Batch-Operated Condensed Droplet Polymerization to Understand the Effect of Temperature on the Size Distribution of Polymer Nanodomes
Batch-Operated Condensed Droplet Polymerization to Understand the Effect of Temperature on the Size Distribution of Polymer Nanodomes
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DOI：
10.1055/s-0043-1761311
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发表时间：
2023-01
影响因子：
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通讯作者：
Jeremiah James;Rong Yang
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文献类型：
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作者：
Jeremiah James;Rong Yang
尺寸可控聚合物纳米穹顶(PND)有利于现有和新兴技术的广泛领域。凝聚液滴聚合(CDP)是一种以单体为原料一步合成PND的真空合成技术。然而，合成和工艺条件对PND尺寸分布的影响仍然难以捉摸。在尺寸分布控制方面，我们报道了衬底温度对PND尺寸分布的影响，单体液滴在衬底温度下凝聚。我们采取了一种简化的方法，并在批处理模式下运行CDP，以匹配凝聚研究中常用的条件。值得注意的是，尽管在滴状缩合方面有丰富的知识基础，但像常见单体甲基丙烯酸羟乙酯(HEMA)这样的非极性液体的行为还没有被很好地理解。我们通过证明HEMA的滴状凝聚遵循两个阶段的增长过程来弥合这一差距。早期生长以液滴成核和长大为主，尺寸相对均匀，呈对数正态分布；后期生长以液滴合并和重成核共同作用为主，尺寸分布呈双峰分布。这一了解PND规模分布的新框架使PND的人口达到了前所未有的水平。其受控的尺寸分布有可能使紧急材料的可编程特性成为可能。
Size-controlled polymer nanodomes (PNDs) benefit a broad cross-section of existing and emerging technologies. Condensed droplet polymerization (CDP) is a vacuum-based synthesis technology that produces PNDs from monomer precursors in a single step. However, the effect of synthesis and processing conditions on the PND size distribution remains elusive. Towards size distribution control, we report the effect of substrate temperature, on which monomer droplets condense, on the size distribution of PNDs. We take a reductionist approach and operate the CDP under batch mode to match the conditions commonly used in condensation research. Notably, despite the rich knowledge base in dropwise condensation, the behavior of nonpolar liquids like a common monomer, i.e., 2-hydroxyethyl methacrylate (HEMA), is not well understood. We bridge that gap by demonstrating that dropwise condensation of HEMA follows a two-stage growth process. Early-stage growth is dominated by drop nucleation and growth, giving rise to relatively uniform sizes with a lognormal distribution, whereas late-stage growth is dominated by the combined effect of drop coalescence and renucleation, leading to a bimodal size distribution. This new framework for understanding the PND size distribution enables an unprecedented population of PNDs. Their controlled size distribution has the potential to enable programmable properties for emergent materials.