Solid-state polymer adsorption for surface modification: The role of molecular weight

Wenyang Xu; Karl Mihhels; Nikolay Kotov; Sakari Lepikko; Robin H.A. Ras; C. Magnus Johnson; Torbjörn Pettersson; Eero Kontturi

doi:10.1016/j.jcis.2021.07.062

Solid-state polymer adsorption for surface modification: The role of molecular weight

Wenyang Xu^*, Karl Mihhels, Nikolay Kotov, Sakari Lepikko, Robin H.A. Ras, C. Magnus Johnson, Torbjörn Pettersson^*, Eero Kontturi^*

^*Corresponding author for this work

KTH Royal Institute of Technology

Research output: Contribution to journal › Article › Scientific › peer-review

14 Citations (Scopus)

221 Downloads (Pure)

Abstract

Hypothesis: Solid-state polymer adsorption offers a distinct approach for surface modification. These ultrathin, so-called Guiselin layers can easily be obtained by placing a polymer melt in contact with an interface, followed by a removal of the non-adsorbed layer with a good solvent. While the mechanism of formation has been well established for Guiselin layers, their stability, crucial from the perspective of materials applications, is not. The stability is a trade-off in the entropic penalty between cooperative detachment of the number of segments directly adsorbed on the substrate and consecutively pinned monomers.

Experiments: Experimental model systems of Guiselin layers of polystyrene (PS) on silicon wafers with native oxide layer on top were employed. The stability of the adsorbed layers was studied as a function of PS molecular weight and polydispersibility by various microscopic and spectroscopic tools as well as quasi-static contact angle measurements.

Findings: Adsorbed layers from low molecular weight PS were disrupted with typical spinodal decomposition patterns whereas high molecular weight (>500 kDa) PS resulted in stable, continuous layers. Moreover, we show that Guiselin layers offer an enticing way to modify a surface, as demonstrated by adsorbed PS that imparts a hydrophobic character to initially hydrophilic silicon wafers.

Original language	English
Pages (from-to)	441-450
Number of pages	10
Journal	Journal of Colloid and Interface Science
Volume	605
Early online date	21 Jul 2021
DOIs	https://doi.org/10.1016/j.jcis.2021.07.062
Publication status	Published - Jan 2022
MoE publication type	A1 Journal article-refereed

Funding

W.X. acknowledges the funding from Tandem Forest Values (Project STRONGAD). Prof. Pekka Peljo is thanked for helping with contact angle measurements. Olle Engkvists Stiftelse (Sweden) is acknowledged for funding the nano infrared microscope as well as a postdoc scholarship for K.N. Dr. Leena-Sisko Johansson is thanked for assisting with XPS analyses and data interpretation. Dr. Katja Heise is thanked for helping with GPC measurements. Dr. Zhuojun Meng and Tao Zou (M.Sc.) are thanked for valuable discussions. This work made use of Aalto University Bioeconomy and RawMatters Facilities. We also acknowledge the provision of facilities and technical support by Aalto University at OtaNano - Nanomicroscopy Center (Aalto-NMC). The study is a part of FinnCERES Materials Bioeconomy Ecosystem. W.X. acknowledges the funding from Tandem Forest Values (Project STRONGAD). Prof. Pekka Peljo is thanked for helping with contact angle measurements. Olle Engkvists Stiftelse (Sweden) is acknowledged for funding the nano infrared microscope as well as a postdoc scholarship for K.N. Dr. Leena-Sisko Johansson is thanked for assisting with XPS analyses and data interpretation. Dr. Katja Heise is thanked for helping with GPC measurements. Dr. Zhuojun Meng and Tao Zou (M.Sc.) are thanked for valuable discussions. This work made use of Aalto University Bioeconomy and RawMatters Facilities. We also acknowledge the provision of facilities and technical support by Aalto University at OtaNano - Nanomicroscopy Center (Aalto-NMC). The study is a part of FinnCERES Materials Bioeconomy Ecosystem.

