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Gyroid Nickel Nanostructures from Diblock Copolymer Supramolecules

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Orientational interactions in block copolymer melts: self-consistent field theory.

Wei Zhao¹, Thomas P Russell, Gregory M Grason

¹Department of Polymer Science and Engineering, University of Massachusetts Amherst, Amherst, Massachusetts 01003, USA.

The Journal of Chemical Physics

|September 18, 2012

Summary

We investigated how orientational interactions affect diblock copolymer phase behavior. Increased stiffness (K) of orientational interactions raises the microphase separation threshold and creates asymmetric phase diagrams.

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Published on: October 10, 2016

Area of Science:

Polymer physics
Materials science
Soft matter physics

Background:

Diblock copolymers exhibit complex phase behavior crucial for materials applications.
Segmental interactions typically depend on monomer type, not orientation.
Understanding orientation-dependent interactions is key to controlling self-assembly.

Purpose of the Study:

To investigate the influence of orientation-dependent segmental interactions on diblock copolymer phase behavior.
To develop a theoretical framework incorporating orientational order and elasticity.
To analyze the impact of orientational stiffness (K) on microphase separation and morphology.

Main Methods:

Self-consistent field theory (SCFT) applied to diblock copolymer melts.
Development of a generalized coarse-grained model using orientational order parameters.
Analysis of two-dimensional melt morphologies across a range of Frank elastic constant (K) values.

Main Results:

Increasing orientational stiffness (K) elevates the critical chi N (χN) for microphase separation.
Strong orientational interactions lead to highly asymmetric phase diagrams.
A significant energetic penalty for high-splay morphologies (e.g., cylindrical phase) was observed.

Conclusions:

Orientational interactions significantly alter diblock copolymer self-assembly thermodynamics.
The Frank elastic constant (K) is a critical parameter controlling phase boundaries and morphology stability.
This work provides insights into designing polymers with tunable phase behavior through engineered orientational interactions.