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International audience; Wetting of polymer-grafted nanoparticles (NPs) in a polymer nanocomposite (PNC) film is driven by a difference in surface energy between components as well as bulk thermodynamics, namely, the value of the interaction parameter, χ. The interplay between these contributions is investigated in a PNC containing 25 wt % polymethyl methacrylate (PMMA)-grafted silica NPs (PMMA-NPs) in poly(styrene-ran-acrylonitrile) (SAN) upon annealing above the lower critical solution temperature (LCST, 160 °C). Atomic force microscopy (AFM) studies show that the areal density of particles increases rapidly and then approaches 80% of that expected for random close-packed hard spheres. A slightly greater areal density is observed at 190 °C compared to 170 °C. The PMMA-NPs are also shown to prevent dewetting of PNC films under conditions where the analogous polymer blend is unstable. Transmission electron microscopy (TEM) imaging shows that PMMANPs symmetrically wet both interfaces and form columns that span the free surface and substrate interface. Using grazingincidence Rutherford backscattering spectrometry (GI-RBS), the PMMA-NP surface excess (Z*) initially increases rapidly with time and then approaches a constant value at longer times. Consistent with the areal density, Z* is slightly greater at deeper quench depths, which is attributed to the more unfavorable interactions between the PMMA brush and SAN segments. The Z* values at early times are used to determine the PMMA-NP diffusion coefficients, which are significantly larger than theoretical predictions. These studies provide insights into the interplay between wetting and phase separation in PNCs and can be utilized in nanotechnology applications where surface-dependent properties, such as wettability, durability, and friction, are important.

Understanding the kinetic pathways of self-assembly in block copolymers (BCPs) has been a long-standing challenge, mostly due to limitations of in situ monitoring techniques. Here, we demonstrate an approach that uses optical birefringence, determined by spectroscopic ellipsometry (SE), as a measure of domain formation in cylinder- and lamellae-forming BCP films. The rapid experimental acquisition time in SE (ca. 1 sec) enables monitoring of the assembly/disassembly kinetics of BCP films during solvent-vapor annealing (SVA). We demonstrate that upon SVA, BCP films form ordered domains that are stable in the swollen state, but disorder upon rapid drying. Surprisingly, the disassembly during drying strongly depends on the duration of solvent exposure in the swollen state, explaining previous observations of loss of order in SVA processes. SE thus allows for decoupling of BCP self-assembly and disordering that occurs during solvent annealing and solvent evaporation, which is difficult to probe using other, slower techniques.

International audience; In this work, we examine binary and ternary nanocomposites of poly(methyl methacrylate) grafted silica nanoparticles (PMMA-NP), in poly(styrene-ran-acrylonitrile) (SAN), and poly(methyl methacrylate) matrices as a platform to directly probe governing parameters guiding phase behavior and nanoparticle assembly in composite materials. Through the addition of PMMA matrix chains similar in molecular weight to the grafted PMMA chains and significantly smaller than the SAN matrix chains, we observe increased nanoparticle miscibility in off-critical compositions due to interfacial segregation of PMMA matrix chains. A simple interfacial model provides a general guideline for predicting the extent of compatibilization. Further insights on compatibilization behavior are provided by polymer particle pair correlation functions and structure factors obtained using polymer reference interaction site model theory calculations as well as polymer concentration profiles from molecular dynamics simulations. This study serves as a guideline to facilitate PNC processing and design of materials for a broad range of technological applications.