Guilhem P. Baeza

Bio: Guilhem P. Baeza is an academic researcher from Institut national des sciences Appliquées de Lyon. The author has contributed to research in topics: Thermoplastic elastomer & Crystallization. The author has an hindex of 14, co-authored 33 publications receiving 734 citations. Previous affiliations of Guilhem P. Baeza include Centre national de la recherche scientifique & Foundation for Research & Technology – Hellas.

Network dynamics in nanofilled polymers

Abstract: It is well accepted that adding nanoparticles (NPs) to polymer melts can result in significant property improvements. Here we focus on the causes of mechanical reinforcement and present rheological measurements on favourably interacting mixtures of spherical silica NPs and poly(2-vinylpyridine), complemented by several dynamic and structural probes. While the system dynamics are polymer-like with increased friction for low silica loadings, they turn network-like when the mean face-to-face separation between NPs becomes smaller than the entanglement tube diameter. Gel-like dynamics with a Williams-Landel-Ferry temperature dependence then result. This dependence turns particle dominated, that is, Arrhenius-like, when the silica loading increases to ∼31 vol%, namely, when the average nearest distance between NP faces becomes comparable to the polymer's Kuhn length. Our results demonstrate that the flow properties of nanocomposites are complex and can be tuned via changes in filler loading, that is, the character of polymer bridges which 'tie' NPs together into a network.

Multiscale Filler Structure in Simplified Industrial Nanocomposite Silica/SBR Systems Studied by SAXS and TEM

Abstract: Simplified silica (Zeosil 1165 MP) and SBR (140k carrying silanol end-groups) nanocomposites have been formulated by mixing of a reduced number of ingredients with respect to industrial applications. The thermo-mechanical history of the samples during the mixing process was monitored and adjusted to identical final temperatures. The filler structure on large scales up to micrometers was studied by transmission electron microscopy (TEM) and very small-angle X-ray scattering (SAXS). A complete quantitative model extending from the primary silica nanoparticle (of radius \approx 10 nm), to nanoparticles aggregates, up to micrometer-sized branches with typical lateral dimension of 150 nm is proposed. Image analysis of the TEM-pictures yields the fraction of zones of pure polymer, which extend between the branches of a large-scale filler network. This network is compatible with a fractal of average dimension 2.4 as measured by scattering. On smaller length scales, inside the branches, small silica aggregates are present. Their average radius has been deduced from a Kratky analysis, and it ranges between 35 and 40 nm for all silica fractions investigated here (\phi_si = 8-21% vol.). A central piece of our analysis is the description of the interaggregate interaction by a simulated structure factor for polydisperse spheres representing aggregates. A polydispersity of 30% in aggregate size is assumed, and interactions between these aggregates are described with a hard core repulsive potential. The same distribution in size is used to evaluate the polydisperse form factor. Comparison with the experimental intensity leads to the determination of the average aggregate compacity (assumed identical for all aggregates in the distribution, between 31% and 38% depending on \phi_si), and thus aggregation number (ca. 45, with a large spread). Because of the effect of aggregate compacity and of pure polymer zones, the volume fraction of aggregates is higher in the branches than \phi_si. The repulsion between aggregates has a strong effect on the apparent isothermal compressibility: it leads to a characteristic low-q depression, which cannot be interpreted as aggregate mass decrease in our data. In addition, the reinforcement effect of these silica structures in the SBR-matrix is characterized with oscillatory shear and described with a model based on the same aggregate compacity. Finally, our results show that it is possible to analyze the complex structure of interacting aggregates in nanocomposites of industrial origin in a self-consistent and quantitative manner.

Multiscale Filler Structure in Simplified Industrial Nanocomposite Silica/SBR Systems Studied by SAXS and TEM

Abstract: Simplified silica (Zeosil 1165 MP) and SBR (140k carrying silanol end-groups) nanocomposites have been formulated by mixing of a reduced number of ingredients with respect to industrial applications. The thermo-mechanical history of the samples during the mixing process was monitored and adjusted to identical final temperatures. The filler structure on large scales up to micrometers was studied by transmission electron microscopy (TEM) and very small-angle X-ray scattering (SAXS). A complete quantitative model extending from the primary silica nanoparticle (of radius ≈10 nm), to nanoparticle aggregates, up to micrometer-sized branches with typical lateral dimension of 150 nm is proposed. Image analysis of the TEM-pictures yields the fraction of zones of pure polymer, which extend between the branches of a large-scale filler network. This network is compatible with a fractal of average dimension 2.4 as measured by scattering. On smaller length scales, inside the branches, small silica aggregates are presen...

Effect of Grafting on Rheology and Structure of a Simplified Industrial Nanocomposite Silica/SBR

Abstract: An un-cross-linked SBR-system filled with precipitated silica nanoparticles of radius ≈10 nm by mixing is studied as a function of the fraction of graftable matrix chains (140 kg mol–1) varying from 0% to 100%, for a low (ΦSi = 8.5 vol %) and high (16.7 vol %) silica volume fraction. The linear rheology in shear shows a strong impact of the grafting on the terminal flow regime, and a shift to longer relaxation times with increasing grafting. Simultaneously, the plateau modulus stays approximately constant for the low ΦSi, suggesting a link to the silica content. The microstructure of the silica is characterized by using a combination of transmission electron microscopy and small-angle X-ray scattering data. We apply a quantitative model of interacting aggregates, and determine the average aggregation number (decreasing from 160 to 30 with grafting), aggregate size (50 to 30 nm), and compacity (55% to 35%). While the linear rheology seems to be dominated by the matrix composition, both the mixing rheology ...

