Characterization of the initial stages of SBA-15 synthesis by in situ time-resolved small-angle X-ray scattering

The initial stages of SBA-15 synthesis have been studied by using in situ time-resolved small-angle X-ray scattering with a synchrotron radiation source. The quantitative analysis of X-ray scattering and diffraction intensities allows the structures of intermediates to be identified at the different stages of SBA-15 synthesis. Following tetraethylorthosilicate (TEOS) addition, an intense small-angle scattering and an associated secondary maximum are observed, which are attributed to non-interacting surfactant template micelles encrusted with silicate species. After 25-30 min of the reaction, the broad scattering disappears and narrow Bragg diffraction peaks typical of hexagonally ordered structure are observed. The cylindrical micelles identified from X-ray scattering data appear to be the direct precursors of 2D hexagonal SBA-15 structure. Just after the formation of the SBA-15 hexagonal phase, the cylindrical micelles are only weakly linked in the hexagonal structure. As the synthesis proceeds, the solvent in the void volume between the cylindrical micelles is gradually replaced by more dense silicate species. The unit cell parameter of SBA-15 is progressively decreasing during the SBA-15 synthesis, which can be related to the condensation and densification of silicate fragments in the spaces between the cylinders. The volume fraction of the 2D hexagonally ordered phase is sharply growing during the first 2 h of the reaction. The inner core radius of SBA-15 material remains almost constant during the whole synthesis and is principally affected by the size of the poly(propylene oxide) inner core in the original cylindrical micelles.     

Small angle neutron scattering studies on micellar systems part 1. Ammonium octanoate,ammonium decanoate and ammonium perfluoroocatanoate

Small angle neutron scattering has been used to examine the size and shape of micelles of ammonium octanoate, ammonium decanoate and ammonium perfluoro-octanoate. Ammonium octanoate was found to form micelles with a micellar weight of 1640 and ammonium decanoate with a micellar weight of 12,576; both materials appeared to form spherical micelles. Ammonium perfluoro-octanoate formed micelles with a micellar weight of 17,610. Evidence from the scattering experiments suggested that the micelles were cylindrical and a model for the micelle is proposed.     

Time-resolved in situ studies of the formation of cubic mesoporous silica formed with triblock copolymers

The mechanism of formation of two different cubic mesoporous silica materials formed with Pluronic triblock copolymers is investigated with in situ time-resolved small-angle synchrotron X-ray scattering, in situ time-resolved 1H nuclear magnetic resonance, and time-resolved transmission electron microscopy. The materials studied are the micellar cubic (Imm) SBA-16 formed with Pluronic F108 and the bicontinuous cubic (Iad) silica material formed with Pluronic P103 and NaI. The formation mechanisms of the two cubic structures are shown to be dissimilar. For the Imm material, in the early stages of the synthesis, flocs of unordered micelles are observed, but areas where the micelles have started to order are also present. With time, there is an increase in order; however, there is a coexistence of unordered micelles and ordered material all through this study. The bicontinuous cubic silica is formed via a different path. The system is phase-separated already before the addition of the silica source, which implies that a concentrated phase is present, acting as the structure director of the Iad structure. The results are compared with earlier reports on the formation of the hexagonal SBA-15 material.     

New insights into the initial steps of the formation of SBA-15 materials: an in situ small angle neutron scattering investigation

Time-resolved in situ SANS investigations have provided direct experimental evidence for the three initial steps in the formation of the SBA-15 mesoporous material: an induction period is followed by a shape transformation of the micelles from spherical to cylindrical ones followed by the precipitation of a two-dimensional hexagonal phase.     

Structural characterization of surfactant aggregates adsorbed in cylindrical silica nanopores

The self-assembly of nonionic surfactants in the cylindrical pores of SBA-15 silica with a pore diameter of 8 nm was studied by small-angle neutron scattering (SANS) at different solvent contrasts. The alkyl ethoxylate surfactants C(10)E(5) and C(12)E(5) exhibit strong aggregative adsorption in the pores as indicated by the sigmoidal shape of the adsorption isotherms. The SANS intensity profiles can be represented by a sum of two terms, one accounting for diffuse scattering from surfactant aggregates in the pores and the other for Bragg scattering from the pore lattice of the silica matrix. The Bragg reflections are analyzed with a form factor model in which the radial density profile of the surfactant in the pore is approximated by a two-step function. Diffuse scattering is represented by a Teubner-Strey-type scattering function which indicates a preferred distance between adsorbed surface aggregates in the pores. Our results suggest that adsorption starts with formation of discrete surface aggregates which increase in number and eventually merge to interconnected patches as the plateau value of the adsorption isotherm is approached. A grossly different behavior, viz. formation of micelles as in solution, is found for the maltoside surfactant C(10)G(2), in agreement with the observed weak adsorption of this surfactant in SBA-15.     

