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Ref Arxiv: 2509.19942
DOI: 10.1021/acs.langmuir.5c04088
Ref. & Cit.: NASA ADS
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The thermosensitivity and microstructure of microgels made by copolymerizing standard microgelforming monomers with more hydrophilic comonomers is investigated, with the aim of increasing the volume phase transition temperature (VPTT). We precisely determine the incorporation of N-(hydroxymethyl)acrylamide (HMAM) and purpose-synthesized N-(2-hydroxyisopropyl)acrylamide (HIPAM) into microgels-neither of which forms microgels on its own by precipitation polymerization. The swelling properties and microstructure of the resulting copolymer microgels with Nisopropylacrylamide (NIPAM, LCST ca. 32°C) and N-isopropylmethacrylamide (NIPMAM, LCST ca. 44°C) are then characterized via turbidimetry, DLS, and AFM. At low comonomer contents, all microgel particles exhibit moderate growth in size. Beyond a system-specific threshold, we observe a significant jump in size, and smoother swelling behavior. For NIPAM-HIPAM, the size increase is linked to a strong rise in swelling capacity, and the formation of a thick corona. The effect of the hydrophilic comonomers on the VPTT correlates linearly with their true composition, allowing us to extrapolate the VPTT of hypothetical pure HMAM and HIPAM microgels. This leads to 99°C for HMAM, and 68°C for HIPAM for the respective VPTT. These numbers can be seen as useful indicators of the effect of these monomers on the VPTT in the copolymerized microgels. The observed changes in VPTT, swelling, size, and morphology suggest that high-VPTT microgels possess unique internal molecular composition gradients, likely due to hydrophobic interactions during synthesis. Our results have potential implications for developing temperature-sensitive microgel-based membranes that can self-adapt their permeability at higher operating temperatures in energy applications.

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Gravity affects the flow and the behavior at rest of complex fluids and flows by inducing sedimentation, drainage, and interfacial deformation, which can mask more fundamental physical processes. On Earth, standard countermeasures against gravity come with limitations in terms of possible formulations or the quality and homogeneity of the applied strain. Alternatively, one can run these experiments in free-fall or in orbit where the effects of gravity are canceled i.e., under microgravity conditions. In this short review, we present several European Space Agency-led projects of interest to rheologists that leverage microgravity environments: FAST/FASTER , which studies interfacial rheology using Capillary Pressure Tensiometers; SMD-FOAM, fundamental experiments on foam coarsening ; SMD-PASTA and SEEDS, aimed at understanding the dynamics of emulsion droplets, its evolution and microrheology using Diffusing Wave Spectroscopy; results associated with studies on granular materials in microgravity, including AstEx and CompGran; COLIS, which examines the thermally driven perturbation of soft colloidal glasses monitored by Dynamic Light Scattering; BIOMICS/KRABS, investigating the aggregation and migration of soft particles and red blood cells under flow. Microgravity experiments allowed for high-precision measurements of interfacial viscoelasticity, detailed studies of emulsion aging and drop coalescence, observed plastic rearrangements in colloidal glasses, characterized the dynamics under flow of red blood cell analogues, and rationalized the impact of gravity on convection and fluidization in agitated granular matter. Collectively, these experiments demonstrate the complementarity and the relevance of ESA's microgravity platforms in expanding the frontiers of soft matter rheology.

Commentaires: Accepted for publication in Journal of Rheology

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DOI: 10.1371/journal.pone.0333021
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Plastic pollution is a major and global threat to ecosystems and human health, resulting from the spreading and breakdown of plastic litter in the environment. In an aquatic environment, the first causes of this degradation are exposure to natural ultraviolet light and abrasion or collisions in the water. The extent of such degradation on a plastic object after a given time remains very difficult to quantify, especially regarding the relative production of microplastics, nanoplastics and soluble species along with volatile compounds. All of these degradation products may contribute differently to environmental pollution. Therefore, when evaluating the pollution caused by plastic objects, we should consider how much of each byproduct is generated. We propose a novel method based on conservation of the carbon mass during the degradation process. This approach is the first to enable quantification of carbon retrieved in each type of degradation product (Microplastics, Nanoplastics, Solubles, Volatile Compounds), as well as its evolution with exposure time. By applying this method to polypropylene granules, we demonstrate its effectiveness in tracking carbon footprint throughout the aging process. One of the unexpected results of this study is to show that the amount of carbon released in volatile form is far from negligible (17%) compared to MP (55%). The procedure we present is general enough to be applied to any type of polymer, and can be a valuable tool for assessing the amount of by-products of a given size released into the environment.

