Direct Structural Evidence for Interfacial Gradients in Asymmetric Polymer Nanocomposite Blends

Genix, Anne-Caroline; Bocharova, Vera; Carroll, Robert J.; Dieudonné-George, Philippe; Sztucki, Michael; Schweins, Ralf; Sokolov, Alexei P.; Oberdisse, Julian

doi:10.1021/acsami.1c06971

Direct Structural Evidence for Interfacial Gradients in Asymmetric Polymer Nanocomposite Blends

Journal Article · Thu Jul 22 00:00:00 EDT 2021 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.1c06971· OSTI ID:1870250

^[1]; ^[2]; ^[2]; Dieudonné-George, Philippe ^[1]; ^[3]; ^[4]; ^[5]; ^[1]

University of Montpellier (France)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
European Synchrotron Radiation Facility (ESRF), Grenoble (France)
Inst. Laue-Langevin (ILL), Grenoble (France)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)

Understanding the complex structure of polymer blends filled with nanoparticles (NPs) is key to design their macroscopic properties. In this work, the spatial distribution of hydrogenated (H) and deuterated (D) polymer chains asymmetric in mass is studied by small-angle neutron scattering. Depending on the chain mass, a qualitatively new large-scale organization of poly(vinyl acetate) chains beyond the random-phase approximation is evidenced in nanocomposites with attractive polymer–silica interactions. The silica is found to systematically induce bulk segregation. Only with long H-chains, a strong scattering signature is observed in the q range of the NP size: it is the sign of interfacial isotopic enrichment, that is, of contrasted polymer shells close to the NP surface. A quantitative model describing both the bulk segregation and the interfacial gradient (over ca. 10–20 nm depending on the NP size) is developed, showing that both are of comparable strength. In all cases, NP surfaces trap the polymer blend in a non-equilibrium state, with preferential adsorption around NPs only if the chain length and isotopic preference toward the surface combine their entropic and enthalpic driving forces. This structural evidence for interfacial polymer gradients will open the road for quantitative understanding of the dynamics of many-chain nanocomposite systems.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1870250

Journal Information:: ACS Applied Materials and Interfaces, Journal Name: ACS Applied Materials and Interfaces Journal Issue: 30 Vol. 13; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (55)

