91 research outputs found
Well dispersed fractal aggregates as filler in polymer-silica nanocomposites: long range effects in rheology
We are presenting a new method of processing polystyrene-silica
nanocomposites, which results in a very well-defined dispersion of small
primary aggregates (assembly of 15 nanoparticles of 10 nm diameter) in the
matrix. The process is based on a high boiling point solvent, in which the
nanoparticles are well dispersed, and controlled evaporation. The filler's fine
network structure is determined over a wide range of sizes, using a combination
of Small Angle Neutron Scattering (SANS) and Transmission Electronic Microscopy
(TEM). The mechanical response of the nanocomposite material is investigated
both for small (ARES oscillatory shear and Dynamical Mechanical Analysis) and
large deformations (uniaxial traction), as a function of the concentration of
the particles. We can investigate the structure-property correlations for the
two main reinforcement effects: the filler network contribution, and a
filler-polymer matrix effect. Above a silica volume fraction threshold, we see
a divergence of the modulus correlated to the build up of a connected network.
Below the threshold, we obtain a new additional elastic contribution of much
longer terminal time than the matrix. Since aggregates are separated by at
least 60 nm, this new filler-matrix contribution cannot be described solely
with the concept of glassy layer (2nm)
Modeling of Intermediate Structures and Chain Conformation in Silica-Latex Nanocomposites Observed by SANS During Annealing
The evolution of the polymer structure during nanocomposite formation and
annealing of silica-latex nanocomposites is studied using contrast-variation
small angle neutron scattering. The experimental system is made of silica
nanoparticles (Rsi \approx 8 nm) and a mixture of purpose-synthesized
hydrogenated and deuterated nanolatex (Rlatex \approx 12.5 nm). The progressive
disappearance of the latex beads by chain interdiffusion and release in the
nanocomposites is analyzed quantitatively with a model for the scattered
intensity of hairy latex beads and an RPA description of the free chains. In
silica-free matrices and nanocomposites of low silica content (7%v), the
annealing procedure over weeks at up to Tg + 85 K results in a molecular
dispersion of chains, the radius of gyration of which is reported. At higher
silica content (20%v), chain interdiffusion seems to be slowed down on
time-scales of weeks, reaching a molecular dispersion only at the strongest
annealing. Chain radii of gyration are found to be unaffected by the presence
of the silica filler
Origin of micro-scale heterogeneity in polymerisation of photo-activated resin composites
Photo-activated resin composites are widely used in industry and medicine. Despite extensive chemical characterisation, the micro-scale pattern of resin matrix reactive group conversion between filler particles is not fully understood. Using an advanced synchrotron-based wide-field IR imaging system and state-of-the-art Mie scattering corrections, we observe how the presence of monodispersed silica filler particles in a methacrylate based resin reduces local conversion and chemical bond strain in the polymer phase. Here we show that heterogeneity originates from a lower converted and reduced bond strain boundary layer encapsulating each particle, whilst at larger inter-particulate distances light attenuation and monomer mobility predominantly influence conversion. Increased conversion corresponds to greater bond strain, however, strain generation appears sensitive to differences in conversion rate and implies subtle distinctions in the final polymer structure. We expect these findings to inform current predictive models of mechanical behaviour in polymer-composite materials, particularly at the resin-filler interface
Gradient of glass transition temperature in filled elastomers
By studying model systems consisting of poly(ethyl acrylate)
polymer chains covalently bound to silica particles, we show here
how the temperature dependence of the modulus of filled
elastomers can be explained by a long-ranged gradient of the
polymer matrix glass transition temperature in the vicinity of
the particles. We are led to this conclusion by comparing NMR and
mechanical data. We show thereby that the mechanisms of
reinforcement are the same as those which lead to an increase of
the glass transition temperature of strongly adsorbed thin
polymer films. It allows us in particular to propose a new
time-temperature superposition law for the filled elastomers
viscoelasticity
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