Effect of Extreme Nanoconfinement on the Thermodynamics and Transport Phenomena in Multiphasic Nanocomposite Coatings

极端纳米约束对多相纳米复合涂层热力学和传输现象的影响

• 批准号: 1933704
• 负责人: Daeyeon Lee
• 金额: $ 39.31万
• 依托单位: University of Pennsylvania
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2019
• 资助国家: 美国
• 起止时间: 2019-11-01 至 2024-10-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1933704&HistoricalAwards=false
• 关键词: Effect; Extreme; Nanoconfinement; Thermodynamics; Transport

Due to their flexibility, low density and recyclability, polymer films and coatings are playing an increasingly important role in the regulation of gas transport in a wide range of applications such as gas barriers for food, beverage, microelectronics and medical device packaging. Adding nanoparticles and/or blending multiple polymers together have proven to be effective methods to tune gas transport properties of nanocomposite films. Adding high concentrations of nanoparticles, in particular, is a powerful approach for producing high performance gas barriers and gas separation membranes. In this work the investigators will produce polymer films with high nanoparticle loadings via solvent-driven infiltration of polymers (SIP) into layers of nanoparticles. In this process, layers of nanoparticles, sitting on top of a polymer layer, are filled with a solvent. Some of this solvent moves into the polymer layer and softens or plasticizes, the polymer material. Once the polymer is plasticized, it can move into the nanoparticle layer, filling in the gaps between nanoparticles, by attractive interactions with either the solvent or the nanoparticles. The investigators will study which of these interactions are most important for polymer infiltration and how to tune these interactions to obtain polymer films with high loadings of nanoparticles. These hard, solid nanoparticles maintain barriers which limit polymer's ability to expand. These constrained polymers are expected to exhibit improved gas barrier properties, making them attractive for various packaging applications.The investigators hypothesize the dynamics and thermodynamics of polymer chains in the interstices of nanoparticle packings under extreme nanoconfinement will be dominated by the thermodynamics of the interfaces. Solvent-infiltration of polymers (SIP) provides an ideal platform to characterize the dynamics and thermodynamics of confined polymers and transport of gas molecules through a binary polymer phase under extreme nanoconfinement. This work will lead to fundamental understandings of how polymer-solvent-nanoparticle interactions affect the infiltration mechanism and dynamics, as well as the thermodynamics of polymers under extreme nanoconfinement. The dynamics and resulting structure of SIP will be studied using in situ spectroscopic ellipsometry as well as molecular dynamics (MD) simulations. Efficient field-theoretic simulations, including self-consistent field theory, will be used to understand the thermodynamics in the packings and guide both the experiments and MD simulations. The structure-transport property relationship of SIP nanocomposites for different polymer molecular weight and polymer-nanoparticle interactions will be established by characterizing the structure using transmission electron microscopy, MD, and by testing the transport properties through quartz crystal microbalance with dissipation. Because theoretical frameworks to predict the dynamics and thermodynamics of SIP are not currently available, whenever possible, computation-based approaches will provide important guidelines for experimental conditions. The investigators will support involvement from underrepresented minority students by leading cooperative efforts with University of Puerto Rico-Humacao, Advancing Women in Engineering and Louise-Stoke Alliance for Minority Participation and Rachleff Scholars Program. The PIs also plan to develop educational programs and exhibits that showcase the nanocomposites with ultra-high loadings of natural nanomaterials with the help of undergraduate/graduate students for use during outreach activities organized through local high schools and science cafe events.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

