Is Osmotic Pressure Relevant in the Mechanical Confinement of a Polymer Brush?

Is Osmotic Pressure Relevant in the Mechanical Confinement of a Polymer Brush?

The structures of polymer brushes under confinement were measured using a combination of neutron reflectivity and a surface force type apparatus. The samples were either poly­(ethylene oxide), PEO, used to investigate the effect of the grafting density or poly­(acrylic acid), PAA, used to determine...

Ausführliche Beschreibung

Gespeichert in:
Bibliographische Detailangaben
Veröffentlicht in:Macromolecules 2015-04, Vol.48 (7), p.2224-2234
Hauptverfasser: Abbott, Stephen B, de Vos, Wiebe M, Mears, Laura L. E, Cattoz, Beatrice, Skoda, Maximilian W. A, Barker, Robert, Richardson, Robert M, Prescott, Stuart W
Format: Artikel
Sprache:eng
Online-Zugang:Volltext
Tags: Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
container_end_page 2234
container_issue 7
container_start_page 2224
container_title Macromolecules
container_volume 48
creator Abbott, Stephen B
de Vos, Wiebe M
Mears, Laura L. E
Cattoz, Beatrice
Skoda, Maximilian W. A
Barker, Robert
Richardson, Robert M
Prescott, Stuart W
description The structures of polymer brushes under confinement were measured using a combination of neutron reflectivity and a surface force type apparatus. The samples were either poly­(ethylene oxide), PEO, used to investigate the effect of the grafting density or poly­(acrylic acid), PAA, used to determine the effect of charge on the structure of a polymer brushes under confinement. Without confinement both PEO and PAA brushes are found to be highly swollen with water, >50% v/v, with the expected parabolic brush structure. Compression of the PEO brushes with as little as 0.5 bar of confinement is found experimentally to reduce the brush to a polymer block of uniform density that is significantly dehydrated,
doi_str_mv 10.1021/ma502246r
format Article
fullrecord <record><control><sourceid>acs_cross</sourceid><recordid>TN_cdi_crossref_primary_10_1021_ma502246r</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>f9310884</sourcerecordid><originalsourceid>FETCH-LOGICAL-a294t-9f63ed3e5cf79d1575b48fd2d4d1140095aa48e4954e9c984e873016d42683493</originalsourceid><addsrcrecordid>eNptkM1KxDAYRYMoWEcXvkE2LlxU8_OlbVaixZ-B0RlE1yWmX2iHtpGkFebtrYy4cnUX93C5HELOObviTPDr3igmBGThgCRcCZaqQqpDkjAmINVC58fkJMYtY5wrkAl5WUa6jr0fW0s3AWOcAtJX7PDLDCNtBzo2SJ_RNmZorelo6QfXDtjj3HpHDd34btdjoHdhis3NKTlypot49psL8v5w_1Y-pav147K8XaVGaBhT7TKJtURlXa5rrnL1AYWrRQ0158CYVsZAgaAVoLa6ACxyyXhWg8gKCVouyOV-1wYfY0BXfYa2N2FXcVb9iKj-RMzsxZ41NlZbP4VhfvYP9w1keFtO</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype></control><display><type>article</type><title>Is Osmotic Pressure Relevant in the Mechanical Confinement of a Polymer Brush?</title><source>American Chemical Society Journals</source><creator>Abbott, Stephen B ; de Vos, Wiebe M ; Mears, Laura L. E ; Cattoz, Beatrice ; Skoda, Maximilian W. A ; Barker, Robert ; Richardson, Robert M ; Prescott, Stuart W</creator><creatorcontrib>Abbott, Stephen B ; de Vos, Wiebe M ; Mears, Laura L. E ; Cattoz, Beatrice ; Skoda, Maximilian W. A ; Barker, Robert ; Richardson, Robert M ; Prescott, Stuart W</creatorcontrib><description>The structures of polymer brushes under confinement were measured using a combination of neutron reflectivity and a surface force type apparatus. The samples were either poly­(ethylene oxide), PEO, used to investigate the effect of the grafting density or poly­(acrylic acid), PAA, used to determine the effect of charge on the structure of a polymer brushes under confinement. Without confinement both PEO and PAA brushes are found to be highly swollen with water, &gt;50% v/v, with the expected parabolic brush structure. Compression of the PEO brushes with as little as 0.5 bar of confinement is found experimentally to reduce the brush to a polymer block of uniform density that is significantly dehydrated, &lt;12% v/v. Further subsequent increases in the confinement pressure only marginally decrease the hydration and thickness of the polymer block. The grafting density of the brush does not significantly influence this behavior. PAA polymer brushes with little (pH 3) or an intermediate level of charging (pH 5.5) are also found to be compressed into a single uniform density polymer block with a confinement of 5 bar. However, with a high level of charge (pH 9) the brush structure is believed to be partially retained due to the repulsion between the internal charges. These experimental results are compared against a theoretical model based on numerical self-consistent field (nSCF) theory as well as to osmotic, SFA, and AFM data. While the nSCF model correctly predicts the observed transition from a brush to a block profile, experimentally it occurs at a pressure 2 orders of magnitude lower than the simulations would suggest. The results acquired through simulation are consistent with available osmotic pressure data; however, SFA and AFM measurements are consistent with the neutron reflection experimental data presented here. This significant disagreement between the two data sets indicates that in a confined system the effective osmotic counter pressure to an applied mechanical pressure is much less than the osmotic pressure expected from the local polymer concentration.