Influence of the Structure of Block Copolymer Nanoparticles on the Growth of Calcium Carbonate
Influence of the Structure of Block Copolymer Nanoparticles on the Growth of Calcium Carbonate
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DOI：
10.1021/acs.chemmater.8b02912
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发表时间：
2018-10-23
影响因子：
8.6
通讯作者：
Meldrum, Fiona C.
中科院分区：
文献类型：
--
作者：
Kim, Yi-Yeoun;Fielding, Lee A.;Meldrum, Fiona C.
嵌段共聚物纳米颗粒是多用途的晶体生长添加剂，其可用于改变晶体形态并通过其在晶格内的包藏引入新的性质。然而，使这些纳米颗粒成为有效添加剂的结构特征还不清楚。本研究采用了一系列的共聚物纳米粒子，包括疏水性核心和冠的羧酸盐和羟基聚合物链，以建立设计规则，管理的纳米粒子的活性。纳米粒子冠的化学组成和链的长度的系统变化使我们能够探索两个密切相关的现象：晶体习性修改和纳米粒子的晶格内的闭塞。我们表明，纳米粒子的活性不直接与羧酸盐含量和纳米粒子包含50%羧酸盐/50%羟基基团更有效地纳入比那些包含100%羧酸盐链。羧基的可接近性也很重要，当羧酸根基团嵌入冠内而不是位于颗粒表面时，活性降低。最后，我们证明，闭塞和晶体习性/形态的变化可以独立发生。这些结果提供了一个新的框架，设计纳米粒子作为晶体生长添加剂，这为制备无机纳米复合材料提供了一种新的策略。
Block copolymer nanoparticles are versatile crystal growth additives that can be used to both modify crystal morphologies and introduce new properties through their occlusion within the crystal lattice. However, the structural features that make these nanoparticles such effective additives are as yet unclear. This study employs a series of copolymer nanoparticles comprising hydrophobic cores and coronas of carboxylate and hydroxyl polymer chains to establish the design rules that govern the activity of the nanoparticles. Systematic variation of the chemical composition of the nanoparticle coronas and the length of the chains enabled us to explore two closely linked phenomena: crystal habit modification and nanoparticle occlusion within the crystal lattice. We show that nanoparticle activity does not scale directly with carboxylate content and that nanoparticles comprising 50% carboxylate/50% hydroxyl groups were incorporated more effectively than those comprising 100% carboxylate chains. The accessibility of the carboxyl groups is also important, and activity is reduced when the carboxylate groups are embedded within the corona rather than being located on the particle surface. Finally, we demonstrate that occlusion and changes in crystal habit/morphology can occur independently. These results offer a new framework for designing nanoparticles as crystal growth additives, where this provides a novel strategy for preparing inorganic nanocomposites.