Utilizing vapor swelling of surface-initiated polymer brushes to develop quantitative measurements of brush thermodynamics and grafting density

Orski, Sara V.; Sheridan, Richard J.; Chan, Edwin P.; Beers, Kathryn L.

doi:10.1016/j.polymer.2015.05.030

Cited by 33 publications

(49 citation statements)

References 61 publications

(54 reference statements)

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“…Unfortunately, there is currently no known way to measure σ nondestructively. 42,43 As mentioned earlier, in a grafted polymer film, the dry thickness (h) is proportional to MW*σ. Assuming that the MW of the PtBMA chains does not depend on σ, any variation in h is due primarily to variation in σ.…”

Section: Macromoleculesmentioning

confidence: 86%

Instability of Surface-Grafted Weak Polyacid Brushes on Flat Substrates

et al. 2015

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We study the stability of weak polyacid brush (WPAB) gradients in aqueous media covering a range in grafting density (σ) spanning 0.05−0.5 chains/nm 2 using two analogous surface-anchored bromoisobutyrate-based initiators for atom transfer radical polymerization (ATRP) bearing either an ester or amide linker. Variations in dry thickness of ester-based WPABs as a function of time and pH are consistent with WPAB degrafting via linker hydrolysis catalyzed by mechanical tension in the grafted chains. Sources of tension considered include high σ, as well as swelling and electrostatic repulsion associated with increasing degree of deprotonation (α) of repeat units in the WPAB. Normalized thickness of the WPAB decreases by a maximum amount at intermediate σ between ∼0.05−0.15 chains/nm 2 , implying that contributions to tension by α are counterbalanced by charge regulation in the WPAB at high σ. Amide-based WPABs are more stable up to 264 h incubation, suggesting that commonly used ester-bearing ATRP initiators are more susceptible to hydrolysis over the time scales examined.

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Section: Macromoleculesmentioning

confidence: 86%

Instability of Surface-Grafted Weak Polyacid Brushes on Flat Substrates

et al. 2015

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“…We have successfully applied a new swelling model, a model based on Painter‐Shenoy for gel‐like swelling that incorporates the Leibler‐Sekimoto theory for Langmuir sorption, to extract the network parameters of the polyamide thin films. We anticipate that this proposed model can be applied to a variety of heterogeneous polymeric materials where swelling behavior is a function of physical properties, such as polyelectrolyte layer‐by‐layer films, polymer brushes, nanophase segregated materials, as well as polymer glasses.…”

Section: Discussionmentioning

confidence: 99%

Thickness‐dependent swelling of molecular layer‐by‐layer polyamide nanomembranes

Chan

Lee

2017

J Polym Sci B Polym Phys

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The thickness‐dependent water vapor swelling of molecular layer‐by‐layer polyamide films is studied via specular X‐ray reflectivity. The maximum swelling ratio of these ultrathin films scale inversely with thickness but more importantly show a dual‐mode sorption behavior characterized by Langmuir‐like sorption at low relative humidity and network swelling at high relative humidity. The thickness‐dependent network parameters are extracted using a proposed model that builds on Painter‐Shenoy network swelling model while taking into account the glass‐like characteristic below a critical swelling ratio, which also scales inversely with thickness. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017, 55, 412–417

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“…Sheiko [75] presents a methodology that leads to materials with triple shape memory, in which various shapes may be encoded at the same temperature. The paper by Beers [76] discusses the swelling behavior of extended polymer brushes and provides a method to determine graft density based on solvation thermodynamics. Mueller [77] offers detailed fundamental studies of the morphological behavior (phase separation in the bulk phase) of a series of triblock copolymers, in which the block sizes are systematically varied.…”

Section: Contents Lists Available At Sciencedirectmentioning

confidence: 99%

Introduction to the special issue of Polymer on “Macromolecular Engineering” dedicated to Professor Krzysztof Matyjaszewski on the occasion of his 65th birthday

Tsarevsky

2015

Polymer

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Utilizing vapor swelling of surface-initiated polymer brushes to develop quantitative measurements of brush thermodynamics and grafting density

Cited by 33 publications

References 61 publications

Instability of Surface-Grafted Weak Polyacid Brushes on Flat Substrates

Instability of Surface-Grafted Weak Polyacid Brushes on Flat Substrates

Thickness‐dependent swelling of molecular layer‐by‐layer polyamide nanomembranes

Introduction to the special issue of Polymer on “Macromolecular Engineering” dedicated to Professor Krzysztof Matyjaszewski on the occasion of his 65th birthday

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