Fundamentals of Mesostructuring Through Evaporation-Induced Self-Assembly†
TL;DR: In this paper, the meso-organization of thin silica films using tetraethylorthosilicate (TEOS) as the inorganic source and cetyltrimethylammonium bromide (CTAB) as structuring agent is investigated.
Abstract: This article gives an overall view of the mechanisms involved in the mesostructuring that takes place during the formation of surfactant-templated inorganic materials by evaporation. Since such a method of preparation is well suited to fabricating thin films by dip coating, spin coating, casting, or spraying, it is of paramount interest to draw a general description of the processes occurring during the formation of self-assembled hybrid organic/inorganic materials, taking into account all critical parameters. The following study is based on very recent works on the meso-organization of thin silica films using tetraethylorthosilicate (TEOS) as the inorganic source and cetyltrimethylammonium bromide (CTAB) as the structuring agent, but we will show that the method can also be extended to other systems based on non-silica oxides and block copolymer surfactants. We demonstrate that the organization depends mainly on the chemical composition of the film when it reaches the modulable steady state (MSS), where the inorganic framework is still flexible and the composition is stable after reaching an equilibrium in the diffusion of volatile species. This MSS state is generally attained seconds after the drying line, and the film's composition depends on various parameters: the relative vapor pressures in the environment, the evaporation conditions, and the chemical conditions in the initial solution. Diagrams of textures, in which the stabilized structures are controlled by local minima, are proposed to explain the complex phenomena associated with mesostructuring induced by evaporation.
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TL;DR: Materials found in nature combine many inspiring properties such as sophistication, miniaturization, hierarchical organizations, hybridation, resistance and adaptability to propose more reliable, efficient and environment-respecting materials requires a multidisciplinary approach.
Abstract: Materials found in nature combine many inspiring properties such as sophistication, miniaturization, hierarchical organizations, hybridation, resistance and adaptability. Elucidating the basic components and building principles selected by evolution to propose more reliable, efficient and environment-respecting materials requires a multidisciplinary approach.
1,262 citations
Cites background from "Fundamentals of Mesostructuring Thr..."
...Exploring the existence of domains and subdomains of these hybrid phases in situ during their formation and under controlled chemical and processing parameters is essential for obtaining reproducible product...
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TL;DR: The versatility of the sol-gel process with regard to the design of films for specific optical chemical sensor applications is highlighted, which facilitates tailoring of the physico-chemical film properties to optimize sensor performance.
Abstract: Optical chemical sensors have been the focus of much research attention in recent years because of their importance in industrial, environmental and biomedical applications [1]. This class of sensors combines chemical and biological recognition with advances in optoelectronic technologies. The application of solgel materials to these sensors, especially in the form of thin films, has attracted considerable interest due to the ease of fabrication and design flexibility of the process. The nature of the sol-gel process lends itself very well to the deposition of thin films using a variety of techniques such as dip-coating, spin-coating and spraying. In many sensor applications, the sol-gel film is used to provide a micro-porous support matrix in which analyte-sensitive molecules are entrapped and into which smaller analyte species may diffuse and interact [2,3]. Sol-gel films have many advantages as support matrices over polymer supports, including, for example, strong adhesion, good mechanical strength as well as excellent optical transparency. The versatility of the process facilitates tailoring of the physico-chemical film properties to optimize sensor performance. For example, films can be designed which have optimum porosity while minimizing leaching of the indicator molecules. In this chapter, the versatility of the sol-gel process with regard to the design of films for specific optical chemical sensor applications is highlighted.
936 citations
TL;DR: In this article, the authors classify different types of sol-gel precursors and how these can influence a solgel process, from self-assembly and ordering in the initial solution, to phase separation during the gelation process and finally to crystallographic transformations at high temperature.
Abstract: From its initial use to describe hydrolysis and condensation processes, the term ‘sol–gel’ is now used for a diverse range of chemistries. In fact, it is perhaps better defined more broadly as covering the synthesis of solid materials such as metal oxides from solution-state precursors. These can include metal alkoxides that crosslink to form metal–oxane gels, but also metal ion–chelate complexes or organic polymer gels containing metal species. What is important across all of these examples is how the choice of precursor can have a significant impact on the structure and composition of the solid product. In this review, we will attempt to classify different types of sol–gel precursor and how these can influence a sol–gel process, from self-assembly and ordering in the initial solution, to phase separation during the gelation process and finally to crystallographic transformations at high temperature.
932 citations
TL;DR: In this paper, the authors present an extensive discussion on the major advances in the field of periodically organized mesoporous thin films (POMTFs) obtained via surfactant templated growth of inorganic or hybrid polymers.
Abstract: This review presents an extensive discussion on the major advances in the field of periodically organized mesoporous thin films (POMTFs) obtained via surfactant templated growth of inorganic or hybrid polymers. A large variety of templating agents can be coupled with inorganic polymerization reactions for the design of periodically organized nanostructured hybrid phases that yield POMTFs. The tuning of the interface between the template and the polymerizing phase and the control over chemical and processing conditions are the key parameters in producing tailor-made POMTFs with a high degree of reproducibility. This dynamic coupling between chemical and processing conditions dictates extensive use of complementary ex situ measurements with in situ characterization techniques that follow, in real time, film formation from the molecular precursor solutions to the final stabilized POMTF. Among modern analytical tools, 2D-GISAXS, ellipsoporosimetry, HRTEM, X-ray reflectometry, WAXS, time-resolved infrared spec...
726 citations