-maleic acid]-co-[styrene-alt-(N-3,4-dihydroxyphenylethyl-maleamic acid)]}

Self-assembled polymeric micelles can be used as efficient particulate emulsifiers. To explore the relationship between the structure and the oil-water interfacial behavior of the micelle emulsifiers, a new type of amphiphilic random copolymer, poly{(styrene-alt-maleic acid)-co-[styrene-alt-(N-3,4-dihydroxyphenylethyl-maleamic acid)]} (SMA-Dopa), was synthesized, self-assembled into micelles, and used as emulsifiers. SMA-Dopa was synthesized via an aminolysis reaction between dopamine and commercial alternating copolymer poly(styrene-alt-maleic anhydride) (SMA). Dopamine moiety facilitated the self-assembly of the SMA-Dopa in selective-solvent into stable micelles, and increased the adsorption of the SMA-Dopa at the oil-water interface. Additionally, the structural transition of the self-assembled SMA-Dopa52 micelles in response to pH and salinity changes were confirmed by means of TEM, AFM, DLS, aqueous electrophoresis techniques, potentiometric titration, and pyrene fluorescence probe methods. Micelles shrunk with increasing salinity, and flocculation of the shrunken primary micelles occurred at salt concentration exceeding 0.1 M. The micelles swelled with increasing pH, and the disassociation of the SMA-Dopa52 micelles occurred at pH above approximately 6.5. The structure of the micelles plays a crucial role in the oil-water interfacial performance. Micelles with various structures were used as emulsifiers to adsorb at the styrene-water and toluene-water interfaces. The emulsifying characteristics demonstrated that self-assembled SMA-Dopa52 micelles with moderately swollen structure (at 2 < pH < 6) combine the advantages of the solid particulate emulsifiers and polymeric surfactants, possessing excellent emulsifying efficiency and good emulsion stability. Moreover, the emulsifying performance of the SMA-Dopa52 micelles could be enhanced by the addition of salt.     

Small-Angle Neutron Scattering Study of Nonionic Surfactant Micelles and Phase Transitions in w/o Microemulsion

The structure of micelles formed by a four component water-in-oil nonionic microemulsion surfactant polyoxyethene (20) sorbitan monoleate (Tween 80), sorbitan monolaurate (Span 20) at ethyl oleate and deuterated water interface have been probed by small-angle neutron scattering (SANS). The total surfactant concentration in each of the samples studied (Tween 80: Span 20) is fixed at 3:2. The deuterated water content is variable at 5–60% w/w. The experimental SANS data from all the seven samples are fit well by spherical micelles interacting with hard sphere potential. Increased deuterated water leads to spherical to lamellar and rod-like micelle geometry featured in the SANS scattering data. The observed change in micelle geometry supports the characterization of phase transition between the self-assembled micelles of the nonionic microemulsion.      

Amphiphilic polymeric micelle as pseudostationary phase in electrokinetic chromatography for analysis of eight corticosteroids in cosmetics

Amphiphilic polymeric micelle, as a novel pseudostationary phase in EKC was used to determine eight kinds of corticosteroids namely hydrocortisone, prednisolone, hydrocortisone acetate, prednisone, cortisone acetate, prednisolone acetate, dexamethasone, and triamcinolone acetonide in cosmetics. Amphiphilic random copolymer poly(methyl methacrylate‐co‐methacrylic acid) (P(MMA‐co‐MAA)) was micellizated via neutralization in alkaline aqueous solution. The influences of the molar ratio of monomer MMA to MAA, the concentration of polymer and pH on the polymeric micelle microstructure and EKC performances were investigated. As molar ratio of MMA to MAA in P(MMA‐co‐MAA) increased, both CMC and environmental polarity of the inner core in polymeric micelle decreased dramatically. With increasing monomer ratio, the size of polymeric micelles increased firstly, and then decreased, finally increased again. ζ potential of the micelle had a slight decline trend. As increment of polymer concentration, the size of the polymeric micelle increased steadily. By optimizing the monomer ratio, the polymer concentration, and pH of the running buffer, as well as operation conditions such as separation voltage and temperature, the eight analytes could be separated within 16.5 min using 7.5 mg/mL polymer with the monomer ratio of 7:3 dissolved in pH 9.2 borax buffer as the running buffer. The method has been used for analysis of corticosteroids in cosmetic samples with simple extraction; the recoveries for eight analytes were between 85.9 and 106%. This method was of accuracy, repeatability, pretreatment simplicity, and could be applied to the quality control of cosmetics.     

