Dynamic Surface Elasticity of Polyelectrolyte/Surfactant Adsorption Films at the Air/Water Interface: Carboxylmethylchitosan and Cetyltrimethylammonium Bromide

The dynamic surface elasticity of the solution of carboxymethylchitosan (CMCH) and cetyltrimethylammonium bromide (C₁₆TAB) was measured as a function of the surfactant concentration and the surface age by the oscillating drop method. The results showed that the surface layer of the CMCH/C₁₆TAB solution transformed from loose to structured with the increase in the surfactant concentration. The surface elasticity versus the surface pressure curve during the adsorption showed different features at different surfactant concentration ranges, which was connected with the structural transformation of the surface layer. Our results show that the measurement of dynamic surface dilational properties is a powerful tool for studying the surface kinetics, which is helpful for dealing non-equilibrium systems in industry.     

MODULAR SYNTHESIS OF AMPHIPHILIC MOLECULES - 7 NEW ROUTE TO LONG CHAIN N-ALKYLBETAINES STUDY OF THEIR ADSORPTION ONTO WOOL FIBERS

Anionic and cationic surfactants have formed the subject of numerous physicochemical investigations, but few studies have been devoted to amphoteric amphiphilic agents. In a series of investigations on new synthetic routes to novel surfactants, we devised a simple method for the preparation of N-alkylbetaïnes with different chain lengths:

In addition, we investigated the adsorption of these compounds onto wool fibers in aqueous media. The effects of pH, temperature and chain length on the adsorption isotherms were investigated. A relationship between the behavior of the surfactant at the solid/liquid interface and its behavior in solution was detected. Maximum adsorption was observed for values close to the critical micellar concentration.     

长链烷基季铵盐插层氧化石墨的结构变化

基于改进的Hummers法制备氧化石墨(GO),并以长链烷基季铵盐(CnTAB)对其进行插层处理;通过改变CnTAB的链长、浓度,得到系列CnTAB/GO插层复合物。采用XRD和元素分析对产物的最大底面间距及CnTAB插入量进行表征。结果表明,随着Cn TAB链长的增长、CnTAB浓度的增大,CnTAB/GO插层复合物的最大底面间距逐渐增大。CnTAB通过离子键作用和疏水键作用插入到GO层间,在GO片层上的吸附规律符合修正型(Modified)Langmuir模型,即CnTAB以单分子层吸附在GO片层上。根据CnTAB/GO插层复合物最大底面间距及CnTAB插入量的变化规律分析,得出CnTAB在GO层间的排布模式有单层平躺模式、类双层平躺模式、单层倾斜模式和单层直立模式。     

长链烷基季铵盐插层氧化石墨的结构变化

基于改进的Hummers法制备氧化石墨(GO),并以长链烷基季铵盐(C_nTAB)对其进行插层处理;通过改变C_nTAB的链长、浓度,得到系列C_nTAB/GO插层复合物。采用XRD和元素分析对产物的最大底面间距及C_nTAB插入量进行表征。结果表明,随着C_nTAB链长的增长、C_nTAB浓度的增大,C_nTAB/GO插层复合物的最大底面间距逐渐增大。C_nTAB通过离子键作用和疏水键作用插入到GO层间,在GO片层上的吸附规律符合修正型(Modified)Langmuir模型,即C_nTAB以单分子层吸附在GO片层上。根据C_nTAB/GO插层复合物最大底面间距及C_nTAB插入量的变化规律分析,得出C_nTAB在GO层间的排布模式有单层平躺模式、类双层平躺模式、单层倾斜模式和单层直立模式。     

Bulk Properties of Carboxymethylchitosan and Cationic Surfactant Mixtures: Fluorescence and Surface Tension Studies

The interactions between carboxymethylchitosan and alkyltrimethylammoniumbromides were studied in aqueous solution. The dependences of aggregation behavior on surfactant concentration, polyelectrolyte concentration, as well as surfactant chain length were investigated mainly using fluorescence spectroscopy method. The variation of I ₁/I ₃ of pyrene fully characterized the aggregation behavior of the polymer-surfactant complex. Meanwhile, based on that Nile red has the sensitivity to the environmental polarity different to pyrene, the changes of aggregates size and number can be reflected by the fluorescence spectroscopy of Nile red.     

