In situ SAXS study on a new mechanism for mesostructure formation of ordered mesoporous carbons: thermally induced self-assembly

A new mechanism for mesostructure formation of ordered mesoporous carbons (OMCs) was investigated with in situ small-angle X-ray scattering (SAXS) measurements: thermally induced self-assembly. Unlike the well-established evaporation-induced self-assembly (EISA), the structure formation for organic-organic self-assembly of an oligomeric resol precursor and the block-copolymer templates Pluronic P123 and F127 does not occur during evaporation but only by following a thermopolymerization step at temperatures above 100 °C. The systems investigated here were cubic (Im3m), orthorhombic Fmmm) and 2D-hexagonal (plane group p6mm) mesoporous carbon phases in confined environments, as thin films and within the pores of anodic alumina membranes (AAMs), respectively. The thin films were prepared by spin-coating mixtures of the resol precursor and the surfactants in ethanol followed by thermopolymerization of the precursor oligomers. The carbon phases within the pores of AAMs were made by imbibition of the latter solutions followed by solvent evaporation and thermopolymerization within the solid template. This thermopolymerization step was investigated in detail with in situ grazing incidence small-angle X-ray scattering (GISAXS, for films) and in situ SAXS (for AAMs). It was found that the structural evolution strongly depends on the chosen temperature, which controls both the rate of the mesostructure formation and the spatial dimensions of the resulting mesophase. Therefore the process of structure formation differs significantly from the known EISA process and may rather be viewed as thermally induced self-assembly. The complete process of structure formation, template removal, and shrinkage during carbonization up to 1100 °C was monitored in this in situ SAXS study.     

In-situ study of sol–gel processing by time-resolved infrared spectroscopy

Sol–gel processing of thin films involves time dependent phenomena which are basically driven by solvent evaporation. An example is evaporation induced self-assembly that is used to prepare mesoporous ordered films through self-organization of templating micelles. The possibility to follow in situ as a function of time the evolution of the system can give a better knowledge of the process and the physics and chemistry beneath. Time-resolved infrared techniques have been applied to different sol–gel systems to study time-dependent phenomena, in particular rapid scan time resolved infrared spectroscopy has been used to monitor in situ the process and as a tool to design the sol–gel synthesis.     

Y2O3和Nd2O3介孔薄膜的制备与表征

以聚乙烯合丁烯-嵌-聚氧乙烯嵌段共聚物(PHB-PEO)作模板, 采用蒸发诱导自组装方法, 分别制备了Y2O3和Nd2O3介孔薄膜. 用小角、广角X射线衍射和透射电子显微镜对薄膜样品在不同的热处理阶段进行了表征. 结果表明, 所制备的Y2O3和Nd2O3薄膜样品呈现一种大孔径(平均孔径分别约为11.5和12.5 nm)、有序的立方扭曲球形孔排列、稳定于450 ℃并具有部分晶态孔壁结构的介孔薄膜材料.     

Formation of zein spheres by evaporation-induced self-assembly

Zein is an amphiphilic protein capable of self-assembly into microspheres. Zein microspheres may form by evaporation-induced self-assembly (EISA) of zein solutions in ethanol/water. The formation of microspheres is of particular interest for the development of delivery systems. Zein solutions in ethanol/water 75?% (v/v) were slowly evaporated to promote self-assembly of microspheres. The ethanol content of the solvent decreased during EISA changing solvent polarity which induced self-assembly of zein particles. The growth of zein spheres was modeled from the hydrophobic and hydrophilic contributions to the interfacial free energy (R ²?=?0.92). The good fit indicated that during EISA zein microspheres increased in size due to hydrophobic interactions between zein molecules. The model may allow the prediction of evaporation time and thus control over microsphere size.     

Macroscopic, free-standing ag-reduced, graphene oxide janus films prepared by evaporation-induced self-assembly

A facile, efficient, and unique self-assembly process for the preparation of the macroscopic, free-standing, Ag-reduced, graphene oxide (Ag-RGO) Janus films, which exhibit a unique asymmetry of their two surfaces with macroscopic dimensions, is presented. A novel strategy using an evaporation-induced, self-assembly (EISA) process is shown to be a powerful and flexible method for synthesizing well-defined Janus thin films.     

