Direct Observation of Conformational Relaxation of Polymer Chains at Surfaces.

Sum-frequency generation spectroscopy was employed to follow the conformation evolution of polystyrene chains at the surface of a spin-coated film in a temperature-ramping mode as well as under isothermal annealing. The conformation of surface chains in an as-cast film was observed to be in a nonequilibrium state, in accordance with reported results for polymer chains in thin spin-coated films. While the relaxation of surface nonequilibrium chains was induced by the enhanced surface mobility, the whole chain motion such as reptation might be a key factor in determining the time scale for equilibrating the surface chain conformation.

[1]  Manabu Inutsuka,et al.  Conformational Relaxation of Poly(styrene-co-butadiene) Chains at Substrate Interface in Spin-Coated and Solvent-Cast Films , 2018 .

[2]  Manabu Inutsuka,et al.  Reorientation Kinetics of Local Conformation of Polyisoprene at Substrate Interface. , 2018, ACS macro letters.

[3]  Manabu Inutsuka,et al.  Depth-resolved local conformation and thermal relaxation of polystyrene near substrate interface. , 2017, The Journal of chemical physics.

[4]  Rodney D. Priestley,et al.  Direct measurement of glass transition temperature in exposed and buried adsorbed polymer nanolayers , 2016 .

[5]  Keiji Tanaka,et al.  Flattening Process of Polymer Chains Irreversibly Adsorbed on a Solid. , 2016, ACS macro letters.

[6]  N. Yamada,et al.  Effect of local chain dynamics on a bioinert interface. , 2015, Langmuir : the ACS journal of surfaces and colloids.

[7]  Xiaolin Lu,et al.  Molecular ordering of phenyl groups at the buried polystyrene/metal interface. , 2014, Langmuir : the ACS journal of surfaces and colloids.

[8]  Paul Z. Hanakata,et al.  Interfacial mobility scale determines the scale of collective motion and relaxation rate in polymer films , 2014, Nature Communications.

[9]  James A. Forrest,et al.  Dynamics near Free Surfaces and the Glass Transition in Thin Polymer Films: A View to the Future , 2014 .

[10]  M. Asplund,et al.  Observation of sub-surface phenyl rings in polystyrene with vibrationally resonant sum-frequency generation , 2013 .

[11]  Keiji Tanaka,et al.  Design of a dynamic polymer interface for chiral discrimination. , 2013, Journal of the American Chemical Society.

[12]  Ali Khademhosseini,et al.  Engineered nanomembranes for directing cellular organization toward flexible biodevices. , 2013, Nano letters.

[13]  C. McNeill,et al.  Observation of a distinct surface molecular orientation in films of a high mobility conjugated polymer. , 2013, Journal of the American Chemical Society.

[14]  M. Doi,et al.  Local Conformation and Relaxation of Polystyrene at Substrate Interface , 2012 .

[15]  Keewook Paeng,et al.  Direct measurement of molecular motion in freestanding polystyrene thin films. , 2011, Journal of the American Chemical Society.

[16]  M. Wübbenhorst,et al.  The lifetime of the deviations from bulk behaviour in polymers confined at the nanoscale , 2011 .

[17]  S. Napolitano,et al.  Possible Origin of Thickness-Dependent Deviations from Bulk Properties of Thin Polymer Films , 2010 .

[18]  A. Jen,et al.  Effect of the phenyl ring orientation in the polystyrene buffer layer on the performance of pentacene thin-film transistors , 2010 .

[19]  C. Stafford,et al.  Quantifying residual stress in nanoscale thin polymer films via surface wrinkling. , 2009, ACS nano.

[20]  J. Forrest,et al.  Measuring the Surface Dynamics of Glassy Polymers , 2008, Science.

[21]  Tobin J Marks,et al.  Polymer Gate Dielectric Surface Viscoelasticity Modulates Pentacene Transistor Performance , 2007, Science.

[22]  G. Reiter,et al.  Residual stresses in thin polymer films cause rupture and dominate early stages of dewetting , 2005, Nature materials.

[23]  Z. Pászti,et al.  Measuring polymer surface ordering differences in air and water by sum frequency generation vibrational spectroscopy. , 2002, Journal of the American Chemical Society.

[24]  Zhan Chen,et al.  Studies of polymer surfaces by sum frequency generation vibrational spectroscopy. , 2002, Annual review of physical chemistry.

[25]  G. Reiter,et al.  Spin-cast, thin, glassy polymer films: Highly metastable forms of matter , 2001 .

[26]  J. Stephenson,et al.  Absolute Molecular Orientational Distribution of the Polystyrene Surface , 2001 .

[27]  Ronald L. Jones,et al.  Chain Conformation in Ultrathin Polymer Films Using Small-Angle Neutron Scattering , 2001 .

[28]  Keiji Tanaka,et al.  Rheological Analysis of Surface Relaxation Process of Monodisperse Polystyrene Films , 2000 .

[29]  J. Stöhr,et al.  Surface Relaxations in Polymers , 1997 .

[30]  Atsushi Takahara,et al.  Surface molecular motion of the monodisperse polystyrene films , 1997 .

[31]  R. F. W. Pease,et al.  Structure in Thin and Ultrathin Spin-Cast Polymer Films , 1996, Science.

[32]  W. Prest,et al.  The alignment of polymers during the solvent‐coating process , 1980 .

[33]  D. Y. Yoon,et al.  Conformational Characteristics of Polystyrene , 1975 .

[34]  P. Flory,et al.  Optical Anisotropy of Vinyl Polymer Chains. I. Strain Birefringence of Polypropylene and Polystyrene , 1970 .