由于其灵活性、低密度和可回收性，聚合物薄膜和涂层在食品、饮料、微电子和医疗器械包装的气体屏障等广泛应用中的气体输送调节中发挥着越来越重要的作用。添加纳米颗粒和/或将多种聚合物共混在一起已被证明是调节纳米复合材料膜的气体传输性能的有效方法。特别是添加高浓度的纳米颗粒是生产高性能气体阻隔和气体分离膜的有力方法。在这项工作中，研究人员将通过溶剂驱动的聚合物（SIP）渗透到纳米粒子层中来生产具有高纳米粒子负载的聚合物薄膜。在这个过程中，位于聚合物层顶部的纳米颗粒层充满了溶剂。该溶剂中的一些移动到聚合物层中并软化或塑化聚合物材料。一旦聚合物被塑化，它就可以移动到纳米颗粒层中，通过与溶剂或纳米颗粒的吸引相互作用填充纳米颗粒之间的间隙。研究人员将研究这些相互作用中哪些对聚合物渗透最重要，以及如何调整这些相互作用以获得具有高纳米颗粒负载的聚合物膜。这些坚硬的固体纳米颗粒保持了限制聚合物膨胀能力的屏障。这些约束的聚合物有望表现出改善的气体阻隔性能，使他们有吸引力的各种packaging application.The研究人员假设的动力学和热力学的聚合物链的间隙中的纳米粒子包装极端nanoconfinition下将占主导地位的界面的热力学。聚合物的溶剂渗透（SIP）提供了一个理想的平台来表征受限聚合物的动力学和热力学以及气体分子在极端纳米限制下通过二元聚合物相的传输。这项工作将导致聚合物-溶剂-纳米颗粒相互作用如何影响渗透机制和动力学，以及极端纳米约束下的聚合物热力学的基本理解。SIP的动力学和由此产生的结构将使用原位光谱椭圆偏振法以及分子动力学（MD）模拟进行研究。有效的场论模拟，包括自洽场理论，将被用来了解在填料的热力学和指导实验和MD模拟。SIP纳米复合材料的结构-传输性能的关系，不同的聚合物分子量和聚合物-纳米粒子的相互作用，将建立通过表征的结构，使用透射电子显微镜，MD，并通过测试的传输性能，通过石英晶体微天平与耗散。由于理论框架来预测SIP的动力学和热力学目前还没有，只要有可能，基于计算的方法将提供重要的指导方针的实验条件。调查人员将通过与波多黎各大学-Humacao，工程妇女进步和路易斯-斯托克少数民族参与联盟和Rachleff学者计划的合作努力，支持代表性不足的少数民族学生的参与。PI还计划开发教育计划和展览，展示具有超高天然纳米材料负载的纳米复合材料，并在本科生/研究生的帮助下，在通过当地高中和科学咖啡馆活动组织的推广活动中使用。该奖项反映了NSF的法定使命，并通过使用基金会的智力价值和更广泛的影响审查标准进行评估，被认为值得支持。

项目成果

Effect of polymer–nanoparticle interactions on solvent-driven infiltration of polymer (SIP) into nanoparticle packings: a molecular dynamics study

• DOI: 10.1039/c9me00148d
• 发表时间: 2020-03
• 作者: R. Venkatesh;Tianren Zhang;N. Manohar;K. Stebe;Robert A. Riggleman;Daeyeon Lee

Increases in Miscibility of a Binary Polymer Blend Confined within a Nanoparticle Packing

• DOI: 10.1021/acs.macromol.2c01918
• 发表时间: 2023-01
• 期刊: Macromolecules
• 影响因子: 5.5
• 作者: Anastasia Neuman;Shan Zhang;Daeyeon Lee;Robert A. Riggleman

Polymer-Infiltrated Nanoparticle Films Using Capillarity-Based Techniques: Toward Multifunctional Coatings and Membranes

使用基于毛细作用的技术的聚合物渗透纳米颗粒薄膜：迈向多功能涂层和膜

• DOI: 10.1146/annurev-chembioeng-101220-093836
• 发表时间: 2021
• 期刊: Annual Review of Chemical and Biomolecular Engineering
• 影响因子: 8.4
• 作者: Venkatesh, R. Bharath;Manohar, Neha;Qiang, Yiwei;Wang, Haonan;Tran, Hong Huy;Kim, Baekmin Q.;Neuman, Anastasia;Ren, Tian;Fakhraai, Zahra;Riggleman, Robert A.
• 通讯作者: Riggleman, Robert A.