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DOI: 10.1016/j.polymer.2024.127927
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A combined SAXS-shear analysis of polymer nanocomposites for the first time between parallel plates is presented. This set-up allows investigating microstructural changes accompanying macroscopic rheological phenomena, such as the Payne effect. The latter is known to induce filler network destruction and subsequent flocculation when the shear strain amplitude is increased or decreased, respectively. First, a detailed SAXS analysis of the microstructure of carbon black in styrene-butadiene nanocomposites is applied to a series of increasing filler loading. The average size and mass of primary particles and small aggregates are estimated using a model of inter-aggregate polydisperse hardsphere interactions. In a second time, the impact of a new geometry of the shear experiments with a horizontal X-ray beam passing through a disc-shaped nanocomposite on the SAXS pattern is analyzed in terms of sample heterogeneity (different positions), anisotropy (orientations), and sample thickness (transmission and heterogeneity). Application of our quantitative analysis shows that hot molding induces a slight anisotropy of the aggregate shapes into prolate ellipsoids oriented parallel to the rubber sheet. The Payne effect is then followed by scattering, surprisingly showing no modification of the intensity under oscillatory shear. Thus, the aggregate structure observed on the scale of standard SAXS is not broken up during Payne experiments, hinting at either an averaging effect over oscillation periods, or to the reorganization of large-scale agglomerate or network structures.

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DOI: 10.1021/acsami.5c11985
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Mesoporous systems are ubiquitous in membrane science and applications due to their high internal surface area and tunable pore size. A new synthesis pathway of hydrolytic ionosilica films with mesopores formed by ionic liquid (IL) templating is proposed and compared to the traditional nonhydrolytic strategy. For both pathways, the multi-scale formation of pores has been studied as a function of IL content, combining results of thermogravimetric analysis (TGA), nitrogen sorption, and small-angle X-ray scattering (SAXS). The combination of TGA and nitrogen sorption provides access to ionosilica and pore volume fractions, with contributions of meso-and macropores. We then elaborate an original and quantitative geometrical model to analyze the SAXS data based on small spheres (Rs = 1 -2 nm) and cylinders (Lcyl = 10 -20 nm) with radial polydispersity provided by the nitrogen sorption isotherms. As a main result, we found that for a given incorporation of templating IL, both synthesis pathways produce very similar pore geometries, but the better incorporation efficacy of the new hydrolytic films provides a higher mesoporosity. Our combined study provides a coherent view of mesopore geometry, and thereby an optimization pathway of porous ionic membranes in terms of accessible mesoporosity contributing to the specific surface. Possible applications include electrolyte membranes of improved ionic properties, e.g., in fuel cells and batteries, as well as molecular storage.

Ref HAL: hal-05335459_v1
DOI: 10.1038/s41467-025-64557-x
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Bacteria’s ability to withstand mechanical challenges is enhanced in their biofilm lifestyle, where they are encased in a viscoelastic polymer matrix. Under fluid flow, biofilms can form as streamers – slender filaments tethered to solid surfaces and suspended in the flowing fluid. Streamers thrive in environments subjected to intense hydrodynamic stresses, such as medical devices and water filters, often resulting in catastrophic clogging. Their colonisation success may depend on a highly adaptable mechanical response to varying stress conditions, though the evidence and underlying mechanisms of this adaptation remain elusive. Here, we demonstrate that biofilm streamers exhibit a stress-hardening behaviour, with both differential elastic modulus and effective viscosity increasing linearly with external stress. This stress-hardening is consistent across biofilms with different matrix compositions, formed by various bacterial species, and under diverse growth conditions. We further demonstrate that this mechanical response originates from the properties of extracellular DNA (eDNA) molecules, which constitute the structural backbone of the streamers. In addition, our results identify extracellular RNA (eRNA) as a modulator of the matrix network, contributing to both the structure and rheological properties of the eDNA backbone. Our findings reveal an instantaneous, purely physical mechanism enabling streamers to adapt to hydrodynamic stresses. Given the ubiquity of extracellular nucleic acids (eNA) in biofilms, this discovery prompts a re-evaluation of their functional role in biofilm mechanics, with potential implications for biofilm structural integrity, ecological resilience, and colonisation dynamics.