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Title: Chain Conformation near the Buried Interface in Nanoparticle-Stabilized Polymer Thin Films

Journal Article · · Macromolecules

It is known that when nanoparticles are added to polymer thin films, they often migrate to the film-substrate interface and form an “immobile interfacial layer”, which has been believed as the origin of suppression of dewetting. We here report an alternative mechanism of dewetting suppression from the structural aspect of a polymer. Dodecane thiol-functionalized gold (Au) nanoparticles embedded in PS thin films prepared on Si substrates were used as a model. It was found that thermal annealing promotes irreversible polymer adsorption onto the substrate surface along with the surface migration of the nanoparticles. We also revealed that the surface migration causes additional nanoconfined space for the adsorbed polymer chains. As a result, the self-organization process of the strongly adsorbed polymer chains on the solid surface was so hindered that the chain conformations were randomized and expanded in the film normal direction. Here, the resultant chain conformation allows the interpenetration between free chains and the adsorbed chains, promoting adhesion and hence stabilizing the thin film.

Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0012704
OSTI ID:
1434769
Report Number(s):
BNL-203495-2018-JAAM
Journal Information:
Macromolecules, Vol. 50, Issue 19; ISSN 0024-9297
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 21 works
Citation information provided by
Web of Science

References (72)

Independent optically addressable nanoparticle-polymer optomechanical composites journal June 2002
Nanoparticle–polymer photovoltaic cells journal April 2008
Detection and differentiation of normal, cancerous, and metastatic cells using nanoparticle-polymer sensor arrays journal June 2009
Toward the Ideal Organic Light-Emitting Diode. The Versatility and Utility of Interfacial Tailoring by Cross-Linked Siloxane Interlayers journal August 2005
Annealing-Induced Changes in the Molecular Orientation of Poly-3-hexylthiophene at Buried Interfaces journal July 2013
Suppression of Dewetting in Nanoparticle-Filled Polymer Films journal May 2000
Influence of Dendrimer Additives on the Dewetting of Thin Polystyrene Films journal February 2002
Dewetting of Star Nanogel/Homopolymer Blends from an Immiscible Homopolymer Substrate journal October 2004
Polystyrene-Based Single-Walled Carbon Nanotube Nanocomposite Thin Films:  Dynamics of Structural Instabilities journal December 2004
Control of Interfacial Instabilities in Thin Polymer Films with the Addition of a Miscible Component journal December 2006
Effect of Nanoscopic Fillers on Dewetting Dynamics journal April 2006
Stabilizing Thin Film Polymer Bilayers against Dewetting Using Multiwalled Carbon Nanotubes journal December 2007
Self-Assembled Multilayers of Nanocomponents journal February 2007
Improved polymer thin-film wetting behavior through nanoparticle segregation to interfaces journal August 2007
Nanoparticles for dewetting suppression of thin polymer films used in chemical sensors journal July 2006
Direct observation of interfacial C 60 cluster formation in polystyrene–C 60 nanocomposite films journal February 2009
Stability and Dewetting of Metal Nanoparticle Filled Thin Polymer Films: Control of Instability Length Scale and Dynamics journal June 2010
Spinodal Clustering in Thin Films of Nanoparticle-Polymer Mixtures journal July 2010
Glass Transition Temperature of Polymer–Nanoparticle Composites: Effect of Polymer–Particle Interfacial Energy journal May 2013
Interplay of Substrate Surface Energy and Nanoparticle Concentration in Suppressing Polymer Thin Film Dewetting journal January 2015
Influence of C 60 Nanoparticles on the Stability and Morphology of Miscible Polymer Blend Films journal October 2011
Using nanoparticles to create self-healing composites journal September 2004
Origin of Dynamical Properties in PMMA−C 60 Nanocomposites journal June 2007
Control of the entropic interactions and phase behavior of athermal nanoparticle/homopolymer thin film mixtures journal January 2009
The structure of chain end-grafted nanoparticle/homopolymer nanocomposites journal January 2011
Nanoscale adsorbed structures as a robust approach for tailoring polymer film stability journal January 2016
Adsorption of Poly(methyl methacrylate) Melts on Quartz journal October 1999