Fabrication of Honeycomb-Structured Poly(DL-lactide) and Poly[(DL-lactide)-co-glycolide)] Films and their Use as Scaffolds for Osteoblast-Like Cell Culture

Summary: Surfactant-free honeycomb-structured Poly(DL lactide) (PDL LA) and Poly-(DL lactide-co-glycolide) PDL LGA thin films were fabricated by water droplet templating methods. Thin films with uniform pore structure were obtained after controlled evaporation of solvents in a humid atmosphere. Solvent, polymer concentration and humidity were found to be important factors in the formation of honeycomb-structured thin films. Preliminary cell culture studies with MG-63 osteoblast-like cell lines showed promising degrees of cell attachment and proliferation on these films, suggesting that they are applicable as scaffolds for tissue engineering.     

Hierarchical mesostructures of biodegradable triblock copolymers via evaporation-induced self-assembly directed by alkali metal ions

Hierarchical mesostructures of poly(ε-caprolactone)-b-poly(ethylene oxide)-b-poly(ε-caprolactone) (PCL-PEO-PCL) triblock copolymers have been grown from evaporation-induced self-assembly directed by alkali metal ions. The self-assembly process began with a dilute homogeneous solution of the triblock copolymers in a mixture of tetrahydrofuran (THF) and water. THF preferentially evaporated under reduced pressure and induced the formation of amphiphilic polymer micelles. The spherical polymer micelles formed both in deionized water and NaOH aqueous solution. However, different mesostructures were discovered during the film depositing process for scanning electron microscopy observation. The polymer micelles were observed for the deposition sample in deionized water while sisal-like hierarchical mesostructures resulted from the film deposition of polymer micelles in NaOH aqueous solution. The sisal-like mesostructures and their formation process were observed through scanning electron microscopy, transmission electron microscopy, fluorescent microscopy, X-ray diffraction, and Fourier transform infrared spectroscopy. Detailed study revealed that during evaporation-induced self-assembly of PCL-PEO-PCL amphiphilic triblock copolymer directed by alkali metal ions, the sodium ions and polymer micelles increasingly concentrated in NaOH aqueous solution and the solvent quality for the diblock progressively decreased, which resulted in the stronger coordination between alkali metal ions and PEO ligands in the block copolymer and PEO segment crystallization.     

Instabilities during the formation of electroactive polymer thin films

The solvent-induced film structure of poly(n-vinyl carbazole) (PVK) thin films on indium tin oxide (ITO)-coated glass was examined. PVK thin films were prepared via spin-coating using five different solvents. We investigated the relationship between the solvent characteristics and film properties, including surface roughness and structure, film thickness, and density. The spin-coated polymer thin films are not in thermodynamic equilibrium; rather, the film properties are affected by the dynamics of the spin-coating process. We found that water present in tetrahydrofuran (THF) induces dewetting of PVK films during the spin-coating process. Solvents with a high evaporation rate lead to high surface roughness due to Marangoni convection. The results show that the surface roughness and structure of the films are dominated by the dynamics of the film formation process, rather than thermodynamic interactions between the polymer and solvents.     

Design and post-functionalisation of ordered mesoporous zirconia thin films

Bidimensional hexagonal or centred-rectangular mesoporous zirconia thin films have been reproducibly prepared by evaporation-induced self-assembly (EISA), which are stable up to 300 degrees C, with pore size around 35 A; the films can be post-functionalised with organic ligands presenting different functions, opening a land of opportunities for the design of new hybrid mesostructured materials, based on the synergy of a transition metal oxide network and organic groups.     

Surfactant removal and silica condensation during the photochemical calcination of thin film silica mesophases

The evolution of photochemical surfactant removal and silica condensation from organically templated thin film silica nanocomposites with mesoscopic ordering has been probed using a combined application of Fourier transform infrared (FT-IR) spectroscopy and single wavelength ellipsometry. Thin films of silica nanocomposites were prepared by a previously reported evaporation-induced self-assembly process. Specifically, oxidized silicon and gold substrates were withdrawn at 25 mm/min from a subcritical micelle concentration solution containing an ethylene oxide surfactant as a structure-directing agent and tetraethyl orthosilicate as a silica precursor. Real-time grazing incidence difference FT-IR spectra of the nanocomposite films on gold taken during exposure to short-wavelength ultraviolet light (184-257 nm) show that surfactant removal and silica condensation occur gradually and concomitantly. Surfactant removal and silica reconstructions were found to be nearly complete after 90 min of exposure. Further, a transient feature was observed in the FT-IR spectra around 1713 cm(-1) during the UV exposure process and was assigned to a carbonyl (C=O) stretching mode absorption, reflecting the transient formation of a partially oxidized surfactant intermediate. From these data we propose a stepwise model for surfactant removal from the nanocomposite films. Ellipsometrically determined index of refraction values collected as a function of UV exposure are also shown to support such a stepwise mechanism of surfactant removal from the ordered nanocomposite silica thin film mesophases studied here.     

