Conformational Relaxation of Poly(styrene-<i>co</i>-butadiene) Chains at Substrate Interface in Spin-Coated and Solvent-Cast Films

Zuo, Biao; Inutsuka, Manabu; Kawaguchi, Daisuke; Wang, Xinping; Tanaka, Keiji

doi:10.1021/acs.macromol.7b02756

Cited by 49 publications

(30 citation statements)

References 80 publications

(128 reference statements)

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“…Hence, it can be claimed that the relaxation of the SFG peaks is directly connected to the intrinsic dynamics of chains in the strongly adsorbed layer. 42 Similarly, we also reported that PI chains in direct contact with the SiO 2 surface were relaxed at (T g b + 125) K. 41 Although the adsorbed PI chains were fully relaxed with increasing temperature up to (T g b + 130) K, 41 such a full relaxation was not here observed for adsorbed NBR chains. At 423 K, (∼(T g b + 180) K), while the SFG peaks corresponding to different CH stretching vibration modes decreased, the peak arisen from CN groups increased, as shown in Figure 3.…”

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confidence: 72%

Dynamics Gradient of Polymer Chains near a Solid Interface

et al. 2019

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The relaxation dynamics of polyisoprene (PI) and nitrile butadiene rubber (NBR) chains at the SiO2 interface were directly probed as a function of distance from the SiO2 surface using time-resolved evanescent wave-induced fluorescence anisotropy, dielectric relaxation spectroscopy, and sum-frequency generation spectroscopy. We found the presence of the dynamics gradient of chains in the interfacial region with the SiO2 surface and tried to assign it to the two kinds of adsorbed chains, namely, loosely and strongly adsorbed, at the interface. The segmental relaxation of chains in the strongly adsorbed layer at the interface could be slower than that of bulk chains by more than 10 orders.

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confidence: 72%

Dynamics Gradient of Polymer Chains near a Solid Interface

et al. 2019

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“…These results indicate the tangential orientation of the phenyl rings in immediate contact with the NP surface, which gradually decreases as the radial distance increases. 62 − 67 As a matter of fact, the styrene chains in the interfacial region expose mainly their phenyl rings to the NP ( Figure 7 c). Interestingly, even though the torsion of the styrene segment is only considered a representing torsion of the segment, the orientational order parameter S for the SSBR/TESPT-PIL composite model requires greater separation to reach the average bulk value ( S = 0) than that in the SSBR/TESPT composite model at the same temperature.…”

Section: Resultsmentioning

confidence: 99%

Role of Interface Structure and Chain Dynamics on the Diverging Glass Transition Behavior of SSBR-SiO₂-PIL Elastomers

Sattar

Patnaik

2020

ACS Omega

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Intermolecular interactions between the constituents of a polymer nanocomposite at the polymer–particle interface strongly affect the segmental mobility of polymer chains, correlated with their glass transition behavior, and are responsible for the improved dynamical viscoelastic properties. In this work, we emphasized on the evolution of characteristic interfaces and their dynamics in silica (SiO 2 NP)-reinforced, solution-polymerized, styrene butadiene rubber (SSBR) composites, whose relative prevalence varied with the phosphonium ionic liquid (PIL) volume fraction, used as an interfacial modifier. The molecular origins of such interfaces were examined through systematic dielectric spectroscopy, molecular dynamics (MD) simulations, and dynamic-mechanical analyses. The PIL facilitated H-bonding, cation−π, surface–phenyl, and van der Waals interfacial interactions between SSBR and SiO 2 NP, thereby regulating the polymer chain dynamics, orientation, and mean-square displacement. Specifically, the mass density profiles from MD simulations revealed the dynamic gradient of polymer chains in the interfacial region as a function of radial distance from the center of mass of the SiO 2 NP surface. The results showed a structuring effect to result in well-resolved density peaks at specific radial distances with the tangential orientation of styrene monomers in the vicinity of the SiO 2 NP surface. These domino effects highlighted strong interfacial interactions to have an indispensable effect on the viscoelastic performance and thermal motion of SSBR molecular chains, leading to a higher glass transition temperature ( T g ) by ∼15 K, validating the experimental data. More importantly, our results gave new insights into the fundamental understanding of the fact that the strength of intermolecular interactions induced by PIL at the polymer–particle interface is the key to control the α-relaxation dynamics and T g optimization, desired for specific applications.

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“…However, these techniques lack general monolayer surface and interfacial selectivity and sensitivity. Over the past three decades, sum frequency generation (SFG) vibrational spectroscopy has proven to be a powerful technique to directly and nondestructively study polymer surfaces/interfaces due to its inherently surface/interfacial specific selectivity and sensitivity, and its capability to provide molecular level structural information in situ. − SFG has been used extensively to characterize molecular structures at buried polymer/solid or polymer/liquid interfaces. ,, In this study, we push the boundaries of SFG to systematically analyze chemical reactions at the buried polymer/polymer interface of nylon and maleic-anhydride grafted polyethylene.…”

Section: Introductionmentioning

confidence: 99%

Observing a Chemical Reaction at a Buried Solid/Solid Interface in Situ

Andre

Chen

et al. 2020

Anal. Chem.

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Chemical reactions are the most important phenomena in chemistry. However, chemical reactions at buried solid/solid interfaces are very difficult to study in situ. In this research, the chemical reaction between two solid polymer materials, a nylon film and a maleic anhydride (MAH) grafted poly(ethylene-octene) (MAHgEO) sample, was directly analyzed at the buried nylon/MAHgEO interface at the molecular level in real time and in situ, using surface and interface sensitive sum-frequency generation (SFG) vibrational spectroscopy. Disappearance of nylon signals indicated a chemical reaction between amine and hydrolyzed amide groups of nylon and MAH groups on the MAHgEO at the buried interface. The appearance of SFG signals from reaction products was also observed at the buried nylon/MAHgEO interface. The mechanism of the observed interfacial reaction was further analyzed. Temperature-dependent SFG experiments were performed to measure the activation energy of the interfacial reaction, enabling a comparison with that reported for the bulk materials. The interfacial chemical reaction between nylon and MAHgEO greatly improved the adhesion of these dissimilar materials. The detailed analysis of a chemical reaction between two polymers at the polymer/polymer buried interface underscores the utility of SFG as a powerful analytical tool to build understanding of buried interfaces and to accelerate the design of interfacial structures with desired properties.

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Conformational Relaxation of Poly(styrene-co-butadiene) Chains at Substrate Interface in Spin-Coated and Solvent-Cast Films

Cited by 49 publications

References 80 publications

Dynamics Gradient of Polymer Chains near a Solid Interface

Dynamics Gradient of Polymer Chains near a Solid Interface

Role of Interface Structure and Chain Dynamics on the Diverging Glass Transition Behavior of SSBR-SiO₂-PIL Elastomers

Observing a Chemical Reaction at a Buried Solid/Solid Interface in Situ

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Conformational Relaxation of Poly(styrene-co-butadiene) Chains at Substrate Interface in Spin-Coated and Solvent-Cast Films

Cited by 49 publications

References 80 publications

Dynamics Gradient of Polymer Chains near a Solid Interface

Dynamics Gradient of Polymer Chains near a Solid Interface

Role of Interface Structure and Chain Dynamics on the Diverging Glass Transition Behavior of SSBR-SiO2-PIL Elastomers

Observing a Chemical Reaction at a Buried Solid/Solid Interface in Situ

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Product

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Role of Interface Structure and Chain Dynamics on the Diverging Glass Transition Behavior of SSBR-SiO₂-PIL Elastomers