Supramolecular self-assembly of multiblock copolymers in aqueous solution

A unique pH-dependent phase behavior from a copolymer micellar solution to a collapsed hydrogel with micelles ordered in a hexagonal phase was observed. Small-angle neutron scattering (SANS) was used to follow the pH-dependent structural evolution of micelles formed in a solution of a pentablock copolymer consisting of poly((diethylaminoethyl methacrylate)-b-(ethylene oxide)-b-(propylene oxide)-b-(ethylene oxide)-b-(diethylaminoethyl methacrylate)) (PDEAEM25-b-PEO100-b-PPO65-b-PEO100-b-PDEAEM25). Between pH 3.0 and pH 7.4, we observed the presence of charged spherical micelles. Increasing the pH of the micelle solution above pH 7.4 resulted in increasing the size of the micelles due to the increasing hydrophobicity of the PDEAEM blocks above their pKa of 7.6. The increase in size of the spherical micelles resulted in a transition to a cylindrical micelle morphology in the pH range 8.1-10.5, and at pH >11, the copolymer solution undergoes macroscopic phase separation. Indeed, the phase separated copolymer sediments and coalesces into a hydrogel structure that consists of 25-35 wt % water. Small-angle X-ray scattering (SAXS) clearly indicated that the hydrogel has a hexagonal ordered phase. Interestingly, the process is reversible, as lowering of the pH below 7.0 leads to rapid dissolution of the solid into homogeneous solution. We believe that the hexagonal structure in the hydrogel is a result of the organization of the cylindrical micelles due to the increased hydrophobic interactions between the micelles at 70 degrees C and pH 11. Thus we have developed a pH-/temperature-dependent, reversible hierarchically self-assembling block copolymer system with structures spanning nano- to microscale dimensions.     

混合稀电解质条件下合成球状SBA-15粒子

在酸性合成法基础上, 不添加有机共溶剂和其它模板剂, 通过加入少量NH4F和Cu(NO3)2得到了分散的球状形貌SBA-15粒子. 对所得样品用小角X射线衍射(XRD)、N2吸脱附曲线、扫描电镜(SEM)进行表征, 讨论了不同电解质对样品形貌和孔结构的影响. 结果发现, 随着酸浓度增加, 得到了分散的规则六边形SBA-15粒子, 而加入一定量的氟化铵则得到了球形纠结状形貌的SBA-15. 实验表明, 氟离子在形成球状粒子的过程中起主要作用, 而Cu2+阻碍了球状粒子的纠结. 随着Cu2+浓度的增加, 部分硅源不能参与自组装生成SBA-15, 其原因可能是Cu2+与模板剂中亲水的聚氧乙烯形成PEO/Cu2+端基, 影响了硅源正常的缩聚.     

Mechanism of mesoporous silica formation. A time-resolved NMR and TEM study of silica-block copolymer aggregation

The dynamics of the synthesis of a mesoporous silica material SBA-15 is followed using time-resolved in situ 1H NMR and transmission electron microscopy (TEM). Block copolymer-silica particles of two-dimensional hexagonal symmetry evolve from an initially micellar solution. The synthesis was carried out with the block copolymer Pluronic P123 (EO20-PO70-EO20) at 35 degrees C and using tetramethyl orthosilicate as the silica precursor. By using TEM, we can image different stages during the evolution of the synthesis. Flocs of spherical micelles held together by the polymerizing silica are observed prior to precipitation. With time, the structure of these flocs evolves and the transition from spherical to cylindrical hexagonally packed micelles can be monitored. The signal from the methyl protons of the PO part was recorded with 1H NMR. One observes a continuous increase in the signal width but with distinct changes in the spectral characteristics occurring in narrow time intervals. The spectral changes can be attributed to structural changes of the self-assembled aggregates. The 1H NMR and TEM studies reveal the same mechanism of formation. It is concluded that the aggregation is caused by a micelle-micelle attraction induced by oligomeric/polymeric silica that adsorbs to the EO palisade layer of the micelles and has the ability to bridge to another micelle. This adsorption also favors the formation of cylindrical aggregates relative to spherical micelles. The sequence of NMR and TEM observations can then be interpreted as the following sequence of events: (i) silicate adsorption on globular micelles possibly accompanied with some aggregate growth, (ii) the association of these globular micelles into flocs, (iii) the precipitation of these flocs, and (iv) micelle-micelle coalescence generating (semi)infinite cylinders that form the two-dimensional hexagonal packing.     

