Order Remains Interior to a Ceramic Ionic Nanocluster Sterically Hindered by Covalently Attached Polymer Segments

Abstract

When a ceramic ionic-crystal nanocluster is group-substituted with polymer chain segments to form an ionomeric aggregate, is the ordered structure maintained within the sterically hindered nanocluster? We observed, for Na-salt sulfonated polystyrene ionomer, the electron-diffraction lattice fringes of the nanoclusters, which proved their internal crystalline ordering driven by electrostatic attractions overcoming steric hindrance. Kinetically, the nanoclusters’ enhanced melting endotherm upon aging indicate their quasi-, slow-ordering character. Extended tight binding molecular dynamics simulations provide an insight into the mechanism underlying the ionic-group aggregation during nanoclustering. We hence proposed an uncommon state of order, polymer-bound ceramic quasicrystal, supplementary to the order phenomena in crystalline ceramics.

Keywords

ceramic ionic nanocluster / polymer chain segment / morphology / order / molecular dynamics simulation

References

[1] Huang WT, He GJ, Tang WD, et al. . A Facile Approach to Realize Simultaneously Chain Extension and Crystallization Promotion of Poly (ethylene terephthalate). Polymer Degradation and Stability, 2021, 190: 109 644 J]

[2] Wang H, Yang Y, Nishiura M, et al. . Synthesis of Self-Healing Polymers by Scandium-Catalyzed Copolymerization of Ethylene and Anisylpropylenes. Journal of the American Chemical Society, 2019, 141(7): 3 249-3 257 J]

[3] Gilmour D, Tomkovic T, Kuanr N, et al. . Catalytic Amine Functionalization and Polymerization of Cyclic Alkenes Creates Adhesive and Self-Healing Materials. ACS Applied Polymer Materials, 2021, 3(5): 2 330-2 335 J]

[4] Kakinuma K, Kawamoto M, Tamoto K, et al. . Evaluation of Ionomer Distribution on Electrocatalysts for Polymer Electrolyte Fuel Cells by Use of a Low Acceleration Voltage Scanning Electron Microscope. Journal of the Electrochemical Society, 2021, 168(5): 054 510 J]

[5] Xu Z, Wang Y, Cao J, et al. . Adhesion between Asphalt Molecules and Acid Aggregates under Extreme Temperature: A Reaxff Reactive Molecular Dynamics Study. Construction and Building Materials, 2021, 285: 122 882 J]

[6] Fan Z, Lin J, Chen Z, et al. . Multiscale Understanding of Interfacial Behavior between Bitumen and Aggregate: From the Aggregate Mineralogical Genome Aspect. Construction and Building Materials, 2021, 271: 121 607 J]

[7] Tazikeh S, Kondori J, Zendehboudi S, et al. . Molecular Dynamics Simulation to Investigate the Effect of Polythiophene-Coated Fe₃O₄ Nanoparticles on Asphaltene Precipitation. Chemical Engineering Science, 2021, 237: 116 417 J]

[8] Longworth R, Vaughan DJ. Physical Structure of Ionomers. Nature, 1968, 218: 85-87 J]

[9] Delf B, MacKnight WJ. Low Angle X-ray Scattering from Ethylene-Methacrylic Acid Copolymers and Their Salts. Macromolecules, 1969, 2: 309-310 J]

[10] Yarusso DJ, Cooper SL. Microstructure of Ionomers: Interpretation of Small-Angle X-ray Scattering Data. Macromolecules, 1983, 16: 1 871-1 880 J]

[11] Born M, Green HS. A General Kinetic Theory of Liquids I. The Molecular Distribution Functions. Proceedings of the Royal Society of London. Series A, Mathematical and Physical Sciences, 1946, 188(1012): 10-18[C]

[12] Eisenberg A, Hird BT, Moore RB. A New Multiplet-Cluster Model for the Morphology of Random Ionomers. Macromolecules, 1990, 23: 4 098-4 107 J]

[13] Li C, Register RA, Cooper SL. Direct Observation of Ionic Aggregates in Sulphonated Polystyrene Ionomers. Polymer, 1989, 30(7): 1 227-1 233 J]

[14] Laurer JH, Winey KI. Direct Imaging of Ionic Aggregates in Zn-Neutralized Poly(ethylene-co-methacrylic acid) Copolymers. Macromolecules, 1998, 31(25): 9 106-9 108 J]

