Tae-Young Heo, Théophile Ienn, Julien Bernard, Robert A. Riggleman, Daeyeon Lee
{"title":"统计共聚物成分对毛细管上升渗透动力学的非单调影响","authors":"Tae-Young Heo, Théophile Ienn, Julien Bernard, Robert A. Riggleman, Daeyeon Lee","doi":"10.1021/acs.macromol.4c01708","DOIUrl":null,"url":null,"abstract":"Infiltration dynamics of poly(styrene-<i>stat</i>-2-vinylpyridine) (PS-<i>stat</i>-P2VP) statistical copolymers (StCPs) undergoing capillary rise infiltration into the interstices of silica nanoparticle (SiO<sub>2</sub> NP) packings are investigated by in situ spectroscopic ellipsometry with varying ratios of strongly interacting 2-vinylpyridine (2VP) and weakly interacting styrene (S) repeat units. As the fraction of 2VP (<i>f</i><sub>P2VP</sub>) increases, a nonmonotonic dependence is observed in the time required to fully fill the interstices of the SiO<sub>2</sub> NP packings (<i>t</i><sub>inf</sub>) and the effective viscosity (η<sub>eff</sub>). To understand the mechanism behind the nonmonotonic trend in infiltration dynamics, polymer properties such as zero-shear viscosity (η<sub>0</sub>) and glass transition temperature (<i>T</i><sub>g</sub>) are considered; however, these factors fail to explain the trend. When the strong interactions between 2VP and SiO<sub>2</sub> are suppressed by modifying the surface of SiO<sub>2</sub> NPs with the epoxide group, the infiltration dynamics no longer show strong dependence on <i>f</i><sub>P2VP</sub>. This result indicates the important role played by the 2VP unit in the anomalous slowdown observed in StCPs, possibly by controlling its conformation on the pore surface and the interactions between the surface-adsorbed chains and chains that are translated through the pores.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"5 1","pages":""},"PeriodicalIF":5.1000,"publicationDate":"2024-10-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Nonmonotonic Impact of Statistical Copolymer Composition on the Kinetics of Capillary Rise Infiltration\",\"authors\":\"Tae-Young Heo, Théophile Ienn, Julien Bernard, Robert A. Riggleman, Daeyeon Lee\",\"doi\":\"10.1021/acs.macromol.4c01708\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Infiltration dynamics of poly(styrene-<i>stat</i>-2-vinylpyridine) (PS-<i>stat</i>-P2VP) statistical copolymers (StCPs) undergoing capillary rise infiltration into the interstices of silica nanoparticle (SiO<sub>2</sub> NP) packings are investigated by in situ spectroscopic ellipsometry with varying ratios of strongly interacting 2-vinylpyridine (2VP) and weakly interacting styrene (S) repeat units. As the fraction of 2VP (<i>f</i><sub>P2VP</sub>) increases, a nonmonotonic dependence is observed in the time required to fully fill the interstices of the SiO<sub>2</sub> NP packings (<i>t</i><sub>inf</sub>) and the effective viscosity (η<sub>eff</sub>). To understand the mechanism behind the nonmonotonic trend in infiltration dynamics, polymer properties such as zero-shear viscosity (η<sub>0</sub>) and glass transition temperature (<i>T</i><sub>g</sub>) are considered; however, these factors fail to explain the trend. When the strong interactions between 2VP and SiO<sub>2</sub> are suppressed by modifying the surface of SiO<sub>2</sub> NPs with the epoxide group, the infiltration dynamics no longer show strong dependence on <i>f</i><sub>P2VP</sub>. This result indicates the important role played by the 2VP unit in the anomalous slowdown observed in StCPs, possibly by controlling its conformation on the pore surface and the interactions between the surface-adsorbed chains and chains that are translated through the pores.\",\"PeriodicalId\":51,\"journal\":{\"name\":\"Macromolecules\",\"volume\":\"5 1\",\"pages\":\"\"},\"PeriodicalIF\":5.1000,\"publicationDate\":\"2024-10-24\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Macromolecules\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1021/acs.macromol.4c01708\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"POLYMER SCIENCE\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Macromolecules","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acs.macromol.4c01708","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"POLYMER SCIENCE","Score":null,"Total":0}
Nonmonotonic Impact of Statistical Copolymer Composition on the Kinetics of Capillary Rise Infiltration
Infiltration dynamics of poly(styrene-stat-2-vinylpyridine) (PS-stat-P2VP) statistical copolymers (StCPs) undergoing capillary rise infiltration into the interstices of silica nanoparticle (SiO2 NP) packings are investigated by in situ spectroscopic ellipsometry with varying ratios of strongly interacting 2-vinylpyridine (2VP) and weakly interacting styrene (S) repeat units. As the fraction of 2VP (fP2VP) increases, a nonmonotonic dependence is observed in the time required to fully fill the interstices of the SiO2 NP packings (tinf) and the effective viscosity (ηeff). To understand the mechanism behind the nonmonotonic trend in infiltration dynamics, polymer properties such as zero-shear viscosity (η0) and glass transition temperature (Tg) are considered; however, these factors fail to explain the trend. When the strong interactions between 2VP and SiO2 are suppressed by modifying the surface of SiO2 NPs with the epoxide group, the infiltration dynamics no longer show strong dependence on fP2VP. This result indicates the important role played by the 2VP unit in the anomalous slowdown observed in StCPs, possibly by controlling its conformation on the pore surface and the interactions between the surface-adsorbed chains and chains that are translated through the pores.
期刊介绍：
Macromolecules publishes original, fundamental, and impactful research on all aspects of polymer science. Topics of interest include synthesis (e.g., controlled polymerizations, polymerization catalysis, post polymerization modification, new monomer structures and polymer architectures, and polymerization mechanisms/kinetics analysis); phase behavior, thermodynamics, dynamic, and ordering/disordering phenomena (e.g., self-assembly, gelation, crystallization, solution/melt/solid-state characteristics); structure and properties (e.g., mechanical and rheological properties, surface/interfacial characteristics, electronic and transport properties); new state of the art characterization (e.g., spectroscopy, scattering, microscopy, rheology), simulation (e.g., Monte Carlo, molecular dynamics, multi-scale/coarse-grained modeling), and theoretical methods. Renewable/sustainable polymers, polymer networks, responsive polymers, electro-, magneto- and opto-active macromolecules, inorganic polymers, charge-transporting polymers (ion-containing, semiconducting, and conducting), nanostructured polymers, and polymer composites are also of interest. Typical papers published in Macromolecules showcase important and innovative concepts, experimental methods/observations, and theoretical/computational approaches that demonstrate a fundamental advance in the understanding of polymers.
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