Thermodynamic and Dynamic Control of Nanoparticles in Polymer Matrices

聚合物基质中纳米颗粒的热力学和动态控制

• 批准号: 1905912
• 负责人: Russell Composto
• 金额: $ 62万
• 依托单位: University of Pennsylvania
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2019
• 资助国家: 美国
• 起止时间: 2019-09-01 至 2024-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1905912&HistoricalAwards=false
• 关键词: Thermodynamic; Dynamic; Control; Nanoparticles; Polymer

NON-TECHNICAL SUMMARYPolymer nanocomposites, mixtures of flexible long-chain molecules (polymers) and hard functional particles, are found in everyday applications from automobile tires to paints and adhesives. To promote the progress of science, the focus of this project is to study polymer nanocomposite coatings that have the potential to improve the ability of solar cell devices to utilize a broader section of the solar spectrum allowing for more efficient energy production. The fundamental issue that the project seeks to address is how to combine dissimilar materials in such a way that the properties can be varied by controlling how well the particles are distributed In addition to experiments, computer simulations will be used to guide the selection of polymer and particles and to help interpret experimental results. Block copolymers, which are two different polymer molecules tied to each other, will be manipulated to create horizontal and vertical alternating domains (like a stack of cards) that contain nanoparticles of complementary functionality. To determine the location of particles and size of aggregates, state-of-the-art characterization tools will be used. This research will produce phase diagrams that allow for the determination of environmental conditions that promote good mixing between the polymer and particles. Besides producing a well-educated, scientifically skilled workforce, the integration of research and education benefits society at several levels. For example, graduate and undergraduate students will participate in annual public events including Nanotechnology Day at Penn, Philly Materials Day, and the Philadelphia Science Festival. An additional exciting outreach program is Girls in Engineering Mathematics and Science Camp (GEMS), a weeklong day-camp that introduces middle-school girls from the Delaware Valley to Science, Technology, Engineering, and Math. TECHNICAL SUMMARYThe goal of this project is to understand the fundamental principles that control the spatial distribution and assembly of nanoparticles (NPs) in block copolymers (BCPs) and to understand the thermodynamics and phase separation pathways of polymer nanocomposites (PNCs). The overarching goal is to perform systematic studies that build on expertise in polymer and NP diffusion as well as NP assembly in PNCs. (1) The first aim is to tune the nanoscale separation between plasmonic NPs and upconverting nanoplates/nanospheres in horizontally and vertically aligned lamellar BCPs. By functionalizing the NP with polymer brushes, the two NP species will be located in alternating BCP domains. The effect of domain spacing and particle loading will be investigated. PNC field-theoretic simulations (PNC-FT) will be used to determine the free energies of these PNCs and predict the cylinder-to-lamellar phase transition. (2) The second aim is to study the thermodynamic behavior of binary (A/NP) and ternary (A/B/NP) PNCs. The phase diagrams will be mapped out using transmission electron microscopy (TEM) on isothermal samples as well as the new in situ X-ray scattering capabilities. As in the first aim, PNC-FT will provide guidance for selecting materials parameters and help interpret results. (3) The third aim is to investigate phase separation dynamics of binary (A/NP) PNCs to elucidate the fundamental parameters that determine aggregate size and percolating morphologies in kinetically trapped systems. PNC-FT modified to include dynamics will guide experiments and provide insight into the balance between thermodynamics and dynamics that dictate the final morphology. Particle diffusion will be measured using Rutherford backscattering spectrometry. Polymer brush relaxation and ion diffusion through percolated morphologies will also be measured. In summary, although fundamental in nature, the proposed work has the potential to create PNCs with enhanced upconversion luminescence and fast ion mobility, which is of importance for solar energy and energy storage devices, respectively. .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.

