Nanostructure stability and swelling of ternary block copolymer/homopolymer blends: A direct comparison between dissipative particle dynamics and experiment

Abstract

Ternary block copolymer (BCP)-homopolymer (HP) blends offer a simple method for tuning nanostructure sizes to meet application-specific demands. Comprehensive dissipative particle dynamic (DPD) simulations were performed to study the impact of polymer interactions, molecular weight, and HP volume fraction (φ HP ) on symmetric ternary blend morphological stability and domain spacing. DPD reproduces key features of the experimental phase diagram, including lamellar domain swelling with increasing φ HP , the formation of an asymmetric bicontinuous microemulsion at a critical HP concentration φ * HP , and macrophase separation with further HP addition. Simulation results matched experimental values for φ * HP and lamellar swelling as a function of HP to BCP chain length ratio, α = N HP /N BCP . Structural analysis of blends with fixed φ HP but varying α confirmed that ternary blends follow the wet/dry brush model of domain swelling with the miscibility of HPs and BCPs depending on α. Longer HPs concentrate in the center of domains, boosting their swelling efficiencies compared to shorter chains. These results advance our understanding of BCP-HP blend phase behavior and demonstrate the value of DPD for studying polymeric blends.

Integration of Polymer Synthesis and Self‐Assembly for Controlled Periodicity and Photonic Properties

“…The bright regions correspond to the PS domains with a higher mechanical modulus [17] that expanded in size with increasing polymerization time. As reported in previous work, [18] this expansion correlates well with the content of synthesized homopolymer, which could be estimated by the increase of film thickness measured by spectroscopic ellipsometry (Table S1, Supporting Information). As the polymerization time increased from 25 to 180 min, the homopolymer content increased from 4.9% to 19.0% (Table S1, Supporting Information).…”

“…In A‐ b ‐B/A/B ternary BCP‐homopolymer blends forming LAM structures, it has been reported that shorter homopolymers are less efficient at swelling BCP domains. [ 18 ] In other words, domain swelling decreases with decreasing molecular weight of homopolymers for a given volume fraction of homopolymer in the blend. Similar effects are seen in the in‐film polymerized films.…”

High-throughput morphology mapping of self-assembling ternary polymer blends

“…14,21,22,29 This is in contrast to more well-studied blends with higher molecular weight homopolymers, where homopolymer localization at domain centers leads to substantial increases in domain widths and spacings. 14,15,[30][31][32][33][34][35] The combination of enhanced ordering kinetics with reduced domain spacing makes blending of wet brush homopolymers especially appealing for nanolithographic applications, motivated by decreased dimensions required by continued device scaling 3,5 or patterned magnetic media. 36 Blending is also a powerful approach to rationally control self-assembled nanodomain morphology, 35,[37][38][39][40][41] in some cases obtaining ordered morphologies that are inaccessible using neat (unblended) BCPs.…”

DPD Study on the Interfacial Properties of PEO/PEO-PPO-PEO/PPO Ternary Blends: Effects of Pluronic Structure and Concentration

“…We constructed the model of this work based on our previous studies and other studies, refs. [ 19 , 20 , 21 , 22 , 23 , 24 , 25 , 26 , 27 , 28 , 29 , 30 , 31 , 32 , 33 , 34 , 35 , 36 ]. Interested readers could refer to the details in these works.…”