Rheological behavior of PAA–C n TAB complex: influence of PAA charge density and surfactant tail length in PAA semidilute aqueous solution

Interactions between anionic polyelectrolyte, poly(acrylic acid) (PAA), and cationic surfactant, alkyltrimethylammonium bromide (C _n TAB), were investigated by rheological measurements in semidilute PAA solution. The dependences of the rheological behavior on the chain length of the surfactant, PAA neutralization degree, and temperature were discussed. The results revealed that both dodecyl and cetyltrimethylammonium bromides (C₁₂TAB and C₁₆TAB) could increase the viscosity of PAA solution when the surfactant amounts surpassed a critical surfactant concentration (C _c), and C _c of C₁₆TAB was lower than that of C₁₂TAB at same PAA neutralization degree. The increase of viscosity is attributed to the surfactant micelles bridging of the polymer chains and confine the mobility PAA chain. On the other hand, it is found that the hydrogen bonding also played an important role in the PAA–C _n TAB system, especially in lower neutralization degree PAA solution, which results in the viscosity increase rapidly with the added surfactant into lower neutralization degree PAA solution.     

Study of host–guest interaction between ß-cyclodextrin and alkyltrimethylammonium bromides in water

Cyclodextrins were found to play important roles in self-assembly systems of surfactants. The interactions between host molecule ß-cyclodextrin (CD) and model cationic surfactants, alkyltrimethylammonium bromides with different alkyl chain length: dodecyl-(C₁₂TAB), tetradecyl-(C₁₄TAB) and hexadecyl-(C₁₆TAB) are studied by means of conductivity measurements at 313.2 K. The data obtained indicate that inclusion complexes (CD:S⁺) had formed, and apparent critical micelle concentration (CMC*) is equivalent to the combined concentrations of surfactant monomers complexed with the CD and that of a free dissolved monomer in equilibrium with the micellized surfactant without CD. Inclusion complexes were characterized by an equilibrium binding constant K ₁₁, which value increases as the length of alkyl chains, and consequently the hydrophobicity, increases. From mathematical model the concentrations of the uncomplexed cyclodextrin, uncomplexed surfactant ion, and inclusion complex in the submicellar, as well as in the micellar range were calculated. The competition between the micellization and complexation processes leads to the existence of a significant concentration of free CD in equilibrium with the micellar aggregates. The percentage of uncomplexed cyclodextrin in equilibrium with the micelles is independent on cyclodextrin concentration for a particular ternary system and is 31, 37, and 34 % for C₁₂TAB/water/ß-CD, C₁₄TAB/water/ß-CD and C₁₆TAB/water/ß-CD, respectively. By using standard Gibbs free energy for micellization and surfactant complexation by CD, we can explain the observed behavior.     

Effect of Surfactant Chain Length on the Rheological Properties of Cationic Surfactants and a Hydrophobic Counterion

The rheological behavior of alkyimethylammonium 2-hydroxy-1-carboxy-naphthoate, C_xTA-2.1-HCN (x = 16, 14, 12, 10, and 8) is presented. With increasing 2.1 HNC/C_xTAOH (x = 16, 14, 12) ratio, the viscoelasticity of the solutions changes due to a transition in the micellar shape from small micelles to rodlike micelles and finally to multilamellar vesicles (MLV). On the other hand, a transition from small micelles to multilamellar vesicles (MLV) was observed for solution with C_xTA-2.1-HCN (x = 10 and 8). The MLV phases behave like a weak gel and have a yield stress value. Rheological measurements were performed for these viscoelastic systems in order to find out the dependency of the viscoelastic behavior on the surfactant chain length and hydrophobic counterion concentration. Some theoretical models as reptation mechanism was also applied in order to get some structural details and to illustrate the rheological behavior of these viscoelastic systems. Some models that correlate MLV-modulus on the surfactant morphology are also presented and discussed.     

