Abstract
Polyhedral oligomeric silsesquioxane (POSS) based materials are a class of organic/inorganic hybrid nanomaterials with many interesting properties. Recent experiments have demonstrated that self-assembly of tethered POSS nanocubes is a promising route to the synthesis of novel materials with highly ordered, complex nanostructures. Using a coarsegrained model developed for tethered POSS, we perform molecular simulations of POSS molecules tethered by short polymers to investigate how the novel architecture of these hybrid building blocks can be exploited to achieve useful structures via self-assembly. We systematically explore the parameters that control the assembly process and the resulting equilibrium structures, including concentration, temperature, tethered POSS molecular topology, and solvent conditions. We report preliminary results of lamellar and cylindrical structures that are typically found in conventional block copolymer and surfactant systems, but with interesting modifications of the phase behavior caused by the bulkiness and cubic geometry of the POSS molecules.
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References
G. S. Grest and K. Kremer, “Molecular-Dynamics Simulation for Polymers in the Presence of a Heat Bath,” Physical Review A, vol. 33, pp. 3628–3631, 1986.
J. D. Lichtenhan, “Polyhedral Oligomeric Silsesquioxanes - Building-Blocks for Silsesquioxane-Based Polymers and Hybrid Materials,” Comments on Inorganic Chemistry, vol. 17, pp. 115–130, 1995.
A. Provatas and J. G. Matisons, “Silsesquioxanes: Synthesis and applications,” Trends in Polymer Science, vol. 5, pp. 327–332, 1997.
R. M. Laine, C. X. Zhang, A. Sellinger, and L. Viculis, “Polyfunctional cubic silsesquioxanes as building blocks for organic/inorganic hybrids,” Applied Organometallic Chemistry, vol. 12, pp. 715–723, 1998.
C. Sanchez, G. Soler-Illia, F. Ribot, T. Lalot, C. R. Mayer, and V. Cabuil, “Designed hybrid organic-inorganic nanocomposites from functional nanobuilding blocks,” Chemistry of Materials, vol. 13, pp. 3061–3083, 2001.
J. D. Lichtenhan, J. J. Schwab, and W. A. Reinerth, “Nanostructured chemicals: A new era in chemical technology,” Chemical Innovation, vol. 31, pp. 3–5, 2001.
F. J. Feher and T. A. Budzichowski, “Silasesquioxanes as Ligands in Inorganic and Organometallic Chemistry,” Polyhedron, vol. 14, pp. 3239–3253, 1995.
G. Z. Li, L. C. Wang, H. L. Ni, and C. U. Pittman, “Polyhedral oligomeric silsesquioxane (POSS) polymers and copolymers: A review,” Journal of Inorganic and Organometallic Polymers, vol. 11, pp. 123–154, 2001.
R. Knischka, F. Dietsche, R. Hanselmann, H. Frey, R. Mulhaupt, and P. J. Lutz, “Silsesquioxane-based amphiphiles,” Langmuir, vol. 15, pp. 4752–4756, 1999.
K. M. Kim, D. K. Keum, and Y. Chujo, “Organic-inorganic polymer hybrids using polyoxazoline initiated by functionalized silsesquioxane,” Macromolecules, vol. 36, pp. 867–875, 2003.
G. Cardoen, E. Burgaz, S. P. Gido, and E. B. Coughlin, “Self-assembly of organic-inorganic hybrid copolymers,” Polymer Preprints (American Chemical Society, Division of Polymer Chemistry), vol. 44, pp. 252–253, 2003.
B. S. Kim and P. T. Mather, “Amphiphilic telechelics incorporating polyhedral oligosilsesquioxane: 1. Synthesis and characterization,” Macromolecules, vol. 35, pp. 8378–8384, 2002.
C. M. Leu, G. M. Reddy, K. H. Wei, and C. F. Shu, “Synthesis and dielectric properties of polyimide-chain-end tethered polyhedral oligomeric silsesquioxane nanocomposites,” Chemistry of Materials, vol. 15, pp. 2261–2265, 2003.
J. Pyun, K. Matyjaszewski, J. Wu, G. M. Kim, S. B. Chun, and P. T. Mather, “ABA triblock copolymers containing polyhedral oligomeric silsesquioxane pendant groups: synthesis and unique properties,” Polymer, vol. 44, pp. 2739–2750, 2003.
L. Zheng, S. Hong, G. Cardoen, E. Burgaz, S. P. Gido, and E. B. Coughlin, “Polymer Nanocomposites through Controlled Self-Assembly of Cubic Silsesquioxane Scaffolds,” Macromolecules, vol. 37, pp. 8606–8611, 2004.
Z. L. Zhang, M. A. Horsch, M. H. Lamm, and S. C. Glotzer, “Tethered nano building blocks: Toward a conceptual framework for nanoparticle self-assembly,” Nano Letters, vol. 3, pp. 1341–1346, 2003.
M. H. Lamm, T. Chen, and S. C. Glotzer, “Simulated assembly of nanostructured organic/inorganic networks,” Nano Letters, vol. 3, pp. 989–994, 2003.
G. S. Grest, M. D. Lacasse, K. Kremer, and A. M. Gupta, “Efficient continuum model for simulating polymer blends and copolymers,” Journal of Chemical Physics, vol. 105, pp. 10583–10594, 1996.
X. Zhang, E. R. Chan, F. Qi, J. Kieffer, and S. C. Glotzer, manuscript in preparation.
E. R. Chan, X. Zhang, C.-Y. Lee, M. Neurock, and S. C. Glotzer, “Simulations of Tetra-Tethered Organic/Inorganic Nanocube-Polymer Assemblies,” Macromolecules, submitted.
L. C. Ho, E. R. Chan, X. Zhang, and S. C. Glotzer, manuscript in preparation.
F. S. Bates and G. H. Fredrickson, “Block copolymers - Designer soft materials,” Physics Today, vol. 52, pp. 32–38, 1999.
C. I. Huang and T. P. Lodge, “Self-consistent calculations of block copolymer solution phase behavior,” Macromolecules, vol. 31, pp. 3556–3565, 1998.
Acknowledgments
Financial support for this work has been provided by the National Science Foundation under grant no. DMR-0103399. We thank P.T. Cummings, J. Kieffer, C. McCabe, and M. Neurock for insightful conversations and collaboration as part of a larger effort to model POSS-polymer systems. We also thank the National Partnership for Advanced Computational Infrastructure (NPACI) and the University of Michigan Center for Advanced Computing for computer cluster support.
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Zhang, X., Chan, E.R., Ho, L.C. et al. Simulations of Organic-tethered Silsesquioxane Nanocube Assemblies. MRS Online Proceedings Library 847, 1–5 (2004). https://doi.org/10.1557/PROC-847-EE13.12
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DOI: https://doi.org/10.1557/PROC-847-EE13.12