</description><identifier>ISSN: 0024-9297</identifier><identifier>EISSN: 1520-5835</identifier><identifier>DOI: 10.1021/ma502246r</identifier><language>eng</language><publisher>American Chemical Society</publisher><ispartof>Macromolecules, 2015-04, Vol.48 (7), p.2224-2234</ispartof><rights>Copyright © American Chemical Society</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a294t-9f63ed3e5cf79d1575b48fd2d4d1140095aa48e4954e9c984e873016d42683493</citedby><cites>FETCH-LOGICAL-a294t-9f63ed3e5cf79d1575b48fd2d4d1140095aa48e4954e9c984e873016d42683493</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/ma502246r$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/ma502246r$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>314,780,784,2765,27076,27924,27925,56738,56788</link.rule.ids></links><search><creatorcontrib>Abbott, Stephen B</creatorcontrib><creatorcontrib>de Vos, Wiebe M</creatorcontrib><creatorcontrib>Mears, Laura L. E</creatorcontrib><creatorcontrib>Cattoz, Beatrice</creatorcontrib><creatorcontrib>Skoda, Maximilian W. A</creatorcontrib><creatorcontrib>Barker, Robert</creatorcontrib><creatorcontrib>Richardson, Robert M</creatorcontrib><creatorcontrib>Prescott, Stuart W</creatorcontrib><title>Is Osmotic Pressure Relevant in the Mechanical Confinement of a Polymer Brush?</title><title>Macromolecules</title><addtitle>Macromolecules</addtitle><description>The structures of polymer brushes under confinement were measured using a combination of neutron reflectivity and a surface force type apparatus. The samples were either poly­(ethylene oxide), PEO, used to investigate the effect of the grafting density or poly­(acrylic acid), PAA, used to determine the effect of charge on the structure of a polymer brushes under confinement. Without confinement both PEO and PAA brushes are found to be highly swollen with water, &gt;50% v/v, with the expected parabolic brush structure. Compression of the PEO brushes with as little as 0.5 bar of confinement is found experimentally to reduce the brush to a polymer block of uniform density that is significantly dehydrated, &lt;12% v/v. Further subsequent increases in the confinement pressure only marginally decrease the hydration and thickness of the polymer block. The grafting density of the brush does not significantly influence this behavior. PAA polymer brushes with little (pH 3) or an intermediate level of charging (pH 5.5) are also found to be compressed into a single uniform density polymer block with a confinement of 5 bar. However, with a high level of charge (pH 9) the brush structure is believed to be partially retained due to the repulsion between the internal charges. These experimental results are compared against a theoretical model based on numerical self-consistent field (nSCF) theory as well as to osmotic, SFA, and AFM data. While the nSCF model correctly predicts the observed transition from a brush to a block profile, experimentally it occurs at a pressure 2 orders of magnitude lower than the simulations would suggest. The results acquired through simulation are consistent with available osmotic pressure data; however, SFA and AFM measurements are consistent with the neutron reflection experimental data presented here. This significant disagreement between the two data sets indicates that in a confined system the effective osmotic counter pressure to an applied mechanical pressure is much less than the osmotic pressure expected from the local polymer concentration.</description><issn>0024-9297</issn><issn>1520-5835</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2015</creationdate><recordtype>article</recordtype><recordid>eNptkM1KxDAYRYMoWEcXvkE2LlxU8_OlbVaixZ-B0RlE1yWmX2iHtpGkFebtrYy4cnUX93C5HELOObviTPDr3igmBGThgCRcCZaqQqpDkjAmINVC58fkJMYtY5wrkAl5WUa6jr0fW0s3AWOcAtJX7PDLDCNtBzo2SJ_RNmZorelo6QfXDtjj3HpHDd34btdjoHdhis3NKTlypot49psL8v5w_1Y-pav147K8XaVGaBhT7TKJtURlXa5rrnL1AYWrRQ0158CYVsZAgaAVoLa6ACxyyXhWg8gKCVouyOV-1wYfY0BXfYa2N2FXcVb9iKj-RMzsxZ41NlZbP4VhfvYP9w1keFtO</recordid><startdate>20150414</startdate><enddate>20150414</enddate><creator>Abbott, Stephen B</creator><creator>de Vos, Wiebe M</creator><creator>Mears, Laura L. E</creator><creator>Cattoz, Beatrice</creator><creator>Skoda, Maximilian W. A</creator><creator>Barker, Robert</creator><creator>Richardson, Robert M</creator><creator>Prescott, Stuart W</creator><general>American Chemical Society</general><scope>AAYXX</scope><scope>CITATION</scope></search><sort><creationdate>20150414</creationdate><title>Is Osmotic Pressure Relevant in the Mechanical Confinement of a Polymer Brush?