The structure and phase transitions in polymer blends, diblock copolymers and liquid crystalline polymers: The Landau-Ginzburg approach Hołyst, Robert; Vilgis, Thomas A. Macromolecular Theory and Simulations, Vol. 5, Issue 4 https://doi.org/10.1002/mats.1996.040050401	journal	July 1996
Formation of regular two-phase structure during solution casting of a polymer blend Yasuda, Osamu; Ougizawa, Toshiaki; Inoue, Takashi Journal of Polymer Science: Polymer Letters Edition, Vol. 21, Issue 10 https://doi.org/10.1002/pol.1983.130211006	journal	October 1983
Determining the phase behavior of nanoparticle-filled binary blends He, Gang; Ginzburg, Valeriy V.; Balazs, Anna C. Journal of Polymer Science Part B: Polymer Physics, Vol. 44, Issue 17 https://doi.org/10.1002/polb.20887	journal	January 2006
Depercolation of aggregates upon polymer grafting in simplified industrial nanocomposites studied with dielectric spectroscopy Baeza, Guilhem P.; Oberdisse, Julian; Alegria, Angel Polymer, Vol. 73 https://doi.org/10.1016/j.polymer.2015.07.045	journal	September 2015
Structuration, selective dispersion and compatibilizing effect of (nano)fillers in polymer blends Taguet, A.; Cassagnau, P.; Lopez-Cuesta, J. -M. Progress in Polymer Science, Vol. 39, Issue 8 https://doi.org/10.1016/j.progpolymsci.2014.04.002	journal	August 2014
Variations on contrast in SANS: determination of self and distinct correlation functions Cotton, J. P. Advances in Colloid and Interface Science, Vol. 69, Issue 1-3 https://doi.org/10.1016/s0001-8686(96)00306-5	journal	December 1996
Compatibilizing effect of a filler in binary polymer mixtures Nesterov, A. E.; Lipatov, Y. S. Polymer, Vol. 40, Issue 5 https://doi.org/10.1016/s0032-3861(98)00277-8	journal	March 1999
A Thorny Problem? Spinodal Decomposition in Polymer Blends Higgins, Julia S.; Cabral, João T. Macromolecules, Vol. 53, Issue 11 https://doi.org/10.1021/acs.macromol.0c00581	journal	June 2020
Bridging-Controlled Network Microstructure and Long-Wavelength Fluctuations in Silica–Poly(2-vinylpyridine) Nanocomposites: Experimental Results and Theoretical Analysis Zhou, Yuxing; Yavitt, Benjamin M.; Zhou, Zhengping Macromolecules, Vol. 53, Issue 16 https://doi.org/10.1021/acs.macromol.0c01391	journal	August 2020
Interfacial Compatibilization in Ternary Polymer Nanocomposites: Comparing Theory and Experiments Maguire, Shawn M.; Krook, Nadia M.; Kulshreshtha, Arjita Macromolecules, Vol. 54, Issue 2 https://doi.org/10.1021/acs.macromol.0c02345	journal	January 2021
Origin of Small-Angle Scattering from Contrast-Matched Nanoparticles: A Study of Chain and Filler Structure in Polymer Nanocomposites Banc, Amélie; Genix, Anne-Caroline; Dupas, Christelle Macromolecules, Vol. 48, Issue 18 https://doi.org/10.1021/acs.macromol.5b01424	journal	September 2015
Analyzing the Interfacial Layer Properties in Polymer Nanocomposites by Broadband Dielectric Spectroscopy Carroll, Bobby; Cheng, Shiwang; Sokolov, Alexei P. Macromolecules, Vol. 50, Issue 16 https://doi.org/10.1021/acs.macromol.7b00825	journal	August 2017
Enhancing the Mechanical Properties of Glassy Nanocomposites by Tuning Polymer Molecular Weight Genix, Anne-Caroline; Bocharova, Vera; Kisliuk, Alexander ACS Applied Materials & Interfaces, Vol. 10, Issue 39 https://doi.org/10.1021/acsami.8b13109	journal	September 2018
Understanding the Static Interfacial Polymer Layer by Exploring the Dispersion States of Nanocomposites Genix, Anne-Caroline; Bocharova, Vera; Carroll, Bobby ACS Applied Materials & Interfaces, Vol. 11, Issue 19 https://doi.org/10.1021/acsami.9b04553	journal	April 2019
