Fabrication of mesoporous nanoparticle structures via co-solvent evaporation

• Applicant: Professor Dr. Marcus Müller
• Subject Area: Experimental and Theoretical Physics of Polymers ; Polymer Materials ; Statistical Physics, Nonlinear Dynamics, Complex Systems, Soft and Fluid Matter, Biological Physics
• Term: from 2014 to 2024
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 250780975

• Final Report Year: 2025

Final Report Abstract

Mesoporous materials hold significant promise for applications in catalysis, sensing, and lithium-ion batteries. Typically, these mesoporous structures are formed by solvent evaporation-induced self-assembly (EISA). As the relevant interactions are concentration-dependent, they vary in the course of evaporation, rendering the kinetics of structure formation – such as crystallization, macro- and microphase separation – process-dependent. We have investigated EISA using continuum models, in which solvent concentration profiles are obtained by numerically solving diffusion equations. In parallel, we have employed computationally efficient, soft coarse-grained particle models that inherently capture nonequilibrium molecular configurations and the coupling between segmental dynamics and collective kinetic processes. Our studies address a range of phenomena: crystallization at a receding film surface, evaporation kinetics in mixed solvent systems as well as systems containing active species, the interplay between single-chain dynamics and structure formation in diblock and multiblock copolymers, and the development of techniques to address the broad range of timescales associated with the slow, competitive adsorption of polymers onto surfaces. By combining and comparing continuum and particle-based simulations, we achieve a more comprehensive understanding of the structure formation process. Our work not only suggests improvements of the continuum models but also enables the optimization of processing conditions for the fabrication of well-ordered mesostructures.

Publications

• Anomalous Ostwald Ripening Enables 2D Polymer Crystals via Fast Evaporation. Physical Review Letters, 123(20).
  Tang, Qiyun; Müller, Marcus; Li, Christopher Y. & Hu, Wenbing
  
• Impact of Molecular Architecture on Defect Removal in Lamella-Forming Triblock Copolymers. Macromolecules, 53(13), 5337-5349.
  Ren, Yongzhi & Müller, Marcus
  
• Kinetic Pathways of Block Copolymer Directed Self-Assembly: Insights from Efficient Continuum Modeling. ACS Nano, 14(10), 13986-13994.
  Rottler, Jörg & Müller, Marcus
  
• Nonequilibrium Molecular Conformations in Polymer Self-Consistent Field Theory. Macromolecules, 53(23), 10457-10474.
  Müller, Marcus; Sollich, Peter & Sun, De-Wen
  
• Prediction of Kinetically Stable Nanotheranostic Superstructures: Integral of First-Passage Times from Constrained Simulations. Biomacromolecules, 21(12), 5008-5020.
  Tang, Qiyun; Rossner, Christian; Vana, Philipp & Müller, Marcus
  
• Process-directed self-assembly of copolymers: Results of and challenges for simulation studies. Progress in Polymer Science, 101, 101198.
  Müller, Marcus
  
• Self‐Assembly of Surface‐Acylated Cellulose Nanowhiskers and Graphene Oxide for Multiresponsive Janus‐Like Films with Time‐Dependent Dry‐State Structures. Small, 16(44).
  Liu, Huan; Pang, Bo; Tang, Qiyun; Müller, Marcus; Zhang, Hua; Dervişoğlu, Riza & Zhang, Kai
  
• Dynamics of Nonequilibrium Single-Chain Conformations in Triblock Copolymers. Macromolecules, 54(13), 6296-6311.
  Müller, Marcus
  
• Evaporation-Induced Liquid Expansion and Bubble Formation in Binary Mixtures. Physical Review Letters, 126(2).
  Tang, Qiyun & Müller, Marcus
  
• Liquid and Droplet Transport in Brush-Coated Cylindrical Nanochannels: Brush-Assisted Droplet Formation. The Journal of Physical Chemistry B, 125(1), 442-449.
  Pastorino, C. & Müller, M.
  
• Microscopic Model to Quantify the Difference of Energy-Transfer Rates between Bonded and Nonbonded Monomers in Polymers. Macromolecules, 54(23), 10969-10983.
  Pigard, Louis; Mukherji, Debashish; Rottler, Jörg & Müller, Marcus
  
• Nonequilibrium Processes in Polymer Membrane Formation: Theory and Experiment. Chemical Reviews, 121(22), 14189-14231.
  Müller, Marcus & Abetz, Volker
  
• Memory in the relaxation of a polymer density modulation. The Journal of Chemical Physics, 156(12).
  Müller, Marcus
  
• Phase Separation of Randomly Cross-Linked Diblock Copolymers. Macromolecules, 55(13), 5567-5580.
  Wang, Gaoyuan; Zippelius, Annette & Müller, Marcus
  
• Predicting protracted binding kinetics of polymers: Integral of first-passage times. Physical Review E, 110(4).
  Tang, Qiyun; Huang, Yifan & Müller, Marcus
  
• Suppression of bubbles in unstable active liquids via fast evaporation. Physical Review E, 110(5).
  Tang, Qiyun; Tang, Chuan; Huang, Yifan; Müller, Marcus & Ma, Yu-Qiang
  
• Can Dynamic Helical Polymers be Reduced to Linear Chains of Spins? Non-Local Effects from Polymer Self-Avoidance. Macromolecules, 58(11), 5408-5420.
  Chauhan, Keerti; Müller, Marcus & Daoulas, Kostas Ch