Continuous synthesis process of hexagonal nanoplates of P6m ordered mesoporous silica

Hexagonally ordered mesoporous silica coined COK-12 was synthesized in a continuous process by combining streams of sodium silicate and citric acid/sodium citrate buffered solution of (ethylene oxide)(20)-(propylene oxide)(70)-(ethylene oxide)(20) triblock copolymer (Pluronic P123) from separate reservoirs. COK-12 precipitated spontaneously upon combining both streams at nearly neutral pH and ambient temperature. Stable intermediates of the COK-12 formation process could be prepared by limiting sodium silicate addition. Investigation of these intermediates using small-angle X-ray scattering revealed COK-12 formed via an assembly process departing from spherical uncharged core-shell P123-silica micelles. The sterical stabilization of these micelles decreased upon accumulation of silicate oligomers in their shell. Aggregation of the spherical micelles led to cylindrical micelles, which aligned and adopted the final hexagonal organization. This unprecedentedly fast formation of P6m ordered mesoporous silica was caused by two factors in the synthesis medium: the neutral pH favoring uncharged silicate oligomers and the high salt concentration promoting hydrophobic interactions with surfactant micelles leading to silica accumulation in the PEO shell. The easy continuous synthesis process is convenient for large-scale production. The platelet particle morphology with short and identical internal channels will be advantageous for many applications such as pore replication, nanotube or fiber growth, catalytic functionalization, drug delivery, film and sensor development, and in nano dyes as well as for investigation of pore diffusion phenomena.     

Patchy worm-like micelles: solution structure studied by small-angle neutron scattering

Triblock terpolymers exhibit a rich self-organization behavior including the formation of fascinating cylindrical core-shell structures with a phase separated corona. After crystallization-induced self-assembly of polystyrene-block-polyethylene-block-poly(methyl methacrylate) triblock terpolymers (abbreviated as SEMs = Styrene-Ethylene-Methacrylates) from solution, worm-like core-shell micelles with a patchy corona of polystyrene and poly(methyl methacrylate) were observed by transmission electron microscopy. However, the solution structure is still a matter of debate. Here, we present a method to distinguish in situ between a Janus-type (two faced) and a patchy (multiple compartments) configuration of the corona. To discriminate between both models the scattering intensity must be determined mainly by one corona compartment. Contrast variation in small-angle neutron scattering enables us to focus on one compartment of the worm-like micelles. The results validate the existence of the patchy structure also in solution.     

Structure and diffusion characterization of SBA-15 materials

In situ formation of the micro- and mesoporous structures of SBA-15 materials was investigated. It was found that the structure is significantly different from that for cylindrical or hexagonal pores, which suggests that the SBA-15 is more complex than an array of hexagonally ordered channels. Nitrogen adsorption isotherms at 77 K provided evidence that large (primary) mesopores are accompanied by a certain amount of significantly smaller pores with a broad distribution in the micropore/small-mesopore range within the mesoporous walls of main channels. It was found that the microporosity can be controlled by the time of heating as well as the synthesis temperature. The diffusion properties of n-heptane as a probe molecule in four selected SBA-15 samples with different micropore volumes were studied by the standard zero length column technique and related to their structural characteristics. The results have shown that the diffusion process involving n-heptane at a low concentration level takes place inside the walls of main mesoporous channels and depends on the relative content of micropores. In the samples that have a relatively high content of micropores, n-heptane diffusivities are relatively low, their activation energies are high, and the process is similar to diffusion in typical microporous adsorbents, like zeolites. As the micropore content is decreased, diffusion becomes more and more controlled by secondary mesopores of the intrawall pore structure, rendering diffusion faster and activation energies lower.     

Morphological manipulation of ionic block copolymer micelles using an electric field

We present an electric-field-triggered sphere-to-cylinder transition of negatively charged block copolymer micelles with a radically low electric field of 30 V/cm. The system investigated is dilute solutions of strong polyelectrolyte containing ionic-b-neutral block copolymers (i.e., poly(styrenesulfonate-b-methylbutylene)). We have carried out in situ small-angle X-ray scattering experiments equipped with a dc power supply, combined with electron microscopy and atomic force microscopy. The application of small electrical fields across the solutions of spherical micelles results in the transient morphology of interconnected spheres, which are eventually transformed into a cylindrical shape with time. The E-field-induced cylindrical micelles revert to spherical micelles when the E field is switched off.     

Micelle structure in isotropic aqueous colloids of a poly(oxyethylene) amphiphile C12E8

Micelle structure in aqueous colloids in the isotropic liquid phase (L₁) of a nonionic amphipile (n-dodecyl octa(oxyethylene glycol) monoether (C₁₂E₈) has been investigated as a function of concentration and temperature using light scattering (LS), viscometry, NMR, and small-angle X-ray scattering (SAXS).The spherical micelles, having a radius of 28–31 Å, remain in a wide concentration range from very dilute to ca. 42 wt %. The micelle size increases sligthly with increasing temperature in the range of 25–60 °C. In the concentrated colloids, the spherical micelles are likely to be arranged in a certain ordered structure. Even at such a high concentration as 30 wt %, the isotropic colloid shows Newtonian flow. This suggests that interaction between micelles in the ordered structure is very weak and the structure is very fragile. Moreover, coexistence of the isotropic phase and the ordered structure in L₁ phase is discussed.     

