Probing deep glassy states with ultrastable polymer glass

自从安德森现在著名的引言(科学，1995)指出，固态理论中最深刻和最有趣的悬而未决的问题可能是玻璃的性质和玻璃转变的理论。人们对这一领域的兴趣持续增长。最近的实验和理论突破使我们非常接近一个新的理解水平。然而，几十年来关于玻璃状态是否存在的讨论再次被带到了风口浪尖。在理论方面，一种新的理论毫无疑问地证明了(在无限维中)存在到理想玻璃态的真正相变。在实验方面，通过物理蒸汽沉积产生的玻璃可以表现出动力学稳定性的发现(它们可以在玻璃转变温度以上显著加热，然后重新变成过冷液体)，这表明这些材料类似于那些已经老化了数千年甚至数百万年的材料。这些新的极端非晶态材料提供了一种机制，可以生产出近乎理想的玻璃，而不必在地质时代老化。前人在这方面的工作主要集中在分子玻璃上，金属稳定玻璃也得到了制备和研究。我们最近开发并演示了一种可靠和可重复地制造聚合物材料稳定玻璃的技术。这些材质在两个关键方面与以前所有其他类别的材质不同。首先，大多数聚合物不具有结晶基态，这一点具有极其重要的实际意义和根本意义。这意味着与其他材料相比，避免结晶是微不足道的。其次，这些材料包含一个可以调整的额外参数-聚合指数N。我们目前拥有显著的竞争优势，该提案将充分利用这一优势。我们将把物理气相沉积(PVD)生产的聚合物稳定玻璃与类似的材料进行比较，这些材料已恢复活力成为平衡液体，淬火成玻璃，并老化(可访问的时间)。这将使我们能够确定PVD样本在多大程度上真实地模拟了在玻璃状态下老化的样本。我们将使用局域和基于设备的技术来研究PVD聚合物玻璃中的局域弛豫过程。我们将利用我们团队在玻璃表面迁移率研究方面长达15年的经验，对稳定和正常的玻璃表面进行比较研究。通过这些研究，我们将能够确定制造最稳定玻璃的最佳方法。对这些自然无法制造的极端非晶态材料的研究不仅有望极大地增加我们对玻璃材料的理解，还将为软电子、制药、气膜甚至聚合物电池的新进展铺平道路。参与这些研究的HQP将为学术或私营部门在物理、化学或工程领域的机会做好准备。

Since Anderson's now famous quote (Science, 1995)  that the "The deepest and most interesting unsolved problem in solid state theory is probably the theory of the nature of glass and the glass transition." interest in this area has continued to grow. Recent experimental and theoretical breakthroughs have brought us tantalizingly close to a new level of understanding.  The decades of discussion about whether an "ideal" glassy state exists have been brought to the forefront once more.  On the theory side, a new theory demonstrates without question that  (in infinite dimensions) there is a real phase transition to an ideal glass state. On the experimental side, the discovery that glasses produced by physical vapour deposition can show a kinetic stability (they can be heated significantly above the glass transition temperature before rejuvenating to a supercooled liquid)  which suggests the materials are similar to those that have been aged for thousands or even millions of years. These new extreme amorphous materials provide a mechanism to produce near-ideal glasses without having to age for geological times. Previous work in this area has focused on molecular glasses, and metallic stable glasses have also been prepared and studied. We have recently developed and demonstrated a technique to reliably and reproducibly make stable glasses of polymeric materials. These materials differ from all other previous classes of materials in two key ways. First, and of tremendous practical and fundamental importance, most polymers do not have a crystalline ground state.  This means that avoiding crystallization is trivial compared to other materials. Second, these materials contain an additional parameter that can be tuned- the polymerisation index N. We currently have a significant competitive advantage and the proposal will take full advantage of that. We will compare polymer stable glasses produced by physical vapour deposition (PVD) to similar materials that have been rejuvenated into an equilibrium liquid, quenched to a glass, and aged (for accessible times). This will allow us to determine how well a PVD sample truly mimics one that is aged in the glassy state. We will study local relaxation processes in PVD polymer glass using both local and facility based techniques. We will use our group's 15 years of  experience in studies of surface mobility in glasses to make comparative studies of stable and normal glass surfaces. Through these studies we will be able to determine the best way to make the most stable glasses possible. The study of these extreme amorphous materials that can not be made by nature promises to not only dramatically increase our understanding about glassy materials but also pave the way to new advances in soft electronics, pharmaceuticals, gas membranes, and even polymer batteries. HQP involved in these studies will be well equipped for either academic or private sector opportunities in physics, chemistry, or engineering fields.