Department of Chemical Engineering and Materials Science, University of Minnesota, Minneapolis, Minnesota 55455, USA.
J Am Chem Soc. 2012 May 9;134(18):7636-9. doi: 10.1021/ja301770v. Epub 2012 Apr 30.
A dodecagonal quasicrystalline (QC) morphology is identified in a poly(styrene-b-isoprene-b-styrene-b-ethylene oxide) (SISO) tetrablock terpolymer based on evidence provided by transmission electron microscopy (TEM), small-angle X-ray scattering, and dynamic mechanical spectroscopy measurements. The QC state occurs at temperatures between those associated with simple hexagonal order (HEX) and the σ-phase (P4(2)/mnm), T(HEX) < T(QC) < T(σ) < T(ODT), where T(ODT) is the order-disorder transition temperature. All three morphologies are formed from spherical domains containing an O core surrounded by a shell of S that screens unfavorable segment-segment interactions with an I-rich matrix. TEM analysis reveals a QC morphology with 12-fold rotational symmetry but devoid of long-range translational order, along with locally coordinated structures consistent with dodecagonal quasicrystalline approximants. The SISO molecular architecture decouples control over the domain shape and interdomain interactions, leading to a multiplicity of packing symmetries.
在基于透射电子显微镜(TEM)、小角 X 射线散射和动态力学谱测量的证据基础上,鉴定了一种基于苯乙烯-异戊二烯-苯乙烯-嵌段共聚物(SISO)的十二面体准晶(QC)形态。QC 态出现在与简单六方有序(HEX)和 σ 相(P4(2)/mnm)相关的温度之间,T(HEX) < T(QC) < T(σ) < T(ODT),其中 T(ODT) 是有序-无序转变温度。所有这三种形态都是由包含 O 核的球形畴形成的,该核被 S 壳包围,该 S 壳屏蔽了与富 I 基质的不利段-段相互作用。TEM 分析揭示了具有 12 重旋转对称性但没有长程平移有序的 QC 形态,以及与十二面体准晶类似物一致的局部协调结构。SISO 分子结构分离了对畴形状和畴间相互作用的控制,导致了多种堆积对称性。