Ionic liquid-directed self-assembly of block copolymers

离子液体引导嵌段共聚物自组装

• 批准号: 2432821
• 金额: --
• 依托单位: Aston University
• 依托单位国家: 英国
• 项目类别: Studentship
• 财政年份: 2020
• 资助国家: 英国
• 起止时间: 2020 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=studentship-2432821
• 关键词: Ionic; liquid; directed; self; assembly

The necessity for sufficient and more developed energy and data storage has triggered emerging research fields over the past two decades in both industry and in academia.Energy storage is vital in this day and age, particularly for storing clean energy produced from renewable resources. Novel materials must be generated to meet this ever-growing demand, and self-assembled block copolymers can be used to generate so-called ionogels (gel materials comprising an ionic liquid (IL) immobilised in a cross-linked polymer matrix) which are a class of materials that offer much promise. The use of ILs offers benefits for energy storage applications due to their unique properties including high ionic conductivity and high thermal & chemical stability.Data storage is another important area in which IL-polymer systems can offer significant advances. According to a 2018 IDC White Paper (US44413318), the Global Datasphere is predicted to increase by 530 per cent to 175 zettabytes (1.75x1023 bytes) between 2018 and 2025. To tackle this astronomical rise, we must produce storage devices with ever-increasing areal density (data storage density). To do this, we must generate nanopatterns with sub-10 nm domains, and strongly segregated block copolymers (BCPs) offer a potential route to such small features. BCPs are polymers synthesised using two or more monomers that are chemically distinct, and they can be arranged in an array of different sequences giving rise to different classifications. A synthetic technique that can be used to develop such BCPs is reversible addition-fragmentation chain transfer (RAFT) polymerisation. Utilising RAFT enables stringent control on the polymerisation process such as controlling the molecular weight and polydispersity such that the resulting polymers are very well-defined. A key advantage of using RAFT is that the process is that the reactions can be carried out using a wide range of functional monomers. There has been increasing interest in RAFT-mediated polymerisation-induced self-assembly (PISA), a technique that will be frequently used in this project to synthesise the desired BCPs. PISA has shown to be advantageous relative to other well established self-assembly routes which customarily involve additional post-polymerization steps.This project will focus on the synthesis and characterisation of BCPs with amphiphilic character in ILs (i.e. containing at least one IL-philic and one IL-phobic block). Importantly, industrially-sourced (BASF) ILs will be used to maximise the commercial relevance of the IL-polymer formulations. Formulations will be developed to induce BCP self-assembly, both in solution (to obtain ionogels for energy storage applications) and in the bulk (to generate ordered materials with very small domain sizes for nanoelectronics). Small-angle X-ray scattering (SAXS) will be an important characterisation technique to determine the size and shape (i.e. the morphologies) of the resulting self-assembled species.Bulk self-assembly requires solvent vapour annealing, thermal annealing or spin casting, and the final observed nanopattern can be dependent on whether an IL is present or absent. Low molecular weight block copolymers that exhibit strong microphase separation have yielded great interest amongst research due to their ability to microphase separate into very small (< 10 nm) domains. Solution self-assembly in the presence of ILs yields ionogels, which vastly improve the mechanical properties of ILs, whilst offering the same optimal properties (e.g. ionic conductivity) and thus have the potential to be used in energy storage applications.

在过去的二十年里，对充足和更先进的能源和数据存储的需求引发了工业界和学术界的新兴研究领域。能源存储在当今时代至关重要，特别是用于存储由可再生资源产生的清洁能源。必须产生新的材料以满足这种不断增长的需求，并且自组装嵌段共聚物可以用于产生所谓的离子凝胶（包含固定在交联聚合物基质中的离子液体（IL）的凝胶材料），其是一类提供很大前景的材料。由于离子液体具有高离子电导率和高热化学稳定性等独特性能，因此离子液体的使用为储能应用提供了优势。数据存储是离子液体聚合物系统可以提供显著进步的另一个重要领域。根据2018年IDC白色白皮书（US 44413318），全球数据网预计将在2018年至2025年期间增长530%，达到175 zettabytes（1.75x1023字节）。为了应对这一天文数字的增长，我们必须生产具有不断增加的面密度（数据存储密度）的存储设备。要做到这一点，我们必须生成具有亚10 nm域的纳米粒子，而强隔离嵌段共聚物（BCP）为这种小特征提供了一条潜在的途径。BCP是使用两种或更多种化学上不同的单体合成的聚合物，并且它们可以排列成不同序列的阵列，从而产生不同的分类。可用于开发此类BCP的合成技术是可逆加成-断裂链转移（RAFT）聚合。利用RAFT能够对聚合过程进行严格控制，例如控制分子量和多分散性，使得所得聚合物非常明确。使用RAFT的一个关键优点是，该方法是可以使用广泛的功能单体进行反应。RAFT介导的聚合诱导自组装（比萨），一种将在本项目中经常使用的技术，合成所需的BCP的兴趣越来越大。比萨已被证明是相对于其他完善的自组装路线，通常涉及额外的后聚合步骤的优势。本项目将集中在合成和表征的BCP的两亲性的IL（即包含至少一个IL-亲和一个IL-疏嵌段）。重要的是，工业来源的（BASF）IL将用于最大限度地提高IL-聚合物制剂的商业相关性。将开发配方以诱导BCP自组装，无论是在溶液中（以获得用于能量存储应用的离子凝胶）还是在本体中（以生成用于纳米电子学的具有非常小的域尺寸的有序材料）。小角X射线散射（SAXS）将是一个重要的表征技术，以确定所产生的自组装物种的大小和形状（即形态）。本体自组装需要溶剂蒸气退火，热退火或旋转铸造，和最终观察到的纳米图案可以取决于是否存在IL。表现出强微相分离的低分子量嵌段共聚物由于其微相分离成非常小（< 10 nm）的域的能力而在研究中产生了极大的兴趣。在离子液体存在下的溶液自组装产生离子凝胶，其极大地改善了离子液体的机械性能，同时提供相同的最佳性能（例如离子电导率），因此具有用于能量存储应用的潜力。