Enabling Kinetics and Structural Control of Polymer-Grafted Nanoparticle Superstructures via Solvent Vapor Annealing

非技术概述混合材料正在使纳米光子学、纳米纤维、燃料电池、光化学、纳米膜、电池等领域的新应用和技术成为可能。合理设计的聚合物-纳米颗粒复合材料可以协同聚合物和无机材料的属性，产生新的合成和加工可能性以及单一均匀材料无法获得的物理性能。通过这个项目，在材料研究部的固态和材料化学项目的支持下，印第安纳州大学的Xingchen Ye教授和他的研究小组正在通过自组装开发多功能纳米复合材料。这项研究正在扩大合成和加工工具箱，以便通过设计实现纳米复合材料。该项目为研究生和本科生提供纳米材料合成和表征方面的培训。此外，夏季研究机会提供给代表性不足的群体的成员通过与北卡罗来纳州AT州立大学和团体学者计划在印第安纳州University.Technical概要下一代聚合物纳米复合材料的发展需要在纳米粒子和聚合物基质的合成，精确的工程的有机-无机界面，和三维结构控制的同时进步。自组装承诺可扩展性，提供分子水平的构建模块设计，并生产三维材料。通过自组装实现对单个纳米颗粒的空间分布的复杂控制的关键挑战在于缺乏探测和操纵纳米复合材料形成途径的能力。 该项目由材料研究部的固态和材料化学计划支持，通过使用聚合物接枝纳米颗粒（PGNP）构建块来理解和控制使用溶剂蒸气退火的PGNP超结构的动力学途径和相行为来解决这一挑战。具体而言，该项目将（i）建立多组分PGNP超结构合成的溶剂退火的多功能性，（ii）通过改变溶剂退火参数来展示途径控制和多晶型选择，以及（iii）将形状各向异性的PGNP组装成紧密堆积和低密度的超结构并阐明组装途径。这项研究将为决定PGNP组装结果的热力学和动力学因素之间的相互作用提供基本和定量的见解，并将为预测合成具有动力学途径控制的有序PGNP超结构奠定基础，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。

NON-TECHNICAL SUMMARY Hybrid materials are enabling new applications and technologies in nanophotonics, nanofabrication, fuel cells, photovoltaics, nanomembranes, batteries, and more. Rationally designed polymer-nanoparticle composites can synergize the attributes of polymeric and inorganic materials, generating new synthesis and processing possibilities and physical properties that are unattainable with a single homogeneous material. With this project, supported by the Solid State and Materials Chemistry program in the Division of Materials Research, Professor Xingchen Ye and his research group at Indiana University are developing multifunctional nanocomposite materials through self-assembly. This research is expanding the synthetic and processing toolbox in order to achieve nanocomposites by design. This project provides training in nanomaterial synthesis and characterization to both graduate and undergraduate students. In addition, summer research opportunities are provided to members of underrepresented groups through partnerships with North Carolina A&T State University and the Groups Scholars Program at Indiana University.TECHNICAL SUMMARY The development of next-generation polymer nanocomposites requires simultaneous advances in the synthesis of nanoparticles and polymer matrices, precise engineering of the organic-inorganic interface, and three-dimensional structural control. Self-assembly promises scalability, provides molecular-level design of building blocks and produces three-dimensional materials. The key challenge in achieving sophisticated control over the spatial distribution of individual nanoparticles through self-assembly lies in the lack of ability to probe and manipulate the pathways of nanocomposite formation. This project, supported by the Solid State and Materials Chemistry program in the Division of Materials Research, is addressing this challenge by using polymer-grafted nanoparticle (PGNP) building blocks to understand and control the kinetic pathways and phase behaviors of PGNP superstructures using solvent vapor annealing. Specifically, this project will (i) establish the versatility of solvent annealing for the synthesis of multicomponent PGNP superstructures, (ii) demonstrate pathway control and polymorph selection by changing solvent annealing parameters, and (iii) assemble shape-anisotropic PGNP into close-packed and low-density superstructures and elucidate assembly pathways. This research will provide fundamental and quantitative insight into the interplay between thermodynamic and kinetic factors that dictate PGNP assembly outcome, and will lay the groundwork for predictive synthesis of ordered PGNP superstructures with kinetic pathway control, unprecedented compositional and structural diversity as well as reconfigurability.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.