Addition of Short Polymer Chains Mechanically Reinforces Glassy Poly(2-vinylpyridine)–Silica Nanoparticle Nanocomposites Bocharova, Vera; Genix, Anne-Caroline; Carrillo, Jan-Michael Y. ACS Applied Nano Materials, Vol. 3, Issue 4 https://doi.org/10.1021/acsanm.0c00180	journal	March 2020
Resolving Segmental Polymer Dynamics in Nanocomposites by Incoherent Neutron Spin–Echo Spectroscopy Musino, Dafne; Oberdisse, Julian; Farago, Bela ACS Macro Letters, Vol. 9, Issue 6 https://doi.org/10.1021/acsmacrolett.0c00369	journal	June 2020
Butterfly Patterns: Small-Angle Neutron Scattering from Deuterated Mobile Chains in a Randomly Cross-Linked Polystyrene Network Ramzi, A.; Zielinski, F.; Bastide, J. Macromolecules, Vol. 28, Issue 10 https://doi.org/10.1021/ma00114a010	journal	May 1995
Development of modulated structure during solution casting of polymer blends Inoue, Takashi; Ougizawa, Toshiaki; Yasuda, Osamu Macromolecules, Vol. 18, Issue 1 https://doi.org/10.1021/ma00143a009	journal	January 1985
Study of miscibility and critical phenomena of deuterated polystyrene and hydrogenated poly(vinyl methyl ether) by small-angle neutron scattering Shibayama, Mitsuhiro; Stein, Richard S.; Han, Charles C. Macromolecules, Vol. 18, Issue 11 https://doi.org/10.1021/ma00153a020	journal	November 1985
Influence of Nanoparticles on Miscibility of Polymer Blends. A Simple Theory Ginzburg, Valeriy V. Macromolecules, Vol. 38, Issue 6 https://doi.org/10.1021/ma0482821	journal	February 2005
Real Space Structure and Scattering Patterns of Model Polymer Nanocomposites Hooper, Justin B.; Schweizer, Kenneth S. Macromolecules, Vol. 40, Issue 19 https://doi.org/10.1021/ma071147e	journal	September 2007
Direct Measurement of Polymer Chain Conformation in Well-Controlled Model Nanocomposites by Combining SANS and SAXS Jouault, Nicolas; Dalmas, Florent; Said, Sylvère Macromolecules, Vol. 43, Issue 23 https://doi.org/10.1021/ma101682t	journal	December 2010
Combined FTIR and Dielectric Investigation of Poly(vinyl acetate) Adsorbed on Silica Particles Füllbrandt, Marieke; Purohit, Purv J.; Schönhals, Andreas Macromolecules, Vol. 46, Issue 11 https://doi.org/10.1021/ma400461p	journal	May 2013
Polymer Chain Conformations in CNT/PS Nanocomposites from Small Angle Neutron Scattering Tung, Wei-Shao; Bird, Vikki; Composto, Russell J. Macromolecules, Vol. 46, Issue 13 https://doi.org/10.1021/ma400765v	journal	June 2013
Conformation of Polymer Chain in the Bulk Cotton, J. P.; Decker, D.; Benoit, H. Macromolecules, Vol. 7, Issue 6 https://doi.org/10.1021/ma60042a033	journal	November 1974
Thermally Induced Phase Separation Behavior of Compatible Polymer Mixtures Nishi, T.; Wang, T. T.; Kwei, T. K. Macromolecules, Vol. 8, Issue 2 https://doi.org/10.1021/ma60044a025	journal	March 1975
Concentration Fluctuations, Local Order, and the Collective Structure of Polymer Nanocomposites Hall, Lisa M.; Anderson, Benjamin J.; Zukoski, Charles F. Macromolecules, Vol. 42, Issue 21 https://doi.org/10.1021/ma901523w	journal	November 2009
Effect of Deuterium Substitution on the Physical Properties of Polymer Melts and Blends White, Ronald P.; Lipson, Jane E. G.; Higgins, Julia S. Macromolecules, Vol. 43, Issue 9 https://doi.org/10.1021/ma902707u	journal	May 2010
Kinetics of Surface Segregation and the Approach to Wetting in an Isotopic Polymer Blend Geoghegan, M.; Nicolai, T.; Penfold, J. Macromolecules, Vol. 30, Issue 14 https://doi.org/10.1021/ma9603948	journal	July 1997