Adsorption of SDBS and Its Effect on Rheology of Preformed Particle Gels

The adsorption of anionic surfactant sodium dodecylbenzenesulfonate (SDBS) onto preformed particle gels (PPGs) and the effect of SDBS on the swelling ratio and rheology of PPGs were investigated. SDBS molecules can adsorb onto PPGs because of the hydrophobic association with the chain of PPGs at low concentration and the association of the SDBS micelles with the chains of PPGs at high concentration. PPGs contract and the shear stress of PPGs decreases after adsorption of SDBS. In addition, the storage modulus decreases first and then increases with increasing SDBS concentration.     

Adsorption of oppositely charged polyelectrolyte/gemini surfactant mixtures at the air/water interface and the effects of NaBr: a surface tension study

The adsorption of mixed solutions containing an anionic polyelectrolyte, carboxymethylchitosan (CMCH), and cationic gemini surfactants, alkanediyl-bis-(dimethyldodecyl-ammonium bromide) (C₁₂-s-C₁₂, s?=?2, 6, 12), has been investigated by surface tension method. The oppositely charged polyelectrolyte and the surfactants co-adsorb at the surface to form highly surface-active complexes. Combining the surface tension data with the Gibbs equation, it is referred that the surface layers of the mixed solutions have the multi-level structure, which includes the sublayers beneath an outermost layer. The gemini surfactant spacer with different length takes different conformations in the surface layers. The salt (NaBr) effects on the adsorption of the mixtures have also been studied. The spacer length of C₁₂-s-C₁₂ influences the responses of CMCH/C₁₂-s-C₁₂ mixtures to the salt effects. The comprehensive salt effects depend on the competition between the salt-enhancing effect and the salt-weakening effect.     

The influence of mixed cationic–anionic surfactants on the three-phase contact parameters in silica–solution systems

The formation of thin wetting films on silica surface from aqueous solution of (a) tetradecyltrimetilammonium bromide (C₁₄TAB) and (b) surfactant mixture of the cationic C₁₄TAB with the anionic sodium alkyl- (straight chain C₁₂–, C₁₄– and C₁₆–) sulfonates, was studied using the microscopic thin wetting film method developed by Platikanov. Film lifetimes, three-phase contact (TPC) expansion rates, receding contact angles and surface tension were measured. It was found that the mixed surfactants caused lower contact angles, lower rates of the thin aqueous film rupture and longer film lifetimes, as compared to the pure C₁₄TAB. This behavior was explained by the strong initial adsorption of interfacial complexes from the mixed surfactant system at the air/solution interface, followed by adsorption at the silica interface. The formation of the interfacial complexes at the air/solution interface was proved by means of the surface tension data. It was also shown, that the chain length compatibility between the anionic and cationic surfactants controls the strength of the interfacial complex and causes synergistic lowering in the surface tension. The film rupture mechanism was explained by the heterocoagulation mechanism between the positively charged air/solution interface and the solution/silica interface, which remained negatively charged.     

Phase Behavior of Bicontinuous and Water/Diesel Fuel Microemulsions Using Nonionic Surfactants Combined with Hydrophilic Alcohol Ethoxylates

Bicontinuous and water-in-diesel microemulsions were formulated using single nonionic alkyl poly glycol ethers combined with hydrophilic alcohol ethoxylates. The phase behavior at temperatures ranging from 0°C to 50°C was investigated. Visual inspection as well as cross-polarizers were used to detect anisotropy. The fish phase diagrams were determined. The presence of the hydrophilic alcohol ethoxylates was necessary to initiate both types of microemulsions. Increasing the hydrophobic chain length of the surfactant led to a wider range of temperature stability at lower surfactant concentration. Meanwhile, increasing the ethylene oxide units in the headgroup by two units led to a phase diagram that is dominated by lyotropic liquid crystal. The formulated water in diesel microemulsions were tested experimentally in a 4-cylinder diesel engine. From this it is observed that the emissions of NO_x, soot, and CO₂ were reduced substantially compared to neat diesel, while for the CO the reduction occurs just at low load.