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Cristina Resetco
Polymer and Materials Science

Self-Healing Materials
Motivation: Self-healing materials are smart materials that can
intrinsically repair damage leading to longer lifetimes, reduction of
inefficiency caused by degradation and material failure.
Applications: shock absorbing materials, paints and anti-corrosion
(1) Restoration of Conductivity with TTF-TCNQ Charge-Transfer Salts
(2) Self-Healing Materials with Interpenetrating Microvascular
(3) Coaxial Electrospinning of Self-Healing Coatings
(4) Nanoscale Shape-Memory Alloys for Ultrahigh Mechanical Damping

Self-Healing Materials .

d) damage is removed by directed mass transport towards the damage site and local mending reaction through (re)connection of crack planes by physical interactions and/or chemical bonds e) after the healing of the damage the previously mobile material is immobilised again.Self-Healing Materials a) damage is inflicted on the material b) a crack occurs c) generation of a “mobile phase” triggered either by the occurrence of damage (in the ideal case) or by external . resulting in restored mechanical properties http://www.autonomicmaterials.

Self-Healing Methods Material Design .

Funct.Restoration of Conductivity with TTF-TCNQ Charge-Transfer Salts A new microcapsule system restores conductivity in mechanically damaged electronic devices in which the repairing agent is not conductive until its release. J. et al. 20. Mater. 2010. Moore. Adv. 1721– .

et al. Funct. Tetrathiafulvalene Tetracyanoquinodimethane tetrathiafulvalene–tetracyanoquinodimethane Non-conducting Non-conducting Conducting Moore. Mater. Two core solutions travel by capillary action to the relevant damage site before forming the conductive salt. 1721– . 20.Restoration of Conductivity with TTF-TCNQ ChargeTransfer Salts Conductive healing agent is generated upon mechanical damage. J. The major advantage of this approach is greater mobility of precursor solutions compared to suspensions of conductive particles. Adv. 2010.

2010. Moore. Adv. 1721– . and D) TCNQ-PA MCs. and phenyl acetate (PA). 20. Mater. Electron impact mass spectra of the dried microcapsule core solutions confirmed the presence of TTF and TCNQ in the microcapsules. B) MCs containing powdered TTF-TCNQ salt suspended in PA. Poly(urea-formaldehyde) (PUF) core–shell microcapsules were prepared using an in situ emulsification polymerization in an oil-in-water suspension. C) TTF-PA MCs. et al. J.Microcapsule Synthesis TTF and TCNQ were individually incorporated into microcapsule cores as saturated solutions in chlorobenzene (PhCl). Optical microscope images from A) an attempt to encapsulate crystalline TTF-TCNQ salt in PA. ethyl phenylacetate (EPA). All scale bars are 200mm. Funct. Figure 1. inset: ruptured MCs containing powdered TTFTCNQ salt in PA.

et al. 719–730 . no. 6. Microencapsulation. Brown.. E. 20. 2003. J.Microencapsulation by in-situ Polymerization Microencapsulation of DCPD utilizing acidcatalyzed in situ polymerization of urea with formaldehyde to form capsule wall. vol.

When mixtures of TTF and TCNQ microcapsules were ruptured. C) 50mg TCNQ-PA MCs. et al. B) 50mg TTF-PA MCs. 1721– . 20. a dark-brown color was immediately observed. Mater. Adv. Moore. J. IR spectroscopy was used to verify chargetransfer salt formation. Microcapsules crushed between two glass slides: A) 50mg PAMCs. D) 50mg each TTFPA and TCNQ-PA MCs. indicative of the TTF-TCNQ charge-transfer salt formation. 2010.Damage and Formation of Charge-Transfer Salt Figure. Funct.

Adv. Funct. J. 2010. TCNQ-PA. 1721– microcapsules.Restoration of Conductivity by TTF-TCNQ Charge-Transfer Salt Figure 7. I–V measurements of analytes on glass slides measured between two tungsten probe tips spaced approximately 100mm apart for neat ruptured TTF-PA. Mater. 20. and TTF-PA:TCNQPA in a 1:1 ratio (wt%) Moore. . et al.

1721– . Funct. 20. J. et al. Mater.Optimization of Precursor Concentration Moore. Adv. 2010.