Synthesis and Surface Properties of Novel N-Alkyl Quinoline-Based Cationic Gemini Surfactants

Two series of cationic dimeric (gemini) surfactants are prepared with respect to key surfactants properties, such as surface activity and solubilization. The influence of both the dimerization and the spacer group is examined in order to establish structure-property relationships. The surface tension and critical micelle concentration can be markedly reduced compared to the monomeric surfactants in the pure state. The critical micelle concentration (cmc) of each series has been determined using equilibrium surface tension measurements. Furthermore, air/water interface parameters including effectiveness (π_cmc), efficiency (P_C20), maximum surface excess (Γ _max ), and minimum surface area (A _min ) have been also derived using Gibb's adsorption equation at 25°C. Standard free energies of micellization and adsorption were calculated. Solubilization behaviors of the synthesized surfactants were measured towards paraffin oil as solubilized material using light transmission technique.     

Electrocoagulation of Crude Oil From Oil-In-Water Emulsions Using a Rectangular Cell with a Horizontal Aluminium Wire Gauze Anode

Separation of crude oil from oil-in-water emulsions in a square batch electrocoagulation cell, using an aluminum screen as the sacrificial anode was studied, the cathode was a rectangular aluminum plate placed on the cell bottom below the anode. The oil separation efficiency was insensitive to the sodium chloride electrolyte concentration. Increasing current density increased the rate of oil separation from the emulsion. Also it was found that increasing the number of screens per stack at the same current intensity, does not affect the efficiency of oil separation. The removal doesn't depend on the initial pH in the range of pH ～3?8.     

Kinetics of the Micellar Effects on the Alkaline Hydrolysis of 2-Chloro-quinoxaline in Acetonitrile-Water Mixtures at 35°C

Pseudo-first-order reaction rate for alkaline hydrolysis of 2-chloroquinoxaline (2-CQX) is carried out in acetonitrile (AN)-water (H₂O) mixtures at 35°C. Cationic surfactants as dodecyltrimethylammonium bromide (DOTAB) and an anionic surfactant as sodium dodecylsulphate (SDS) are used above their critical micelle concentration (cmc) to study the effect of micelles on reaction rate. When increasing the percentage of volume of AN, the rate profiles with DOTAB are shown to slightly increase with increasing surfactant concentration, while that with SDS are found to smoothly decrease. The micellar effect is explained in terms of a modified pseudo-phase ion exchange model. The binding constant (K_S) between 2-CQX and DOTAB as micelle showed a decrease by increasing percentage of volume of AN, while that with SDS increased. The counterion micellar coverage degrees (β) are found to be 0.55 and 0.85 with DOTAB and SDS systems, respectively, at all range of volume percentage of AN. Finally, the calculated ratio between rate constants in water to that in the micelle region k_w/k_M at different volume percentage of AN indicated that DOTAB enhances the reaction rate while SDS inhibits it.      

Mixed Micelles of Tetradecyltrimethylammonium and n-Alkyltriphenylphosphonium Bromides

The critical micelle concentrations (CMC) of binary mixtures of tetradecyltrimethylammonium bromide and n-alkyltriphenylphosphonium bromide (ATPPB) with alkyl chain length of 10, 12, 14, and 16 have been determined in water by conductivity measurements. The CMCs were lower than predicted from ideal mixing theory indicating positive synergistic interactions in mixed micelle formation. The results of the mixed systems were analyzed using the regular solution theory which allowed for the determination of the composition of the mixed micelle, the activity coefficients, and the pair-wise molecular interaction parameter β. The average β values were all negative showing significant deviation from ideality which increases as the chain length of the n-ATPPB increases. The excess free energy of the mixed systems was also calculated, and the values were all negative for the four mixed systems studied, an indication that the mixed micelles are thermodynamically stable relative to the individual component.      

Effects of SDS on the thermo- and pH-sensitive structural changes of the poly(acrylic acid)-based copolymer containing both poly(N-isopropylacrylamide) and monomethoxy poly(ethylene glycol) grafts in water

The effects of SDS on the structural changes of the thermally induced polymeric micelles from a graft copolymer comprising poly(acrylic acid) (PAAc) as the backbone and poly(N-isopropylacrylamide) (PNIPAAm) and monomethoxy poly(ethylene glycol) (mPEG) as the grafts in aqueous solution are studied. At low temperature, SDS micelles form via the hydrophobic association of SDS molecules with the PNIPAAm grafts at a critical aggregation concentration of SDS (cac(SDS)) much lower than its critical micelle concentration. Consequently, the critical aggregation temperature of the graft copolymer is elevated. The corresponding structure of the thermally induced polymeric micelles is characterized by an abrupt reduction in the particle size and an increased tendency toward formation of the monocore structure with a more compact and hydrophobic PNIPAAm microdomain being developed. On the other hand, upon the polymeric micelle formation at high temperature, the copolymer-bound SDS micelle structure is disrupted and the dissociated SDS molecules migrate to the core-shell interface with their alkyl chains residing in the liquidlike region of the hydrophobic PNIPAAm microdomain. The correlation between the polymeric particles and copolymer-bound micelles is further substantiated by showing the change of the colloidal particle size in response to changes in cac(SDS) via adjusting the pH of the aqueous copolymer/SDS solutions.     

