AFM study on the wettability of mica and graphite modified with surfactant DTAB

In this work atomic force microscopy (AFM) was applied to study the wettability of mica and graphite modified with surfactant dodecyltrimethylammonium bromide (DTAB) at varying DTAB concentrations (below the cmc) and adsorption time. The coverage states of DTAB on surfaces were analyzed from the AFM images, while the contact angle measurement was made for the wettability of DTAB-modified surfaces. The experimental results have shown that the adsorption aggregates formed as needle-like dots covering on the mica surface with the surfactant concentration of 10^?6–10^?4?mol/L. The coverage of DTAB aggregates increased with the increasing concentration, leading to a strong hydrophobicity on the surfaces. However, the large aggregates which might be caused by bilayer adsorption of surfactant occurred on mica surface at surfactant concentration of 10^?3?mol/L, resulting in the reverse of the wettability as the adsorption time extended. In the case of hydrophobic graphite, DTAB aggregates mainly formed as stripe covering on the surfaces, leading to the reduction of hydrophobicity. This reduction became stronger as more DTAB aggregates covered on graphite surfaces.     

ON THE ADSORPTION OF HYDROPHOBIC POLLUTANTS ON SURFACTANT/CLAY COMPLEXES: COMPARISON OF THE INFLUENCE OF A CATIONIC AND A NONIONIC SURFACTANT

The adsorption of the cationic surfactant dodecyl trimethyl ammonium bromide (DTAB) and of the nonionic surfactant dodecyl octaethylene glycol ether (C₁₂E₈) on four different layer silicates and their influence on the sorption processes of the fungizide biphenyl were studied. Unexpectedly, no great differences were found in comparing the adsorption of the two surfactants on the basis of physicochemical investigations, although the adsorption mechanism up to monolayer formation is fundamentally different (ion exchange and physisorption). Thus, the plateau values of the adsorption isotherms and the molar enthalpies of displacement Δ ₂₁h are of the same order of magnitude for both surfactants and the same basal spacing by intercalation is observed in the case of swelling clays. The isotherms of the hydrophobic contaminant biphenyl are of the linear Cl-type at all layer silicates and very low adsorption takes place approximately proportionally to the BET (N₂) surface area. If the surface is weakly hydrophobized by surfactants (c_surfactant<< critical;micelle concentration (CMC)), biphenyl adsorption is clearly increased. These processes can be adequately described using the distribution coefficients K and K_OC (Henry coefficient related to the organic carbon content). K_OC is hardly influenced by the type of layer silicate for DTA⁺-layer silicates, whereas the C₁₂E₈ layer silicate complexes generally show higher, but also different K_OC values. If the surfactant concentrations are above the CMC, solubilization and adsorption compete for the pollutant molecules, which leads to a significant decrease in biphenyl adsorption.     

Adsorption of cetyltrimethylammonium bromide at the silica gel/water interface

The adsorption isotherms of cetyltrimethylammonium ion (CTA+) together with that of the Br counterion on silica gel, and the effects of pH and added salts (NaF, NaCl and NaBr) have been systematically determined at 25°C. Electrophoretic mobilities of the silica gel particles have also been measured in the same conditions. The adsorption isotherm of CTA⁺ consists of four regions. Region I, at low concentrations of surfactant, the adsorption results primarily from electrostatic force between CTA⁺ and the negatively charged silica surface. Region II (first plateau), at medium concentrations, the adsorption is due to both the electrostatic force and the specific attraction (vdW forces) between CTA⁺ and the surface. Region III, characterized by an abrupt increase in the slope of the isotherm when the concentration reaches a particular point known as hemimicelle concentration (HMC). The abrupt increase in the adsorption is due to the hydrophobic interaction between hydrocarbon chains. Region IV (second plateau), at or above CMC, the limiting adsorption is reached as the micelle is not adsorbed. Based on this model, the experimental results can be explained reasonably. The results show that the HMC is about half of the CMC. According to the assumption that each adsorbed CTA⁺ ion in the first plateau is an active center for surface aggregation, the average aggregation number of hemimicelle have been calculated.     

