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How much information is in my scattering data? Some recent approaches to the structure of microgels, polymers and nanoparticles
Auteur(s): Oberdisse J.
Conférence invité: MZL User Meeting (Munich (online), DE, 2020-12-08)
Ref HAL: hal-03371654_v1
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Résumé: Recent progress with soft nanostructures will be reviewed. Traditionally, data analysis follows two approaches, roughly depending on your geographic position with respect to the Rhine river. While “inversion” predominates in the east, “modeling” is more western. In short, “inversion” minimizes the use of a-priori knowledge, while modeling starts with an idea of what the structure might be, which may be wrong … and fit perfectly. Of course many implementations ignoring geography have been developed, and we advocate a mixed approach based on known ingredients: e.g., assembling nanoparticles in nanocomposites, or monomers within microgels. In polymer nanocomposites, we will show that SANS can be used to analyze the polymer interfacial region within a nm to NPs – which impacts dynamics as measured by BDS and NSE. On micron scales, thousands of NP are embedded in the polymer, and their dispersion affects both I(q) and the mechanics of the material. A statistical method based on RMC of this many-parameter problem will be presented, showing that key features like percolation can be described. Finally, the structure of core-shell microgels has been studied by SANS using deuteration. A model describing the polymer density profiles has been developed, and the surprising result is that the shell may not necessarily be where the intuition of the synthetic chemist located it. This leads to new nanostructures of striking mechanical properties, the study of which is an on-going endeavor.
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Rejuvenating the structure and rheological properties of silica nanocomposites based on natural rubber
Auteur(s): Boonsomwong Kanyarat, Genix A.-C., Chauveau E., Fromental J.-M., Dieudonne-George P., Sirisinha Chakrit, Oberdisse J.
(Article) Publié:
Polymer, vol. 189 p.122168 (2020)
Texte intégral en Openaccess :
Ref HAL: hal-03004917_v1
Ref Arxiv: 2011.07820
DOI: 10.1016/j.polymer.2020.122168
WoS: WOS:000513011400007
Ref. & Cit.: NASA ADS
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Résumé: The antagonistic effect of processing and thermal annealing on both the filler structure and the polymer matrix is explored in polymer nanocomposites based on natural rubber with precipitated silica incorporated by coagulation from aqueous suspension followed by roll-milling. Their structure and linear and non-linear rheology have been studied, with a particular emphasis on the effect of high temperature thermal treatment and the number of milling passes. Small-angle X-ray scattering intensities show that the silica is organized in small, unbreakable aggregates containing ca. 50 primary nanoparticles, which are reorganized on a larger scale in filler networks percolating at the highest silica contents. As expected, the filler network structure is found to be sensitive to milling, more milling inducing rupture, as evidenced by the decreasing Payne effect. After thermal treatment, the nanocomposite structure is found to be rejuvenated, erasing the effect of the previous milling on the low-strain modulus. In parallel, the dynamics of the samples described by the rheology or the calorimetric glass-transition temperature remain unchanged, whereas the natural latex polymer network structure is modified by milling towards a more fluid-like rheology, and cannot be recovered.
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Partition of Coating Agents between Nanoparticle Interfaces and the Polymer in Nanocomposites
Auteur(s): Musino D., Oberdisse J., Sztucki Michael, Alegria Angel, Genix A.-C.
(Article) Publié:
Macromolecules, vol. 53 p.8083-8094 (2020)
Texte intégral en Openaccess :
Ref HAL: hal-03004954_v1
Ref Arxiv: 2011.07830
DOI: 10.1021/acs.macromol.0c01506
Ref. & Cit.: NASA ADS
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Résumé: Industrial and model polymer nanocomposites are often formulated with coating agents to improve polymer-nanoparticle (NP) compatibility. Here the localization of silane coating agents in styrene-butadiene nanocomposite is investigated through the segmental dynamics of the polymer matrix by broadband dielectric spectroscopy (BDS), allowing the detection of silanes in the matrix through their plasticization effect. This acceleration of dynamics was followed via the shift of τmax of the α-relaxation induced by the presence of coating agents of different molecular weight and quantity, for different amounts of incorporated colloidal silica NPs (R ≈ 12.5 nm, polydispersity 12%). Any noteworthy contribution of interfacial polymer layers on τmax has been excluded by reference measurements with bare NPs. Our approach allowed quantifying the partition between the matrix and the NP interfaces, and was confirmed independently by calorimetry. As a control parameter, the silane grafting reaction could be activated or not, which was confirmed by the absence (resp. presence) of partitioning with the matrix. Our main result is that in the first steps of material formulation, before any grafting reaction, coating agents both cover the silica surface by adsorption and mix with the polymer matrix-in particular if the latter has chemical compatibility via its functional groups. Silane adsorption was found to be comparable to the grafted amount (1.1 nm-2), and does not increase further, confirming that the plateau of the adsorption isotherm is reached in industrial formulations. These results are hoped to contribute to a better understanding of the surface reactions taking place during complex formulation processes of nanocomposites, namely the exact amounts at stake, e.g., in industrial mixers. Final material properties are affected both through NP-matrix compatibility and plasticization of the latter by unreacted molecules. 2
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Resolving Segmental Polymer Dynamics in Nanocomposites by Incoherent Neutron Spin-Echo Spectroscopy
Auteur(s): Musino D., Oberdisse J., Farago Bela, Alegria Angel, Genix A.-C.
