Influence of methanol on the phase behavior of nonionic fluorinated surfactant: Relation to the structure of mesoporous silica materials

We have investigated the effect of methanol addition on the R^F₈(EO)₉ and R^F₇(EO)₈ surfactant-based systems. While upon the addition of methanol the L₁ micellar phase grows, the direct hexagonal (H₁) and the lamellar (L_α) liquid crystals progressively melt with the increase of alcohol content. Phase behavior and SAXS measurements proved that methanol molecules interact with the oxyethylene units of the surfactant. This involves a folding up of the hydrophobic chains in the liquid crystal phases. Moreover, for the R^F₇(EO)₈ surfactant, the cloud point curve is shifted to high temperatures upon addition of alcohol. Starting from these systems, we have prepared mesoporous materials. Results show that due to the hydrogen bonds between the alcohol and the EO groups, the hexagonal structure of the mesostructured silica obtained from R^F₈(EO)₉ is lost when the content of CH₃OH is increased. In contrast, for the compounds prepared from the R^F₇(EO)₈-based system, the pore ordering occurs in the presence of alcohol. This phenomenon has been related to the moving of the cloud point curve toward high temperatures with the addition of methanol. Our study reveals also that under our conditions the methanol released during the hydrolysis of the silica precursor does not affect the self-assembly mechanism in a positive or negative way.     

Supercritical carbon dioxide processing of fluorinated surfactant templated mesoporous silica thin films

The effect of processing mesoporous silica thin films with supercritical CO2 immediately after casting is investigated, with a goal of using the penetration of CO2 molecules in the tails of fluorinated surfactant templates to tailor the final pore size. Well-ordered films with two-dimensional hexagonal close-packed pore structure are synthesized using a cationic fluorinated surfactant, 1-(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl)pyridinium chloride, as a templating agent. Hexagonal mesopore structures are obtained for both unprocessed films and after processing the cast films in CO2 at constant pressure (69-172 bar) and temperature (25-45 degrees C) for 72 h, followed by traditional heat treatment steps. X-ray diffraction and transmission electron microscopy analysis reveal significant increases in pore size for all CO2-treated thin films (final pore diameter up to 4.22 +/- 0.14 nm) relative to the unprocessed sample (final pore diameter of 2.21 +/- 0.20 nm) before surfactant extraction. Similar pore sizes are obtained with liquid and supercritical fluid treatments over the range of conditions tested. These results demonstrate that combining the tunable solvent strength of compressed and supercritical CO2 with the "CO2-philic" nature of fluorinated tails allows one to use CO2 processing to control the pore size in ordered mesoporous silica films.     

Phase behavior and preparation of mesoporous silica in aqueous mixtures of fluorinated surfactant and hydrophobic fluorinated polymer

The phase behavior and formation of self-assemblies in the ternary water/fluorinated surfactant (C(8)F(17)EO(10))/hydrophobic fluorinated polymer (C(3)F(6)O)(n)COOH system and the application of those assemblies in the preparation of mesostructured silica have been investigated by means of phase study, small angle X-ray scattering, and rheology. Hexagonal (H(1)), bicontinuous cubic (V(1)) with Ia3d symmetry, and polymer rich lamellar (L(alpha)(')) are observed in the ternary diagram. C(8)F(17)EO(10) molecules are dissolved in polymer rich aggregates, whereas (C(3)F(6)O)(n)COOH molecules are practically insoluble in the surfactant lamellar phase due to packing restrictions. Hence, two types of lamellar phases exist: one with surfactant rich (L(alpha)) and the other with polymer rich (L(alpha)(')) in the water/C(8)F(17)EO(10)/(C(3)F(6)O)(n)COOH system. As suggested by rheological measurements, worm-like micelles are present in C(8)F(17)EO(10) aqueous solutions but a rod-sphere transition takes place by solubilization of (C(3)F(6)O)(n)COOH. C(8)F(17)EO(10) acts as a structure directing agent for the preparation of hexagonal mesoporous silica by the precipitation method. The addition of (C(3)F(6)O)(n)COOH induces the formation of larger but disordered pores.     

Structural control of mesoporous silica nanoparticles in a binary surfactant system

The grain size and regularity of the hexagonal array of mesoporous silica nanoparticles were investigated in a binary surfactant system composed of cetyltrimethylammonium chloride and triblock copolymer EO106PO60EO106. Structural control was achieved by varying the parameters for the prior hydrolysis of silicon alkoxide under an acidic condition and the subsequent assembly of silicates and surfactants under a basic condition. The formation of the mesoscale architectures was based on the balance between the ordered assembly of anionic silicates and the cationic surfactant through electrostatic interaction and the inhibition of grain growth with a nonionic amphiphilic agent through hydrogen bonds.     

