Precise analyses of short-time relaxation at asymmetric polystyrene interface in terms of molecular weight by time-resolved neutron reflectivity measurements

Daisuke Kawaguchi, Andrew Nelson, Yuichi Masubuchi, Jaroslaw P. Majewski, Naoya Torikai, Norifumi L. Yamada, A. R. Siti Sarah, Atsushi Takano, Yushu Matsushita

Research output: Contribution to journalArticle

10 Citations (Scopus)

Abstract

The short-time mutual diffusion at an interface of linear polystyrene/linear deuterated polystyrene with different molecular weights was examined by time-resolved neutron reflectivity (TR-NR) measurements. The model scattering length density (b/V) profiles obtained by solving a partial differential equation for the diffusion process, using the segmental diffusion coefficients as the only fitting parameter were used to analyze the TR-NR data. In short-time diffusion, the asymmetric (b/V) profiles derived from a segmental relaxation model were able to model the data much better than those obtained by center-of-mass diffusion based on reptation model and by a simple error function. These analyses clearly indicate that even if the molecular weights of both components are larger than the critical molecular weight for entanglement, the initial interfacial broadening of bilayer films with different molecular weight proceeds with asymmetric mobility being proportional to N-1. Time dependence of the interfacial positions, u(t), was extracted from the (b/V) profiles. The exponent of α in u(t) ∼ tα reflects the asymmetric mobility of the components. This analysis also gave the time dependence of mutual diffusion coefficients, D. The D value gradually decreases with increasing time and reaches a constant value.

Original languageEnglish
Pages (from-to)9424-9433
Number of pages10
JournalMacromolecules
Volume44
Issue number23
DOIs
Publication statusPublished - Dec 13 2011

Fingerprint

Polystyrenes
Relaxation time
Neutrons
Molecular weight
Partial differential equations
Scattering

All Science Journal Classification (ASJC) codes

  • Organic Chemistry
  • Polymers and Plastics
  • Inorganic Chemistry
  • Materials Chemistry

Cite this

Precise analyses of short-time relaxation at asymmetric polystyrene interface in terms of molecular weight by time-resolved neutron reflectivity measurements. / Kawaguchi, Daisuke; Nelson, Andrew; Masubuchi, Yuichi; Majewski, Jaroslaw P.; Torikai, Naoya; Yamada, Norifumi L.; Siti Sarah, A. R.; Takano, Atsushi; Matsushita, Yushu.

In: Macromolecules, Vol. 44, No. 23, 13.12.2011, p. 9424-9433.

Research output: Contribution to journalArticle

Kawaguchi, D, Nelson, A, Masubuchi, Y, Majewski, JP, Torikai, N, Yamada, NL, Siti Sarah, AR, Takano, A & Matsushita, Y 2011, 'Precise analyses of short-time relaxation at asymmetric polystyrene interface in terms of molecular weight by time-resolved neutron reflectivity measurements', Macromolecules, vol. 44, no. 23, pp. 9424-9433. https://doi.org/10.1021/ma201717e
Kawaguchi, Daisuke ; Nelson, Andrew ; Masubuchi, Yuichi ; Majewski, Jaroslaw P. ; Torikai, Naoya ; Yamada, Norifumi L. ; Siti Sarah, A. R. ; Takano, Atsushi ; Matsushita, Yushu. / Precise analyses of short-time relaxation at asymmetric polystyrene interface in terms of molecular weight by time-resolved neutron reflectivity measurements. In: Macromolecules. 2011 ; Vol. 44, No. 23. pp. 9424-9433.
@article{71cb7a2daccf4457b70f9f0569d120b2,
title = "Precise analyses of short-time relaxation at asymmetric polystyrene interface in terms of molecular weight by time-resolved neutron reflectivity measurements",
abstract = "The short-time mutual diffusion at an interface of linear polystyrene/linear deuterated polystyrene with different molecular weights was examined by time-resolved neutron reflectivity (TR-NR) measurements. The model scattering length density (b/V) profiles obtained by solving a partial differential equation for the diffusion process, using the segmental diffusion coefficients as the only fitting parameter were used to analyze the TR-NR data. In short-time diffusion, the asymmetric (b/V) profiles derived from a segmental relaxation model were able to model the data much better than those obtained by center-of-mass diffusion based on reptation model and by a simple error function. These analyses clearly indicate that even if the molecular weights of both components are larger than the critical molecular weight for entanglement, the initial interfacial broadening of bilayer films with different molecular weight proceeds with asymmetric mobility being proportional to N-1. Time dependence of the interfacial positions, u(t), was extracted from the (b/V) profiles. The exponent of α in u(t) ∼ tα reflects the asymmetric mobility of the components. This analysis also gave the time dependence of mutual diffusion coefficients, D. The D value gradually decreases with increasing time and reaches a constant value.",
author = "Daisuke Kawaguchi and Andrew Nelson and Yuichi Masubuchi and Majewski, {Jaroslaw P.} and Naoya Torikai and Yamada, {Norifumi L.} and {Siti Sarah}, {A. R.} and Atsushi Takano and Yushu Matsushita",
year = "2011",
month = "12",
day = "13",
doi = "10.1021/ma201717e",
language = "English",
volume = "44",
pages = "9424--9433",
journal = "Macromolecules",
issn = "0024-9297",
publisher = "American Chemical Society",
number = "23",

