Collaborative Research: Solution Processing with Entropy-Controlled Stratification of Architecturally-Complex Polymer Blends

合作研究：结构复杂的聚合物共混物的熵控制分层溶液处理

• 批准号: 1934045
• 负责人: Rafael Verduzco
• 金额: $ 26.8万
• 依托单位: William Marsh Rice University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2020
• 资助国家: 美国
• 起止时间: 2020-01-01 至 2022-12-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1934045&HistoricalAwards=false
• 关键词: Collaborative; Research; Solution; Processing; Entropy

A variety of consumer products are manufactured by using solvents to deposit a thin polymer film on a surface, including anti-fouling coatings, membranes for water purification, and electronic devices. Solvent-based manufacturing processes are attractive because they are fast, inexpensive, and scalable to large areas. However, as the solvent evaporates, the polymers arrange themselves in ways that are difficult to predict or control. This collaborative research award develops new solvent-based manufacturing processes where different types of polymers are spontaneously sorted into layers according to their size and shape. This unique approach can be used to decouple the surface and bulk properties of the film, allowing for independent optimization of each attribute. Furthermore, the polymers can be degradable to facilitate their disassembly and recyclability. As a result, the principles established through this research can facilitate the development of high-performing polymer films for end-use applications in biomedical devices, desalination and filtration systems, and devices for clean energy, which greatly impacts society and the U.S. economy. Laboratory research engages graduate and undergraduate students and is complemented by education and outreach programs that include new modules for undergraduate and graduate courses at collaborating institutions; short courses and symposia for the broader scientific community; activities that teach science to the blind and visually impaired; and a student exchange program between the two institutions.The goal of this collaborative research project is to develop solution deposition processes that produce vertical stratification of bottlebrush copolymers and linear homopolymers in thin films. The research tasks are designed to test the hypothesis that bottlebrush copolymers are entropically attracted toward the vapor-liquid interface, leading to "bottlebrush-on-top" stratification for a broad range of material chemistries and processing conditions. Importantly, by leveraging these entropic effects during processing, the bottlebrush copolymer additives can be synthesized with "high energy" polar, ionic and hydrogen-bonding moieties. Such chemistries are critical for tuning a range of surface and interfacial properties, including wettability, friction, fouling resistance, adhesion strength, degradability, conductivity, and stimuli-responsiveness. The research plan examines the interplay between materials design (polymer architecture, chemistry) and processing variables (evaporation rate, diffusion rates) on stratification profiles, using existing models for vertical stratification of colloidal particles to guide experimental design. The collaboration consists of synthesis of a set of bottlebrush copolymer additives and characterization of transport-related parameters. The systematic research plan involves preparation and characterization of 400 independent samples, evenly split between the two institutions. Significantly, the principles established by this research redefines what types of polymers are characterized as "surface active" and transforms current approaches to surface engineering in polymeric materials.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.

通过使用溶剂在表面上存款薄聚合物膜来制造各种消费品，包括防污涂层、用于水净化的膜和电子器件。基于溶剂的制造工艺是有吸引力的，因为它们快速，廉价，并且可扩展到大面积。然而，随着溶剂的蒸发，聚合物以难以预测或控制的方式排列。该合作研究奖开发了新的溶剂型制造工艺，其中不同类型的聚合物根据其大小和形状自发地分类成层。这种独特的方法可用于分离膜的表面和本体性质，允许对每个属性进行独立优化。此外，聚合物可以是可降解的，以促进它们的分解和可回收性。因此，通过这项研究建立的原则可以促进高性能聚合物薄膜的开发，用于生物医学设备，脱盐和过滤系统以及清洁能源设备的最终用途，这对社会和美国经济产生了巨大影响。实验室研究吸引研究生和本科生参与，并辅之以教育和外联方案，包括合作机构的本科生和研究生课程新模块;面向更广泛科学界的短期课程和专题讨论会;向盲人和视力受损者教授科学的活动;以及两个机构之间的学生交流计划。这个合作研究项目的目标是开发溶液沉积过程，产生垂直分层的瓶刷共聚物和线性均聚物。研究任务的目的是测试的假设，瓶刷共聚物的熵吸引向气-液界面，导致“瓶刷上的顶部”分层的材料化学和加工条件的范围很广。重要的是，通过在加工过程中利用这些熵效应，瓶刷共聚物添加剂可以与“高能”极性、离子和氢键部分合成。这种化学性质对于调节一系列表面和界面性质是至关重要的，包括润湿性、摩擦力、耐污性、粘附强度、降解性、导电性和刺激响应性。该研究计划研究材料设计（聚合物结构，化学）和处理变量（蒸发速率，扩散速率）之间的相互作用分层配置文件，使用现有的模型垂直分层的胶体颗粒，以指导实验设计。该合作包括一组瓶刷共聚物添加剂的合成和运输相关参数的表征。系统的研究计划涉及400个独立样本的制备和表征，平均分配给两个机构。值得注意的是，这项研究所确立的原则重新定义了哪些类型的聚合物具有“表面活性”的特征，并改变了目前聚合物材料表面工程的方法。该奖项反映了NSF的法定使命，并通过使用基金会的知识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

Understanding interfacial segregation in polymer blend films with random and mixed side chain bottlebrush copolymer additives

• DOI: 10.1039/d1sm01146d
• 发表时间: 2021-09-08
• 期刊: SOFT MATTER
• 影响因子: 3.4
• 作者: Mei, Hao;Mahalik, Jyoti P.;Verduzco, Rafael
• 通讯作者: Verduzco, Rafael

Rapid Processing of Bottlebrush Coatings through UV-Induced Cross-Linking

• DOI: 10.1021/acsmacrolett.0c00384
• 发表时间: 2020-08-18
• 期刊: ACS MACRO LETTERS
• 影响因子: 7.015
• 作者: Mei, Hao;Mah, Adeline Huizhen;Verduzco, Rafael
• 通讯作者: Verduzco, Rafael

Analysis of Surface Segregation of Bottlebrush Polymer Additives in Thin Film Blends with Attractive Intermolecular Interactions

具有有吸引力的分子间相互作用的薄膜共混物中洗瓶刷聚合物添加剂的表面偏析分析

• DOI: 10.1021/acs.macromol.0c00744
• 发表时间: 2020
• 期刊: Macromolecules
• 影响因子: 5.5
• 作者: Miyagi, Kazuma;Mei, Hao;Terlier, Tanguy;Stein, Gila E.;Verduzco, Rafael
• 通讯作者: Verduzco, Rafael

Impact of Processing Effects on Surface Segregation of Bottlebrush Polymer Additives

• DOI: 10.1021/acs.macromol.2c01418
• 发表时间: 2022-09-29
• 期刊: MACROMOLECULES
• 影响因子: 5.5
• 作者: Lee，Dongjoo;Charpota，Nilesh;Verduzco，Rafael
• 通讯作者: Verduzco，Rafael