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SELF-HEALING         MATERIALSCristina ResetcoPolymer and Materials Science
Self-Healing Materials  Motivation: Self-healing materials are smart materials that can  intrinsically repair damage leadi...
Self-Healing Materials
Self-Healing Materialsa) damage is inflicted on the materialb) a crack occursc) generation of a “mobile phase” triggered e...
Self-Healing Methods  Material Design
Restoration of Conductivity withTTF-TCNQ Charge-Transfer Salts A new microcapsule system restores conductivity in mechanic...
Restoration of Conductivity with TTF-TCNQ Charge-Transfer SaltsConductive healing agent is generated upon mechanical damag...
Microcapsule SynthesisTTF and TCNQ were individuallyincorporated into microcapsule coresas saturated solutions in chlorobe...
Microencapsulation by in-situ Polymerization   Microencapsulation of DCPD utilizing acid-catalyzed in   situ polymerizatio...
Damage and Formation of Charge-Transfer Salt       Figure. Microcapsules crushed between two glass slides: A) 50mg       P...
Restoration of Conductivity by TTF-TCNQ            Charge-Transfer SaltFigure 7. I–V measurements of analytes on glass sli...
Optimization of Precursor Concentration                            Moore, J. et al. Adv. Funct. Mater. 2010, 20, 1721–1727.
Self-Healing Materials with Interpenetrating MicrovascularNetworks                                                Key adva...
Direct-Write Assembly with Dual Fugitive Inks            (a) Epoxy substrate is leveled for writing            (b) Wax ink...
Repeated Repair Cycles      Once a crack contacts the microvascular network, epoxy resin and      hardener wick into the c...
Coaxial Electrospinning of Self-Healing CoatingsHealing agent encapsulated in a bead-on-string structureand electrospun on...
One-Step Coaxial Electrospinning Encapsulation                             Spinneret contains two                         ...
Core–Shell Bead-on-String StructuresFigure. SEM images of a) the core–shell bead-on-string morphology and b) healing agent...
Self-Healing after Microcapsule Rupture                          Self-healing by                          polycondensation...
Self-Healing by PolymerizationFigure. SEM images of scribed region of the self-healing sample after healing a) 458crosssec...
Nanoscale Shape-Memory Alloys for  Ultrahigh Mechanical DampingNanoscale Pillars of shape-memory alloys exhibitmechanical ...
Dissipation of mechanical energy by reversibletransformation between Austenite and Martensitedue to stress.               ...
Size Effect of Cu-Al-Ni Nanopillars                                                      Figure. SEM image of Cu–Al–Ni pil...
Comparison of High Damping Materials    Merit index = E1/2 ΔW/πWmax    W – dissipated energy per stress-release cycle    Δ...
What is Next ?Go Nano !
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Self-healing Materials

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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 include shock absorbing materials, paints and anti-corrosion coatings and more recently, conductive self-healing materials for circuits and electronics.

Published in: Technology, Business
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Self-healing Materials

  1. 1. SELF-HEALING MATERIALSCristina ResetcoPolymer and Materials Science
  2. 2. 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 coatings. Outline(1) Restoration of Conductivity with TTF-TCNQ Charge-Transfer Salts(2) Self-Healing Materials with Interpenetrating Microvascular Networks(3) Coaxial Electrospinning of Self-Healing Coatings(4) Nanoscale Shape-Memory Alloys for Ultrahigh Mechanical Damping
  3. 3. Self-Healing Materials
  4. 4. Self-Healing Materialsa) damage is inflicted on the materialb) a crack occursc) generation of a “mobile phase” triggered either by the occurrence of damage (in the ideal case) or by external stimuli.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 bondse) after the healing of the damage the previously mobile material is immobilised again, resulting in restored mechanical properties http://www.autonomicmaterials.com/technology/
  5. 5. Self-Healing Methods Material Design
  6. 6. Restoration of Conductivity withTTF-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. Moore, J. et al. Adv. Funct. Mater. 2010, 20, 1721–1727.
  7. 7. Restoration of Conductivity with TTF-TCNQ Charge-Transfer SaltsConductive healing agent is generated upon mechanical damage. Two coresolutions travel by capillary action to the relevant damage site beforeforming the conductive salt.The major advantage of this approach is greater mobility of precursorsolutions compared to suspensions of conductive particles. Tetrathiafulvalene Tetracyanoquinodimethane tetrathiafulvalene–tetracyanoquinodimethane Non-conducting Non-conducting Conducting Moore, J. et al. Adv. Funct. Mater. 2010, 20, 1721–1727.
  8. 8. Microcapsule SynthesisTTF and TCNQ were individuallyincorporated into microcapsule coresas saturated solutions in chlorobenzene(PhCl), ethyl phenylacetate (EPA), andphenyl acetate (PA).Poly(urea-formaldehyde) (PUF)core–shell microcapsules wereprepared using an in situemulsification polymerization in anoil-in-water suspension. Figure 1. Optical microscope images from A) an attempt to encapsulate crystalline TTF-TCNQ salt in PA, B) MCs containingElectron impact mass spectra of the powdered TTF-TCNQ salt suspended in PA; inset: ruptured MCs containing powdered TTFTCNQ salt in PA, C) TTF-PA MCs, anddried microcapsule core solutions D) TCNQ-PA MCs. All scale bars are 200mm.confirmed the presence of TTF andTCNQ in the microcapsules. Moore, J. et al. Adv. Funct. Mater. 2010, 20, 1721–1727.
  9. 9. Microencapsulation by in-situ Polymerization Microencapsulation of DCPD utilizing acid-catalyzed in situ polymerization of urea with formaldehyde to form capsule wall. Brown, E. et al.; J. