Structure of colloidal complexes obtained from neutral/poly- electrolyte copolymers and oppositely charged surfactants

We report on the phase behavior and scattering properties of colloidal complexes made from block copolymers and surfactants. The copolymer is poly(sodium acrylate)-b-poly(acrylamide), hereafter abbreviated as PANa-PAM, with molecular weight 5000 g/mol for the first block and 30000 g/mol for the second. In aqueous solutions and neutral pH, poly(sodium acrylate) is a weak polyelectrolyte, whereas poly(acrylamide) is neutral and in good-solvent conditions. The surfactant is dodecyltrimethylammonium bromide (DTAB) and is of opposite charge with respect to the polyelectrolyte block. Combining dynamical light scattering and small-angle neutron scattering, we show that in aqueous solutions PANa-PAM diblocks and DTAB associate into colloidal complexes. For surfactant-to-polymer charge ratios Z lower than a threshold (Z(C) approximately 0.3), the complexes are single surfactant micelles decorated by few copolymers. Above the threshold, the colloidal complexes reveal an original core-shell microstructure. We have found that the core of typical radius 100-200 A is constituted from densely packed surfactant micelles connected by the polyelectrolyte blocks. The outer part of the colloidal complex is a corona and is made from the neutral poly(acrylamide) chains. Typical hydrodynamic sizes for the whole aggregate are around 1000 A. The aggregation numbers expressed in terms of numbers of micelles and copolymers per complex are determined and found to be comprised between 100-400, depending on the charge ratio Z and on the total concentration. We have also shown that the sizes of the complexes depend on the exact procedure of the sample preparation. We propose that the driving mechanism for the complex formation is similar to that involved in the phase separation of homopolyelectrolyte/surfactant systems. With copolymers, the presence of the neutral blocks prevents the macroscopic phase separation from occurring.     

Weakly charged lamellar bilayer system: Interplay between thermal undulations and electrostatic repulsion

We study the interplay between thermal undulations and electrostatic interactions for weakly charged surfactant bilayers by measuring the backscattering of light from very dilute lamellar phases of the non-ionic surfactant triethylene glycol monodecyl ether (C₁₀E₃) doped with small amounts of the anionic surfactant sodium dodecyl sulphate (SDS), both with and without added electrolyte. Upon charging, the lamellar phases show a transition from undulation to electrostatic stabilization. Non-lamellar structures develop if the molar mixing ratio exceeds . Deviations from ideal swelling, , where is the lamellar repeating distance and the membrane volume fraction, were detected for all lamellar phases. Salt-free lamellar phases with charge densities below , as well as more highly charged lamellar phases at high ionic strength show a universal logarithmic deviation from ideal swelling that was analyzed using theories for undulation stabilized lamellar phases. Deviations from ideal swelling for electrostatically stabilized lamellar phases were analyzed using theories recently developed for undulations in charged lamellar phases. The fits to the various theories yield a value of for the bending modulus of the C₁₀E₃ bilayers. Received 21 June 1999 and Received in final form 25 August 1999     

Observations of the collapse of dilute lyotropic lamellar phases under shear flow

Experimental evidence of the collapse of dilute lamellar phases due to shear flow is presented. Two systems are used: one composed of brine and an ionic surfactant, and another composed of water, a nonionic surfactant, and cosurfactant. We observe this transition for a range of lamellar spacings and brine salinity. The results are in reasonable agreement with recent theory in which the suppression of fluctuations by shear plays an important role.     