Nonlinear shear and uniaxial extensional rheology of polyether-ester-sulfonate copolymer ionomer melts

Abstract: We present unique nonlinear shear and extensional rheology data of unentangled amorphous polyester ionomers based on polyethers and sulphonated phthalates with sodium/lithium counterions. Previous linear viscoelastic measurements showed significant elasticity in these ionomers due to the formation of strong ionic aggregates. These ionomer melts exhibit viscoelastic properties similar to well-entangled melts with an extended rubbery plateau. To evaluate the effects of nonlinear deformation, the rheology of these ionomers was investigated using uniaxial extension and shear. The measurements were performed on a filament stretching rheometer and on a strain controlled rotational rheometer equipped with a cone-partitioned-plate setup. In extension, ionomer samples exhibited a decreasing strain hardening trend with increasing extension rates. At the same Weissenberg number, the same strain hardening was observed for different counterions. The presence of high solvating poly(ethylene oxide), PEO, along the backb...

Fast parallel algorithms for short-range molecular dynamics

Abstract: Three parallel algorithms for classical molecular dynamics are presented. The first assigns each processor a fixed subset of atoms; the second assigns each a fixed subset of inter-atomic forces to compute; the third assigns each a fixed spatial region. The algorithms are suitable for molecular dynamics models which can be difficult to parallelize efficiently—those with short-range forces where the neighbors of each atom change rapidly. They can be implemented on any distributed-memory parallel machine which allows for message-passing of data between independently executing processors. The algorithms are tested on a standard Lennard-Jones benchmark problem for system sizes ranging from 500 to 100,000,000 atoms on several parallel supercomputers--the nCUBE 2, Intel iPSC/860 and Paragon, and Cray T3D. Comparing the results to the fastest reported vectorized Cray Y-MP and C90 algorithm shows that the current generation of parallel machines is competitive with conventional vector supercomputers even for small problems. For large problems, the spatial algorithm achieves parallel efficiencies of 90% and a 1840-node Intel Paragon performs up to 165 faster than a single Cray C9O processor. Trade-offs between the three algorithms and guidelines for adapting them to more complex molecular dynamics simulations are also discussed.

Small Angle X-ray Scattering for Nanoparticle Research

Abstract: X-ray scattering is a structural characterization tool that has impacted diverse fields of study. It is unique in its ability to examine materials in real time and under realistic sample environments, enabling researchers to understand morphology at nanometer and angstrom length scales using complementary small and wide angle X-ray scattering (SAXS, WAXS), respectively. Herein, we focus on the use of SAXS to examine nanoscale particulate systems. We provide a theoretical foundation for X-ray scattering, considering both form factor and structure factor, as well as the use of correlation functions, which may be used to determine a particle’s size, size distribution, shape, and organization into hierarchical structures. The theory is expanded upon with contemporary use cases. Both transmission and reflection (grazing incidence) geometries are addressed, as well as the combination of SAXS with other X-ray and non-X-ray characterization tools. We conclude with an examination of several key areas of research w...

50th Anniversary Perspective: Are Polymer Nanocomposites Practical for Applications?

Abstract: The field of polymer nanocomposites has been at the forefront of research in the polymer community for the past few decades. Foundational work published in Macromolecules during this time has emphasized the physics and chemistry of the inclusion of nanofillers; remarkable early developments suggested that these materials would create a revolution in the plastics industry. After 25 years of innovative and groundbreaking research, PNCs have enabled many niche solutions. To complement the extensive literature currently available, we focus this Perspective on four case studies of PNCs applications: (i) filled rubbers, (ii) continuous fiber reinforced thermoset composites, (iii) membranes for gas separations, and (iv) dielectrics for capacitors and insulation. After presenting synthetic developments we discuss the application of polymer nanocomposites to each of these topic areas; successes will be noted, and we will finish each section by highlighting the various technological bottlenecks that need to be over...

Composites Part A: Applied Science and Manufacturing

Abstract: Reference EPFL-ARTICLE-184271doi:10.1016/j.compositesa.2012.08.001View record in Web of Science Record created on 2013-02-27, modified on 2017-05-10

A Microscopic Model for the Reinforcement and the Non Linear Behaviour of Filled Elastomers and Thermoplastic Elastomers (Payne and Mullins Effects)

Abstract: We extend a model regarding the reinforcement of nanofilled elastomers and thermoplastic elastomers. The model is then solved by numerical simulations on mesoscale. This model is based on the presence of glassy layers around the fillers. Strong reinforcement is obtained when glassy layers between fillers overlap. It is particularly strong when the corresponding clusters—fillers + glassy layers—percolate, but it can also be significant even when these clusters do not percolate but are sufficiently large. Under applied strain, the high values of local stress in the glassy bridges reduce their lifetimes. The latter depend on the history, on the temperature, on the distance between fillers, and on the local stress in the material. We show how the dynamics of yield and rebirth of glassy bridges account for the nonlinear Payne and Mullins effects, which are a large drop of the elastic modulus at intermediate deformations and a progressive recovery of the initial modulus when the samples are subsequently put at ...