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Abstract By utilizing bicontinuous and nanoporous ordered nanonetworks, such as double gyroid (DG) and double diamond (DD), metamaterials with exceptional optical and mechanical properties can be fabricated through the templating synthesis of functional materials. However, the volume fraction range of DG in block copolymers is significantly narrow, making it unable to vary its porosity and surface‐to‐volume ratio. Here, the theoretically limited structural volume of the DG phase in coil‐coil copolymers is overcome by enlarging the conformational asymmetry through the association of mesogens, providing fast access to achieving flexible structured materials of ultra‐high porosities. The new materials design, dual‐extractable nanocomposite, is created by incorporating a photodegradable block with a solvent‐extractable mesogen (m) into an accepting block, resulting in a new hollow gyroid (HG) with the largely increased surface‐to‐volume ratio and porosity of 77 vol%. The lightweight HG exhibits a low refractive index of 1.11 and a very high specific reduced modulus, almost two times that of the typical negative gyroid (porosity≈53%) and three times that of the positive gyroid (porosity≈24%). This novel concept can significantly extend the DG phase window of block copolymers and the corresponding surface‐to‐volume ratio, being applicable for nanotemplate‐synthesized nanomaterials with a great gain of mechanical, catalytic, and optoelectronic properties. 

Defects are symmetry breaking features within a crystal. They can be created during growth as well as by applied mechanical forces. We address point, line and surface defects in block copolymer crystals, concentrating on the structure of defects in the tubular network double gyroid and double diamond phases. Experimental results using 3D slice and view scanning electron microscopic tomographic imaging for many types of defects are presented and the nature of the structural details and symmetries are described. Often defects are considered detrimental to the properties and performance of the material, but if the mesoscale defects in 3D periodic block copolymers can be controlled, they can be utilized to achieve various advantageous such as new optical functionalities. 

Herein, this work aims to demonstrate the topological effect on the mechanicalx characteristics of selfassembled block copolymers (BCPs). The lamellae-forming polystyrene- block -polydimethylsiloxane (PSb -PDMS) can be self-assembled into various nanostructured monoliths with the use of PS-selective solvent for solvent annealing, giving diamond, gyroid, and cylinder structures with increasing the swelling degree of PS domain (the effective volume fraction of the PS segment after solvent annealing followed by evaporation). The stiffness of the self-assembled monoliths is scrutinized by nanoindentation test. For intrinsic PS- b -PDMS monolith with lamellar structure, the reduced elastic modulus as calculated from the measured stiffness is 0.91 GPa. By contrast, the PS- b -PDMS monolith with cylinder structure gives a significant reduction in reduced elastic modulus with the value of 0.52 GPa due to the introduced microporosity to the PS domain from solvent annealing using PS-selective solvent, resulting in the lower confrontation for continuous layer-by-layer deformation of hard PS and soft PDMS domains. In the case of gyroid-structured PS- b -PDMS monolith, it is unexpected to exhibit a significant increase in the reduced elastic modulus with a value of 1.6 GPa: note that the effect of microporosity is still significant. Accordingly, the enhancement of the reduced elastic modulus is attributed to the effect of deliberate structuring with network topology ( i.e., three-dimensional co-continuous hard PS and soft PDMS domains) that is able to hold the occurrence of large-scale deformation. In contrast to the gyroid with a three-strut texture, the diamond-structured PS- b -PDMS monolith with a four-strut texture is superior to the gyroid with a reduced elastic modulus of 2.2 GPa, further confirming the suggested topology effect. 

A twin boundary (TB) is a common low energy planar defect in crystals including those with the atomic diamond structure (C, Si, Ge, etc.). We study twins in a self-assembled soft matter block copolymer (BCP) supramolecular crystal having the double diamond (DD) structure, consisting of two translationally shifted, interpenetrating diamond networks of the minority polydimethyl siloxane block embedded in a polystyrene block matrix. The coherent, low energy, mirror-symmetric double tubular network twin has one minority block network with its nodes offset from the (222) TB plane, while nodes of the second network lie in the plane of the boundary. The offset network, although at a scale about a factor of 10 3 larger, has precisely the same geometry and symmetry as a (111) twin in atomic single diamond where the tetrahedral units spanning the TB retain nearly the same strut (bond) lengths and strut (bond) angles as in the normal unit cell. In DD, the second network undergoes a dramatic restructuring—the tetrahedral nodes transform into two new types of mirror-symmetric nodes (pentahedral and trihedral) which alternate and link to form a hexagonal mesh in the plane of the TB. The collective reorganization of the supramolecular packing highlights the hierarchical structure of ordered BCP phases and emphasizes the remarkable malleability of soft matter. 

3D reconstruction of nonsingular screw dislocations enables understanding of the dynamics of block copolymer structural color.