Demulsification of Gas Oil/Water Emulsion via High-Intensity Ultrasonic Standing Wave

High-intensity ultrasonic standing wave field was established in a horizontal direction and its effect on “gas oil” in “water” emulsion separation rate was studied. Also, effects of four parameters on emulsion instability behavior were investigated: ultrasound irradiation time (5–30 min), emulsion position in ultrasound field (17–37 cm), ultrasound input intensity (20, 45, and 75%) and dispersed phase concentration (0.5, 2, and 10%). Emulsion light absorbance, droplet diameter and distribution were measured to analyze separation efficiency. The optimum states were 10% oil in water emulsion treated at 17 cm distance from ultrasound source under 30 minutes irradiation time and 20% sound intensity.     

Effects of a Novel Organic Alkali on the Interfacial Tension and Emulsification Behaviors Between Crude Oil and Water

Experiments have been carried out to investigate the interfacial tension (IFT) and emulsification behaviors between Shengli crude oil and a novel organic alkali (OA). The dynamic IFT and minimum IFT are adopted to characterize the IFT behaviors; the microscopic method, Turbiscan stability index, separated water rate, and laser particle size analysis method are used to show the emulsification behaviors. The dynamic and minimum IFT both decrease continuously with the increase of OA concentration whether surfactant is added or not; because of the synergy of OA and surfactant, the minimum IFT will be reduced to the ultralow value. The synergy is also crucial for the crude oil emulsification. When OA and surfactant are used together, owing to the mosaic and cross-multiple adsorption of OA, surfactant and in situ soap at the interfacial film, the oil can be emulsified more easily, the quantity of emulsified droplets is higher, and the emulsion is more stable with OA concentration increases. The relationship of the minimum IFT and emulsification is investigated; it indicates that the emulsion stability improves, the degree of dispersed homogeneity of oil droplets increases, and the median diameter of emulsified oil droplets decreases with the decline of the minimum IFT.     

Self-Aggregation of Cationic Dimeric and Anionic Monomeric Surfactants with Nonionic Surfactant in Aqueous Medium

Spectrofluorometric measurements have been used to elaborate the self-aggregation of mixture of anioinic, sodium dodecylbenzenesulfonate (SDBS), and cationic gemini, alkanediyl-α, ω-bis (tetradecyldimethylammonium bromide) (14-4-14) with nonionic surfactant, polyoxyethylene 10 cetyl ether (Brij-56). The critical micelle concentration (cmc) of the binary mixtures has been investigated. Application of the regular solution theory (RST) to the experimental data yield the interaction parameter at mixed micelles (β), indicate an attractive interaction and reflect the synergistic behavior in both Brij-56/SDBS and Brij-56/14-4-14 systems. The micelle aggregation number (N _agg) was measured using a steady state fluorescence quenching method. The N _agg values of the mixed surfactant system were larger than those of pure components. The micropolarity of various combinations and the binding constants (K _sv) were determined from the ratio of intensity of peaks (I ₁/I ₃) of pyrene fluorescence emission spectrum and its quenching, respectively.     

Unique Micellization and CMC Aspects of Gemini Surfactant: An Overview

Critical micelle concentration (CMC) is an essential fundamental property of surfactant molecules, as the CMC value provides significant information regarding the surfactant for industrial use. The industrial efficacy of surfactant molecules totally depends on its CMC value. Without a complete perceptive approach of CMC, it is impractical to employ surfactant molecules efficiently. This article provides an elaborate discussion of dimeric gemini surfactant and pays particular attention to the aggregation behavior, that is, micelle formation, CMC, and thermodynamics of micellization. Micelles structures, packing parameters, and properties of the micelles are summarized. The principles and techniques involved in the determination of CMC are discussed. Thermodynamics of micellization of dimeric surfactants including free energy, enthalpy, and entropy is successively reviewed. Superiority of gemini surfactant in respect of their CMC values is interpreted.