Tuning Pore Dimensions of Mesoporous Inorganic Films by Homopolymer Swelling

The functionality and applications of mesoporous inorganic films are closely linked to their mesopore dimensions. For material architectures derived from a block copolymer (BCP) micelle coassembly, the pore size is typically manipulated by changing the molecular weight corresponding to the pore-forming block. However, bespoke BCP synthesis is often a costly and time-consuming process. An alternative method for pore size tuning involves the use of swelling agents, such as homopolymers (HPs), which selectively interact with the core-forming block to increase the micelle size in solution. In this work, poly(isobutylene)-block-poly(ethylene oxide) micelles were swollen with poly(isobutylene) HP in solution and coassembled with aluminosilicate sol with the aim of increasing the resulting pore dimensions. An analytical approach implementing spectroscopic ellipsometry (SE) and ellipsometric porosimetry (EP) alongside atomic force microscopy (AFM) and small-angle X-ray scattering (SAXS) in transmission and grazing-incidence (GISAXS) modes enabled us to study the material evolution from solution processing through the manifestation of the mesoporous inorganic film after BCP removal. The in-depth SE/EP analysis evidenced an increase of more than 45% in mesopore diameter with HP swelling and a consistent scaling of the overall void volume and number of pores. Importantly, our analytical toolbox enabled us to study the effect of swelling on the connecting necks between adjacent pores, with observed increases as high as ≈35%, offering novel pathways to sensing, electrochemical, and other mass-transfer-dependent applications

Robust Operation of Mesoporous Antireflective Coatings under Variable Ambient Conditions

Generating mesoporous films with adequate film thickness and refractive index is a common method to achieve amplitude and phase matching in low-cost interference-based antireflective coatings (ARCs). For high-surface-energy materials, pores on the 2-50 nm (i.e., on the subwavelength scale) are subject to capillary condensation by surrounding gas phase water molecules, which hampers their functioning. In this work, we examine the effect of relative humidity on mesoporous ARCs and present a simple method for the preparation of ARCs with robust operation under variable conditions. The materials route is based on the generation of well-defined porous aluminosilicate networks by block copolymer co-assembly with poly(isobutylene)- block-poly(ethylene oxide) and postsynthesis grafting of trichloro(octyl)silane molecules to the pore walls. The functionalized films exhibited a maximum transmittance value of 99.8%, with an average transmittance of 99.1% in the visible wavelength range from 400 to 700 nm. Crucially, the antireflection performance was maintained at high humidity values, with an average transmittance decrease of only 0.2% and maximum values maintained at 99.7%. This compared to maximum and average losses of 3.6 and 2.7%, respectively, for nonfunctionalized reference samples. The ARCs were shown to retain their optical properties within 50 humidity cycles, indicating long-term stability against fluctuating environmental conditions

Photocatalytic Template Removal by Non-Ozone-Generating UV Irradiation for the Fabrication of Well-Defined Mesoporous Inorganic Coatings

The processing of mesoporous inorganic coatings typically requires a high-temperature calcination step to remove organic precursors that are essential during the material assembly. Lowering the fabrication energy costs and cutting back on the necessary resources would provide a greater scope for the deployment in applications such as architectural glass, optical components, photovoltaic cells, and energy storage, as well as further compatibilize substrates with low temperature stability. Organic removal methods based on UV–ozone treatment are increasing in popularity, but concerns remain regarding large-scale ozone generation and usage of mercury-containing UV lamps. To this end, we present a method that relies on non-ozone-generating UV radiation at 254 nm (UV254) and incorporation of small amounts of photocatalytic material in the formulation, here demonstrated with TiO2 nanocrystals. At concentrations as low as 5 wt % relative to the main inorganic aluminosilicate material, the TiO2 nanocrystals catalyze a “cold combustion” of the organic components under UV254 irradiation to reveal a porous inorganic network. Using block copolymer-based co-assembly in conjunction with photocatalytic template removal, we produce well-defined mesoporous inorganic thin films with controlled porosity and refractive index values, where the required processing time is governed by the amount of TiO2 loading. This approach provides an inexpensive, flexible, and environmentally friendly alternative to traditional organic removal techniques, such as UV–ozone degradation and thermal calcination

Determination of nutrient salts by automatic methods both in seawater and brackish water: the phosphate blank

9 páginas, 2 tablas, 2 figurasThe main inconvenience in determining nutrients in seawater by automatic methods is simply solved: the preparation of a suitable blank which corrects the effect of the refractive index change on the recorded signal. Two procedures are proposed, one physical (a simple equation to estimate the effect) and the other chemical (removal of the dissolved phosphorus with ferric hydroxide).Support for this work came from CICYT (MAR88-0245 project) and Conselleria de Pesca de la Xunta de GaliciaPeer reviewe

