Interaction of Fluorocarbon Containing Hydrophobically Modified Polyelectrolyte with Nonionic Surfactants

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Interaction of Fluorocarbon Containing Hydrophobically Mdified Polyelectrolyte with Nonionic Surfactants

The interaction of fluorocarbon containing hydrophobically modified polyelectrolyte(FMPAANa) with two kinds of nonionic surfactants(hydrogenated and fluorinated)in a semidilute (0.5wt%) aqueous solution had been studied by rheological measurements,Association behavior was found in both systems.The hydrophobic interaction of FMPAANa with fluorinated surfactant(FC171) is much stronger than that with hydrogenated surfactant(NP7.5) at low surfactoant concentrations.The interaction is strengthened by surfactants being added for the density of active junctions increased.Whereas distinct phenomena for FC171 and NP7.5 start to be found as the surfactants added over their respective certain concentration.The interaction of polyelectrolyte with fluorinated surfactant increases dramatical ly while that with hydrogenated surfactant decreases.     

Size-controlled synthesis of CuO–ZrO<Subscript>2</Subscript> nanoparticles prepared through reverse micelle method

In this research, CuO–ZrO₂ nanoparticles are synthesized using microreactors made of surfactant/water/cyclohexane microemulsions. The effect of different microemulsion variables on the particle size and its distribution, such as water-to-surfactant molar ratio (W ₀) and different surfactants are discussed. Three different surfactant types including cationic (CTAB), anionic (AOT), and nonionic (Brij56) are used. Also a different amount of water to surfactant in nano composite synthesis is used. The powders were characterized by DTA/TG, XRD, SEM, EDS, TEM and BET techniques and their physical properties are compared. The results show a decrease of particles size in presence of cationic surfactant. Narrow particles size distribution of the resultant CuO–ZrO₂ nanocomposite in presence of cationic surfactant, anionic and nonionic surfactant is compared. Also for AOT surfactant, by raising water to surfactant molar ratio the particles size is increased and the optimum ratio is H₂O: Surfactant = 0.32:0.055, respectively.     

Effect of Surfactants on the Formation,Morphology, and Surface Property of Synthesized SiO2 Nanoparticles

Abstract

This study investigated the effect of cationic, anionic (saturated and unsaturated), and nonionic surfactants on the formation, morphology, and surface properties of silica nanoparticles synthesized by the ammonium‐catalyzed hydrolysis of tetraethoxysilane in alcoholic media. Results indicate that at a relatively low surfactant concentration (1 × 10^?3–1 × 10^?6 M), cationic surfactants significantly affected the growth of silica particles as measured by dynamic light scattering and transmission electron microscopic analyses. In contrast, the anionic and nonionic surfactants showed relatively minor effects in the low concentration range. The magnitude of negative zeta potential was reduced for silica colloids that were synthesized in the presence of cationic surfactant because of charge neutralization. The presence of anionic surfactants only slightly increased the negative zeta potential while the nonionic surfactant showed no obvious effects. At high surfactant concentrations (>1 × 10^?3 M), cationic and anionic surfactants both induced colloid aggregation, while the nonionic surfactant showed no effect on particle size. Raman spectroscopic analysis suggests that molecules of cationic surfactants adsorb on silica surfaces via head groups, aided by favorable electrostatic attraction, while molecules of anionic and nonionic surfactants adsorb via their hydrophobic tails.     

Thermosensitive amphiphilic polyphosphazenes and their interaction with ionic surfactants

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

Steady-state fluorescence investigations of aqueous binary mixtures of myristyl alcohol based bis-sulfosuccinate anionic gemini surfactant and effect of different conventional surfactants therein

The present research work is associated with the fluorescence investigations of binary aqueous mixed surfactants solutions of anionic bis-sulfosuccinate gemini surfactant (BSGSMA_1,8) and three different conventional surfactants—anionic viz. sodium dodecyl sulfate (SDS), cationic viz. cetyl trimethyl ammonium bromide (CTAB), and nonionic surfactant viz. Triton X 100. Steady-state fluorescence spectroscopy technique has been utilized to examine the micellization behavior of aqueous solution of pure myristyl alcohol-based BSGSMA_1,8 having flexible methylene chain [(CH₂)₈] as spacer group. Critical micelle concentration (CMC), aggregation number (N), and micropolarity of pure and mixed surfactants systems were explored during the investigations. The results revealed the best synergism behavior of prepared gemini BSGSMA_1,8 with SDS as compared to CTAB and Triton X 100. The maximum reduction in the value of pyrene intensity ratio (I₁/I₃) was observed for gemini and SDS mixed surfactant solution. On the other hand, the increased I₁/I₃ value of mixed gemini with Triton X 100 exhibited that mixed surfactant system of anionic gemini BSGSMA_1,8 with non-ionic Triton X 100 is not as compact as other mixed surfactant systems. Aggregation number increased and micropolarity decreased with increased concentration of gemini surfactants.     