Keywords

Contact angle
Dewetting
Polymer adsorption
Polystyrene
Silicon wafers
Surface modification

Access to Document

10.1016/j.jcis.2021.07.062Licence: CC BY

CHEM_Xu_et_al_Solid-state_Polymer_2021_Journal_of_Colloid_and_Interface_ScienceFinal published version, 2.24 MBLicence: CC BY

Cite this

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title = "Solid-state polymer adsorption for surface modification: The role of molecular weight",

abstract = "Hypothesis: Solid-state polymer adsorption offers a distinct approach for surface modification. These ultrathin, so-called Guiselin layers can easily be obtained by placing a polymer melt in contact with an interface, followed by a removal of the non-adsorbed layer with a good solvent. While the mechanism of formation has been well established for Guiselin layers, their stability, crucial from the perspective of materials applications, is not. The stability is a trade-off in the entropic penalty between cooperative detachment of the number of segments directly adsorbed on the substrate and consecutively pinned monomers. Experiments: Experimental model systems of Guiselin layers of polystyrene (PS) on silicon wafers with native oxide layer on top were employed. The stability of the adsorbed layers was studied as a function of PS molecular weight and polydispersibility by various microscopic and spectroscopic tools as well as quasi-static contact angle measurements. Findings: Adsorbed layers from low molecular weight PS were disrupted with typical spinodal decomposition patterns whereas high molecular weight (>500 kDa) PS resulted in stable, continuous layers. Moreover, we show that Guiselin layers offer an enticing way to modify a surface, as demonstrated by adsorbed PS that imparts a hydrophobic character to initially hydrophilic silicon wafers.",

keywords = "Contact angle, Dewetting, Polymer adsorption, Polystyrene, Silicon wafers, Surface modification",

author = "Wenyang Xu and Karl Mihhels and Nikolay Kotov and Sakari Lepikko and Ras, \{Robin H.A.\} and Johnson, \{C. Magnus\} and Torbj{\"o}rn Pettersson and Eero Kontturi",

note = "Funding Information: W.X. acknowledges the funding from Tandem Forest Values (Project STRONGAD). Prof. Pekka Peljo is thanked for helping with contact angle measurements. Olle Engkvists Stiftelse (Sweden) is acknowledged for funding the nano infrared microscope as well as a postdoc scholarship for K.N. Dr. Leena-Sisko Johansson is thanked for assisting with XPS analyses and data interpretation. Dr. Katja Heise is thanked for helping with GPC measurements. Dr. Zhuojun Meng and Tao Zou (M.Sc.) are thanked for valuable discussions. This work made use of Aalto University Bioeconomy and RawMatters Facilities. We also acknowledge the provision of facilities and technical support by Aalto University at OtaNano - Nanomicroscopy Center (Aalto-NMC). The study is a part of FinnCERES Materials Bioeconomy Ecosystem. Funding Information: W.X. acknowledges the funding from Tandem Forest Values (Project STRONGAD). Prof. Pekka Peljo is thanked for helping with contact angle measurements. Olle Engkvists Stiftelse (Sweden) is acknowledged for funding the nano infrared microscope as well as a postdoc scholarship for K.N. Dr. Leena-Sisko Johansson is thanked for assisting with XPS analyses and data interpretation. Dr. Katja Heise is thanked for helping with GPC measurements. Dr. Zhuojun Meng and Tao Zou (M.Sc.) are thanked for valuable discussions. This work made use of Aalto University Bioeconomy and RawMatters Facilities. We also acknowledge the provision of facilities and technical support by Aalto University at OtaNano - Nanomicroscopy Center (Aalto-NMC). The study is a part of FinnCERES Materials Bioeconomy Ecosystem. Publisher Copyright: {\textcopyright} 2021 The Author(s)",

year = "2022",

month = jan,

doi = "10.1016/j.jcis.2021.07.062",

language = "English",

volume = "605",

pages = "441--450",

journal = "Journal of Colloid and Interface Science",

issn = "0021-9797",

publisher = "Elsevier",

}

TY - JOUR

T1 - Solid-state polymer adsorption for surface modification: The role of molecular weight

AU - Xu, Wenyang

AU - Mihhels, Karl

AU - Kotov, Nikolay

AU - Lepikko, Sakari

AU - Ras, Robin H.A.

AU - Johnson, C. Magnus

AU - Pettersson, Torbjörn

AU - Kontturi, Eero

N1 - Funding Information: W.X. acknowledges the funding from Tandem Forest Values (Project STRONGAD). Prof. Pekka Peljo is thanked for helping with contact angle measurements. Olle Engkvists Stiftelse (Sweden) is acknowledged for funding the nano infrared microscope as well as a postdoc scholarship for K.N. Dr. Leena-Sisko Johansson is thanked for assisting with XPS analyses and data interpretation. Dr. Katja Heise is thanked for helping with GPC measurements. Dr. Zhuojun Meng and Tao Zou (M.Sc.) are thanked for valuable discussions. This work made use of Aalto University Bioeconomy and RawMatters Facilities. We also acknowledge the provision of facilities and technical support by Aalto University at OtaNano - Nanomicroscopy Center (Aalto-NMC). The study is a part of FinnCERES Materials Bioeconomy Ecosystem. Funding Information: W.X. acknowledges the funding from Tandem Forest Values (Project STRONGAD). Prof. Pekka Peljo is thanked for helping with contact angle measurements. Olle Engkvists Stiftelse (Sweden) is acknowledged for funding the nano infrared microscope as well as a postdoc scholarship for K.N. Dr. Leena-Sisko Johansson is thanked for assisting with XPS analyses and data interpretation. Dr. Katja Heise is thanked for helping with GPC measurements. Dr. Zhuojun Meng and Tao Zou (M.Sc.) are thanked for valuable discussions. This work made use of Aalto University Bioeconomy and RawMatters Facilities. We also acknowledge the provision of facilities and technical support by Aalto University at OtaNano - Nanomicroscopy Center (Aalto-NMC). The study is a part of FinnCERES Materials Bioeconomy Ecosystem. Publisher Copyright: © 2021 The Author(s)

