Crystallisation in the Real World: Delivering Control through Theory and Experiment

结晶是一个迷人的过程。从窗户上的冰或水壶里的水垢的形成等常见观察来看，结晶对几乎每个科学领域都很重要，并且是陶瓷、药品、精细化学品、纳米材料和生物矿物生产等各种过程的核心。同样重要的是防止不必要的结晶，如风化、水垢或肾结石。只有了解了材料是如何结晶的，我们才有希望控制这些过程。尽管结晶很重要，但我们对这一基本现象背后的许多机制仍然知之甚少。这是因为结晶是由分子尺度过程控制的，很难通过实验来研究。例如，虽然实验可以确定产生特定晶体多晶的反应条件，但它们不能单独解释为什么会发生这种情况。这项计划补助金将结合实验和理论来应对这一挑战。我们的实验项目将液相透射电镜和功能扫描探针显微镜等前沿分析技术带到了前台，这将使我们能够前所未有地研究结晶过程中固体和溶液的变化。随着建模的最新进展，我们将能够在可比的时间和长度尺度上进行成核和生长过程的模拟，为在纳米尺度上充分理解晶体的成核和生长提供一个独特的机会。这些研究将与更简单的散装实验联系起来，以提供现实世界中结晶的整体观点。我们将使用这种方法来解决无机化合物结晶中的六个主要挑战。每一项挑战，不仅具有根本性的重要性，而且最终对工业具有重要意义，并具有各种实际应用，如洗碗机的防垢，牙科再矿化和纸张涂层的定制颗粒形状。散装溶液中均匀结晶的研究将为我们的成核研究奠定基础，揭示我们如何通过改变溶液和环境条件来指导成核途径。然后，我们将在这项工作的基础上探索多态性的迷人问题，为我们提供提供特定晶体多态性的条件的预测性理解。然后转向无处不在的表面定向结晶现象，理论和前沿的分析方法都将带来对表面及其在邻近溶液中引起的变化如何控制结晶的新理解。这自然导致我们去寻找有效的成核剂，尽管经典成核理论的承诺，已知的只有少数系统。控制晶体生长以产生具有确定形状和大小的颗粒是另一个具有重要工业意义的课题，可溶性添加剂被广泛用于实现这一目标。通过了解晶体/添加剂的相互作用，我们的目标是预先选择添加剂来生长具有目标特性的晶体，或抑制不需要的结晶。最后，我们将研究有限体积内的结晶；这最终将使我们能够使用约束来控制结晶。这些雄心勃勃的目标只能在项目资助的框架内实现，项目资助提供了灵活性和长期资助，将理论和实验的不同学科结合在一起。虽然每个单独的任务都集中在一个明确的问题上，但它们通过共同的方法和理解在整个项目中紧密联系在一起，一个任务的发展将推动其他任务的进步。

Crystallisation is a fascinating process. From common observations such as the formation of ice on a window or scale in a kettle, crystallisation is important to virtually every area of science, and lies at the heart of processes as varied as the production of ceramics, pharmaceuticals, fine chemicals, nanomaterials and biominerals. Equally important is the prevention of unwanted crystallisation in the form of weathering, scale or kidney stones. Only by understanding how materials crystallise can we hope to control these processes.Despite the importance of crystallisation, we still have a poor understanding of many of the mechanisms that underlie this fundamental phenomenon. This is due to the fact that crystallisation is governed by molecular scale processes that are very difficult to study experimentally. For example, while experiments can identify reaction conditions that generate specific crystal polymorphs, they cannot alone explain why this occurred. This Programme Grant will couple experiment and theory to address this challenge. Our experimental programme brings to the fore such frontier analytical techniques as liquid-phase TEM and functional scanning probe microscopies that will allow us to study the changes in solid and solution during crystallisation as never before. With recent advances in modelling we shall be able to perform simulations of nucleation and growth processes on comparable time- and length-scales, providing a unique opportunity to fully understand crystal nucleation and growth at the nanoscale. These studies will be linked to simpler bulk experiments to provide a holistic view of crystallisation in the real world. We will use this approach to address six major challenges in the crystallisation of inorganic compounds. Each challenge, as well as being of fundamental importance, is ultimately significant to industry and has practical applications as varied as scale prevention in dishwashers, dental remineralisation and tailoring particle shape for paper coatings. Investigations of homogeneous crystallisation in bulk solution will lay the foundation for our nucleation studies, revealing how we can direct nucleation pathways by varying solution and environmental conditions. We will then build on this work to explore the fascinating question of polymorphism, giving us predictive understanding of conditions which deliver specific crystal polymorphs. Turning then to the ubiquitous phenomenon of surface-directed crystallisation, both theory and cutting-edge analytical methods will bring new understanding of how surfaces - and the changes they cause in the adjacent solution - govern crystallisation. This naturally leads us to a search for effective nucleating agents, which, despite the promises of classical nucleation theory, are known for only a small number of systems. Control of crystal growth to generate particles with defined shapes and sizes is another topic of great industrial importance, and soluble additives are widely used to achieve this goal. By understanding crystal/ additive interactions we aim to pre-select additives to grow crystals with target properties, or to inhibit unwanted crystallisation. Finally, we will study crystallisation within confined volumes; this will ultimately enable us to use confinement to control crystallisation.These ambitious objectives can only be met within the framework of a Programme Grant, which provides the flexibility and long-term funding to bring together the very different disciplines of theory and experiment. While each of the individual tasks focuses on a distinct problem in crystallisation, they are intimately linked over the entire project by common methods and understanding, and developments in one task will drive advances in others.