Affinity of Polystyrene Films to Hydrogen-Passivated Silicon and Its Relevance to the T g of the Films journal October 2009
Immobilized Polymer Layers on Spherical Nanoparticles journal April 2010
Impact of an Irreversibly Adsorbed Layer on Local Viscosity of Nanoconfined Polymer Melts journal November 2011
Adsorption Kinetics of Ultrathin Polymer Films in the Melt Probed by Dielectric Spectroscopy and Second-Harmonic Generation journal November 2011
The lifetime of the deviations from bulk behaviour in polymers confined at the nanoscale journal March 2011
Revealed Architectures of Adsorbed Polymer Chains at Solid-Polymer Melt Interfaces journal December 2012
Formation Mechanism of High-Density, Flattened Polymer Nanolayers Adsorbed on Planar Solids journal April 2014
Kinetics of Irreversible Chain Adsorption journal May 2014
Effect of CO 2 on a Mobility Gradient of Polymer Chains near an Impenetrable Solid journal March 2015
Stability of Polymer Ultrathin Films (<7 nm) Made by a Top-Down Approach journal July 2015
Direct Measurement of Glass Transition Temperature in Exposed and Buried Adsorbed Polymer Nanolayers journal June 2016
Solvent Assisted Rinsing: Stability/Instability of Ultrathin Polymer Residual Layer journal February 2016
Flattening Process of Polymer Chains Irreversibly Adsorbed on a Solid journal March 2016
Untangling the Effects of Chain Rigidity on the Structure and Dynamics of Strongly Adsorbed Polymer Melts journal June 2015
New Mechanism of Nonequilibrium Polymer Adsorption journal February 1992
A Simple Kinetic Model of Polymer Adsorption and Desorption journal December 1993
Irreversible Adsorption of a Concentrated Polymer Solution journal January 1992
Effect of strongly favorable substrate interactions on the thermal properties of ultrathin polymer films journal March 1996
Polymer Adsorption from Bulk Solution onto Planar Surfaces: Effect of Polymer Flexibility and Surface Attraction in Good Solvent journal February 2010
Confinement enhances dispersion in nanoparticle–polymer blend films journal May 2014
Molecular Structure of Polystyrene at Air/Polymer and Solid/Polymer Interfaces journal October 2000
Structure in Thin and Ultrathin Spin-Cast Polymer Films journal August 1996
Local Conformation and Relaxation of Polystyrene at Substrate Interface journal May 2012
Plasma Treatment of Polystyrene Thin Films Affects More Than the Surface journal June 2012
Structural properties of atactic polystyrene adsorbed onto solid surfaces journal November 2011
Confinement effects on the chain conformation in thin polymer films journal January 2000
Dewetting Dynamics of Nanofilled Polymer Thin Films journal July 2004
Many paths to dewetting of thin films: anatomy and physiology of surface instability journal November 2003
Scaling Law for Entropic Effects at Interfaces between Grafted Layers and Polymer Melts journal June 1998
Rubber-rubber adhesion with connector molecules journal May 1992
Thin Film Instability Induced by Long-Range Forces journal March 1999
Improving adhesion via connector polymers to stabilize non-wetting liquid films journal January 1996
Instabilities of Thin Polymer Films on Layers of Chemically Identical Grafted Molecules journal January 1996
Mobility of Polymers in Films Thinner than Their Unperturbed Size journal September 1993
Dewetting of thin polymer films journal January 1992
Surface- and Structure-Dependent Catalytic Activity of Au Nanoparticles for Oxygen Reduction Reaction journal February 2010
Organization of Nanoparticles on Soft Polymer Surfaces journal March 2002
Stretching and folding of 2-nanometer hydrocarbon rods journal January 2014
At What Chain Length Do Unbranched Alkanes Prefer Folded Conformations? journal February 2014
Reduced Viscosity of the Free Surface in Entangled Polymer Melt Films journal February 2010
‘Marker’ grazing-incidence X-ray photon correlation spectroscopy: a new tool to peer into the interfaces of nanoconfined polymer thin films journal October 2012
Influence of surface cleaning on dewetting of thin polystyrene films journal November 2003
Low-density polymer thin film formation in supercritical carbon dioxide journal November 2003
Analysis of x-ray reflectivity data from low-contrast polymer bilayer systems using a Fourier method journal May 2000
X-ray and neutron reflectivity for the investigation of polymers journal January 1990

Cited By (2)

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