PY - 2022/1

Y1 - 2022/1

N2 - Hypothesis: Solid-state polymer adsorption offers a distinct approach for surface modification. These ultrathin, so-called Guiselin layers can easily be obtained by placing a polymer melt in contact with an interface, followed by a removal of the non-adsorbed layer with a good solvent. While the mechanism of formation has been well established for Guiselin layers, their stability, crucial from the perspective of materials applications, is not. The stability is a trade-off in the entropic penalty between cooperative detachment of the number of segments directly adsorbed on the substrate and consecutively pinned monomers. Experiments: Experimental model systems of Guiselin layers of polystyrene (PS) on silicon wafers with native oxide layer on top were employed. The stability of the adsorbed layers was studied as a function of PS molecular weight and polydispersibility by various microscopic and spectroscopic tools as well as quasi-static contact angle measurements. Findings: Adsorbed layers from low molecular weight PS were disrupted with typical spinodal decomposition patterns whereas high molecular weight (>500 kDa) PS resulted in stable, continuous layers. Moreover, we show that Guiselin layers offer an enticing way to modify a surface, as demonstrated by adsorbed PS that imparts a hydrophobic character to initially hydrophilic silicon wafers.

AB - Hypothesis: Solid-state polymer adsorption offers a distinct approach for surface modification. These ultrathin, so-called Guiselin layers can easily be obtained by placing a polymer melt in contact with an interface, followed by a removal of the non-adsorbed layer with a good solvent. While the mechanism of formation has been well established for Guiselin layers, their stability, crucial from the perspective of materials applications, is not. The stability is a trade-off in the entropic penalty between cooperative detachment of the number of segments directly adsorbed on the substrate and consecutively pinned monomers. Experiments: Experimental model systems of Guiselin layers of polystyrene (PS) on silicon wafers with native oxide layer on top were employed. The stability of the adsorbed layers was studied as a function of PS molecular weight and polydispersibility by various microscopic and spectroscopic tools as well as quasi-static contact angle measurements. Findings: Adsorbed layers from low molecular weight PS were disrupted with typical spinodal decomposition patterns whereas high molecular weight (>500 kDa) PS resulted in stable, continuous layers. Moreover, we show that Guiselin layers offer an enticing way to modify a surface, as demonstrated by adsorbed PS that imparts a hydrophobic character to initially hydrophilic silicon wafers.

KW - Contact angle

KW - Dewetting

KW - Polymer adsorption

KW - Polystyrene

KW - Silicon wafers

KW - Surface modification

UR - https://www.scopus.com/pages/publications/85111278426

U2 - 10.1016/j.jcis.2021.07.062

DO - 10.1016/j.jcis.2021.07.062

M3 - Article

AN - SCOPUS:85111278426

SN - 0021-9797

VL - 605

SP - 441

EP - 450

JO - Journal of Colloid and Interface Science

JF - Journal of Colloid and Interface Science

ER -

Solid-state polymer adsorption for surface modification: The role of molecular weight

Abstract

Funding

Keywords

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STRONGAD: Strongly adsorbed polymer layers for modification of cellulose surfaces towards new functional materials

FinnCERES: Competence Center for the Materials Bioeconomy: A Flagship for our Sustainable Future

Bioeconomy Research Infrastructure

OtaNano

OtaNano - Nanomicroscopy Center

Cite this

Solid-state polymer adsorption for surface modification: The role of molecular weight

Abstract

Funding

Keywords

Access to Document

Other files and links

Fingerprint

Projects

STRONGAD: Strongly adsorbed polymer layers for modification of cellulose surfaces towards new functional materials

FinnCERES: Competence Center for the Materials Bioeconomy: A Flagship for our Sustainable Future

Equipment

Bioeconomy Research Infrastructure

OtaNano

OtaNano - Nanomicroscopy Center

Cite this