Competitive adsorption of nonionic surfactant and nonionic polymer on silica

Competitive adsorption of the nonionic polymer poly(ethylene oxide) (PEO) and the nonionic surfactant of the type poly(ethylene oxide) alkyl ether from aqueous solutions on a silica surface is examined. From one-component solutions, both species readily adsorb onto silica and, in the bulk of mixed (two-component) solutions, polymer-surfactant complexes are not observed. Because both species bind by the same mechanism to silica, subtle differences in layer structure, or other species-specific parameters, determine whether one or both of the species will adsorb. It was found that various surfactants can displace PEO up to a certain critical molecular weight. Surfactants with a high aggregation number, in bulk and on the surface, can displace PEO with a higher molar mass than surfactants with a low aggregation number. As the molar mass of the polymer increases, the time a surfactant needs to completely displace the polymer increases. We can explain both the existence of the critical molar mass and the decrease in adsorption kinetics with a shift in the critical surface association concentration (CSAC).     

Mixed systems based on the cationic surfactant with a butyl carbamate fragment and nonionic surfactant Tween 80: Aggregation behavior and solubilization properties

Mixed micelles are formed in the binary compositions based on the cationic surfactant functionalized by the butyl carbamate fragment and nonionic surfactant Tween 80 in aqueous solutions. The aggregation parameters of the formed micelles (critical micelle concentration, size, and surface potential) depend on the component ratio in the system. The solubilization effect of individual and mixed micelles on the drugs of the heterocyclic series, indomethacin and 1-[5-(4-chlorophenyl)-3-phenylpyrrol-2-yl)]benzimidazol-2(3H)-one, was quantitatively characterized.     

Titanium-rich highly ordered mesoporous silica synthesized by using a mixed surfactant system

A new titanium-rich highly ordered 2-D hexagonal mesoporous titanium silicate has been synthesized using a mixture of cationic (cetyltrimethylammonium bromide, CTAB) and non-ionic (Brij-35, C₁₂H₂₅-(OC₂H₄)₂₃-OH, a polyether and aliphatic hydrocarbon chain surfactant) mixed surfactant system as the supramolecular structure directing agent (SDA) in the presence of tartaric acid (TA) as a mineralizer of Ti(IV). XRD, N₂ adsorption and TEM data suggested the presence of mesophase with hexagonal pore arrangements and the UV-visible, FT IR and XPS studies suggested the incorporation of mostly tetrahedral titanium (IV) species in the highly ordered silica network. This mesoporous titanium silicate material showed excellent catalytic activity and selectivity in the epoxidation of styrene using dilute aqueous H₂O₂ as oxidant.     

Three-phase behavior in a mixed nonionic surfactant system

The effect of monodisperse solubilities of each surfactant in an excess oil phase on the three-phase behavior was investigated in a water/octaethyleneglycol dodecyl ether (R₁₂EO₈)/tetraethyleneglycol dodecyl ether (R₁₂EO₄)/heptane system. The mid temperature of the three-phase region is defined as the HLB temperature. The HLB temperature is largely skewed to higher temperature in a dilute region due to the difference in the distribution of each surfactant between excess oil and microemulsion (surfactant) phases forming the three-phase body. Taking account of the monodisperse solubilities, the equation for the HLB temperature was obtained on the basis of geometrical calculation of a particular three-phase triangle. The equation well describes the three-phase behavior for a mixed surfactant system in a space of compositions and temperature.In the mixed surfactant system, the monodisperse solubility of R₁₂EO₈ in oil phase forming a three-phase body is monotonously increased with the rise in temperature, whereas that of R₁₂EO₄ is first increased and then is decreased. Consequently, the sum of both solubilities does not change greatly in a wide range of temperature.     

Formation of fluorinated nonionic surfactant microemulsions in hydrofluorocarbon 134a (HFC 134a)

A structurally related series of fluorinated nonionic oxyethylene glycol surfactants of the type C(m)F(2m+1)(CH(2))(n)O[(CH(2)CH(2)O)(p)H], denoted C(m.n)E(p) (where m=4, 6, or 7, m=1 or 2, and p=4 or 6) were synthesized and their surface behavior in aqueous solution was characterized. The ability of these surfactants to form water-in-hydrofluorocarbon (HFC) propellant 134a microemulsions suitable for use in the aerosolized delivery of water-soluble drugs has been investigated. Phase studies showed that, regardless of the composition used, clear one-phase systems could not be prepared if a fluorinated nonionic surfactant was used alone, or in combination with a short or medium fluorocarbon alcohol cosurfactant. Clear one-phase systems could, however, be prepared if a short-chain hydrocarbon alcohol, such as ethanol, n-propanol, or n-pentanol, was used as cosurfactant, with the extent of the one-phase region increasing with decreased chain length of the alcohol cosurfactant. Light-scattering studies on a number of the hydrocarbon-alcoholcontaining systems in the propellant-rich part of the phase diagram showed that only systems prepared with C(4.2)E(6) and propanol contained microemulsion droplets (all other systems investigated were considered to be cosolvent systems).     