P3HT-Based Solar Cells: Structural Properties and Photovoltaic Performance

Each year we are bombarded with B.Sc. and Ph.D. applications from students that want to improve the world. They have learned that their future depends on changing the type of fuel we use and that solar energy is our future. The hope and energy of these young people will transform future energy technologies, but it will not happen quickly. Organic photovoltaic devices are easy to sketch, but the materials, processing steps, and ways of measuring the properties of the materials are very complicated. It is not trivial to make a systematic measurement that will change the way other research groups think or practice. In approaching this chapter, we thought about what a new researcher would need to know about organic photovoltaic devices and materials in order to have a good start in the subject. Then, we simplified that to focus on what a new researcher would need to know about poly-3-hexylthiophene:phenyl-C61-butyric acid methyl ester blends (P3HT: PCBM) to make research progress with these materials. This chapter is by no means authoritative or a compendium of all things on P3HT:PCBM. We have selected to explain how the sample fabrication techniques lead to control of morphology and structural features and how these morphological features have specific optical and electronic consequences for organic photovoltaic device applications

Impact of Physicochemical Characteristics on the Oxidative Stability of Fish Oil Microencapsulated by Spray-Drying

The aim of the present research was to identify principal parameters determining the oxidative stability of microencapsulated fish oil. Microcapsules were prepared by spray-drying using different types of n-octenylsuccinate- derivatized starch, gum Arabic, sugar beet pectin, sodium caseinate, and/or glucose syrup. Two principal components to classify the different microcapsules accounting for up to 79% of the variance were identified. The principal components were determined by physicochemical parameters reflecting the emulsifying ability of the encapsulant and the drying behavior of the parent emulsion. Microcapsules, which were identified by principal component analysis to be significantly different, exhibited a low stability upon storage, showing that the principal components and, thus, the underlying physicochemical parameters analyzed in the present study are correlated with core material stability

Drying of thin film polymer solar cells

Our focus of investigations is on the dependency of the polymer solar cell (PSC) characteristics on drying conditions like temperature and kinetic effects. We optimized the homogeneity for the doctor bladed active layer in conjunction with viscosity measurements, examined the dependency of cell characteristics on drying kinetics with best results at slow drying and accomplished differential scanning calorimetry (DSC) with solution-processed samples in the typical annealing temperature range

Fractionation of block copolymers for pore size control and reduced dispersity in mesoporous inorganic thin films

Mesoporous inorganic thin films are promising materials architectures for a variety of applications, including sensing, catalysis, protective coatings, energy generation and storage. In many cases, precise control over a bicontinuous porous network on the 10 nm length scale is crucial for their operation. A particularly promising route for structure formation utilizes block copolymer (BCP) micelles in solution as sacrificial structure-directing agents for the co-assembly of inorganic precursors. This method offers pore size control via the molecular weight of the pore forming block and is compatible with a broad materials library. On the other hand, the molecular weight dependence impedes continuous pore tuning and the intrinsic polymer dispersity presents challenges to the pore size homogeneity. To this end, we demonstrate how chromatographic fractionation of BCPs provides a powerful method to control the pore size and dispersity of the resulting mesoporous thin films. We apply a semi-preparative size exclusion chromatographic fractionation to a polydisperse poly(isobutylene)-block-poly(ethylene oxide) (PIB-b-PEO) BCP obtained from scaled-up synthesis. The isolation of BCP fractions with distinct molecular weight and narrowed dispersity allowed us to not only tune the characteristic pore size from 9.1 ± 1.5 to 14.1 ± 2.1 nm with the identical BCP source material, but also significantly reduce the pore size dispersity compared to the non-fractionated BCP. Our findings offer a route to obtain a library of monodisperse BCPs from a polydisperse feedstock and provide important insights on the direct relationship between macromolecular characteristics and the resulting structure-directed mesopores, in particular related to dispersit

Comparison of Surfactant Distributions in Pressure-Sensitive Adhesive Films Dried from Dispersion under Lab-Scale and Industrial Drying Conditions

Film-forming latex dispersions are an important class of material systems for a variety of applications, for example, pressure-sensitive adhesives, which are used for the manufacturing of adhesive tapes and labels. The mechanisms occurring during drying have been under intense investigations in a number of literature works. Of special interest is the distribution of surfactants during the film formation. However, most of the studies are performed at experimental conditions very different from those usually encountered in industrial processes. This leaves the impact of the drying conditions and the resulting influence on the film properties unclear. In this work, two different 2-ethylhexyl-acrylate (EHA)-based adhesives with varying characteristics regarding glass transition temperature, surfactants, and particle size distribution were investigated on two different substrates. The drying conditions, defined by film temperature and mass transfer in the gas phase, were varied to emulate typical conditions encountered in the laboratory and industrial processes. Extreme conditions equivalent to air temperatures up to 250 °C in a belt dryer and drying rates of 12 g/(m²·s) were realized. The surfactant distributions were measured by means of 3D confocal Raman spectroscopy in the dry film. The surfactant distributions were found to differ significantly with drying conditions at moderate film temperatures. At elevated film temperatures the surfactant distributions are independent of the investigated gas side transport coefficients: the heat and mass transfer coefficient. Coating on substrates with significantly different surface energies has a large impact on surfactant concentration gradients, as the equilibrium between surface and bulk concentration changes. Dispersions with higher colloidal stability showed more homogeneous lateral surfactant distributions. These results indicate that the choice of the drying conditions, colloidal stability, and substrates is crucial to control the surfactant distribution. Results obtained under lab-scale drying conditions cannot be transferred directly to the industrial application. The results were similar for both tested adhesive material systems, despite their different properties. This indicates that other properties, such as the particle size distribution and glass transition temperature, have surprisingly little effect on the development of the surfactant distribution