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

Toth, Kristof; Yager, Kevin G.; Doerk, Gregory S.

doi:10.1039/d0ra08491c

Cited by 9 publications

(12 citation statements)

References 82 publications

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“…Similar expansions in interdomain distance as a function of chain length have been found in lamellae, cylinders, and spheres. ,,,− The Hashimoto group worked on phase behavior in mixtures of polystyrene- b -polyisoprene (PS- b -PI) and hPS of various molecular weights. , Their studies demonstrated that as short-chain hPS is selectively incorporated into the PS block, uniform distribution of short hPS chains is preferred. Consequently, there is a high probability for chemical junctions between two the constituent PS and PI blocks to be swollen by short hPS chains so that area per block chain at the swollen chemical junction can increase.…”

Section: Resultsmentioning

confidence: 70%

“…The level of complexity for BCP self-assembly in thin films − and bulk − can be increased by blending a homopolymer. The increased complexity is due to an interplay between spatial distributions of homopolymer chains in a BCP-based blend and the miscibility of homopolymer chains with constituent blocks of a BCP.…”

Section: Introductionmentioning

confidence: 99%

“…For athermal blends (i.e., A- b -B/A blends), there are three different spatial distributions of homopolymer A chains within self-assembled nanodomains: uniform distribution, local segregation, and macro-phase separation. The three different spatial distributions of type-A chains are mainly driven by the translational and conformational entropies. − Furthermore, the morphology (such as domain shape, size, interdomain distance, orientation, and even lattice order) of self-assembled BCP nanodomains can be readily controlled by the molecular weight of homopolymers. The size, orientation, and spatial order of nanodomains have been found to correlate with spatial distributions of added homopolymer chains in blend films. , Also thickness-dependent ordering kinetics and composition-dependent transition temperatures have been found for thin films.…”

Section: Introductionmentioning

confidence: 99%

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Chain Length Effects of Added Homopolymers on the Phase Behavior in Blend Films of a Symmetric, Weakly Segregated Polystyrene-block-poly(methyl methacrylate)

et al. 2022

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We have demonstrated the effects of different chain lengths on the phase behavior in films of binary blends of four different weight fractions in a weak segregation limit. The binary blends were composed of nearly symmetric polystyrene-block-poly(methyl methacrylate), PS-b-PMMA, and homo-polystyrenes (PS) of three different molecular weights (hereafter hPS 2.8 , hPS 6 , and hPS 17 ). Films of two initial thicknesses were prepared by spin coating of the blends. After thermal annealing at 270 °C (1 h), a series of nanodomains, including perforated layers, double gyroid, cylinders, and spheres, were obtained in sequence as the volume fractions of PS increased in blend films. Perforated layers and double gyroid only exist in PS-b-PMMA-rich blend films, with hPS 2.8 /PS-b-PMMA blends overwhelmingly favoring perforated layers, regardless of film thickness. However, with a small amount of hPS 6 chains, PS-b-PMMA-rich blends preferentially form hexagonally perforated layers in thin films but double gyroid in thick films; at the same composition, PS-b-PMMA-rich blends with hPS 17 chains only form hexagonally perforated layers. Cylinders only formed in blend films of equal weight fractions of PS-b-PMMA and PS. The cylinders with hPS 2.8 and hPS 6 chains favor parallel orientation, but cylinders with hPS 17 PS chains favor a mixed orientation. Spheres predominantly formed in PS-rich blend films, where four types of domain ordering (hexagonal packing, body-centered cubic (BCC), face-centered cubic (FCC), and short-range order) were obtained. For blend films prepared in the PS-rich regions, the four types of ordering depend on chain length and film thickness. The PS-b-PMMA blend films with hPS 2.8 chains predominantly favor hexagonal packing of spheres for thin films but BCC packing of spheres for thick films. Under the same PS-rich region, the PS-b-PMMA blend films with hPS 6 chains predominantly favor hexagonal arrays of spheres in thin films but FCC-packed arrays of spheres in thick films. The PS-b-PMMA blend films with hPS 17 chains predominantly favor short-rangeorder spheres or a mixture of spheres and cylinders with no lattice packing. All of the above findings are explained by the correlation between the variations in chain length and alleviating packing frustration.