21. C.Self-Healing Materials with Interpenetrating Microvascular Networks Key advances in direct-write assembly: Healing strategy mimics human skin. in which a minor cut triggers blood flow from the capillary network in the underlying dermal layer to the wound site. et al. 2009. Adv. Two fugitive organic inks possess similar viscoelastic behavior. 1–5. . Hansen. Mater. but different temperaturedependent phase change responses.

pluronic ink is removed (h) Void space from previous pluronic network is re-infiltrated with epoxy (i) Wax ink from both microvascular networks is removed (j) Networks are filled with resin (blue) in one network and hardener (red) in the second network Hansen. 1–5.Direct-Write Assembly with Dual Fugitive Inks (a) Epoxy substrate is leveled for writing (b) Wax ink (blue) is deposited to form one network (c) Pluronic ink (red) is deposited to separate networks (d) Wax ink is deposited to form 2nd microvascular network (e) Wax ink vertical features are printed connecting to both networks (f) Void space is filled with low viscosity epoxy (g) After matrix curing. et al. Adv. . 2009. Mater. 21. C.

2009. 21. epoxy resin and hardener wick into the crack plane due to capillary forces. Healing Efficiency Hansen. . C.Repeated Repair Cycles Once a crack contacts the microvascular network. et al. Adv. Mater. 1–5.

496–499 . Advantages Park. Mater. J. 2010. 22.Coaxial Electrospinning of Self-Healing Coatings Healing agent encapsulated in a bead-on-string structure and electrospun onto a substrate. et al. Adv.

et al. Adv.One-Step Coaxial Electrospinning Encapsulation Spinneret contains two coaxial capillaries Two viscous liquids are fed through inner and outer capillaries simultaneously Electro-hydro-dynamic forces stretch the fluid interface to form coaxial fibers due to electrostatic repulsion of surface charges Park. 22. J. 496–499 . Mater. 2010.

c) Fluorescent optical microscopic image of sequentially spun Rhodamine B (red) doped part A polysiloxane precursor capsules and Coumarin 6 (green) doped part B capsules. 496–499 . Mater. SEM images of a) the core–shell bead-on-string morphology and b) healing agent released from the capsules when ruptured by mechanical scribing.Core–Shell Bead-on-String Structures Figure. 22. Park. J. 2010. d) TEM image of as-spun bean-on-fiber core/sheath structure. Adv. et al.

J. et al. Adv. Mater. Park.Self-Healing after Microcapsule Rupture Self-healing by polycondensation of hydroxyl-terminated PDMS and PDES crosslinker catalyzed by organotin. 496–499 . 2010. 22.

Adv. et al.c . 496–499. 22. Figure 2. Control and self-healing coating samples that were stored under ambient conditions for 2 months after 5 days salt water immersion. 2010. J. SEM images of scribed region of the self-healing sample after healing a) 458 crosssection and b) top view of the scribed region on a steel substrate.Self-Healing by Polymerization Figure. Mater. Park.

2009. Vol. J. San Juan.. et al. 4.Nanoscale Shape-Memory Alloys for Ultrahigh Mechanical Damping Nanoscale Pillars of shape-memory alloys exhibit mechanical damping greater than any bulk material. Nature Nanotech. .

San Juan. et al.. 4. 2009. . Vol.Dissipation of mechanical energy by reversible transformation between Austenite and Martensite due to stress. J. Nature Nanotech.

Vol. 2009. et al. (1) Stabilization of austenite by elimination of martensite nucleation sites (2) Stabilization of martensite by small pillars that relieve elastic energy at the surface by crossing the entire specimen . SEM image of Cu–Al–Ni pillar. mean diameter of 900 nm. 4. Nature Nanotech. San Juan.Size Effect of Cu-Al-Ni Nanopillars Figure.. J. Cu-Al-Ni pillars were produced by focused ion beam (FIB) micromachining of surface sections of Cu-Al-Ni crystals.

. 4. Nature Nanotech. Vol. . 2009. J. et al.Comparison of High Damping Materials Merit index = E1/2 ΔW/πWmax W – dissipated energy per stress-release cycle ΔW.maximum stored energy per unit volume E – Young’s modulus San Juan.

What is Next ? Go Nano ! .