Ref HAL: hal-01656192_v1
DOI: 10.1016/j.jmps.2017.11.019
WoS: 000426536400006
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2 Citations
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A novel experimental technique based on in situ AFM monitoring of the mechanisms of damage and the strain fields associated to the slow steady-state propagation of a fracture in glassy polymers is presented. This micron-scale investigation is complemented by optical measurements of the sample deformation up to the millimetric macroscopic scale of the sample in order to assess the proper crack driving conditions. These multi-scale observations provide important insights towards the modeling of the fracture toughness of glassy polymers and its relationship with the macromolecular structure and non-linear rheological properties. This novel technique is first tested on a standard PMMA thermoplastic in order to both evaluate its performance and the richness of this new kind of observations. Although the fracture propagation in PMMA is well known to proceed through crazing in the bulk of the samples, our observations provide a clear description and quantitative evaluation of a change of fracture mechanism towards shear yielding fracture accompanied by local necking close to the free surface of the sample, which can be explained by the local change of stress triaxiality. Moreover , this primary surface necking mechanism is shown to be accompanied by a network of secondary grooves that can be related to surface crazes propagating towards the interior of the sample. This overall scenario is validated by post-mortem fractographic investigations by scanning electron microscopy.

Ref HAL: hal-01653297_v1
DOI: 10.1039/c7sm01640a
WoS: WOS:000415352100017
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13 Citations
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Quantitative characterization of the average structure of dense nanoparticle assemblies and aggregates is a common problem in nanoscience. Small-angle scattering is a suitable technique, but it is usually limited to not too big assemblies due to the limited experimental range, low concentrations to avoid interactions, and monodispersity to keep calculations tractable. In the present paper, a straightforward analysis of the generally available scattered intensity – even for large assemblies, at high concentrations – is detailed, providing information on the local volume fraction of polydisperse particles with hard sphere interactions. It is based on the identical local structure of infinite homogeneous nanoparticle assemblies and their subsets forming finite-sized clusters. The approach is extended to polydispersity, using Monte-Carlo simulations of hard and moderately sticky hard spheres. As a result, a simple relationship between the observed structure factor minimum – termed the correlation hole – and the average local volume fraction  on the scale of neighboring particles is proposed and validated through independent aggregate simulations. The relationship shall be useful as an efficient tool for the structural analysis of arbitrary aggregated colloidal systems.

Ref HAL: hal-01627751_v1
DOI: 10.1021/acs.macromol.7b01371
WoS: WOS:000412965900033
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5 Citations
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The influence of surface-modification of TiO2-nanoparticles with phosphonic acid molecules on the structure of polymer nanocomposites has been studied by small-angle scattering and transmission electron microscopy. The grafting of phosphonic acids was done by phase transfer into chloroform, and polymer nanocomposites have been formulated by solvent casting with two polymers of slightly different hydrophobicity, PMMA and PEMA. By analyzing the shape of the scattering curves around the interparticle correlation peak, and in particular the depth of the correlation hole, information on nearest neighbor correlations between nanoparticles is obtained. While local nanoparticle arrangements are found to be independent of the global particle volume fraction, they are controlled by the degree of hydrophobicity of the alkyl phosphonic acid grafts with respect to hydrophobicity of matrix. Quantitative analysis of the correlation hole thus evidences the fine-tuning of local nanocomposite structure with phosphonic acids.

Ref HAL: hal-01580200_v2
Ref Arxiv: 1811.08753
DOI: 10.1021/acs.langmuir.7b01199
WoS: WOS:000405536100019
Ref. & Cit.: NASA ADS
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28 Citations
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We study the swelling and shrinking behavior of core-shell microgels adsorbed on silicon wafers. In these systems, the core is made of cross-linked poly(N isopropylmethacrylamide) and the shell consists of cross linked poly(N-n propylacrylamide). In suspension, these particles exhibit an extended linear swelling behavior in the temperature interval between the lower critical solution temperatures of the two polymers. Using ellipsometry and AFM, we show that this linear response is also observed in the adsorbed state.

Ref HAL: hal-01580193_v1
DOI: 10.1021/acs.macromol.7b00954
WoS: WOS:000405642700029
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12 Citations
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The microstructure of polymer nanocomposites made with disordered silica filler (Zeosil(R) 1165MP) of industrial relevance and various coating agents is quantitatively analyzed using a combination of SAXS, TEM, and a recently developed structural model. The polymer matrix is formed by an end-functionalized styrene-butadiene statistical copolymer capable of covalent grafting on the silica nanoparticles. The effect of the coating agents with different alkyl chain length (C8, C12, and C18) on filler structure quantified in terms of aggregate formation, for different concentrations (up to 8%wt with respect to silica), and the effect of a commonly added catalyzer, DPG, are studied using the structural model. As a result we show that a strongly synergetic effect of both DPG and coating agent exist. Our findings open the road to a fundamental understanding and rational design of model and industrial nanocomposite formulation with optimized coating agents.

Ref HAL: hal-01552103_v1
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Ref HAL: hal-01552100_v1
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Résumé:

Small-angle scattering is a powerful and popular technique for the characterization of the average structure of dense nanoparticle assemblies and aggregates. It is usually limited to not too big assemblies due to the limited q-range, and low enough concentrations to avoid interactions. A straightforward and quantitative analysis of the generally available scattered intensity – even for large assemblies, at high concentrations – at intermediate-q is detailed. It is based on the similarity in local structure between infinitely large homogeneous assemblies of hard spheres or moderately sticky hard spheres with any finite-sized nanoparticle assembly dominated by hard sphere interactions. The method provides information on the local volume fraction of particles. The approach is then extended to polydispersities up to 40%, using numerical simulations of hard spheres and mildly sticky hard spheres. As a result, a simple relationship between the observed structure factor minimum – termed the correlation hole – and the local volume fraction on the scale of neighboring particles, which is also linked to the coordination number, is given. This relationship shall be useful as a simple and efficient tool for the structural analysis of arbitrary aggregated colloidal systems. Finally, recent examples of filler structure in model and industrial polymer nanocomposites will be reviewed.