Effects of Charged Surfactants on Interfacial Water Structure and Macroscopic Properties of the Air-Water Interface

Surfactants are used to control the macroscopic properties of the air-water interface. However, the link between the surfactant molecular structure and the macroscopic properties remains unclear. Using sum-frequency generation spectroscopy and molecular dynamics simulations, two ionic surfactants (dodecyl trimethylammonium bromide, DTAB, and sodium dodecyl sulphate, SDS) with the same carbon chain lengths and charge magnitude (but different signs) of head groups interact and reorient interfacial water molecules differently. DTAB forms a thicker but sparser interfacial layer than SDS. It is due to the deep penetration into the adsorption zone of Br⁻ counterions compared to smaller Na⁺ ones, and also due to the flip-flop orientation of water molecules. SDS alters two distinctive interfacial water layers into a layer where H⁺ points to the air, forming strong hydrogen bonding with the sulphate headgroup. In contrast, only weaker dipole-dipole interactions with the DTAB headgroup are formed as they reorient water molecules with H⁺ point down to the aqueous phase. Hence, with more molecules adsorbed at the interface, SDS builds up a higher interfacial pressure than DTAB, producing lower surface tension and higher foam stability at a similar bulk concentration. Our findings offer improved knowledge for understanding various processes in the industry and nature.     

A Comparative Study of the Direct Calorimetric Determination of the Denaturation Enthalpy for Lysozyme in Sodium Dodecyl Sulfate and Dodecyltrimethylammonium Bromide Solutions

The complexes of lysozyme with the anionic surfactant sodium dodecyl sulfate (SDS) and the cationic surfactant dodecyltrimethylammonium bromide (DTAB) have been investigated by isothermal titration calorimetry at pH=7.0 and 27 °C in a phosphate buffer. A new direct calorimetric method was applied to follow the protein denaturation and study the effect of surfactants on the stability of proteins. The extended solvation model was used to represent the enthalpies of lysozyme + SDS interaction over the whole range of SDS concentrations. The solvation parameters recovered from the new equation are attributed to the structural change of lysozyme and its biological activity. At low SDS concentrations, the binding is mainly electrostatic with some simultaneous interaction of the hydrophobic tail with nearby hydrophobic regions of lysozyme. These initial interactions presumably cause some protein unfolding and expose additional hydrophobic sites. The induced enthalpy of denaturation of lysozyme by SDS is 160.81±0.02 kJ⋅mol⁻¹. The lysozyme-DTAB complexes behave very differently from those of the lysozyme-SDS complexes. SDS induces a stronger unfolding of lysozyme than DTAB. The induced enthalpy of lysozyme denaturation by DTAB is 86.46±0.02 kJ⋅mol⁻¹.     

THEORETICAL MODELING OF IONIC SURFACTANT ADSORPTION ON MINERAL OXIDE SURFACES

A model for the adsorption of ionic surfactants on oppositely charged solid surfaces of uniform charge density is developed. The model is based on the assumption that, on the solid surface, adsorbed surfactant monomers, monolayered and bilayered surfactant aggregates of different sizes and specifically adsorbing ions of added electrolyte constitute a mixture of hard discs. It means that only excluded area interactions between the surface discs are taken into account. To avoid a rapid two-dimensional condensation of the adsorbed surfactant the potential energy per molecule in the surface aggregates, which is a sum of chemical and electrostatic interactions, is assumed to decrease linearly with the increasing aggregate size. The electrostatic interactions of ionic species with the charged solid surface are described in terms of the Guy-Chapman theory of the double layer formation. The appropriate equations for adsorption isotherms of surfactant and electrolyte ions are derived and used to predict the experimental adsorption isotherms of DTAB on the precipitated silica at two different salt concentrations in the aqueous solution, On the basis of the obtained results the evolution of the adsorbed phase structure and the charge of silica particles with an increasing surface coverage is discussed.     

Adsorption of phenol and benzyl alcohol onto surfactant modified silica

The adsorption of the surfactant, dodecyltrimethylammonium bromide, DTAB, and the co-adsorption of the additives phenol and benzyl alcohol, onto silica from aqueous solutions are investigated. The adsorption of DTAB is found to increase with increasing alcohol concentration in solutions where the DTAB concentration is below the cmc. Moreover, the corresponding adsorption of DTAB decreases when the DTAB concentration is above the cmc. The co-adsorption of the alcohol is found to increase with increasing alcohol concentration, and benzyl alcohol co-adsorbs more strongly than phenol. The surfactant modified silica shows a very high ability to incorporate phenol and benzyl alcohol. The results are discussed in relation to solubilization site and surfactant aggregate shape.     