(Article) Publié:
Acs Macro Letters, vol. 9 p.910-916 (2020)
Texte intégral en Openaccess :
Ref HAL: hal-02908124_v1
DOI: 10.1021/acsmacrolett.0c00369
WoS: WOS:000542231400022
Exporter : BibTex | endNote
Résumé: The segmental dynamics of styrene-butadiene nanocomposites with embedded silica nanoparticles (NPs, ca. 20%v) has been studied by broadband dielectric (BDS) and neutron spin-echo spectroscopy (NSE). It is shown by BDS that overlapping contributions only allow to conclude on a range of distributions of relaxation times in simplified industrial nanocomposites formed with highly polydisperse NPs. For comparison, structurally similar but less aggregated colloidal nanocomposites have a well-defined distribution of relaxation times due to the reduced influence of interfacial polarization processes. This distribution is widened with respect to the neat polymer, without change in the position of the maximum, and at most a small slowing down visible in the average time. We then demonstrate that incoherent NSE can be used to resolve small modifications of segmental dynamics of the industrial samples. By carefully choosing the q-vector of the measurement, experiments with fully hydrogenated polymer give access to the self-dynamics of the polymer in the presence of silica on the scale of approximately 1 nm. Our high resolution measurements show that the segmental motion is slightly but systematically slowed down also by the presence of the industrial filler NPs.
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Structural identification of percolation of nanoparticles
Auteur(s): Musino D., Genix A.-C., Chauveau E., Bizien Thomas, Oberdisse J.
(Article) Publié:
Nanoscale, vol. 12 p.3907-3915 (2020)
Texte intégral en Openaccess :
Ref HAL: hal-02564183_v1
DOI: 10.1039/C9NR09395H
WoS: 000515391000035
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Résumé: We propose a method relying on structural measurements by small-angle scattering to quantitatively follow aggregation of nanoparticles (NPs) in concentrated colloidal assemblies or suspensions up to percolation, regardless of complex structure factors arising due to interactions. As experimental model system, the dispersion of silica NPs in a styrene-butadiene matrix has been analyzed by small-angle X-ray scattering and transmission electron microscopy (TEM), as a function of particle concentration. A reverse Monte Carlo analysis applied to the NP scattering compared favorably with TEM. By combining it with an aggregate recognition algorithm, series of representative real space structures and aggregation number distribution functions have been determined up to high concentrations, taking into account particle polydispersity. Our analysis demonstrates that the formation of large percolating aggregates on the scale of the simulation box (of linear dimension 1/qmin, here micron-sized) can be mapped onto the macroscopic percolation characterized by rheology. Our method is thus capable of determining aggregate structure in dense NP systems with strong – possibly unknown – interactions visible in scattering. It is hoped to be useful in many other colloidal systems, beyond the case of polymer nanocomposites exemplarily studied here.
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Recent advances in stimuli-responsive core-shell microgel particles: synthesis, characterisation, and applications
Auteur(s): Oberdisse J., Hellweg Thomas
(Article) Publié:
Progress In Colloid And Polymer Science, vol. 298 p.TBA (2020)
Texte intégral en Openaccess :
Ref HAL: hal-02566998_v1
Ref Arxiv: 2011.07823
DOI: 10.1007/s00396-020-04629-0
WoS: WOS:000521913700001
Ref. & Cit.: NASA ADS
Exporter : BibTex | endNote
Résumé: Inspired by the path followed by Matthias Ballauff over the past 20 years, the development of thermosensitive core-shell microgel structures is reviewed. Different chemical approaches, from hard nanoparticle cores to double stimuli-responsive microgels have been devised and successfully implemented by many different groups. Some of the rich variety of these systems is presented, as well as some recent progress in structural analysis of such microstructures by small-angle scattering of neutrons or X-rays, including modeling approaches. In the last part, again following early work by the group of Matthias Ballauff, applications with particular emphasis on incorporation of catalytic nanoparticles inside core-shell structures – stabilizing the nanoparticles and granting external control over activity – will be discussed, as well as core-shell microgels at interfaces.
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