非离子型表面活性剂在SiO2凝胶中的造孔作用

以非离子型表面活性剂C13EO9(或简写为AEO9)为模板剂,在强酸性的乙醇-水体系中通过溶胶-凝胶途径合成SiO2分子筛。结果表明,经焙烧去除模板剂以后的分子筛具有双孔分布的特征,孔径主要集中在2.56nm和13.95nm。经高分辨电镜(HRTEM)和X射线衍射(XRD)测试分析,前者呈有序排列,类似于MSU系列分子筛的孔道结构,而后者则呈无序的排列,它是由胶体粒子聚集而形成的颗粒间孔,并与在相同条件下不加AEO9制备的无定形SiO2凝胶以及用离子型表面活性剂十六烷基三甲基溴化铵(CTAB)代替AEO9为模板剂制备的分子筛进行了比较,二者的孔道结构分别呈无序排列和六方有序排列的单一孔分布特征。     

Thin films of bicontinuous cubic mesostructured silica templated by a nonionic surfactant

Thin films ofbicontinuous cubic mesostructured silica were formed using the nonionic poly(oxyethylene)-alkyl ether surfactant Brij-56 as a structure-directing agent. The synthesis conditions were chosen such that the estimated volume fraction of surfactant in the silica/surfactant films corresponded approximately to the composition at which the bicontinuous cubic phase occurs in the water/surfactant phase diagram. Small-angle X-ray scattering and transmission electron microscopy measurements reveal that the cubic phase corresponds to the Ia3(-)d double-gyroid structure, with some distortion due to anisotropic film shrinkage. The cubic structure grows as faceted domains that are well-oriented with respect to the substrate and often occur in coexistence with a lamellar phase. By adjusting the temperature at which the films are aged, it is possible to create films with 2D hexagonal, cubic, or lamellar structures at a single composition.     

Solvent effect on the aggregate of fluorinated gemini surfactant at silica surface

The aggregate states of partially fluorinated gemini surfactant [(CF3)2CF(CF2)2(CH2)10N(CH3)2]2(CH2)6Br2 (C(F)(5)C10-C6-C10C(F)(5)) on silica surface were investigated with atomic force microscopy (AFM) and water contact angle (CA) measurement by analyzing the effects of bulk concentration and adsorption time on stack state. On surfactant-adsorbed silica surfaces, there was a flat surface layer interspersed with some scattering surfactant aggregates. In the case of short adsorption times, the aggregates would be hemisphere. In the case of long adsorption times, the aggregates would be present in the form of bilayers. With the increase of bulk concentration, the adsorbed amount was enlarged and the surface layer became more compact. The formation of patchy bilayer aggregates indicated the saturation of the surface layer. Furthermore, organic solvent effects on the aggregate state of the surfactant on a silica surface were studied with four organic solvents, including n-hexane, dehydrated ethanol, 1,1,2-trichloro-1,2,2-trifluoroethane, and toluene. With the treatment of different organic solvents, the hemisphere aggregates on the surface layer can rearrange into spherical bilayer, rodlike monolayer, and branched rodlike monolayer aggregates, respectively. The polarity of solvents and affinity of organic solvents for surfactant molecules may have a great impact on the stack state of the fluorinated gemini surfactant molecules.     

Synthesis of mesoporous silica helical fibers using a catanionic-neutral ternary surfactant in a highly dilute silica solution: biomimetic silicification

Mesoporous silica helical fibers in many different shapes have been synthesized in a highly dilute silicate solution at pH approximately 2.0 by using CnTMAB-SDS-P123 (n = 14-18) ternary surfactant as a template. The mesoporous silica helical fibers possess a well-ordered hexagonal mesostructure, high surface area, and large pore volume. Thus, the microtome sections of the helical fibers demonstrate a concentric mesotructure or two hemiconcentric mesostructures. In addition to triblock copolymer, adding the proper amount of 1-butanol or pentanol can promote the yield of the helical fibers as well. The yield of the surfactant-templated helical fibers is also dependent on the water content, reaction temperature, and pH value of the solution. The mesoporous silica helical fiber can be used as a solid template to prepare mesoporous carbon helical fibers via impregnation of phenol-formaldehyde, pyrolysis, and silica removal.     