亚砜类非离子型表面活性剂在固/液界面上的吸附I: 硅胶/水溶液界面上的吸附

测定了癸基和辛基-甲亚基亚砜在硅胶/水溶液界面的吸附以及溶液在石英界面的接触角. 研究了温度和pH值对吸附的影响. 吸附等温线似应归入Giles分类的L4型. 饱和吸附层的平均分子面积为27-30A^2. 二个同系物的γ/γ-c/cmc曲线彼此重叠. 吸附温度系数在低浓度范围是负性的在高浓度范围是正性的. 接触角的测量表面吸附使硅胶表面疏水. 从实验结果考虑到吸附过程由二个阶段组成: 一是在低浓度范围由固体表面和亚砜基之间的相互作用, 另一过程是在高浓度范围中, 被吸附的表面活性剂分子及其在溶液中的疏水作用.     

Volumes and compressibilities of pentanol in aqueous dodecyltrimethylammonium bromide solutions at 15, 25 and 35°C

Ultrasonic velocities and densities of the water-dodecyltrimethylammonium bromide (DTAB)-pentanol (PentOH) ternary system were measured at 15, 25 and 35°C as a function of the surfactant and alcohol concentrations. The apparent molar volumes and isentropic compressibilities of PentOH were calculated. The standard partial molar volumes increase with surfactant concentration continuously whereas the standard partial molar isentropic compressibilities show sharp changes in slope at about 0.25 mol-kg^–1 DTAB, which can be ascribed to a micellar structural transition. The volume data for alcohol in micellar solutions were treated by a model reported for the distribution of polar additives between aqueous and micellar phases. In the application of the model to compressibility, the contributions due to the pressure effect on the shift of both the micellization equilibrium and the alcohol distribution constant cannot be neglected. This is in contrast to what is found in the case of heat capacity. The distribution constant and the partial molar volumes and compressibilities of PentOH in the micellar phase have been derived by linear regression. Also, the apparent molar volumes and isentropic compressibilities of DTAB in water-pentanol mixed solvents at fixed composition have been calculated. These properties as a function of the surfactant concentration show maxima depending on the temperature and the mixed solvent composition. The decrease beyond the maximum can be attributed to the extraction of PentOH from the aqueous into the micellar phase, where its concentration tends to zero with the progressive increase of the surfactant concentration. As a consequence, by increasing the surfactant concentration, the apparent molar properties of the surfactant in the mixed solvent shifts towards the value in water.     

Forces and friction between hydrophilic and hydrophobic surfaces: influence of oleate species

The atomic force microscope has been used to investigate normal surface forces and lateral friction forces at different concentrations of sodium oleate, a frequently used fatty acid in the deinking process. The measurements have been performed using the colloidal probe technique with bead materials consisting of cellulose and silica. Cellulose was used together with a printing ink alkyd resin and mica, whereas silica was used with a hydrophobized silica wafer. The cellulose-alkyd resin system showed stronger double layer repulsion and the friction was reduced with increasing surfactant concentration. The adhesive interaction disappeared immediately on addition of sodium oleate. The normal surface forces for cellulose-mica indicated no apparent adsorption of the sodium oleate however, the friction coefficient increased on addition of sodium oleate, which we ascribe to some limited adsorption increasing the effective surface roughness. The silica-hydrophobic silica system showed a completely different surface force behavior at the different concentrations. An attractive hydrophobic interaction was evident since the surfaces jumped into adhesive contact at a longer distance than the van der Waals forces would predict. The strong adhesion was reflected in the friction forces as a nonlinear relationship between load and friction and a large friction response at zero applied load. Indirect evidence of adsorption to the hydrophilic silica surface was also observed in this case, and QCM studies were performed to confirm the adsorption of material to both surfaces.     