Detection of Surface-Immobilized Components and Their Role in Viscoelastic Reinforcement of Rubber–Silica Nanocomposites Mujtaba, A.; Keller, M.; Ilisch, S. ACS Macro Letters, Vol. 3, Issue 5 https://doi.org/10.1021/mz500192r	journal	April 2014
Theory and experiment of chain length effects on the adsorption of polyelectrolytes onto spherical particles: the long and the short of it Koumarianos, Sperydon; Kaiyum, Rohith; Barrett, Christopher J. Physical Chemistry Chemical Physics, Vol. 23, Issue 1 https://doi.org/10.1039/D0CP04359A	journal	January 2021
Contrast variation SANS measurement of shell monomer density profiles of smart core–shell microgels Cors, Marian; Wiehemeier, Lars; Wrede, Oliver Soft Matter, Vol. 16, Issue 7 https://doi.org/10.1039/c9sm02036e	journal	January 2020
Free Energy of a Nonuniform System. I. Interfacial Free Energy Cahn, John W.; Hilliard, John E. The Journal of Chemical Physics, Vol. 28, Issue 2 https://doi.org/10.1063/1.1744102	journal	February 1958
Many body effects on the phase separation and structure of dense polymer-particle melts Hall, Lisa M.; Schweizer, Kenneth S. The Journal of Chemical Physics, Vol. 128, Issue 23 https://doi.org/10.1063/1.2938379	journal	June 2008
Spinodal decomposition of a symmetric critical mixture of deuterated and protonated polymer Bates, Frank S.; Wiltzius, Pierre The Journal of Chemical Physics, Vol. 91, Issue 5 https://doi.org/10.1063/1.456901	journal	September 1989
Reversal of the isotopic effect in the surface behavior of binary polymer blends Hariharan, Arvind; Kumar, Sanat K.; Russell, Thomas P. The Journal of Chemical Physics, Vol. 98, Issue 5 https://doi.org/10.1063/1.465024	journal	March 1993
Free surfaces of polymer blends. II. Effects of molecular weight and applications to asymmetric polymer blends Hariharan, Arvind; Kumar, Sanat K.; Russell, Thomas P. The Journal of Chemical Physics, Vol. 99, Issue 5 https://doi.org/10.1063/1.466100	journal	September 1993
Focus: Structure and dynamics of the interfacial layer in polymer nanocomposites with attractive interactions Cheng, Shiwang; Carroll, Bobby; Bocharova, Vera The Journal of Chemical Physics, Vol. 146, Issue 20 https://doi.org/10.1063/1.4978504	journal	May 2017
Analysis and visualisation of neutron-scattering data Richard, D.; Ferrand, M.; Kearley, G. J. Journal of Neutron Research, Vol. 4, Issue 1 https://doi.org/10.1080/10238169608200065	journal	December 1996
Multiscale Structure, Interfacial Cohesion, Adsorbed Layers, and Thermodynamics in Dense Polymer-Nanoparticle Mixtures Kim, So Youn; Schweizer, Kenneth S.; Zukoski, Charles F. Physical Review Letters, Vol. 107, Issue 22 https://doi.org/10.1103/physrevlett.107.225504	journal	November 2011
Chain Conformation in Polymer Nanocomposites with Uniformly Dispersed Nanoparticles Crawford, M. K.; Smalley, R. J.; Cohen, G. Physical Review Letters, Vol. 110, Issue 19 https://doi.org/10.1103/physrevlett.110.196001	journal	May 2013
Unexpected Molecular Weight Effect in Polymer Nanocomposites Cheng, Shiwang; Holt, Adam P.; Wang, Huiqun Physical Review Letters, Vol. 116, Issue 3 https://doi.org/10.1103/physrevlett.116.038302	journal	January 2016
Initial Solvent-Driven Nonequilibrium Effect on Structure, Properties, and Dynamics of Polymer Nanocomposites Oh, Sol Mi; Abbasi, Mozhdeh; Shin, Tae Joo Physical Review Letters, Vol. 123, Issue 16 https://doi.org/10.1103/physrevlett.123.167801	journal	October 2019
Critical Behavior of Binary Liquid Mixtures of Deuterated and Protonated Polymers Bates, F. S.; Wignall, G. D.; Koehler, W. C. Physical Review Letters, Vol. 55, Issue 22 https://doi.org/10.1103/physrevlett.55.2425	journal	November 1985