Inter-lamellar interactions modulated by addition of guest components

We have investigated the effects of a guest component (polymer or spherical colloidal particle) confined between flexible lamellar slits on the inter-lamellar interaction by means of a small-angle X-ray scattering technique and a neutron spin echo technique. The dominant interaction between flexible lamellar membranes without guest components is the Helfrich mechanism. The addition of a neutral polymer into the lamellar phase induces an attractive inter-lamellar interaction and finally destabilizes the lamellar phase. On the other hand, spherical colloidal particles confined between flexible lamellar membranes reduce the undulational fluctuations of lamellae and bring a repulsive inter-lamellar interaction. The behavior of the layer compression modulus of the lamellar membrane containing colloidal particles is well described by the entropical repulsive inter-lamellar interaction driven by steric hindrance.Received: 26 March 2004, Published online: 4 May 2004PACS: 82.70.Uv Surfactants, micellar solutions, vesicles, lamellae, amphiphilic systems, (hydrophilic and hydrophobic interactions) - 61.25.Hq Macromolecular and polymer solutions; polymer melts; swelling - 83.80.Hj Suspensions, dispersions, pastes, slurries, colloids - 89.75.Fb Structures and organization in complex systems     

Enhancement of organic nanoparticle preparation by laser ablation in aqueous solution using surfactants

Nanoparticle and metal phthalocyanine (MPc) transparent colloidal aqueous solutions were directly obtained by 355 nm YAG laser ablation. We found that too long an irradiation time does not contribute to producing nanoparticles and their generation efficiency increases with a low solution temperature. We believe this due to nanoparticle reassociation which is caused by hydrophobicity. To prevent generated nanoparticles from reassociating we performed experiments adding two kinds of ionic and nonionic surfactants into solution. We found five characteristics of nanoparticle generation from adding surfactants to a solution regardless of the type of surfactant used. These characteristics are that: (1) production efficiency increases; (2) stability is better after irradiation; (3) irradiation intensity needed to induce nanoparticle generation becomes lower; (4) mean size of the generated nanoparticles becomes smaller; and (5) crystalline structures of oxo(phthalocyaninato) vanadium (IV) (VOPc) are controllable by changing the surfactant concentration.     

Structures of some surfactant—polyelectrolyte complexes

Structures of complexes formed in aqueous solutions by some anionic polyelectrolytes (double and single stranded (ds and ss) DNA, poly(vinyl sulfonate) (PVS), and poly(styrene sulfonate) (PSS)) with a cationic surfactant system consisting of cetyltrimethylammonium bromide (CTAB) and sodium 3-hydroxy-2-naphthoate (SHN) have been determined using small angle X-ray diffraction. All complexes are found to have a two-dimensional (2-D) hexagonal structure at low SHN concentrations. Analysis of the diffraction data shows that the ds DNA—CTAB complex has an intercalated structure, with each DNA strand surrounded by three cylindrical micelles. On increasing SHN concentration, DNA—CTAB—SHN complexes exhibit a hexagonal-to-lamellar transition, whereas PVS complexes show a hexagonal → centered rectangular → lamellar transition. PSS complexes show yet another sequence of structures. These results indicate the significant influence of the chemical nature of the polyelectrolyte on the structure of the complexes.     

Effect of surfactants on the degradation of perfluorooctanoic acid (PFOA) by ultrasonic (US) treatment

Perfluorooctanoic acid (C₇F₁₅COOH, PFOA) is an aqueous anionic surfactant and a persistent organic pollutant. It can be easily adsorbed onto the bubble-water interface and both mineralized and degraded by ultrasonic (US) cavitation at room temperature. The aim of this study is to investigate whether the effect of US on the degradation of PFOA in solution can be enhanced by the addition of surfactant. To achieve this aim, we first investigated the addition of a cationic (hexadecyl trimethyl ammonium bromide, CTAB), a nonionic (octyl phenol ethoxylate, TritonX-100), and an anionic (sodium dodecyl sulfate, SDS) surfactant. We found the addition of CTAB to have increased the degradation rate the most, followed by TritonX-100. SDS inhibited the degradation rate. We then conducted further experiments characterizing the removal efficiency of CTAB at varying surfactant concentrations and solution pHs. The removal efficiency of PFOA increased with CTAB concentration, with the efficiency reaching 79% after 120 min at 25 °C with a 0.12 mM CTAB dose.     