The Adsorption of Dodecyltrimethylammonium Bromide on Mica in Aqueous Solution Studied by X-Ray Diffraction and Atomic Force Microscopy

The adsorption of dodecyltrimethylammonium bromide (DTAB) onto natural muscovite mica and a synthetic expandable mica (EM) in aqueous solution has been investigated using both microscopic and macroscopic surface characterization techniques. The electrokinetic properties of the surfaces were monitored as a function of the concentration of DTAB using atomic force microscopy and microelectrophoresis. The adsorption isotherm of DTAB on EM was measured up to a solution concentration just below the critical micelle concentration of the surfactant. The thickness of the adsorbed layer on EM was determined using X-ray diffraction. Results indicate that the adsorbed layer consists of molecules lying quite flat on the mica surface at low concentrations and adsorbed in interleaved aggregate structures at concentrations approaching the critical micelle concentration of the surfactant in solution. Copyright 2001 Academic Press.     

The adsorption behavior of cationic surfactant onto human hair fibers

Quaternary ammonium surfactants are important ingredients that are frequently formulated into hair care products to modify the properties of hair surface. The adsorption kinetics, isotherms and association structures of cationic surfactants on hair surface, however, are not fully understood due to the heterogeneous nature of human hair fibers. In this work, a quaternary ammonium of surfactant, dimethylpabamidopropyl laurdimonium tosylate (DDABDT) was chosen as a probe to investigate the adsorption behavior of cationic surfactant on cuticles of scalp hair. The results reveal that the adsorption kinetics fit to a pseudo-second-order kinetic model and the adsorption isotherms fit to the Freundlich adsorption model. With the increase of DDABDT adsorption, the wettability of hair fibers changes from hydrophobic to hydrophilic. The association structure could be monolayer or bilayer depending on the initial concentration of the surfactant. In the monolayer structure, the ‘anchor’ surfactant molecules are believed to adsorb vertically on the surface of hair fibers through electrostatic interaction. In the bilayer structure, the second layer molecules may then pile up on top of the first layer with charged groups orienting outward. The thickness of DDABDT film on hair fibers treated with 5 × 10^?4 mol/l DDABDT solution is measured to be 5.42 nm on average with a force–distance method. This figure is very close to the two times of the theoretical molecular size of the DDABDT molecule.     

Structure of DNA-cationic surfactant complexes at hydrophobically modified and hydrophilic silica surfaces as revealed by neutron reflectometry

In this article, we discuss the structure and composition of mixed DNA-cationic surfactant adsorption layers on both hydrophobic and hydrophilic solid surfaces. We have focused on the effects of the bulk concentrations, the surfactant chain length, and the type of solid surface on the interfacial layer structure (the location, coverage, and conformation of the DNA and surfactant molecules). Neutron reflectometry is the technique of choice for revealing the surface layer structure by means of selective deuteration. We start by studying the interfacial complexation of DNA with dodecyltrimethylammonium bromide (DTAB) and hexadecyltrimethylammonium bromide (CTAB) on hydrophobic surfaces, where we show that DNA molecules are located on top of a self-assembled surfactant monolayer, with the thickness of the DNA layer and the surfactant-DNA ratio determined by the surface coverage of the underlying cationic layer. The surface coverages of surfactant and DNA are determined by the bulk concentration of the surfactant relative to its critical micelle concentration (cmc). The structure of the interfacial layer is not affected by the choice of cationic surfactant studied. However, to obtain similar interfacial structures, a higher concentration in relation to its cmc is required for the more soluble DTAB surfactant with a shorter alkyl chain than for CTAB. Our results suggest that the DNA molecules will spontaneously form a relatively dense, thin layer on top of a surfactant monolayer (hydrophobic surface) or a layer of admicelles (hydrophilic surface) as long as the surface concentration of surfactant is great enough to ensure a high interfacial charge density. These findings have implications for bioanalytical and nanotechnology applications, which require the deposition of DNA layers with well-controlled structure and composition.     