</title><author>Abbott, Stephen B ; de Vos, Wiebe M ; Mears, Laura L. E ; Cattoz, Beatrice ; Skoda, Maximilian W. A ; Barker, Robert ; Richardson, Robert M ; Prescott, Stuart W</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a294t-9f63ed3e5cf79d1575b48fd2d4d1140095aa48e4954e9c984e873016d42683493</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2015</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Abbott, Stephen B</creatorcontrib><creatorcontrib>de Vos, Wiebe M</creatorcontrib><creatorcontrib>Mears, Laura L. E</creatorcontrib><creatorcontrib>Cattoz, Beatrice</creatorcontrib><creatorcontrib>Skoda, Maximilian W. A</creatorcontrib><creatorcontrib>Barker, Robert</creatorcontrib><creatorcontrib>Richardson, Robert M</creatorcontrib><creatorcontrib>Prescott, Stuart W</creatorcontrib><collection>CrossRef</collection><jtitle>Macromolecules</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Abbott, Stephen B</au><au>de Vos, Wiebe M</au><au>Mears, Laura L. E</au><au>Cattoz, Beatrice</au><au>Skoda, Maximilian W. A</au><au>Barker, Robert</au><au>Richardson, Robert M</au><au>Prescott, Stuart W</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Is Osmotic Pressure Relevant in the Mechanical Confinement of a Polymer Brush?</atitle><jtitle>Macromolecules</jtitle><addtitle>Macromolecules</addtitle><date>2015-04-14</date><risdate>2015</risdate><volume>48</volume><issue>7</issue><spage>2224</spage><epage>2234</epage><pages>2224-2234</pages><issn>0024-9297</issn><eissn>1520-5835</eissn><abstract>The structures of polymer brushes under confinement were measured using a combination of neutron reflectivity and a surface force type apparatus. The samples were either poly­(ethylene oxide), PEO, used to investigate the effect of the grafting density or poly­(acrylic acid), PAA, used to determine the effect of charge on the structure of a polymer brushes under confinement. Without confinement both PEO and PAA brushes are found to be highly swollen with water, &gt;50% v/v, with the expected parabolic brush structure. Compression of the PEO brushes with as little as 0.5 bar of confinement is found experimentally to reduce the brush to a polymer block of uniform density that is significantly dehydrated, &lt;12% v/v. Further subsequent increases in the confinement pressure only marginally decrease the hydration and thickness of the polymer block. The grafting density of the brush does not significantly influence this behavior. PAA polymer brushes with little (pH 3) or an intermediate level of charging (pH 5.5) are also found to be compressed into a single uniform density polymer block with a confinement of 5 bar. However, with a high level of charge (pH 9) the brush structure is believed to be partially retained due to the repulsion between the internal charges. These experimental results are compared against a theoretical model based on numerical self-consistent field (nSCF) theory as well as to osmotic, SFA, and AFM data. While the nSCF model correctly predicts the observed transition from a brush to a block profile, experimentally it occurs at a pressure 2 orders of magnitude lower than the simulations would suggest. The results acquired through simulation are consistent with available osmotic pressure data; however, SFA and AFM measurements are consistent with the neutron reflection experimental data presented here. This significant disagreement between the two data sets indicates that in a confined system the effective osmotic counter pressure to an applied mechanical pressure is much less than the osmotic pressure expected from the local polymer concentration.</abstract><pub>American Chemical Society</pub><doi>10.1021/ma502246r</doi><tpages>11</tpages><oa>free_for_read</oa></addata></record>
fulltext fulltext
identifier ISSN: 0024-9297
ispartof Macromolecules, 2015-04, Vol.48 (7), p.2224-2234
issn 0024-9297
1520-5835
language eng
recordid cdi_crossref_primary_10_1021_ma502246r
source American Chemical Society Journals
title Is Osmotic Pressure Relevant in the Mechanical Confinement of a Polymer Brush?
url https://sfx.bib-bvb.de/sfx_tum?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2024-12-28T02%3A57%3A03IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-acs_cross&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=Is%20Osmotic%20Pressure%20Relevant%20in%20the%20Mechanical%20Confinement%20of%20a%20Polymer%20Brush?&rft.jtitle=Macromolecules&rft.au=Abbott,%20Stephen%20B&rft.date=2015-04-14&rft.volume=48&rft.issue=7&rft.spage=2224&rft.epage=2234&rft.pages=2224-2234&rft.issn=0024-9297&rft.eissn=1520-5835&rft_id=info:doi/10.1021/ma502246r&rft_dat=%3Cacs_cross%3Ef9310884%3C/acs_cross%3E%3Curl%3E%3C/url%3E&disable_directlink=true&sfx.directlink=off&sfx.report_link=0&rft_id=info:oai/&rft_id=info:pmid/&rfr_iscdi=true