Microstructural analysis of carbonitrided austenitic steels

An austenitic heat resisting steel containing 25% Cr and 19% Ni was internally carbonitrided in an atmosphere of 0.5% C₃H₆, 9.5% H₂ and 90% N₂. Immediately below the alloy surface, globular precipitates were observed. At greater depth, two zones of lamellar morphology precipitates were observed to form. M₇C₃ was found directly beneath the surface and M₂₃C₆ was found closer to the reaction front. The lamellar carbide morphology is more typically characteristic of the precipitates formed during nitriding rather than carburising, suggesting that nitrogen plays some role in the precipitation process. A focused ion beam (FIB) miller was used to create thin, electron transparent locations at specific regions in the precipitation zone in order to characterise, via transmission electron microscopy, the crystallography and composition of the phases present. In this study, thin areas were produced in the lamellar region at the transition between the M₂₃C₆ and M₇C₃ regions. The composition, crystal structure, and orientation relationships are reported and compared to those found previously at both the internal precipitation front and the sample surface.     

NMR studies of restricted diffusion in lyotropic systems

Tortuosity, 1/alpha, and surface-to-volume ratio, S/V, were determined in aqueous solutions of decylammonium, dodecylammonium and tetradecylammonium chlorides of various concentrations by measuring the apparent diffusion coefficient of water, D(app)(delta). This was found to be much smaller than in the bulk state. Such restricted diffusion is interpreted in terms of the Mitra model, where D(delta) depends on diffusion time and is controlled primarily by S/V. The samples exhibit lamellar (L), hexagonal (H) and isotropic (I) liquid crystalline phases. We observed changes in S/V upon phase transition. In the lamellar and hexagonal phases, the system is ordered, resulting in relatively small S/V ratios, compared to the micellar-isotropic phase. We did not observe a dependence on the diffusion time, delta, in the isotropic phase, because the duration of the experiment was not sufficiently short to observe the change from D(app)(delta) to D(eff). We observed the effective diffusion coefficient of water, which directly probes the tortuosity of the system. The S/V ratios were obtained by fitting the Mitra model, using known values of the bulk water diffusion coefficients, and the assumption that D(app) --> D0 for delta --> 0. S/V is correlated with the type of structure, increasing on transition to the isotropic phase and decreasing on transition to other phases. The change in tortuosity is small, but slightly larger for the isotropic phase.     

Interface tailoring of layered silicate/styrene butadiene rubber nanocomposites

To improve the interfacial interaction in clay/SBR nanocomposites prepared by latex compounding method, a novel clay modification for the nanocomposites was introduced before latex compounding with SBR using three kinds of organic modifiers, namely, hexadecyl trimethyl ammonium bromide (C16), bis(hexadecyl) dimethyl ammonium bromide (DC16) and 3-aminopropyl triethoxy silane (KH550). On the other hand, bis(triethoxysilylpropyl)tetrasulfide (Si69) was added into the KH550 modified clay/SBR nanocomposite during later mechanical blending, and was designed to interact with both KH550 and rubber and thus improve the interface. Structure changes of the nanocomposites were followed by study of X-ray diffraction, transmission electron microscopy and rubber process analyzer. Dynamic mechanical analysis and tensile tests were carried out to obtain information about the mechanical properties of the nanocomposites. The results revealed that, with the organic modification, clay was dispersed finely in the rubber matrix with part rubber-intercalated or part modifier-intercalated structure. Compared with the unmodified nanocomposite, the tensile strength, the stress at 300% strain, and the tear strength of modified SBR–clay nanocomposites were significantly improved. Moreover, the type of modifiers and strength of interfacial interaction determined the properties of the nanocomposites. The incorporation of KH550 and Si69 brought the best modification effect among all the modification methods.     

