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Self-Healing Behavior of Metallopolymers in Complex3D-Structures Obtained by DLP-Based 3D-Printing.

Michael Klein1,2, Patrick Fesser1,2, Stefan Zechel1,2

  • 1Laboratory of Organic and Macromolecular Chemistry (IOMC), Friedrich Schiller University Jena, Humboldtstr. 10, 07743, Jena, Germany.

Chemistry (Weinheim an Der Bergstrasse, Germany)
|January 24, 2025
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Summary

This study demonstrates 3D printed metallopolymers with remarkable self-healing capabilities. These advanced materials, utilizing metal complexes, show excellent structural integrity and high healing efficiency after damage.

Keywords:
3D-printinggreen chemistrymetallopolymerspolymerssupramolecular chemistry

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Area of Science:

  • Materials Science
  • Polymer Chemistry
  • Additive Manufacturing

Background:

  • Metallopolymers offer unique properties due to incorporated metal ions.
  • 3D printing enables complex structure fabrication.
  • Self-healing materials can autonomously repair damage.

Purpose of the Study:

  • To investigate the self-healing properties of 3D printed metallopolymers.
  • To explore the influence of different metal complexes on healing.
  • To assess the structural integrity and mechanical properties post-healing.

Main Methods:

  • Synthesis of metallopolymers via photopolymerization of acrylate monomers with ligand-containing units.
  • Incorporation of zinc(II) or nickel(II) metal salts.
  • Fabrication of 3D structures using direct digital light processing (DLP).
  • Characterization using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and dynamic mechanical thermal analysis (DMTA).
  • Controlled damage introduction and subsequent healing at elevated temperatures (70°C or 120°C).

Main Results:

  • Successful 3D printing of metallopolymers with triphenylmethyl(trt)-histidine or terpyridine ligands complexed with Zn(II) or Ni(II).
  • Demonstrated self-healing of introduced damages (20–1500 mN) within 24 hours.
  • Achieved excellent healing efficiencies up to 97%.
  • Maintained structural integrity and demonstrated excellent retention at and above healing temperatures.

Conclusions:

  • 3D printed metallopolymers exhibit significant self-healing capabilities.
  • The choice of metal complex influences the material's properties and healing performance.
  • These materials are promising for applications requiring durable and repairable 3D structures.