非技术概要聚合物纳米复合材料是柔性长链分子（聚合物）和硬质功能颗粒的混合物，存在于从汽车轮胎到油漆和粘合剂的日常应用中。 为了促进科学进步，该项目的重点是研究聚合物纳米复合涂层，这种涂层有可能提高太阳能电池设备利用更广泛的太阳光谱的能力，从而实现更高效的能源生产。该项目寻求解决的基本问题是如何组合不同的材料，通过控制颗粒的分布程度来改变其性能。除了实验之外，计算机模拟还将用于指导聚合物和颗粒的选择，并帮助解释实验结果。 嵌段共聚物是两种相互连接的不同聚合物分子，将被操纵以创建包含互补功能纳米颗粒的水平和垂直交替域（如一堆卡片）。为了确定颗粒的位置和聚集体的尺寸，将使用最先进的表征工具。 这项研究将生成相图，以便确定促进聚合物和颗粒之间良好混合的环境条件。 除了培养受过良好教育、具有科学技能的劳动力队伍之外，研究和教育的结合还可以在多个层面上造福于社会。例如，研究生和本科生将参加年度公共​​活动，包括宾夕法尼亚大学纳米技术日、费城材料日和费城科学节。 另一个令人兴奋的外展项目是女子工程数学和科学营 (GEMS)，这是一个为期一周的日营，向特拉华谷的中学生介绍科学、技术、工程和数学。技术摘要该项目的目标是了解控制嵌段共聚物（BCP）中纳米颗粒（NP）的空间分布和组装的基本原理，并了解聚合物纳米复合材料（PNC）的热力学和相分离途径。总体目标是基于聚合物和 NP 扩散以及 PNC 中 NP 组装的专业知识进行系统研究。 (1) 第一个目标是调整水平和垂直排列的层状 BCP 中等离激元 NP 和上转换纳米板/纳米球之间的纳米级分离。通过用聚合物刷对 NP 进行功能化，两种 NP 物质将位于交替的 BCP 域中。将研究域间距和颗粒负载的影响。 PNC 场论模拟 (PNC-FT) 将用于确定这些 PNC 的自由能并预测圆柱到层状的相变。 (2)第二个目标是研究二元(A/NP)和三元(A/B/NP)PNC的热力学行为。将使用透射电子显微镜 (TEM) 在等温样品上以及新的原位 X 射线散射功能绘制相图。与第一个目标一样，PNC-FT 将为选择材料参数提供指导并帮助解释结果。 (3) 第三个目标是研究二元 (A/NP) PNC 的相分离动力学，以阐明决定动力学捕获系统中聚集体尺寸和渗透形态的基本参数。修改后的 PNC-FT 包括动力学将指导实验，并深入了解决定最终形态的热力学和动力学之间的平衡。将使用卢瑟福背散射光谱法测量粒子扩散。 还将测量聚合物刷松弛和通过渗透形态的离子扩散。总之，虽然本质上是基础性的，但所提出的工作有潜力创建具有增强的上转换发光和快速离子迁移率的 PNC，这分别对于太阳能和储能设备很重要。 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

Dendrimer Ligand Directed Nanoplate Assembly

• DOI: 10.1021/acsnano.9b07348
• 发表时间: 2019-12-01
• 期刊: ACS NANO
• 影响因子: 17.1
• 作者: Elbert, Katherine C.;Thi Vo;Murray, Christopher B.
• 通讯作者: Murray, Christopher B.

Shape Anisotropy Enhances Nanoparticle Dynamics in Nearly Homogeneous Hydrogels

• DOI: 10.1021/acs.macromol.2c01577
• 发表时间: 2022-09
• 期刊: Macromolecules
• 影响因子: 5.5
• 作者: K. A. Rose;Natalie Gogotsi;Jonathan H. Galarraga;J. Burdick;C. Murray;Daeyeon Lee;R. Composto

Effect of Graft Length and Matrix Molecular Weight on String Assembly of Aligned Nanoplates in a Lamellar Diblock Copolymer

• DOI: 10.1021/acs.macromol.1c02478
• 发表时间: 2022-04
• 期刊: Macromolecules
• 影响因子: 5.5
• 作者: Christian Tabedzki;Nadia M. Krook;C. Murray;R. Composto;Robert A. Riggleman

Experiments and Simulations Probing Local Domain Bulge and String Assembly of Aligned Nanoplates in a Lamellar Diblock Copolymer

• DOI: 10.1021/acs.macromol.9b01324
• 发表时间: 2019-11
• 期刊: Macromolecules
• 影响因子: 5.5
• 作者: Nadia M. Krook;Christian Tabedzki;Katherine C. Elbert;K. Yager;C. Murray;Robert A. Riggleman;R. Composto

Nanorod position and orientation in vertical cylinder block copolymer films

垂直圆柱嵌段共聚物薄膜中纳米棒的位置和方向

• DOI: 10.1039/d0sm00043d
• 发表时间: 2020
• 期刊: Soft Matter
• 影响因子: 3.4
• 作者: Rasin, Boris;Lindsay, Benjamin J.;Ye, Xingchen;Meth, Jeffrey S.;Murray, Christopher B.;Riggleman, Robert A.;Composto, Russell J.
• 通讯作者: Composto, Russell J.