Studying Twin Samples Provides Evidence for a Unique Structure-Determining Parameter in Simplifed Industrial Nanocomposites

Baeza, Guilhem P.; Genix, Anne-Caroline; Degrandcourt, Christophe; Gummel, Jérémie; Mujtaba, Anas; Saalwächter, Kay; Thurn‐Albrecht, Thomas; Couty, Marc; Oberdisse, Julian

doi:10.1021/mz500137e

Cited by 27 publications

(31 citation statements)

References 20 publications

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“…8 The grafting density was identified as the key parameter by evidencing the existence of twin samples having a different composition but identical structure and elastic plateau moduli. 9 By combining small-angle scattering, electron microscopy, and numerical simulations, we have described the structure of such complex systems by primary silica beads organized within small aggregates, which themselves fill large-scale fractal branches. The typical size and mass of the aggregates -some forty nanometers in radius, and aggregation numbers of about 45 beads -were deduced from TEM and SAXS data using a quantitative model of interacting aggregates involving an aggregate size polydispersity of 30%.…”

Section: Introductionmentioning

confidence: 99%

A high-temperature dielectric process as a probe of large-scale silica filler structure in simplified industrial nanocomposites

Baeza

Oberdisse

Alegría

et al. 2015

Phys. Chem. Chem. Phys.

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The existence of two independent filler-dependent high-temperature Maxwell-Wagner-Sillars (MWS) dielectric processes is demonstrated and characterized in detail in silica-filled styrene-butadiene (SB) industrial nanocomposites of simplified composition using Broadband Dielectric Spectroscopy (BDS). The uncrosslinked samples are made with 140 kg mol(-1) SB-chains, half of which carry a single graftable end-function (50% D3), and Zeosil 1165 MP silica incorporated by solid-phase mixing. While one high-temperature process is known to exist in other systems, the dielectric properties of a new silica-related process - strength, relaxation time, and activation energy - have been evidenced and described as a function of silica volume fraction and temperature. In particular, it is shown that its strength follows a percolation behavior as observed with the ionic conductivity and rheology. Moreover, activation energies show the role of polymer layers separating aggregates even when they are percolated. Apart from simultaneous characterization over a broad frequency range up to local polymer and silanol dynamics, it is believed that such high-temperature BDS-measurements can thus be used to detect reorganizations in structurally-complex silica nanocomposites. Moreover, they should contribute to a better identification of dynamical processes via the described sensitivity to structure in such systems.

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Section: Introductionmentioning

confidence: 99%

A high-temperature dielectric process as a probe of large-scale silica filler structure in simplified industrial nanocomposites

Baeza

Oberdisse

Alegría

et al. 2015

Phys. Chem. Chem. Phys.

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“…The difficulty with the data presented up to now is that the quantitative characterization has to be carried out for each silica fraction, for each fraction of graftable chains, and for each chain mass. As a next step, a unique structure-determining parameter for these simplified industrial nanocomposites has been proposed [40,41]. We have seen in the preceding section that higher chain masses at fixed matrix composition lead to bigger aggregates, an effect opposite to higher chain grafting.…”

Section: Iii4 Towards a Single Structure-determining Parametermentioning

confidence: 99%

“…Twins have thus an identical structure and viscoelastic plateau modulus, but display different dynamics in the terminal regime due to the widely different chain masses. [41] This suggests that it is possible to control the onset of flow behaviour of twin samples over a wide frequency range by modifying the chain mass at fixed ρD3.…”

Section: Iii4 Towards a Single Structure-determining Parametermentioning

confidence: 99%

Recent advances in structural and dynamical properties of simplified industrial nanocomposites

Genix¹,

Baeza²,

Oberdisse³

2016

European Polymer Journal

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A large body of experimental work on the microstructure and dynamics of simplified industrial nanocomposites made of disordered silica filler in a styrene-butadiene matrix by solid-phase mixing is regrouped and critically discussed in this feature article. Recent results encompass systems with varying polymer mass, grafting functionality, and filler content. They have been obtained by simulation-based structural modelling of nanoparticle aggregate size and mass deduced from smallangle scattering and transmission electron microscopy. Our model has been validated by independent swelling experiments. Comparison of structurally-close nanocomposites of widely different chain mass led to the identification of a unique structure-determining parameter, the grafting density, as well as to a unified picture of aggregate formation mechanisms in complex nanocomposites during mixing. In addition, low-field proton NMR allowed for the characterization of dynamically slowed-down ('glassy') polymer layers, which were shown not to dominate the rheological response, unlike the structural contribution. Finally, broadband dielectric spectroscopy was used in an innovative manner to identify filler percolation -also identified by rheology -via dynamics along filler surfaces.

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“…In recent contributions, we have developed a combined TEM-SAXS-simulation analysis of nanoparticle and aggregate dispersions in systems of disordered silica in styrene-butadiene copolymer of industrial relevance but with a limited number of ingredients [41][42][43][44] . Motivated, in particular by the absence of any additive related to curing but DPG, the system with un-crosslinked SB matrix was termed 'simplified industrial'.…”

Section: Introductionmentioning

confidence: 99%

Synergistic Effect of Small Molecules on Large-Scale Structure of Simplified Industrial Nanocomposites

et al. 2017

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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 endfunctionalized styrene-butadiene statistical copolymer capable of covalent grafting on the silica nanoparticles. The effect of the coating agents with different alkyl chain length (C 8 , C 12 , and C 18 ) 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.

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Studying Twin Samples Provides Evidence for a Unique Structure-Determining Parameter in Simplifed Industrial Nanocomposites

Cited by 27 publications

References 20 publications

A high-temperature dielectric process as a probe of large-scale silica filler structure in simplified industrial nanocomposites

A high-temperature dielectric process as a probe of large-scale silica filler structure in simplified industrial nanocomposites

Recent advances in structural and dynamical properties of simplified industrial nanocomposites

Synergistic Effect of Small Molecules on Large-Scale Structure of Simplified Industrial Nanocomposites

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