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On the absence of structure factors in concentrated colloidal suspensions and nanocomposites

  • Regular Article - Soft Matter
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Abstract

Small-angle scattering is a commonly used tool to analyze the dispersion of nanoparticles in all kinds of matrices. Besides some obvious cases, the associated structure factor is often complex and cannot be reduced to a simple interparticle interaction, like excluded volume only. In recent experiments, we have encountered a surprising absence of structure factors (S(q) = 1) in scattering from rather concentrated polymer nanocomposites (Genix et al. in ACS Appl Mater Interfaces 11(19):17863–17872, 2019). In this case, quite pure form factor scattering is observed. This somewhat “ideal” structure is further investigated here making use of reverse Monte Carlo simulations in order to shed light on the corresponding nanoparticle structure in space. By fixing the target “experimental” apparent structure factor to one over a given q-range in these simulations, we show that it is possible to find dispersions with this property. The influence of nanoparticle volume fraction and polydispersity has been investigated, and it was found that for high concentrations only a high polydispersity allows reaching a state of S = 1. The underlying structure in real space is discussed in terms of the pair-correlation function, which evidences the importance of attractive interactions between polydisperse nanoparticles. The calculation of partial structure factors shows that there is no specific ordering of large or small particles, but that the presence of attractive interactions together with polydispersity allows reaching an almost “structureless” state.

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Adapted with permission from [13]. Copyright 2019 American Chemical Society

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Data Availability

All experimental data have been previously published, and the relevant simulation results are included in the main body of the present article. If anyone wishes to access position files of particles or similar, we can make them available on (reasonable) request.

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Acknowledgements

L. Belloni (Saclay) is warmly thanked for providing us with a numerical tool implementing a solution of OZ integral equations, allowing the cross check of our results in Fig. 1. Fruitful discussion with D. Truzzolillo and M. In (both Montpellier) is gratefully acknowledged. A. Sokolov and V. Bocharova are thanked for setting up the on-going collaboration, which led to the experimental data reproduced in this article.

Funding

The experimental data presented here have been obtained in the framework of an ANR project. We thus acknowledge partial financial funding by the ANR NANODYN Project, Grant ANR-14-CE22-0001-01 of the French Agence Nationale de la Recherche.

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This article reflects joint work by both authors. Both authors have contributed equally to this article.

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Correspondence to Julian Oberdisse.

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Article published on the occasion of the 50-year-celebration of small-angle neutron scattering at ILL (Grenoble, September 2022).

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Genix, AC., Oberdisse, J. On the absence of structure factors in concentrated colloidal suspensions and nanocomposites. Eur. Phys. J. E 46, 46 (2023). https://doi.org/10.1140/epje/s10189-023-00306-6

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