Surfactant effect on the lower critical solution temperature of poly(organophosphazenes) with methoxy-poly(ethylene glycol) and amino acid esters as side groups

 The surfactant effect on the lower critical solution temperature (LCST) of thermosensitive poly(organophosphazenes) with methoxy-poly(ethylene glycol) and amino acid esters as side groups was examined in terms of molecular interactions between the polyphosphazenes and surfactants including various anionic, cationic, and nonionic surfactants in aqueous solution. Most of the anionic and cationic surfactants increased the LCST of the polymers: the LCST increased more sharply with increasing length and hydrophobicity of the hydrophobic part of the surfactant molecule. The ΔLCSTs (T _0.03M− T _0M), the change in the LCST by addition of 0 and 0.03 M sodium dodecyl sulfate (SDS), were found to be 7.0 and 14.5 °C for the polymers bearing ethyl esters of glycine and aspartic acid, respectively. The LCST increase of poly(organophosphazene) having a more hydrophobic aspartic acid ethyl ester was 2 times larger compared with that of the polymer having glycine ethyl ester as a side group. The binding behavior of SDS to the polymer bearing glycine ethyl ester as a hydrophobic group was explained from the results of titration of the polymer solutions containing SDS with tetrapropylammonium bromide. Graphic models for the molecular interactions of polymer/surfactant and polymer/surfactant/salt in aqueous solutions were proposed. Received: 17 February 2000/Accepted: 25 April 2000     

Anionic–Nonionic Mixed Surfactant Systems: Micellar Interaction and Thermodynamic Behavior

The interactions between an anionic surfactant, viz., sodium dodecylbenzenesulfonate and nonionic surfactants with different secondary ethoxylated chain length, viz., Tergitol 15-S-12, Tergitol 15-S-9, and Tergitol 15-S-7 have been studied in the present article. An attempt has also been made to investigate the effect of ethoxylated chain length on the micellar and the thermodynamic properties of the mixed surfactant systems. The micellar properties like critical micelle concentration (CMC), micellar composition (X_A), interaction parameter (β), and the activity coefficients (f_A and f_NI) have been evaluated using Rubingh's regular solution theory. In addition to micellar studies, thermodynamic parameters like the surface pressure (Π_CMC), surface excess values (Γ_CMC), average area of the monomers at the air–water interface (A_avg), free energy of micellization (ΔG_m), minimum energy at the air–water interface (G_min), etc., have also been calculated. It has been found that in mixtures of anionic and nonionic secondary ethoxylated surfactants, a surfactant containing a smaller ethoxylated chain is favored thermodynamically. Additionally, the adsorption of nonionic species on air/water interface and micelle increases with decreasing secondary ethoxylated chain length. Dynamic light scattering and viscometric studies have also been performed to study the interactions between anionic and nonionic surfactants used.     

Interfacial and Thermodynamic Properties of Anionic‐Nonionic Mixed Surfactant System: Influence of Hydrophobic Chain Length of the Nonionic Surfactant

The influence of hydrophobic chain length in nonionic surfactants on interfacial and thermodynamics properties of a binary anionic‐nonionic mixed surfactant was investigated. In this study, nonionic surfactants lauric‐monoethanolamide (C₁₂ MEA) and myrisitic‐monoethanolamide (C₁₄ MEA) were mixed with an anionic surfactant, α‐olefin sulfonate (AOS). The critical micelle concentration (cmc), maximum surface excess (Γ_max), and minimum area per molecule (A_min) were obtained from surface tension isotherms at various temperatures. The thermodynamic parameters of micellization and adsorption were also computed. Micellar aggregation number (N_agg), micropolarity, and binding constant (K_sv) of pure and mixed surfactant system was calculated by fluorescence measurements. Rubingh's method was applied to calculate interaction parameters for the mixed surfactant systems.     