Unusual wetting dynamics of aqueous surfactant solutions on polymer surfaces

Static and dynamic contact angles of aqueous solutions of three surfactants--anionic sodium dodecyl sulfate (SDS), cationic dodecyltrimethylammonium bromide (DTAB), and nonionic pentaethylene glycol monododecyl ether (C(12)E(5))--were measured in the pre- and micellar concentration ranges on polymer surfaces of different surface free energy. The influence of the degree of substrate hydrophobicity, concentration of the solution, and ionic/nonionic character of surfactant on the drop spreading was investigated. Evaporation losses due to relatively low humidity during measurements were taken into account as well. It was shown that, in contrast to the highly hydrophobic surfaces, contact angles for ionic surfactant solutions on the moderately hydrophobic surfaces strongly depend on time. As far as the nonionic surfactant is considered, it spreads well over all the hydrophobic polymer surfaces used. Moreover, the results obtained indicate that spreading (if it occurs) in the long-time regime is controlled not only by the diffusive transport of surfactant to the expanding liquid-vapor interface. Obviously, another process involving adsorption at the expanding solid-liquid interface (near the three-phase contact line), which goes more slowly than diffusion, has to be active.     

Effects of clustering structure on volumetric properties of amino acids in (DMSO + water) mixtures

For a better understanding on the functions of DMSO in biological systems at a relatively lower concentration, apparent molar volumes of three typical amino acids, glycine, l-alanine and l-serine in (DMSO + water) mixtures were determined and the transfer volumes from water to the mixtures were evaluated. Together with static light scattering measurement, the results were utilised to reveal the microscopic solvent structure of (DMSO + water) mixtures and its influence on the interaction between DMSO and amino acids from a clustering point of view. The results demonstrate that the interaction between amino acids and DMSO is greatly related to the clustering structure of the mixed solvent and that amino acids interacted with already established solvent clusters. The linear dependence of transfer volume of amino acids on DMSO concentration up to 2.0 mol ⋅ dm⁻³ could be attributed to the increasing interaction with (DMSO)₁(H₂O)_n clusters. The formation of (DMSO)_m(H₂O)_n cluster via hydrophobic aggregating at higher DMSO concentration led to a decrease in hydrophobic effect of DMSO and its hydrophobic–hydrophilic and hydrophobic–hydrophobic interaction with amino acids. The structure change of solvent and the interaction between amino acid residues and DMSO was reflected by the solvation of proteins. It was found that dependence of hydrodynamic radius of bovine serum albumin and lysozyme on DMSO concentration was the same and similar to that of static light scattered by the mixed solvent, regardless of the difference in conformational change between the two proteins.     

Thermal Study of Surfactant and Anion Adsorption on Clinoptilolite

The mechanism of surfactant adsorption on various forms of clinoptilolite was studied by DTA, TG and DTG analyses. The examined series of surfactant modified clinoptilolite (SMC) was previously prepared by the adsorption of the surface-active oleylamine on Ca²⁺, Na⁺, H⁺ and mechanochemically treated forms of clinoptilolite. The oleylamine was most strongly adsorbed on H⁺-forms of clinoptilolite due to the largest number and strength of adsorption sites. The surfactant adsorption mechanism on H⁺-form of clinoptilolite was studied by recording the series of variously surfactant-loaded samples. The products of sulphate, dihydrogenphosphate and hydrogenchromate adsorption on SMC were analyzed by DTA, TG and DTG in order to investigate the mechanism of anion adsorption.This revised version was published online in November 2005 with corrections to the Cover Date.     

Effects of alkyltrimethylammonium bromide surfactants on the kinetics of the oxidation of tris(1,10-phenanthroline)iron(II) by azido-pentacyanocobaltate(III) complex

The redox reaction between tris(1,10-phenanthroline)iron(II), [Fe(phen)₃]²⁺, and azido-pentacyanocobaltate(III), [Co(CN)₅N₃]^3? was investigated in three cationic surfactants: dodecyltrimethylammonium bromide (DTAB), tetradecyltrimethylammonium bromide (TTAB) and cetyltrimethylammonium bromide (CTAB) in the presence of 0.1?M NaCl at 35°C. Second-order rate constant in the absence and presence of surfactant, k_w and k_ψ, respectively, were obtained in the concentration ranges DTAB?=?0???4.667?×?10^?4?mol?dm^?3, TTAB?=?0–9.364?×?10^?5?mol?dm^?3, CTAB?=?0???6.220?×?10^?5?mol?dm^?3. Electron transfer rate was inhibited by the surfactants with premicelllar activity. Inhibition factors, k_w/k_ψ followed the trend CTAB?>?TTAB?>?DTAB with respect to the surfactant concentrations used. The magnitudes of the binding constants obtained suggest significant electrostatic and hydrophobic interactions. Activation parameters ΔH^≠, ΔS^≠, and E_a have larger positive values in the presence of surfactants than in surfactant-free medium. The electron transfer is proposed to proceed via outer-sphere mechanism in the presence of the surfactants.     

