cracking_2.avi from Drying paint: from micro-scale dynamics to mechanical instabilities

Charged colloidal dispersions make up the basis of a broad range of industrial and commercial products, from paints to coatings and additives in cosmetics. During drying, an initially liquid dispersion of such particles is slowly concentrated into a solid, displaying a range of mechanical instabilities in response to highly variable internal pressures. Here we summarize the current appreciation of this process by pairing an advection-diffusion model of particle motion with a Poisson–Boltzmann cell model of inter-particle interactions, to predict the concentration gradients around a drying colloidal film. We then test these predictions with osmotic compression experiments on colloidal silica, and small-angle X-ray scattering experiments on silica dispersions drying in Hele–Shaw cells. Finally, we use the details of the microscopic physics at play in these dispersions to explore how two macroscopic mechanical instabilities—shear-banding and fracture—can be controlled

Fig7_8_data_saxs.xlsx from Drying paint: from micro-scale dynamics to mechanical instabilities

Data for Figs. 7 and 8, showing the SAXS results, and effective diffusivities across the liquid-solid transition

54 Б1 В ДВ 5 1 Менеджмент конфликтов 2017, 2018 ФОС

Code to generate dimensionless diffusivities, used in Figs. 3 and

cracking_1.avi from Drying paint: from micro-scale dynamics to mechanical instabilities

Along with cracking_2.avi, shows time-lapse images of drying cells for Fig 11

Water-Responsive Internally Structured Polymer–Surfactant Films on Solid Surfaces

Water-insoluble films of oppositely charged polyion–surfactant ion “complex salts” (CS) are readily cast on solid surfaces from ethanolic solutions. The methodology introduces new possibilities to study and utilize more or less hydrated CS. Direct SAXS measurements show that the surface films are water-responsive and change their liquid crystalline structure in response to changes in the water activity of the environment. In addition to the classical micellar cubic and hexagonal phases, a rectangular ribbon phase and a hexagonal close-packed structure have now been detected for CS composed of cationic alkyltrimethylammonium surfactants with polyacrylate counterions. Added cosurfactants, decanol or the nonionic surfactant C₁₂E₅, yield additional lamellar and bicontinuous cubic structures. Images of the surfaces by optical and atomic force microscopy show that the films cover the surfaces well but have a more or less irregular surface topology, including “craters” of sizes ranging from a few to hundreds of micrometers. The results indicate possibilities to create a wealth of water-responsive structured CS films on solid surfaces

Drying Dip-Coated Colloidal Films

We present the results from a small-angle X-ray scattering (SAXS) study of lateral drying in thin films. The films, initially 10 μm thick, are cast by dip-coating a mica sheet in an aqueous silica dispersion (particle radius 8 nm, volume fraction ϕ_s = 0.14). During evaporation, a drying front sweeps across the film. An X-ray beam is focused on a selected spot of the film, and SAXS patterns are recorded at regular time intervals. As the film evaporates, SAXS spectra measure the ordering of particles, their volume fraction, the film thickness, and the water content, and a video camera images the solid regions of the film, recognized through their scattering of light. We find that the colloidal dispersion is first concentrated to ϕ_s = 0.3, where the silica particles begin to jam under the effect of their repulsive interactions. Then the particles aggregate until they form a cohesive wet solid at ϕ_s = 0.68 ± 0.02. Further evaporation from the wet solid leads to evacuation of water from pores of the film but leaves a residual water fraction ϕ_w = 0.16. The whole drying process is completed within 3 min. An important finding is that, in any spot (away from boundaries), the number of particles is conserved throughout this drying process, leading to the formation of a homogeneous deposit. This implies that no flow of particles occurs in our films during drying, a behavior distinct to that encountered in the iconic coffee-stain drying. It is argued that this type of evolution is associated with the formation of a transition region that propagates ahead of the drying front. In this region the gradient of osmotic pressure balances the drag force exerted on the particles by capillary flow toward the liquid–solid front

Pd-Containing Organo­polyoxo­metalates Derived from Dawson Polyoxo­metalate [P₂W₁₅V₃O₆₂]^9–: Lewis Acidity and Dual Site Catalysis

Grafting of a palladium complex to the Dawson vanado­tungstate polyanion [P₂W₁₅V₃O₆₂]^9– via an organic ligand generates a large family of pincer-type hybrid polyoxometalates. The palladium-POM derivatives have dual catalytic properties. Unlike their parent inorganic polyanions, they catalyze allylations while retaining their oxidant character, which leads to single-pot dual site catalysis. This opens a new route for multicatalytic reactions

Aggregation of the Salivary Proline-Rich Protein IB5 in the Presence of the Tannin EgCG

In the mouth, proline-rich proteins (PRP), which are major components of stimulated saliva, interact with tannins contained in food. We report in vitro interactions of the tannin epigallocatechin gallate (EgCG), with a basic salivary PRP, IB5, studied through electrospray ionization mass spectrometry (ESI-MS), small-angle X-ray scattering (SAXS), and dynamic light scattering (DLS). In dilute protein (IB5) solutions of low ionic strength (1 mM), the proteins repel each other, and the tannins bind to nonaggregated proteins. ESI-MS experiments determine the populations of nonaggregated proteins that have bound various numbers of tannin molecules. These populations match approximately the Poisson distribution for binding to <i>n</i> = 8 sites on the protein. MS/MS experiments confirm that complexes containing <i>n</i> = 1 to 8 EgCG molecules are dissociated with the same energy. Assuming that the 8 sites are equivalent, we calculate a binding isotherm, with a binding free energy Δμ = 7.26<i>RT</i>_a (<i>K</i>_d = 706 μM). In protein solutions that are more concentrated (0.21 mM) and at higher ionic strength (50 mM, pH 5.5), the tannins can bridge the proteins together. DLS experiments measure the number of proteins per aggregate. This number rises rapidly when the EgCG concentration exceeds a threshold (0.2 mM EgCG for 0.21 mM of IB5). SAXS experiments indicate that the aggregates have a core–corona structure. The core contains proteins that have bound at least 3 tannins and the corona has proteins with fewer bound tannins. These aggregates coexist with nonaggregated proteins. Increasing the tannin concentration beyond the threshold causes the transfer of proteins to the aggregates and a fast rise of the number of proteins per aggregate. A poisoned growth model explains this fast rise. Very large cationic aggregates, containing up to 10 000 proteins, are formed at tannin concentrations (2 mM) slightly above the aggregation threshold (0.2 mM)