4.7 Article

From Scratch Closure to Electrolyte Barrier Restoration in Self-Healing Polyurethane Coatings

Journal

ACS APPLIED POLYMER MATERIALS
Volume 3, Issue 5, Pages 2802-2812

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acsapm.1c00323

Keywords

self-healing polymer; self-healing coating; polyurethane; polymer architecture; urea; ACET

Funding

  1. Croda Nederland BV
  2. Dutch National Organization for Scientific Research, Domain Applied and Engineering Sciences (NWO-TTW) [15010]

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This study investigates the effects of the soft block fraction and H-bond state in thermoplastic polyurethanes on autonomous entropy-driven scratch closure and barrier restoration. It is found that while softer polyurethanes can efficiently close cracks, they are unable to sufficiently restore barrier properties.
The effects of the soft block fraction and H-bond state in thermoplastic polyurethanes on autonomous entropy-driven scratch closure and barrier restoration are studied. To this aim, comparable polyurethanes with different segmentation states are applied as organic coatings on plain carbon steel plates, scratched under very well-controlled conditions, and the scratch closure and sealing kinetics are studied in detail. The scratch closure is measured optically, while the barrier restoration is probed by the accelerated cyclic electrochemical technique (ACET). Scratch closure, attributed to entropic elastic recovery (EER), is followed in a marked two-step process by barrier restoration governed by local viscous flow and the state of the interfacial hydrogen bonding. Polyurethanes with a lower soft phase fraction lead to a higher urea/urethane ratio, which in turn influences the healing efficiency of each healing step. Interestingly, softer polyurethanes leading to efficient crack closure were unable to sufficiently restore barrier properties. The present work highlights the critical role of the soft/hard block and urea/urethane H-bond state content on crack closure and barrier restoration of anticorrosive organic coatings and points at design rules for the design of more efficient corrosion-protective self-healing polyurethanes.

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