The lamellar-disorder interface: one-dimensional modulated profiles

We study interfacial behavior of a lamellar (stripe) phase coexisting with a disordered phase. Systematic analytical expansions are obtained for the interfacial profile in the vicinity of a tricritical point. They are characterized by a wide interfacial region involving a large number of lamellae. Our analytical results apply to systems with one dimensional symmetry in true thermodynamical equilibrium and are of relevance to metastable interfaces between lamellar and disordered phases in two and three dimensions. In addition, good agreement is found with numerical minimization schemes of the full free energy functional having the same one dimensional symmetry. The interfacial energy for the lamellar to disordered transition is obtained in accord with mean field scaling laws of tricritical points. Received: 28 March 1997 / Revised: 6 February 1998 / Accepted: 16 February 1998     

Nanostructures of colloidal complexes formed in oppositely charged polyelectrolyte/surfactant dilute aqueous solutions

Small-angle neutron scattering measurements were performed on dilute solutions of carboxymethylcellulose/DTAB complexes in water in order to determine their size, shape and internal structures. At low polymer content, the complexes are spherical, rather monodisperse and probably made of polymer chains intercalated between surfactant micelles. Moreover, we show that these micelles have a similar cubic arrangement than found in polymer/surfactant precipitates formed at higher surfactant concentrations. At larger polymer content, in the semi-dilute polyelectrolyte regime, the complexes are larger, softer and polydisperse. However, they possess a similar internal structure in both regimes. Carboxymethylcellulose/CTAB complexes are also large, soft and polydisperse but do not seem to exhibit well-defined internal structures.     

Microphase separation in polymer solutions containing surfactants

A microphase separation in solutions containing a polymer and a mixture of two solvents, one of which consists of amphiphilic molecules (surfactant), is considered theoretically in the weak-segregation regime. A surfactant molecule is described as a dimer consisting of hydrophobic and polar parts. The energy gain due to the orientation of surfactant molecules can lead to the appearance of non-homogeneities in the solution, where density fluctuations cause the orientational ordering of surfactant molecules. The difference in the interaction energies of hydrophobic and polar groups of a surfactant with solvent is considered as a main reason for orienting surfactant molecules. The free energy is calculated for various morphologies (lamellar, cylindrical hexagonal, spherical particles arranged at different cubic lattices). The phase diagrams are presented. With worsening the solvent quality, the transitions from disordered to a macro-separated state at low polymer and surfactant concentrations or to a body-centered-cubic, then hexagonal, and then lamellar structure at high polymer and surfactant concentrations are predicted. The amphiphilicity degree of surfactant molecules should exceed a certain critical value to make a microstructure formation possible. The period of the lamellar microstructure decreases with increasing the surfactant and polymer concentrations.     

Annealing-induced structural transformation of gelatin-capped Se nanoparticles

Selenium nanoparticles were obtained by a new facile synthetic route from gelatin-stabilized aqueous colloidal solutions. The dependence of structural and optical properties of the nanoparticles upon duration of post-synthesis thermal treatment of Se sols was studied by optical absorption, photoluminescence and Raman scattering. We have shown that ageing of colloidal Se solutions at elevated temperatures results in an enlargement and crystallization of selenium nanoparticles, accompanied with noticeable changes in their optical spectra: an enhancement of the photoluminescence of the NPs, incorporated in gelatin films; a “red” shift of both the absorption threshold and emission band maximum; appearance of new peaks in Raman spectra, attributed to the formation of the crystalline phase in the course of the ageing.     

Self-assembled and fluorescence enhancement of semiconductor nanoparticles induced by surfactant adsorption

When semiconductor colloidal CdS nanoparticles and nonylphenol are mixed together in dimethyl sulfoxide at room temperature, a self-assembling process is induced. In the course, the size tunable properties of CdS nanoparticles are amplified. A blue shift in the emission spectrum and a strong photoluminescence enhancement are observed without significant change in the absorption features of the colloidal nanoparticles. These results are attributed to the adsorption of nonylphenol onto the nanoparticles surface and to the association process of the surfactant molecules. The surfactant adsorption process provides a nanoparticle surface passivation and induces an associative phase that enlarges the photoluminescence stability. This strategy opens the possibility to improve simultaneously physicochemical and photoluminescence properties of nanocrystals in solution as well as to control their deposition on two-dimensional surfaces.     