Zinc ion induced polymorphism in macromolecular self-assembly of diblock copolymers

A novel interconnected cylindrical micellar network was prepared from a diblock copolymer, poly(maleic anhydride-alt-styrene)-b-polystyrene, in ethanol under a self-assembly directing agent: Zn²⁺ ions. The solution containing interconnected cylindrical network is bluish and transparent, which is stable for more than 6 months at room conditions without any observable macroscopic phase separation. In aqueous solution, however, hydrolysis of the anhydride yields hydrophilic carboxyl groups, which result in formation of uniform positive spherical micelles from the same diblock polymer. The nanostructures of both the spherical micelles and cylindrical assemblies are characterized with light scattering and transmission electron microscopy (TEM).     

Shape transformation of poly(butadiene)‐b‐poly(ethyleneoxide) plus DTAB compound micelles in aqueous solutions

The micellar shape of Poly(butadiene)‐b‐poly(ethyleneoxide) (PB‐PEO) plus Dodecyltrimethylammoniumbromide (DTAB) compound micelles was investigated by light scattering, small‐angle X‐ray scattering and small‐angle neutron scattering in dependence of the molar ratio between block copolymer and surfactant. The given block copolymer forms cylindrical micelles in binary aqueous solution, which transform to spherical aggregates upon the addition of a sufficiently high amount of DTAB. It is interesting to note that the micellar shape seems to be a bistable feature, in the sense that it depends not only on the molar ratio of BCP and DTAB but also in a predictable manner on the preparation procedure of the solution.     

Designed synthesis of nanostructured siloxane-organic hybrids from amphiphilic silicon-based precursors

This paper reports on recent progress in the synthesis of nanostructured siloxane-organic hybrids based on the self-assembly of amphiphilic silicon-based precursors. A variety of ordered hybrid materials have been obtained by molecular design of the precursors. Alkoxysilanes and chlorosilanes with covalently attached hydrophobic organic tails are hydrolyzed to form amphiphilic molecules containing silanol groups, leading to the formation of layered (lamellar) structures. Transparent and oriented thin films of lamellar hybrids were prepared by the reaction in the presence of tetraalkoxysilane. In addition, the design of molecules having alkyl chains and large oligosiloxane heads led to the formation of mesophases consisting of cylindrical assemblies, providing a direct pathway to ordered porous silica. The synthesis, structural features, and formation processes of these hybrid mesostructures are discussed.     

The role played by salts in the formation of SBA-15, an in situ small-angle X-ray scattering/diffraction study

The influence of salts (NaCl, NaBr, and NaI) on the formation of mesoporous silica SBA-15 was studied in situ by small-angle X-ray scattering and diffraction. Pluronic P104 was used as structure director. The micellar properties and the dynamics of formation were clearly dependent on the presence of salt. It was also shown that the kinetics of mesophase formation, the initial value of the cell parameters, and the extent of long-range order were all influenced by salt additions. The observations are explained to primarily originate from the influence of the anions on the ethylene oxide part of the polymer, i.e., the corona region of the Pluronic micelles. Two effects are identified: a general ion effect causing dehydration of the ethylene oxide part and consequently inducing micellar growth, and a specific ion effect that counterbalances this. The study provides the basis for understanding the means by which addition of simple Na-salts influence the formation of mesoscopically ordered silicas synthesized using nonionic surfactants as structure directors, hence advancing the knowledge base toward a more rational design of mesoporous materials.     

Structure and dynamics of concentrated micellar solutions of sodium dodecyl sulfate

In micellar solutions of sodium dodecyl sulfate, as the concentration of surfactants increases, the spheroid shape of the micelles changes from almost spherical to ellipsoidal with increasing ratio of half-axes ratio, and further the transition to cylindrical micelles occurs. The micelles in an aqueous solution can directly contact (compact aggregates) or be separated from one another by layers of intermicellar medium (periodical colloid structures). In the latter case, the thickness of the layer can significantly exceed the micelle size, and then no mutual correlation in micelle arrangement is observed. According to the data of small-angle X-ray scattering, the relationship between the surfactant concentration and formation of “quasi-crystalline” micellar structure is nonlinear, which can be due to both micelle aggregation processes and nonuniformity of their structure. The possible influence of ordered micellar structures on the diffusion mobility of micelles is shown.