Phase transformation during cubic mesostructured silica film formation

The structural evolution taking place during CTAB/TEOS based solvent evaporation-induced thin film formation has been followed by in-situ time-resolved SAXS; this shows that the final Pm3n cubic structure is formed via the formation of lamellar and hexagonal intermediate structures within the water rich evaporation regime.     

Hidden cavity formations by nanocrystalline self-assembly on various substrates with different hydrophobicities

The effect of surface hydrophobicity is examined in the formation of hidden complex cavities during evaporation-induced nanocrystalline self-assembly taking place on three different substrates bearing different levels of hydrophobicity, namely, cover glass (CG), a gold thin film (Au), and a polystyrene dish (PS). It turns out that the DLVO theory, the relative thermal conductivities between the substrate and nanofluids, and the relationship between the evaporation and the radial outflow motions of nanoparticles comprehensively explain why the number of cavity cells is proportional to nanoparticle concentration and inversely proportional to surface hydrophobicity.     

A pure aqueous route to mesoporous silica thin films via dip-coating of prefabricated hybrid micelles

Journal of Sol-Gel Science and Technology - Mesoporous thin films were prepared by dip-coating with a purely aqueous method, as a substitute for the alcohol-based evaporation-induced self-assembly...     

Kinetics of polycondensation reactions during self-assembly of mesostructured films studied by in situ infrared spectroscopy

In situ synchrotron FTIR experiments have been performed during evaporation-induced self-assembly (EISA) of mesoporous films and the role of silica polycondensation in obtaining highly organized mesostructures has been illuminated.     

Ethanol-assisted graphene oxide-based thin film formation at pentane-water interface

Graphene oxide (GO) can be viewed as an amphiphilic soft material, which form thin films at organic solvent-water interfaces. However, organic solvent evaporation provides little driving force, which results in slow GO transfer in aqueous phase, thus dawdling GO film formation processes for various potential applications. We present an ethanol-assisted self-assembly method for the quick formation of GO or GO-based composite thin films with tunable composition, transmittance, and surface resistivity at pentane-water interface. The thickness of pure GO and reduced GO (rGO) films ranging from ~1 nm to more than 10 nm can be controlled by the concentration of GO in bulk solution. The transmittance of rGO films can be tuned from 72% to 97% at 550 nm while the surface resistivity changes from 8.3 to 464.6 kΩ sq(-1). Ethanol is essential for achieving quick formation of GO thin films. When ethanol is injected into GO aqueous dispersion, it serves as a nonsolvent, compromising the stability of GO and providing driving force to allow GO sheets aggregate at the water-pentane interface. On the other hand, neither the evaporation of pentane nor the mixing between ethanol and water provides sufficient driving forces to allow noteworthy amount of GO sheets to migrate from the bulk aqueous phase to the interface. This method can also be extended to prepare GO-based composites thin films with tunable composition, such as GO/single walled carbon nanotube (SWCNT) composite thin films investigated in this work. Reduced GO/SWCNT composite films show much lower surface resistivity compared to pure rGO thin films. This ethanol-assisted self-assembly method opens opportunities to design and fabricate new functional GO-based hybrid materials for various potential applications.     

Evaporation of water droplets on "lock-and-key" structures with nanoscale features

Highly ordered poly(dimethylsiloxane) microbowl arrays (MBAs) and microcap arrays (MCAs) with "lock-and-key" properties are successfully fabricated by self-assembly and electrochemical deposition. The wetting properties and evaporation dynamics of water droplets for both cases have been investigated. For the MBAs case, the wetting radius of the droplets remains unchanged until the portion of the droplet completely dries out at the end of the evaporation process. The pinning state extends for more than 99.5% of the total evaporation time, and the pinning-shrinking transition is essentially prevented whereas in the case of the MCAs the contact radius exhibits distinct stages during evaporation and the contact line retreats significantly in the middle of the evaporation process. We explain the phenomenon by a qualitative energy balance argument based on the different shrinkage types of the nanoscale-folded contact line.     

