Supporting Info: Multiscale Effects of Interfacial Polymer Confinement in Silica. Nanocomposites

Transcription

1 Supporting Info: Multiscale Effects of Interfacial Polymer Confinement in Silica Nanocomposites H. Samet Varol *,a, M. Alejandra Sánchez a, Hao Lu a, Joe E. Baio b, Christian Malm a, Noemi Encinas c, Marius R. B. Mermet-Guyennet d, Nicolas Martzel e, Daniel Bonn d, Mischa Bonn a, Tobias Weidner a, Ellen H. G. Backus a, Sapun H. Parekh *,a a Departments of Molecular Spectroscopy and c Physics at Interfaces, Max Planck Institute for Polymer Research, Ackermannweg 10, Mainz, Germany b School of Chemical, Biological and Environmental Engineering, Oregon State University, Corvallis, Oregon 97333, United States d Institute of Physics, University of Amsterdam, Science Park 904, 1098 XH Amsterdam, The Netherlands e Manufacture française des pneumatiques MICHELIN, Site de Ladoux, 23 place Carmes Déchaux, Clermont Ferrand, France. Corresponding Authors * varol@mpip-mainz.mpg.de * parekh@mpip-mainz.mpg.de

2 Supporting Figures Figure S1. Aggregate size (R agg ) results from small angle X-Ray spectroscopy (SAXS) analysis of silica/f- SBR (red color horizontal patterned columns) and silica/b-sbr (blue color horizontal patterned columns) samples loaded with 16%vol. and 24%vol. of silica fillers inside shown with the R agg g results from TEM image analysis (solid columns with same colour codes). Asterisks represent statistically significant differences (p < 0.05) of R agg between B-SBR-silica and F-SBR-silica samples (1-way ANOVA with Tukey s). Error bars are standard error of mean.

3 Figure S2. Histogramss from the TEM image size analysiss results of (upper column) simplified and (lower column) full nanocomposites whose images and R agg sizes are presented in Figure 1. Figure S3. FTIR spectra of clean silica windoww (green) and drop cast B-SBR (blue) and F-SBR (red) films on clean silica windows. Each of the presented spectra was averaged over 3 different spectra from 3 different locations on the each sample.

4 Figure S4. Im as a function of frequency obtained from the fitting (smooth traces) and MEM method for F-SBR and B-SBR. The fitting parameters are provided in Table S1.

5 Parameter B_SBR F_SBR Nonresonant CH 2 symmetric stretch CH 3 symmetric stretch Si-CH 3 symmetric stretch, CH 2 asymmetric stretch, or CH 2 Fermi resonance Si-CH 3 asymmetric stretch, CH 3 asymmetric stretch, or CH 3 Fermi resonance CH stretch from C=C CH stretch from C=C amplitude phase amplitude frequency width amplitude frequency width amplitude frequency width amplitude frequency width amplitude frequency width amplitude frequency width Table S1. Fitting parameters for the CH stretch region and possible assignments of the bands based on other SFG work. 1 4 Phases are in radians, while frequencies and widths are in cm -1.

6 Figure S5. Atomic concentration (%) changes of Si, O and C at different etching time during Ar cluster sputtering of spin coated (A) F-SBR and (B) B-SBR on Si wafers. Blue highlighted regions in both graphs showing the etching period for collection of HR XPS data from the polymer film-sii wafer interfaces that are presented in Fig 5.

7 Figure S6. C 1s, O 1s and Si2p XPS spectra of F-SBR and B-SBR samples taken from bulk polymer films (before sputtering the films away) and presented with red and blue circles, respectively CV adv ( ) F-SBR - Teflon B-SBR - Teflon F-SBR - Silica B-SBR - Silica Teflon ica Silic Figure S7. Advancing contact angle (CA) of F-SBR (red) and B-SBR (blue) on Teflon and silica windoww surfaces shown by patterned and solid columns, respectively. As references, CA results of clean Teflon (orange) and silica (green) windows. Significant differences (p < 0.05) were evaluated for the polymer film

8 coated Teflon and silica window surfaces by using 1-way ANOVA with Tukey s. No significant difference of the CA was found between any polymer samples. Error bars indicate the standard deviation. References (1) Wang, J.; Chen, C.; Buck, S. M.; Chen, Z. J. Phys. Chem. B 2001, 105, (2) Chen, Z.; Shen, Y. R.; Somorjai, G. A. Annu. Rev. Phys. Chem. 2002, 53, (3) Vanden Eynde, X.; Servais, J. P.; Lamberigts, M. Surf. Interface Anal. 2003, 35, (4) Kannan, A. G.; Choudhury, N. R.; Dutta, N. K. Polymer 2007, 48,