[15] Winey KI, Laurer JH, Kirkmeyer BP. Ionic Aggregates in Partially Zn-Neutralized Poly(ethylene-ran-methacrylic acid) Ionomers: Shape, Size, and Size Distribution. Macromolecules, 2000, 33(2): 507-513 J]

[16] Castagna A, Wang W, Winey K, et al. . Structure and Dynamics of Zinc-Neutralized Sulfonated Polystyrene Ionomers. Macromolecules, 2011, 44(8): 2791-2798 J]

[17] Benetatos NM, Chan CD, Winey KI. Quantitative Morphology Study of Cu-Neutralized Poly(styrene-ran-methacrylic acid) Ionomers: Stem Imaging, X-ray Scattering, and Real-Space Structural Modeling. Macromolecules, 2007, 40(4): 1 081-1 088 J]

[18] Wang W, Chan TT, Perkowski AJ, et al. . Local Structure and Composition of the Ionic Aggregates in Cu(II)-Neutralized Poly(styrene-co-methacrylic acid) Ionomers Depend on Acid Content and Neutralization Level. Polymer, 2009, 50(5): 1 281-1 287 J]

[19] Castagna AM, Wang W, Winey KI, et al. . Influence of Cation Type on Structure and Dynamics in Sulfonated Polystyrene Ionomers. Macromolecules, 2011, 44(13): 5 420-5 426 J]

[20] Zhou NC, Chan CD, Winey KI. Reconciling Stem and X-ray Scattering Data to Determine the Nanoscale Ionic Aggregate Morphology in Sulfonated Polystyrene Ionomers. Macromolecules, 2008, 41(16): 6 134-6 140 J]

[21] Sauer BB, McLean RS. AFM and X-ray Studies of Crystal and Ionic Domain Morphology in Poly(ethylene-co-methacrylic acid) Ionomers. Macromolecules, 2000, 33(21): 7 939-7 949 J]

[22] Kirkmeyer B, Weiss R, Winey K. Spherical and Vesicular Ionic Aggregates in Zn-Neutralized Sulfonated Polystyrene Ionomers. Journal of Polymer Science Part B: Polymer Physics, 2001, 39(5): 477-483 J]

[23] Kirkmeyer BP, Taubert A, Kim JS, et al. . Vesicular Ionic Aggregates in Poly(styrene-ran-methacrylic acid) Ionomers Neutralized with Cs. Macromolecules, 2002, 35(7): 2 648-2 653 J]

[24] Dalmas F, Leroy E. New Insights into Ionic Aggregate Morphology in Zn-Neutralized Sulfonated Polystyrene Ionomers by Transmission Electron Tomography. Macromolecules, 2011, 44: 8 093-8 099 J]

[25] Batra A, Cohen C, Kim H, et al. . Counterion Effect on the Rheology and Morphology of Tailored Poly(dimethylsiloxane) Ionomers. Macromolecules, 2006, 39(4): 1 630-1 638 J]

[26] Bolintineanu D, Stevens M, Frischknecht A. Influence of Cation Type on Ionic Aggregates in Precise Ionomers. Macromolecules, 2013, 46(13): 5 381-5 392 J]

[27] Wouters M, Goossens JGP, Binsbergen F. Morphology of Neutralized Low Molecular Weight Maleated Ethylene-Propylene Copolymers (MAn-g-EPM) As Investigated by Small-Angle X-ray Scattering. Macromolecules, 2002, 35(1): 208-216 J]

[28] Grady BP, Floyd JA, Genetti WB, et al. . X-ray Absorption Spectroscopy Studies of Zinc-Neutralized Ethylene-Methacrylic Acid Ionomers. Polymer, 1999, 40(2): 283-288 J]

[29] Grady B, Goossens JGP, Wouters M. Morphology of Zinc-Neutralized Maleated Ethylene-Propylene Copolymer Ionomers: Structure of Ionic Aggregates as Studied by X-ray Absorption Spectroscopy. Macromolecules, 2004, 37(23): 8 585-8 591 J]

[30] Yarusso DJ, Ding YS, Pan HK, et al. . EXAFS Analysis of the Structure of Ionomer Microdomains. Journal of Polymer Science: Polymer Physics Edition, 1984, 22(12): 2 073-2 093[J]

[31] Vlaic G, Williams CE, J’erome R, et al. . Microstructure of the Ionic Aggregates in Telechelic Ionomers. Polymer, 1988, 29(1): 173-176 J]

[32] Grady BP, Cooper SL. Extended X-ray Absorption Fine-Structure Studies of the Internal Aggregate Structure in Lightly Sulfonated Polystyrene. 1. Determination of the Coordination Environment about the Cation. Macromolecules, 1994, 27(22): 6 627-6 634 J]