Colloidal transport phenomena of milk components during convective droplet drying

Material segregation has been reported for industrial spray-dried milk powders, which indicates potential material migration during drying process. The relevant colloidal transport phenomenon and the underlying mechanism are still under debate. This study extended the glass-filament single droplet drying technique to observe not only the drying behaviour but also the dissolution behaviour of the correspondingly dried single particle. At progressively longer drying stage, a solvent droplet (water or ethanol) was attached to the semi-dried milk particle and the interaction between the solvent and the particle was video-recorded. Based on the different dissolution and wetting behaviours observed, material migration during milk drying was studied. Fresh skim milk and fresh whole milk were investigated using water and ethanol as solvents. Fat started to accumulate on the surface as soon as drying was started. At the initial stage of drying, the fat layer remained thin and the solubility of the semi-dried milk particle was much affected by lactose and protein present underneath the fat layer. Fat kept accumulating at the surface as drying progressed and the accumulation was completed by the middle stage of drying. The results from drying of model milk materials (pure sodium caseinate solution and lactose/sodium caseinate mixed solution) supported the colloidal transport phenomena observed for the milk drying. When mixed with lactose, sodium caseinate did not form an apparent solvent-resistant protein shell during drying. The extended technique of glass-filament single droplet approach provides a powerful tool in examining the solubility of individual particle after drying.     

Water adsorption-desorption isotherms of two-dimensional hexagonal mesoporous silica around freezing point

Zr-doped mesoporous silica with a diameter of approximately 3.8 nm was synthesized via an evaporation-induced self-assembly process, and the adsorption-desorption isotherms of water vapor were measured in the temperature range of 263-298 K. The measured adsorption-desorption isotherms below 273 K indicated that water confined in the mesopores did not freeze at any relative pressure. All isotherms had a steep curve, resulting from capillary condensation/evaporation, and a pronounced hysteresis. The hysteresis loop, which is associated with a delayed adsorption process, increased with a decrease in temperature. Furthermore, the curvature radius where capillary evaporation/condensation occurs was evaluated by the combined Kelvin and Gibbs-Tolman-Koening-Buff (GTKB) equations for the modification of the interfacial tension due to the interfacial curvature. The thickness of the water adsorption layer for capillary condensation was slightly larger, whereas that for capillary evaporation was slightly smaller than 0.7 nm.     

Self-assembly of an environmentally responsive polymer/silica nanocomposite

Thermoresponsive nanocomposite thin films composed of alternating layers of silica and polymerized N-isopropylacrylamide (NIPAM) or NIPAM plus dodecyl methacrylate (DM) hydrogels were prepared by surfactant-directed evaporation-induced self-assembly (EISA). During EISA, the organic monomers partition within the hydrophobic domains of a lamellar mesophase. In-situ polymerization via a free radical process results in a 1-2 nm thick hydrogel phase sandwiched between layers of silica oriented parallel to the substrate surface. The thermoresponsiveness of PNIPAM is preserved in this confined environment, and the polymeric layers reversibly swell and deswell by a factor of 2 in water upon temperature changes around the transition temperature of PNIPAM (32 degrees C). The composition, mesostructure, and environmental response were studied by detailed NMR, TGA, and SAXS analyses.     

Nonstationary evolution of the size,composition, and temperature of microdroplets of nonideal two- and three-component aqueous solutions

Results of numerical solution have been presented for a set of equations describing the nonstationary and nonisothermal growth or evaporation of microdroplets consisting of ethanol and water, sulfuric acid and water, and sulfuric and nitric acids and water. Time dependences of droplet size, temperature, and composition have been determined at low concentrations of a condensable vapor, as compared with the concentration of a carrier gas in an ambient vapor–gas mixture. The calculations have been performed using different initial conditions and approximations for the dependences of saturation vapor pressures, activity coefficients, and partial heats of condensation of the components, as well as average volumes per molecule on droplet composition and temperature. By the examples of ethanol–water and sulfuric acid–water droplets, it has been shown that nonmonotonic variations in the droplet radius are possible. Regimes of nonmonotonic variations in the temperature of a droplet that precede the onset of its stationary growth or evaporation have been revealed for all systems under consideration.