Study of the Optical Properties of CdZnSe/ZnS-Quantum Dot–Au-Nanoparticle Complexes

The interaction of gold nanoparticles (NPs) and semiconductor alloyed CdZnSe/ZnS quantum dots (QDs) in colloidal solutions is studied. It is shown that the photoluminescence intensity of QDs in a mixture decreases compared to that in the initial QD solution, which is caused by resonance nonradiative energy transfer from QDs to Au NPs in spontaneously formed aggregates. To control the formation of pairs of interacting QDs and Au NPs, we proposed have a method for creating QD–Au NP complexes bound by special molecules—ligands. It is shown that the morphology and optical properties of the samples obtained depend on the method of their preparation, in particular, on the chemical environment of QDs. It is found that the complexes form in the case of addition of hydrophilic Au NPs to hydrophobic QDs and that this almost does not change the optical properties of the latter compared to those of quasi-isolated QDs in colloidal solution.     

Semi-analytical method of calculating the electrostatic interaction of colloidal solutions

We present a semi-analytical method of calculating the electrostatic interaction of colloid solutions for confined and unconfined systems. We expand the electrostatic potential of the system in terms of some basis functions such as spherical harmonic function and cylinder function. The expansion coefficients can be obtained by solving the equations of the boundary conditions, combining an analytical translation transform of the coordinates and a numerical multipoint collection method. The precise electrostatic potential and the interaction energy are then obtained automatically. The method is available not only for the uniformly charged colloids but also for nonuniformly charged ones. We have successfully applied it to unconfined diluted colloid system and some confined systems such as the long cylinder wall confinement, the air–water interfacial confinement and porous membrane confinement. The consistence checks of our calculations with some known analytical cases have been made for all our applications. In theory, the method is applicable to any dilute colloid solutions with an arbitrary distribution of the surface charge on the colloidal particle under a regular solid confinement, such as spherical cavity confinement and lamellar confinement.     

硫氰酸铵-十二烷基二甲基苄基氯化铵-水体系浮选分离汞(Ⅱ)

研究了硫氰酸铵-十二烷基二甲基苄基氯化铵-水体系浮选分离汞(Ⅱ)的行为及其常见金属离子的分离条件。控制pH=5.0,当0.01mol/L硫氰酸铵溶液和0.01mol/L十二烷基二甲基苄基氯化铵(DDBAC)溶液的用量分别为0.30、0.50mL时,体系中形成的不溶于水的三元缔合物(DDBAC)2[Hg(SCN)4]可浮于水相上层形成界面清晰的液-固两相,分相过程中,Hg2+被定量浮选,而Zn2+,Cd2+,Mn2+,Ni2+,Co2+,Fe2+等离子在此条件下不被浮选,实现了Hg2+的定量分离。该方法对合成水样中微量Hg2+进行定量浮选分离测定,浮选率为96.0%—108.8%。     

Topological lifshitz line, off-specular scattering, and mesoporous materials

Ordered phases formed by surfactants in water solutions, and used in technological processes as templates for the synthesis of mesoporous materials, exhibit topological fluctuations. From the results of the Monte Carlo simulations of the lamellar phase we have established a relation between topological fluctuations and the behavior of the off-specular scattering intensity. We have defined the topological Lifshitz line. At this line the peak position in the off-specular scattering intensity moves from the zero (lamellar phase with fixed topology) to the nonzero value of the scattering wave vector (lamellar phase with fluctuating topology).     

Elastic properties of polymer-doped dilute lamellar phases: A small-angle neutron scattering study

We investigate experimentally, using small-angle neutron scattering the elastic properties of polymer-doped dilute lamellar phases. In our system the polymer is water-soluble but nevertheless partially adsorbs onto the negatively charged surfactant bilayers. The effective polymer-mediated interaction between bilayers is less repulsive than the weakly screened electrostatic interaction that prevails at zero polymer content. It even becomes attractive in some regions of the phase diagram. Small-angle neutron scattering allows us to measure directly the Caillé exponent η characterizing the bilayer fluctuations in lamellar (smectic A) phases, and thus indirectly estimate the compression modulus as a measure of the strength of the bilayer-bilayer interactions. The compression modulus appears to be vanishing at a point located on the lamellar-lamellar phase separation boundary, a candidate critical point. Received: 7 August 2000