Microstructure of un-neutralized hydrophobically modified alkali-soluble emulsion latex in different surfactant solutions

At low pH conditions and in the presence of anionic, cationic, and nonionic surfactants, hydrophobically modified alkali-soluble emulsions (HASE) exhibit pronounced interaction that results in the solubilization of the latex. The interaction between HASE latex and surfactant was studied using various techniques, such as light transmittance, isothermal titration calorimetry, laser light scattering, and electrophoresis. For anionic surfactant, noncooperative hydrophobic binding dominates the interaction at concentrations lower than the critical aggregation concentration (CAC) (C < CAC). However, cooperative hydrophobic binding controls the formation of mixed micelles at high surfactant concentrations (C > or = CAC), where the cloudy solution becomes clear. For cross-linked HASE latex, anionic surfactant binds only noncooperatively to the latex and causes it to swell. For cationic surfactant, electrostatic interaction occurs at very low surfactant concentrations, resulting in phase separation. With further increase in surfactant concentration, noncooperative hydrophobic and cooperative hydrophobic interactions dominate the binding at low and high surfactant concentrations, respectively. For anionic and cationic surfactant systems, the CAC is lower than the critical micelle concentration (CMC) of surfactants in water. In addition, counterion condensation plays an important role during the binding interaction between HASE latex and ionic surfactants. In the case of nonionic surfactants, free surfactant micelles are formed in solution due to their relatively low CMC values, and HASE latexes are directly solubilized into the micellar core of nonionic surfactants.     

混合表面活性剂微乳状液的形成和相行为研究进展

讨论了单一表面活性剂,混合表面活性剂,助溶剂等对油／水微乳状液的形成和相行为的影响。对混合表面活性剂微乳状液的形成和相行为研究工作进行了归纳和总结,重点分析了正负离子表面活性剂微乳状液的相行为和表面活性剂微乳状液的相行为和表面活性剂效率,讨论了微乳状液形成的影响因素,并提出了这一研究领域可能的发展前景。     

BINDING OF IONIC SURFACTANTS ON OPPOSITELY CHARGED POLYELECTROLYTES OBSERVED BY FLUORESCENCE METHODS

Our recent studies concerning the binding of ionic surfactants on oppositely charged polyelectrolytes observedwith fluorescence techniques are reviewed. The cationic surfactants cetyltrimethylammonium bromide (CTAB),dodecyltrimethylammonium chloride (DTAC), and nonionic surfactant octaethylene glycol monododecyl ether (C_(12)E_8) wereallowed to bind on anionic poly(2-acrylamido-2-methylpropanesulfonic acid) (PAMPS) and its pyrene and/or naphthalenelabeled copolymers. The relative excimer emission intensity I_E/I_M of a cationic probe l-pyrenemethylamine hydrochloride(PyMeA·HCl) and the non-radiative energy transfer (NRET) I_(Py)/I_(Np) of naphthalene to pyrene for labeled polyelectrolyteswere chosen to monitor the binding process and the conformation change of surfactant-bound polyelectrolytes. The 1:1aggregation of polyelectrolyte-CTAB with respect to the charge was found as long as the CTAB concentration was slightlyhigher than its critical aggregation concentration (CAC). The intermolecular NRET indicated that the CTAB-boundpolyelectrolytes aggregated together through the hydrophobic interaction between the CTAB tails. However, neither 1:1polyelectrolyte-DTAC aggregation nor intermolecular aggregation of DTAC-bound polyelectrolyte was observed owing to itsweaker hydrophobicity of 12 carbon atoms in the tail, which is shorter than that of CTAB. As known from the fluorescenceresults, nonionic surfactant C_(12)E_8 did not bind on the anionic polyelectrolytes, but the presence of PAMPS promoted themicelle formation for C_(12)E_8 at the CAC slightly below its critical micelle concentration (CMC). The solid complex of dansyllabeled AMPS copolymer-surfactant exhibited a decrease in local polarity with increasing charge density of thepolyelectrolyte or with alkane tail length of the surfactant. SAXS suggested a lamella structure for the AMPS copolymer-surfactant solid complexes with a long period of 3.87 nm for CTAB and 3.04 nm for DTAC, respectively.     