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Section: Resultsmentioning

confidence: 70%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Chain Length Effects of Added Homopolymers on the Phase Behavior in Blend Films of a Symmetric, Weakly Segregated Polystyrene-block-poly(methyl methacrylate)

et al. 2022

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“…ESD and GISAXS were used in a way analogous to what has been described in our previous work to systematically survey the combined effects of film thickness and composition. The basis for this survey is schematically depicted in Figure .…”

Section: Results and Discussionmentioning

confidence: 99%

“…Systematic sample preparation and analysis are made possible using electrospray deposition (ESD) , to produce samples with different film thicknesses, all having gradients in composition from pure BCP to pure HP (at 1:1 PS:PMMA mass fractions). These samples are subsequently characterized using grazing-incidence small-angle X-ray scattering (GISAXS), through which domain spacing can be extracted as a function of film thickness and composition. Analysis of these data demonstrates unequivocally that HP can increase or decrease the domain spacing in BCP-HP blends depending on the HP molar mass.…”

Section: Introductionmentioning

confidence: 99%

Film Thickness and Composition Effects in Symmetric Ternary Block Copolymer/Homopolymer Blend Films: Domain Spacing and Orientation

et al. 2021

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We report thickness and homopolymer molar mass dependencies in thin film blends of a compositionally symmetric 75 kg/mol lamellar polystyrene-block-poly(methyl methacrylate) diblock copolymer (PS-b-PMMA) with near-equal volume fractions of PS and PMMA homopolymers on "neutral" surfaces that promote a vertical domain orientation. PS and PMMA homopolymers with equal molar masses of 1, 3, and 22 kg/mol are blended in a 1:1 mass ratio. To efficiently explore this parameter space, we prepared combinatorial samples with gradient homopolymer concentrations using electrospray deposition (ESD) and gradient film thicknesses using flow coating; these samples were subsequently characterized by grazing-incidence small-angle X-ray scattering and scanning electron microscopy, respectively. Our results demonstrate that the added homopolymers increase or reduce domain spacings with respect to the neat (unblended) block copolymer depending on their molar masses, in line with previous reports; a simple heuristic to estimate the domain scaling in ternary blends based on the homopolymer molar mass agrees well with data for the thinnest blend films studied here. More surprisingly, we observe that the measured domain spacing in blends also depends on film thickness, with thicker films exhibiting larger domain spacings than thinner films at the same homopolymer concentration. Furthermore, thickness gradients at fixed homopolymer concentrations reveal a change in lamellae orientation from vertical to horizontal as film thickness is increased beyond the nominal lamellar domain spacing. Coarse-grained molecular dynamics simulations indicate that this change in orientation is induced by homopolymer segregation to film surfaces. Tying these effects together, we hypothesize that the observed dependence of domain spacing on film thickness is a consequence of changes in the vertical homopolymer composition profile in thicker films during lamellae reorientation and the conformational asymmetry between PMMA and PS segments.

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Intelligent Biomaterialomics: Molecular Design, Manufacturing, and Biomedical Applications

Wang

2023

Advanced Materials

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Materialomics integrates experiment, theory, and computation in a high‐throughput manner, and has changed the paradigm for the research and development of new functional materials. Recently, with the rapid development of high‐throughput characterization and machine‐learning technologies, the establishment of biomaterialomics that tackles complex physiological behaviors has become accessible. Breakthroughs in the clinical translation of nanoparticle‐based therapeutics and vaccines have been observed. Herein, recent advances in biomaterials, including polymers, lipid‐like materials, and peptides/proteins, discovered through high‐throughput screening or machine learning‐assisted methods, are summarized. The molecular design of structure‐diversified libraries; high‐throughput characterization, screening, and preparation; and, their applications in drug delivery and clinical translation are discussed in detail. Furthermore, the prospects and main challenges in future biomaterialomics and high‐throughput screening development are highlighted.This article is protected by copyright. All rights reserved

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

Abstract: Compositionally graded electrospray deposition combined with grazing incidence small angle X-ray scattering forms a high-throughput approach for mapping phase behavior in ternary mixtures as demonstrated here using block copolymer blends.

Cited by 9 publications

References 82 publications

Chain Length Effects of Added Homopolymers on the Phase Behavior in Blend Films of a Symmetric, Weakly Segregated Polystyrene-block-poly(methyl methacrylate)

Chain Length Effects of Added Homopolymers on the Phase Behavior in Blend Films of a Symmetric, Weakly Segregated Polystyrene-block-poly(methyl methacrylate)

Film Thickness and Composition Effects in Symmetric Ternary Block Copolymer/Homopolymer Blend Films: Domain Spacing and Orientation

Intelligent Biomaterialomics: Molecular Design, Manufacturing, and Biomedical Applications

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