[33] Tadano K, Hirasawa E, Yamamoto H, et al. . Order-Disorder Transition of Ionic Clusters in Ionomers. Macromolecules, 1989, 22(1): 226-233 J]

[34] Jia Y, Kleinhammes A, Wu Y. NMR Study of Structure and Dynamics of Ionic Multiplets in Ethylene-Methacrylic Acid Ionomers. Macromolecules, 2005, 38(7): 2 781-2 785 J]

[35] Crowther MW, Cabasso I, Levy GC. An NMR Study of Miscible Blends in Concentrated Solution. 1. Poly(vinyl methyl ether)/Polystyrene. Macromolecules, 1988, 21(10): 2 924-2 928 J]

[36] Coughlin J, Reisch A, Markarian M, et al. . Sulfonation of Polystyrene: Toward the “Ideal” Polyelectrolyte. Journal of Polymer Science Part A: Polymer Chemistry, 2013, 51(11): 2 416-2 424 J]

[37] Zundel G. Hydration and Intermolecular Interaction: Infrared Investigations with Polyelectrolyte Membranes, 2012, München. Elsevier

[38] Bannwarth C, Caldeweyher E, Ehlert S, et al. . Extended Tight-Binding Quantum Chemistry Methods. Wiley Interdisciplinary Reviews: Computational Molecular Science, 2021, 11(2): e1 493[J]

[39] Bannwarth C, Ehlert S, Grimme S. GFN2-xTB – An Accurate and Broadly Parametrized Self-Consistent Tight-Binding Quantum Chemical Method with Multipole Electrostatics and Density-Dependent Dispersion Contributions. Journal of Chemical Theory and Computation, 2019, 15(3): 1 652-1 671 J]

[40] Gorges J, Grimme S, Hansen A. Reliable Prediction of Association (Free) Energies of Supramolecular Complexes with Heavy Main Group Elements-the HS13L Benchmark Set. Physical Chemistry Chemical Physics, 2022, 24: 28 831-28 843 J]

[41] Bursch M, Neugebauer H, Grimme S. Structure Optimisation of Large Transition-Metal Complexes with Extended Tight-Binding Methods. Angewandte Chemie International Edition, 2019, 58(32): 11 078-11 087 J]

[42] Marx CL, Cooper SL. The Crystallinity of Ionomers. Journal of Macromolecular Science, 1974, 9(1): 19-33 J]

[43] Tsujita Y, Shibayama K, Takizawa A, et al. . Thermal Properties of Ethylene Ionomers. Journal of Applied Polymer Science, 1987, 33: 1 307-1 314 J]

[44] Kuwabara K, Horii F. Solid-State NMR Analyses of the Crystalline-Noncrystalline Structure and Its Thermal Changes for Ethylene Iono-mers. Journal of Polymer Science Part B: Polymer Physics, 2002, 40: 1 142-1 153 J]

[45] Loo YL, Wakabayashi K, Huang YE, et al. . Thin Crystal Melting Produces the Low-Temperature Endotherm in Ethylene/Methacrylic Acid Ionomers. Polymer, 2005, 46(14): 5 118-5 124 J]

[46] Weiss RA. The Effect of Aging on the Thermal Behavior of Sulfonated Polystyrene. Journal of Polymer Science: Polymer Physics Edition, 1982, 20(1): 65-72[J]

[47] Brozoski BA, Coleman MM, Painter PC. Further Annealing Studies of the Calcium Salt of an Ethylene-Methacrylic Acid Copolymer. Journal of Polymer Science: Polymer Physics Edition, 1983, 21(2): 301-308[J]

[48] Goddard RJ, Grady BP, Cooper SL. The Room Temperature Annealing Peak in Ionomers: Ionic Crystallites or Water Absorption. Macromolecules, 1994, 27(7): 1 710-1 719 J]

[49] Eisenberg A, Kim J. Introduction to Ionomers. Physics Today, 1999, 52(2): 68 J]

[50] Takagi M. Electron-Diffraction Study of Liquid-Solid Transition of Thin Metal Films. Journal of the Physical Society Japan, 1954, 9(3): 359-363 J]

[51] Humphrey W, Dalke A, Schulten K. VMD: Visual Molecular Dynamics. Journal of Molecular Graphics, 1996, 14(1): 33-38 J]

RIGHTS & PERMISSIONS

Wuhan University of Technology and Springer-Verlag GmbH Germany, Part of Springer Nature