ADMET reactions in miniemulsion

This work investigates acyclic diene metathesis (ADMET) polymerization reactions in aqueous miniemulsion. Different types of ruthenium‐based catalysts and different surfactants (anionic, cationic, and nonionic) were evaluated. A Ru‐indenylidene catalyst (Umicore M2) showed higher activity in water if compared to the Ru‐benzylidene catalysts (Hoveyda Grubbs second generation and Grubbs first generation). Moreover, the catalyst activity was affected by the type of the surfactant. In summary, the Umicore M2 catalyst and the nonionic poly(ethylene oxide) based surfactant Lutensol AT80 were found to be the most suitable combination for ADMET reactions in miniemulsion allowing the preparation of polymers with number average molecular weight (M_n) of up to 15 kDa. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1300–1305     

THE EFFECT OF SINGLE MICELLES OF SURFACTANTS ON POLYMERIZATION OF ACRYLAMIDE

The polymerization of acrylamide in micellar solutions of cationic, anionic, zwitterionic and nonionic surfactants, initiated by NaHSO₃, has been studied at 20 and 30° C with time variable method of thermokinetics for the 1. 5-order reaction in this paper. Reaction mechanism has been suggested and rate equations have been derived. The results indicate that ionic (CTAB, TTABDTAB, SDS) and zwitterionic (SLS) surfactants catalyze the polymerization in the order SDS>SLS>DTAB ≈ TTA≈ CTAB, and nonionic surfactant (Brij35) has slight inhibition effect. These effects are mainly caused by the effect of the formation of micelle- HSO₃ complex on the step of initiator to form free radical.     

Interaction of surfactants and aminoindophenol dye

The interaction of dye and surfactants was studied by their spectroscopic and surface properties. Large bathochromic shift (15 nm) in the absorption spectrum was found for aminoindophenol dye at high pH in cationic surfactant, while there is no significant shift in anionic, zwitterionic and nonionic surfactant solutions. The static and dynamic surface properties show there is strong interaction in mixture of cationic surfactant and aminoindophenol dye. Interaction of dye and surfactants on surface and in solution is correlated to the intensity of dye deposition on fiber. The charge complex formation between cationic surfactant and aminoindophenolic dye delays the dye diffusion into keratin fiber. The stronger is the dye/surfactant interaction, the lower dye deposition and diffusion become.     

Effects of nonionic surfactant and sodium dodecyl sulfate layers on electroacoustics of hexadecane/water emulsions

Hexadecane-in-water emulsion droplets were formed in a homogeniser in the presence of a mixture of an anionic surfactant (sodium dodecyl sulfate, SDS) and nonionic surfactants of various chain lengths [nonylphenol ethoxylate (C₉φE_N, N=100, 40 and 30) or an alcohol ethoxylate (Brij35)]. The dynamic mobility of the oil droplets was then measured using a flow-through version of an AcoustoSizer. Large changes were observed in the dynamic mobility of the particles formed with the mixed surfactants compared to particles formed with SDS alone. O'Brien's “gel layer” model was employed to interpret the data. The characteristics of the adsorbed layer appeared to be similar whether the nonionic surfactant was adsorbed concurrently with the SDS as the emulsion formed or was merely added afterwards to the emulsion established. The particle size, the charge and the molar fraction of SDS had virtually no effect. The layers formed with the nonionic surfactants decreased in thickness with decreasing molecular weight as expected. Passage through the homogeniser itself had no effect on the properties of the largest nonionic surfactant and, hence, on the adsorption layer formed with it. Received: 4 October 2000 Accepted: 16 October 2000     

Interfacial and micellar properties of anionic azo dye-surfactant binary systems

The association of an anionic dye C.I. Reactive Orange 16 (RO16) and different types of surfactants, i.e., anionic surfactant sodium dodecylsulfate, nonionic surfactants poly(oxyethylene) ethers (C _m POE₁₀, m = 12, 16, and 18; C₁₂POE _n , n = 4, 10, and 23), was investigated using tensiometry in a certain micellar concentration range. RO16 was shown to aggregate in water when its concentration is above the threshold value. The surface tension lowering and critical micellar concentration (CMC) values were interpreted on the same grounds as those for surfactants mixtures. The tensiometric measurements of dye-surfactant systems are carried out as a function of the molar concentration of solution at 25°C. Using Rubingh’s regular solution theory, the values of interaction parameters were found to be negative for all studied binary mixtures. These negative values indicate that there is an attractive interaction of the surfactants in mixed micelles and reflect synergistic behavior of a mixture. In all studied systems, deviations from ideal behavior were observed depending on the type of surfactant. Interaction parameters calculated using regular solution theory are changed from −2.62 to −12.43. The smallest deviation from ideal behavior is obtained for the RO16-C₁₂POE₄ mixed system; i.e., in the case when nonionic surfactant has the shortest alkyl chain and the smallest number of ethylene oxide units. The text was submitted by the authors in English.     