Cloud point curve of nonionic surfactant related to the structures of mesoporous materials

We have investigated the phase behavior of a fluorinated surfactant R(7)(F)(EO)(7) in water. The cloud point is situated at 19 degrees C for 2 wt% of surfactant. Using this surfactant, mesoporous materials have been synthesized with micellar solution prepared either at 10 degrees C (below the cloud point) or at 40 degrees C (above the cloud point). Results show that whatever the syntheses conditions, only wormhole-like structure is recovered. The effect of perfluorodecalin addition on the fluorinated surfactant/water system was also investigated. Swollen micelles, microemulsion, and lamellar (L(alpha)) liquid crystals were identified. When perfluorodecalin is added, the cloud point is shifted toward higher temperature. As regards the mesoporous syntheses, perfluorodecalin plays a dual role. First, incorporation of perfluorodecalin leads to the formation of well ordered materials. Secondly, the pore size enlargement occurs when perfluorodecalin is added. Our results evidence that the ratio between the volume of the hydrophilic headgroup (V(H)) and the hydrophobic part (V(L)) of the surfactant is not an efficiency parameter to explain the ordering improvement of mesoporous materials and that we should rather consider the existence of the cloud point curve, which disturbs the cooperative templating mechanism (CTM).     

Vesicle formation from temperature jumps in a nonionic surfactant system

When heating a dilute sample of the binary system of tetraethyleneglycol dodecyl ether (C12E4) and water from the micellar phase (L1) into the two-phase region of a lamellar phase (L(alpha)), and excess water (W) vesicles are formed. During heating, one passes a region of phase separation in the micellar phase (L1' + L1') where the initial micelles rapidly fuse into larger aggregates forming the concentrated L1 phase (L1') with a structure of branched cylindrical micelles, a so-called "living network". The static correlation length of the micelles are increasing with increasing concentration, from ca. 10 nm to 80 nm in the concentration range of 0.0001 g/cm3-0.0035 g/cm3. The overlap concentration was determined to 0.0035 g/cm3. When the temperature reaches the L1' + L(alpha) region the network particles transform into bilayer vesicles with a z-average apparent hydrodynamic radius in the order of 200 nm depending on the composition. The size of the final vesicles depends on the extent of aggregation/fusion in the L1' + L1' region and hence on the rate of heating. The aggregation/fusion in the L1' + L1' is slower than diffusion-limited aggregation, and it is shown that 1/100 of the collisions are sticky results in the fusion event.     

Pore-expansion of monodisperse mesoporous silica spheres by a novel surfactant exchange method

By adapting a novel surfactant exchange method, in which surfactants inside mesopores are completely exchanged by surfactants with longer alkyl chain lengths, pore-expansion of monodisperse mesoporous silica spheres (MMSS) with radially ordered hexagonal regularity was attained while retaining spherical morphology and high monodispersity.     

The displacement of adsorbed polymer from silica surfaces by the addition of a nonionic surfactant

The adsorption of polyvinyl alcohol and Synperonic NP8 (nonyl phenol ethoxylate with an average of eight ethylene oxide groups per molecule) on fumed silica has been studied at various pH values. This was followed by an investigation of the competitive adsorption of NP8 and PVA. It was shown that NP8 can displace the polymer from the silica. This was attributed to a higher adsorption energy for the NP8 molecule compared with the value of the individual adsorbed PVA segments. Sediment volume experiments showed that the addition of NP8 to a colloidally stable silica dispersion with adsorbed PVA can induce flocculation as a result of displacement of some or all of the PVA chains from the surface. Initially the adsorption of the NP8 molecules caused an increase in the hydrophobic interaction (resulting in the flocculation) between the alkyl phenol groups which are oriented towards the bulk solution (since the PEO chains preferentially adsorb on the silica surface). Restabilisation at higher NP8 concentrations occur through the formation of bilayers with the PEO chains now dangling in solution.     

Nonionic fluorinated surfactant: investigation of phase diagram and preparation of ordered mesoporous materials

The behavior of fluorinated surfactant F(CF2)8C2H4(OC2H4)9OH in water solution was investigated, and the preparation ofmesoporous molecular sieves was achieved. A direct micellar phase (L1) and a hexagonal (H1) liquid crystal were found. Small-angle X-ray scattering measurements proved that the hydrophobic chains are completely extended and that the cross sectional area remains constant in H1. At 80 degrees C, materials with a hexagonal array of their channel are prepared via a cooperative templating type mechanism in a wide range of surfactant concentrations (5-20 wt %). Decreasing the hydrothermal temperature leads to the formation ofwormhole-like structure. In this case the channel arrangement is no longer governed by the surfactant behavior but by the silica condensation and polymerization. An increase of the mean pore diameter with heating temperature is noted. This result is associated with changes of aggregation number with temperature. A comparison of the characteristics of the materials obtained with both hydrogenated and fluorinated surfactants is also made.