Mean-field and Ising critical behavior of a polymer blend Schwahn, D.; Mortensen, K.; Yee-Madeira, H. Physical Review Letters, Vol. 58, Issue 15 https://doi.org/10.1103/physrevlett.58.1544	journal	April 1987
Surface Enrichment in an Isotopic Polymer Blend Jones, Richard A. L.; Kramer, Edward J.; Rafailovich, Miriam H. Physical Review Letters, Vol. 62, Issue 3 https://doi.org/10.1103/physrevlett.62.280	journal	January 1989
Surface-directed spinodal decomposition Jones, Richard A. L.; Norton, Laura J.; Kramer, Edward J. Physical Review Letters, Vol. 66, Issue 10 https://doi.org/10.1103/physrevlett.66.1326	journal	March 1991
Mean-field Ising crossover and the critical exponents γ, ν, and η for a polymer blend: d -PB/PS studied by small-angle neutron scattering Janssen, S.; Schwahn, D.; Springer, T. Physical Review Letters, Vol. 68, Issue 21 https://doi.org/10.1103/physrevlett.68.3180	journal	May 1992
Chain Conformations and Bound-Layer Correlations in Polymer Nanocomposites Sen, Sudeepto; Xie, Yuping; Kumar, Sanat K. Physical Review Letters, Vol. 98, Issue 12 https://doi.org/10.1103/physrevlett.98.128302	journal	March 2007
A multipurpose instrument for time-resolved ultra-small-angle and coherent X-ray scattering Narayanan, Theyencheri; Sztucki, Michael; Van Vaerenbergh, Pierre Journal of Applied Crystallography, Vol. 51, Issue 6 https://doi.org/10.1107/s1600576718012748	journal	October 2018
Densification of Alkoxide-Derived Fine Silica Powder Compact by Ultra-High-Pressure Cold Isostatic Pressing Kamiya, Hidehiro; Suzuki, Hisao; Kato, Daisuke Journal of the American Ceramic Society, Vol. 76, Issue 1 https://doi.org/10.1111/j.1151-2916.1993.tb03689.x	journal	January 1993
Impact of complex topology of porous media on phase separation of binary mixtures Shimizu, Ryotaro; Tanaka, Hajime Science Advances, Vol. 3, Issue 12 https://doi.org/10.1126/sciadv.aap9570	journal	December 2017
Nanoparticle Polymer Composites: Where Two Small Worlds Meet Balazs, A. C.; Emrick, T.; Russell, T. P. Science, Vol. 314, Issue 5802, p. 1107-1110 https://doi.org/10.1126/science.1130557	journal	November 2006
Mobile nanoparticles and their effect on phase separation dynamics in thin-film polymer blends Chung, H. -J; Taubert, A.; Deshmukh, R. D. Europhysics Letters (EPL), Vol. 68, Issue 2 https://doi.org/10.1209/epl/i2004-10242-2	journal	October 2004
Characterization of the depleted interfacial layer and chain desorption in polymer nanocomposites by SANS using numerical simulations. Caroline, GENIX Anne; Carroll, Bobby; Edouard, Chauveau Institut Laue-Langevin (ILL) https://doi.org/10.5291/ill-data.9-12-505	dataset	January 2018

Similar Records

Entropy and Enthalpy Mediated Segregation of Bottlebrush Copolymers to Interfaces

Journal Article · Tue Nov 12 23:00:00 EST 2019 · Macromolecules · OSTI ID:1606954

Reversal of the isotopic effect in the surface behavior of binary polymer blends

Journal Article · Sun Feb 28 23:00:00 EST 1993 · Journal of Chemical Physics; (United States) · OSTI ID:6771417

Impact of nanoparticle size and shape on selective surface segregation in polymer nanocomposites

Journal Article · Sat Dec 31 23:00:00 EST 2011 · Polymer · OSTI ID:1096327

Related Subjects

36 MATERIALS SCIENCE
chain-mass asymmetry
concentration fluctuations
interfacial segregation
isotopic polymer blends
low-q upturn
polymer nanocomposites
small-angle scattering

Direct Structural Evidence for Interfacial Gradients in Asymmetric Polymer Nanocomposite Blends

Citation Formats

References (55)

Similar Records

Related Subjects