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Copolymers are the products obtained from the polymerization of multiple monomer species. So, in a polymer chain itself, there can be multiple repeating units that come from different monomers. The process of synthesizing a polymer from different monomer species is called copolymerization. When two monomers are involved, the polymer is known as a bipolymer. Polymers with three and four monomers are termed terpolymers and quaterpolymers, respectively. Figure 1 depicts the copolymerization of...
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Polymers are classified as linear or branched on the basis of their chain architecture. The polymer chains in linear polymers have a long chain-like structure with minimal to no branching at all. Even if a polymer features large substituent groups on the monomer, which appear as branches to the skeleton, it is not considered a branched polymer. A branched polymer contains secondary polymer chains that arise from the main polymer chain. The branching occurs when the polymer growth shifts from...
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The polymerization process that involves carbanion as an intermediate is called anionic polymerization. It is also a type of addition or chain-growth polymerization. Anionic polymerization gets initiated by a strong nucleophile such as an organolithium or a Grignard reagent. The most commonly used initiator for anionic polymerization is butyl lithium. Monomers involved in anionic polymerization must possess a vinyl group bonded to one or two electron-withdrawing groups. For instance,...
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The cationic polymerization mechanism consists of three steps: initiation, propagation, and termination. In the initiation step of the polymerization process, the π bond of a monomer gets protonated by the Lewis acid catalyst, which is formed from boron trifluoride and water. The protonation of the π bond generates a carbocation stabilized by the electron‐donating group. In the propagation step, the π bond of the second monomer acts as a nucleophile and attacks the...
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Surface enrichment dictates block copolymer orientation.

Suwon Bae1, Marcus M Noack2, Kevin G Yager1

  • 1Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton, New York 11973, USA. kyager@bnl.gov.

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|March 6, 2023
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Summary
This summary is machine-generated.

Controlling block copolymer (BCP) orientation in thin films is key for nanocoatings. Machine learning guided simulations reveal vertical BCP orientation depends on interfacial energies and block properties, with lamellae being more robust than cylinders.

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Area of Science:

  • Materials Science
  • Polymer Science
  • Computational Materials Science

Background:

  • Orientation of block copolymer (BCP) morphology in thin films is crucial for nanostructured coatings.
  • Controlling BCP orientation across diverse block constituents remains a significant challenge in the field.

Purpose of the Study:

  • To investigate the factors governing diblock copolymer ordering and orientation in thin films.
  • To explore the multi-dimensional parameter space of BCP ordering using a machine-learning approach.

Main Methods:

  • Coarse-grained molecular dynamics simulations were employed to study BCP ordering.
  • A machine-learning approach utilizing a Gaussian process (GP) control algorithm guided the simulation parameter space exploration.
  • The GP model was engineered to capture system symmetries and extract material knowledge.

Main Results:

  • Vertical orientation of BCP phases is influenced by a balance of interfacial energetic contributions, including entropic/enthalpic enrichment, morphological distortion, and interfacial energies.
  • BCP lamellae exhibit robust vertical orientation across a wide range of conditions.
  • BCP cylinders demonstrate high sensitivity to surface tension disparity between constituent blocks.

Conclusions:

  • The study provides a comprehensive understanding of BCP orientation control in thin films.
  • Material knowledge was extracted, highlighting the distinct orientation behaviors of lamellar and cylindrical BCP morphologies.
  • This work advances the ability to tailor BCP thin films for advanced nanostructured coating applications.