Wettability of ionic surfactants SDS and DTAB on wheat (Triticum aestivum) leaf surfaces

Abstract

Due to the important use of pesticide formulation, it is necessary to make it clear how ionic surfactant effect the wettability at leaf surface. In this work, we used the sessile drop method to study the wettability of SDS and DTAB on wheat leaf surfaces at different leaf stages, and reveal the relationship between surfactants structures and leaf stages of wheat leaf surfaces on wettability behavior. Results showed that few surfactant molecules adsorbed at the interface at low concentrations. With the concentration increased, the surfactant replaced the air layer partially within the nano/micro structure of leaf surfaces. When the concentration exceeded to CMC, the adsorption of surfactant molecules was saturated at both air-liquid interface and solid-liquid interface, the wetting state was still the transitional state between Cassie-Baxter’s and Wenzel’s state. In all concentrations, the adhesional tension and surface tension showed the linear relationship and the slope values were all below ?1, suggesting there were more surfactant molecules adsorbed at the solid-liquid interface than the liquid-air interface. As SDS is a common wetting agent and DTAB is a common fungicide in agrochemical, this study will provide potential guidance in practical application of pesticide solutions in leaf surface wetting.     

Experimental observations on the scaling of adsorption isotherms for nonionic surfactants at a hydrophobic solid-water interface

The self-assembly of nonionic surfactants in bulk solution and on hydrophobic surfaces is driven by the same intermolecular interactions, yet their relationship is not clear. While there are abundant experimental and theoretical studies for self-assembly in bulk solution and at the air-water interface, there are only few systematic studies for hydrophobic solid-water interfaces. In this work, we have used optical reflectometry to measure adsorption isotherms of seven different nonionic alkyl polyethoxylate surfactants (CH3(CH2)I-1(OCH2CH2)JOH, referred to as CIEJ surfactants, with I = 10-14 and J = 3-8), on hydrophobic, chemically homogeneous self-assembled monolayers of octadecyltrichlorosilane. Systematic changes in the adsorption isotherms are observed for variations in the surfactant molecular structure. The maximum surface excess concentration decreases (and minimum area/molecule increases) with the square root of the number of ethoxylate units in the surfactant (J). The adsorption isotherms of all surfactants collapse onto the same curve when the bulk and surface excess concentrations are rescaled by the bulk critical aggregation concentration (CAC) and the maximum surface excess concentration. In an accompanying paper we compare these experimental results with the predictions of a unified model developed for self-assembly of nonionic surfactants in bulk solution and on interfaces.     

Hofmeister effects at low salt concentration due to surface charge transfer

We present a theoretical comparison of the surface forces between two graphite-like surfaces at salt concentrations below 10 mM with surfaces charged by various mechanisms. Surface forces include a surface charging or chemisorption contribution to the total free energy. Surfaces are charged by charge regulation (H⁺ binding), site competition (H⁺ and cation binding) and redox charging with electrodes coupled to a countercell. Constant surface charge is also considered. Surface parameters are calibrated to give the same potential when isolated. Nonelectrostatic physisorption energies of the potential determining ions provide a specific and significant contribution to the charging energy. Consequently ion specificity is found in the surface forces at concentrations of 1–10 mM, which is not observed under constant charge conditions. The force between redox electrodes continues to show Hofmeister effects at 0.01 mM. We refer to this low concentration Hofmeister effect as “Hofmeister charging”, and suggest that the more common high concentration ion specific effects may be known as “Hofmeister screening”. Hofmeister series are considered over LiCl, NaCl, KCl and NaNO₃, NaClO₄, NaSCN with the cations (or H⁺) being the potential determining ions. A K⁺ anomaly is attributed to the small size of the weakly hydrated chaotropic K⁺ ion, with Li⁺ and Na⁺ explicitly modelled as strongly hydrated cosmotropes.