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Nanoscale 3D ordered polymer networks

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  • ReceivedAug 3, 2017
  • AcceptedSep 5, 2017
  • PublishedDec 13, 2017

Abstract

Structures having nanoscale 3D geometries are valuable as multifunctional materials, where multi-continuous microphases can synergistically influence mechanical, optical, transport and other properties. Such very high interface surface to volume ratio structures occur in a variety of materials including natural materials such as butter fly wings and sea urchin exoskeletons and in synthetic self-assembled structures such as surfactant/water systems and block polymers. Quantitative morphological characterization of such complex geometric structures is quite challenging. Unit cell sizes range from 10–300 nm with corresponding feature sizes on the 2–50 nm scale. Since these nanoscale network structures are bicontinuous, when one constituent is removed, the structure is still self supporting. Removal of one component produces a nanoporous material that may be in-filled with another component, or the surfaces of the nanopores can be coated with ultra-thin layers by atomic layer deposition to offer multifunctional capabilities. Due to the ability to individually tailor the properties of the network(s) and matrix, for example, to create strong dielectric or impedance contrast, such spatially periodic structures are excellent for the interference of waves (electromagnetic for photonic applications and acoustic for phononic applications) that can lead to bandgaps and hence the control of wave propagation in the material. This mini-review will focus on networks formed by bottom up self assembly of block polymers. In addition to structural issues, we emphasize the special physical properties related to bi- or tri-continuous networks.


Funded by

the U.S. Department of Energy

Office of Science

Office of Basic Energy Sciences(de-sc0014457)


Acknowledgment

This work was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences (de-sc0014457).


Interest statement

The author declares no conflict of interest.


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  • Figure 1

    Network microdomain structures in block polymers. (a) The double diamond (DD) with tetrapod nodes; (b) the double gyroid (DG) with tripod nodes; (c) the Plumber’s Nightmare (P) with hexapod nodes; (d) the noncubic O70 with tripod nodes; (e) the noncubic O52 with tripod nodes. (a), (b) and (d) are reprinted with permission from Macromolecules (Refs. [2], [3], and [4], respectively), copyrights 1986, 2001 and 2004, American Chemical Society. (c) is reprinted with permission from Angewandte Chemie Ref. [5] and (e) is reprinted with permission from Soft Matter Ref. [6] (color online).

  • Figure 2

    Computed domain shapes for cylinders, gyroid, perforated lamellae and diamond. The colors indicate the departure from constant mean curvature. Reprinted with permission from Macromolecules Ref. [38], copyright 1996, American Chemical Society (color online).

  • Figure 3

    TEM tomographic reconstructions of cubic networks. (A) Experimental reconstruction of double gyroid; (B) computational model of double gyroid network; (C) skeletal graph of experimental structure showing tripodal nodes; (D) experimental reconstruction of double diamond; (E) experimental reconstruction of double diamond (left) with skeletal graph (right). (A) and (B) are reprinted with permission from Phys. Rev. Lett. Ref. [42]. (C) is from Phys. Rev. E Ref. [43]. (D) is reprinted with permission from Macromolecules Ref. [18], copyright 2017. (E) is reprinted from Soft Matter Ref. [15], copyright 2015 (color online).

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