Department of Chemical Engineering, University of South Carolina, Columbia, SC 29208.
Department of Food Science, College of Agriculture and Life Sciences, Cornell University, Ithaca, NY 14850.
Proc Natl Acad Sci U S A. 2023 Mar 21;120(12):e2220032120. doi: 10.1073/pnas.2220032120. Epub 2023 Mar 14.
Finely controlled flow forces in extrusion-based additive manufacturing can be exploited to program the self-assembly of malleable nanostructures in soft materials by integrating bottom-up design into a top-down processing approach. Here, we leverage the processing parameters offered by direct ink-writing (DIW) to reconfigure the photonic chiral nematic liquid crystalline phase in hydroxypropyl cellulose (HPC) solutions prior to deposition on the writing substrate to direct structural evolution from a particular initial condition. Moreover, we incorporate polyethylene glycol (PEG) into iridescent HPC inks to form a physically cross-linked network capable of inducing kinetic arrest of the cholesteric/chiral pitch at length scales that selectively reflect light throughout the visible spectrum. Based on thorough rheological measurements, we have found that printing the chiral inks at a shear rate where HPC molecules adopt pseudonematic state results in uniform chiral recovery following flow cessation and enhanced optical properties in the solid state. Printing chiral inks at high shear rates, on the other hand, shifts the monochromatic appearance of the extruded filaments to a highly angle-dependent state, suggesting a preferred orientation of the chiral domains. The optical response of these filaments when exposed to mechanical deformation can be used in the development of optical sensors.
在挤出式增材制造中,可以通过将自下而上的设计集成到自上而下的处理方法中,精细控制流动力来编程可延展纳米结构在软材料中的自组装。在这里,我们利用直接写入(DIW)提供的加工参数,在沉积到书写基底之前,对羟丙基纤维素(HPC)溶液中的光子手性向列液晶相进行重新配置,以从特定的初始条件引导结构演变。此外,我们将聚乙二醇(PEG)掺入到有虹彩效果的 HPC 油墨中,形成一个物理交联的网络,能够在整个可见光范围内选择性反射光的长度尺度上诱导胆甾相/手性螺距的动力学停止。基于彻底的流变学测量,我们发现,在 HPC 分子采用准向列状态的剪切率下打印手性油墨,会导致在停止流动后均匀恢复手性,并在固态下增强光学性能。另一方面,在手性油墨在高剪切率下打印会将挤出细丝的单色外观转移到高度依赖角度的状态,这表明手性域具有优先取向。当这些细丝受到机械变形时的光学响应可用于开发光学传感器。