}

TY - JOUR

T1 - Precise analyses of short-time relaxation at asymmetric polystyrene interface in terms of molecular weight by time-resolved neutron reflectivity measurements

AU - Kawaguchi, Daisuke

AU - Nelson, Andrew

AU - Masubuchi, Yuichi

AU - Majewski, Jaroslaw P.

AU - Torikai, Naoya

AU - Yamada, Norifumi L.

AU - Siti Sarah, A. R.

AU - Takano, Atsushi

AU - Matsushita, Yushu

PY - 2011/12/13

Y1 - 2011/12/13

N2 - The short-time mutual diffusion at an interface of linear polystyrene/linear deuterated polystyrene with different molecular weights was examined by time-resolved neutron reflectivity (TR-NR) measurements. The model scattering length density (b/V) profiles obtained by solving a partial differential equation for the diffusion process, using the segmental diffusion coefficients as the only fitting parameter were used to analyze the TR-NR data. In short-time diffusion, the asymmetric (b/V) profiles derived from a segmental relaxation model were able to model the data much better than those obtained by center-of-mass diffusion based on reptation model and by a simple error function. These analyses clearly indicate that even if the molecular weights of both components are larger than the critical molecular weight for entanglement, the initial interfacial broadening of bilayer films with different molecular weight proceeds with asymmetric mobility being proportional to N-1. Time dependence of the interfacial positions, u(t), was extracted from the (b/V) profiles. The exponent of α in u(t) ∼ tα reflects the asymmetric mobility of the components. This analysis also gave the time dependence of mutual diffusion coefficients, D. The D value gradually decreases with increasing time and reaches a constant value.

AB - The short-time mutual diffusion at an interface of linear polystyrene/linear deuterated polystyrene with different molecular weights was examined by time-resolved neutron reflectivity (TR-NR) measurements. The model scattering length density (b/V) profiles obtained by solving a partial differential equation for the diffusion process, using the segmental diffusion coefficients as the only fitting parameter were used to analyze the TR-NR data. In short-time diffusion, the asymmetric (b/V) profiles derived from a segmental relaxation model were able to model the data much better than those obtained by center-of-mass diffusion based on reptation model and by a simple error function. These analyses clearly indicate that even if the molecular weights of both components are larger than the critical molecular weight for entanglement, the initial interfacial broadening of bilayer films with different molecular weight proceeds with asymmetric mobility being proportional to N-1. Time dependence of the interfacial positions, u(t), was extracted from the (b/V) profiles. The exponent of α in u(t) ∼ tα reflects the asymmetric mobility of the components. This analysis also gave the time dependence of mutual diffusion coefficients, D. The D value gradually decreases with increasing time and reaches a constant value.

UR - http://www.scopus.com/inward/record.url?scp=82955206452&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=82955206452&partnerID=8YFLogxK

U2 - 10.1021/ma201717e

DO - 10.1021/ma201717e

M3 - Article

AN - SCOPUS:82955206452

VL - 44

SP - 9424

EP - 9433

JO - Macromolecules

JF - Macromolecules

SN - 0024-9297

IS - 23

ER -