Effect of Polymer on Dynamic Interfacial Tensions of Anionic–nonionic Surfactant Solutions

The dynamic interfacial tensions (IFTs) of enhanced oil recovery (EOR) surfactant/polymer systems against n-decane have been investigated using a spinning drop interfacial tensiometer in this paper. Two anionic–nonionic surfactants with different hydrophilic groups, C₈PO₆EO₃S (6-3) and C₈PO₆EO₆S (6-6), were selected as model surfactants. Partially hydrolyzed polyacrylamide (HPAM) and hydrophobically modified polyacrylamide (HMPAM) were employed. The influences of surfactant concentration, temperature, polymer concentration, and oleic acid in the oil on IFTs have been studied. The experimental results show that anionic–nonionic surfactants can form compact adsorption films and reach ultralow IFT (10^?3 mN/m) under optimum conditions. The addition of polymer has great influence on dynamic IFTs between surfactant solutions and n-decane mainly by the formation of looser mixed films resulting from the penetration of polymer chains into the interface. The compact surfactant film will also be weakened by the competitive adsorption of oleic acid, which results in the increase of IFT. Moreover, the penetration of polymer chains will be further destroyed surfactant/polymer mixed layer and lead to the obvious increase of IFT. On the other hand, polymers show little effect on the IFTs of 6-6 systems than those of 6-3 because of the hindrance of longer EO chain of 6-6 at the interface.     

Experimental study on methane solubilization by organic surfactant aggregates

Seeking to enhance coal mine safety, an experimental study of a kind of water-based explosion suppression medium for the absorption of mine gas was carried out. Using methane as the model gas, solubilizing experiments with different concentrations of anionic and nonionic surfactants were carried out using headspace gas chromatography for surfactants consisting of sodium fatty alcohol polyoxyethylene ether carboxylate (AEC), fatty acid methyl ester sulfonate (MES), fatty methyl ester ethoxylate (FMEE), hexyl d-glucoside (APG06), octyl beta-d-glucopyranoside (APG08) and n-decyl glucoside (APG10). By selecting individual surfactants, the study investigated the methane solubilization performance of water mist with binary anionic–nonionic surfactants. Furthermore, the release of methane in solution was also examined. The results show that the apparent solubility of methane in solution is linearly and positively correlated with the surfactant concentration. The methane solubilization is significantly improved by the addition of anionic–nonionic surfactants. The optimal solubilizing ratio of the anionic–nonionic surfactant varies with the solution compositions. For a fixed ratio, surfactant compositions exhibit the most distinct synergistic effect and the best performance for methane solubilization. The release of methane from mixed micelles composed of the compound solution is superior to that of a single surfactant. Through the analysis of the solubilization effect and the stability of different absorbents, it is concluded that the anionic–nonionic surfactant system shows much better capability than the other selected surfactants.     

Polymers as Hydrophobic Adsorbent Surface for Some Surfactants

Polyvinyl alcohol (PVA) and polyacrilic acid (PAA) were used as hydrophobic adsorbent surfaces at 25°C for two nonionic surfactants, namely, tetradecyl polyoxyethylenated monolaurate [La(EO)₁₄] and tetradecyl polyoxyethylenated monooleate [Ol(EO)₁₄], and two anionic surfactants, namely, sodium oleic sulfonate [OlSO₃Na] and sodium dodecyl benzene sulfonate [SDBS]. Surface tension measurements were performed to determine the critical micelle concentration (CMC) and the adsorption isotherms of the tested surfactants. All the tested surfactants display L-shape isotherms except that of OlSO₃Na onto PVA. No adsorption behavior has been shown for the anionic SDBS onto both PVA and PAA. The adsorption data show higher adsorption affinity for all the tested nonionic surfactants onto PAA than onto PVA while the investigated anionic surfactant OlSO₃Na possesses close values of Γ_max. The study reveals that the nature of the polymer surface as adsorbent besides the molecular structure of the surfactant defined the types and mechanisms of adsorption.