The internal structure of nanometric microgels in water has been studied as a function of temperature, crosslinker content, and level of deuteration. Small-angle neutron scattering from poly(N isopropylmethacrylamide) (pNIPMAM, volume phase transition ≈ 44 °C) microgel particles of radius well below 100 nm in D2O has been measured. The intensities have been analyzed with a combination of polymer chain scattering and form-free radial monomer volume fraction profiles defined over spherical shells, taking polydispersity in size of the particles determined by AFM into account. A reverse Monte Carlo optimization using a limited number of parameters was developed to obtain smoothly decaying profiles in agreement with the experimentally scattered intensities. Result are compared to the swelling curve of microgel particles in the temperature range from 15 to 55 °C obtained from photon correlation spectroscopy (PCS). In addition to hydrodynamic radii measured by PCS, our analysis provides direct information about internal water content and gradients, the strongly varying steepness of the density profile at the particle-water interface, the total spatial extension of the particles, and the visibility of chains. The model has also been applied to a variation of the crosslinker content, N,N′ methylenebisacrylamide (BIS), from 5 to 15 mol%, providing insight in the impact of chain architecture and crosslinking on water uptake and on the definition of the polymer-water interface. The model can easily be generalized to arbitrary monomer contents and types, in particular mixtures of hydrogenated and deuterated species, paving the way to detailed studies of monomer distributions inside more complex microgels, in particular core-shell particles.

Dynamics in stretched nanocomposites

As an opening lecture to the French-Swedish neutron scattering school held in Uppsala (6th to 9th of December 2016), the basic concepts ofboth soft matter science and neutron scattering are introduced. Typical soft matter systems like self-assembled surfactants in water, microemulsions, (co-)polymers, and colloids are presented. It will be shown that widely different systems have a common underlying physics dominated by the thermal energy, with astonishing consequences on their statistical thermodynamics, and ultimately rheological properties – namely softness. In the second part, the fundamentals of neutron scattering techniques and in particular small-angle neutron scattering as a powerful method to characterize soft matter systems will be outlined.

The addition of nanoparticles to a polymermatrix is a well-known process to improve the mechanicalproperties of polymers. Many studies of mechanical reinforcementin polymer nanocomposites (PNCs) focus on rubberymatrices; however, much less effort concentrates on thefactors controlling the mechanical performance of thetechnologically important glassy PNCs. This paper presentsa study of the effect of the polymer molecular weight (MW)on the overall mechanical properties of glassy PNCs withattractive interaction by using Brillouin light scattering. Wefound that the mechanical moduli (bulk and shear) have anonmonotonic dependence on MW that cannot be predictedby simple rule of mixtures. The moduli increase with increasing MW up to 100 kg/mol followed by a drop at higher MW. Wedemonstrate that the change in the mechanical properties of PNCs can be associated with the properties of the interfacialpolymer layer. The latter depend on the interfacial chain packing and stretching, as well as polymer bridging,which vary differently with the MW of the polymer. These competing contributions lead to the observed nonmonotonicvariations of the glassy PNC moduli with MW. Our work provides a simple, cost-effective, and efficient way to control themechanical properties of glassy PNCs by tuning the polymer chain length. Our finding can be beneficial for the rational designof PNCs with desired mechanical performance.

A gel is a dispersed system which consists of at least two different components: a solid or flexible mesh and a fluid (water in the present case). Microgels are gels in the size range of 10 nm to 1 μm and can be used in a wide range of applications like drug delivery and smart surface coatings. If the microgel consists of acrylamides like N-isopropylmethacrylamide (NIPMAM) or N-n-propylacrylamid (NNPAM) as network component, they show a volume phase transition (VPT) at a certain temperature, the volume phase transition temperature (VPTT). An increase in temperature above the VPTT leads to an abrupt decrease in size and a decrease in temperature leads to an abrupt increase in size. The VPTT is specific for each monomer. To use microgels in sensors or for nanoactuators the thermoresponse has to be precise. That is why we investigated microgels with a core-shell architecture containing NIPMAM and NNPAM. These particles show a tunable linear change in size between 22 °C and 43 °C. Furthermore, we deposited these microgels on surfaces and investigated the properties of the coating. The properties of these particles and coatings can be adjusted by selecting specific synthesis conditions. We then did small angle neutron scattering (SANS) to determine the internal structure of the core-shell microgel.

Proposition d'une modélisation numérique

Structure par diffusion de neutrons aux petits angles