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Title: Structure-induced switching of interpolymer adhesion at a solid–polymer melt interface

Abstract

In this paper, we report a link between the interfacial structure and adhesive property of homopolymer chains physically adsorbed (i.e., via physisorption) onto solids. Polyethylene oxide (PEO) was used as a model and two different chain conformations of the adsorbed polymer were created on silicon substrates via the well-established Guiselin's approach: “flattened chains” which lie flat on the solid and are densely packed, and “loosely adsorbed polymer chains” which form bridges jointing up nearby empty sites on the solid surface and cover the flattened chains. We investigated the adhesion properties of the two different adsorbed chains using a custom-built adhesion testing device. Bilayers of a thick PEO overlayer on top of the flattened chains or loosely adsorbed chains were subjected to the adhesion test. The results revealed that the flattened chains do not show any adhesion even with the chemically identical free polymer on top, while the loosely adsorbed chains exhibit adhesion. Neutron reflectivity experiments corroborated that the difference in the interfacial adhesion is not attributed to the interfacial brodening at the free polymer–adsorbed polymer interface. Instead, coarse-grained molecular dynamics simulation results suggest that the tail parts of the loosely adsorbed chains act as “connector molecules”, bridging the free chainsmore » and substrate surface and improving the interfacial adhesion. Finally, these findings not only shed light on the structure–property relationship at the interface, but also provide a novel approach for developing sticking/anti-sticking technologies through precise control of the interfacial polymer nanostructures.« less

Authors:
 [1];  [1];  [1];  [1];  [1];  [1];  [1];  [2];  [3];  [4];  [4];  [5];  [5]
  1. Stony Brook Univ., NY (United States). Dept. of Materials Science and Chemical Engineering
  2. Stony Brook Univ., NY (United States). Dept. of Materials Science and Chemical Engineering. Dept. of Chemistry
  3. Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II
  4. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States). Center for Neutron Research
  5. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences. Computational Sciences and Engineering Division
Publication Date:
Research Org.:
Oak Ridge National Laboratory, Oak Ridge Leadership Computing Facility (OLCF); Stony Brook Univ., NY (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF)
OSTI Identifier:
1423040
Grant/Contract Number:  
AC05-00OR22725; AC02-98CH10886; CMMI-1332499
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Soft Matter
Additional Journal Information:
Journal Volume: 14; Journal Issue: 7; Journal ID: ISSN 1744-683X
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats

Jiang, Naisheng, Sen, Mani, Zeng, Wenduo, Chen, Zhizhao, Cheung, Justin M., Morimitsu, Yuma, Endoh, Maya K., Koga, Tadanori, Fukuto, Masafumi, Yuan, Guangcui, Satija, Sushil K., Carrillo, Jan-Michael Y., and Sumpter, Bobby G. Structure-induced switching of interpolymer adhesion at a solid–polymer melt interface. United States: N. p., 2018. Web. doi:10.1039/c7sm02279d.
Jiang, Naisheng, Sen, Mani, Zeng, Wenduo, Chen, Zhizhao, Cheung, Justin M., Morimitsu, Yuma, Endoh, Maya K., Koga, Tadanori, Fukuto, Masafumi, Yuan, Guangcui, Satija, Sushil K., Carrillo, Jan-Michael Y., & Sumpter, Bobby G. Structure-induced switching of interpolymer adhesion at a solid–polymer melt interface. United States. doi:10.1039/c7sm02279d.
Jiang, Naisheng, Sen, Mani, Zeng, Wenduo, Chen, Zhizhao, Cheung, Justin M., Morimitsu, Yuma, Endoh, Maya K., Koga, Tadanori, Fukuto, Masafumi, Yuan, Guangcui, Satija, Sushil K., Carrillo, Jan-Michael Y., and Sumpter, Bobby G. Thu . "Structure-induced switching of interpolymer adhesion at a solid–polymer melt interface". United States. doi:10.1039/c7sm02279d. https://www.osti.gov/servlets/purl/1423040.
@article{osti_1423040,
title = {Structure-induced switching of interpolymer adhesion at a solid–polymer melt interface},
author = {Jiang, Naisheng and Sen, Mani and Zeng, Wenduo and Chen, Zhizhao and Cheung, Justin M. and Morimitsu, Yuma and Endoh, Maya K. and Koga, Tadanori and Fukuto, Masafumi and Yuan, Guangcui and Satija, Sushil K. and Carrillo, Jan-Michael Y. and Sumpter, Bobby G.},
abstractNote = {In this paper, we report a link between the interfacial structure and adhesive property of homopolymer chains physically adsorbed (i.e., via physisorption) onto solids. Polyethylene oxide (PEO) was used as a model and two different chain conformations of the adsorbed polymer were created on silicon substrates via the well-established Guiselin's approach: “flattened chains” which lie flat on the solid and are densely packed, and “loosely adsorbed polymer chains” which form bridges jointing up nearby empty sites on the solid surface and cover the flattened chains. We investigated the adhesion properties of the two different adsorbed chains using a custom-built adhesion testing device. Bilayers of a thick PEO overlayer on top of the flattened chains or loosely adsorbed chains were subjected to the adhesion test. The results revealed that the flattened chains do not show any adhesion even with the chemically identical free polymer on top, while the loosely adsorbed chains exhibit adhesion. Neutron reflectivity experiments corroborated that the difference in the interfacial adhesion is not attributed to the interfacial brodening at the free polymer–adsorbed polymer interface. Instead, coarse-grained molecular dynamics simulation results suggest that the tail parts of the loosely adsorbed chains act as “connector molecules”, bridging the free chains and substrate surface and improving the interfacial adhesion. Finally, these findings not only shed light on the structure–property relationship at the interface, but also provide a novel approach for developing sticking/anti-sticking technologies through precise control of the interfacial polymer nanostructures.},
doi = {10.1039/c7sm02279d},
journal = {Soft Matter},
issn = {1744-683X},
number = 7,
volume = 14,
place = {United States},
year = {2018},
month = {1}
}

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Figures / Tables:

Figure 1 Figure 1: Schematic views of the two different adsorbed architectures at the solid-polymer melt interface. As clarified in Ref. [19], during the polymer adsorption process from the melt, polymer molecules arriving first on the solid surface are adsorbed with a flat conformation to increase the number of chain attachments permore » area (i.e., the origin of the flattened chains), while late arriving ones (i.e., the origin of the loosely adsorbed polymer chains), which find fewer empty sites due to the already present flattened chains, form bridges jointing up nearby empty sites. We hereafter assign the adsorbed layer composed of the lone flattened chains as (a) a “flattened layer”, while the adsorbed layer composed of the inner flattened chains and outer loosely adsorbed chains as (b) an “interfacial sublayer”. As will be discussed later, the loosely adsorbed chains can be crystallized, while the flattened chains don’t crystallize themselves.« less

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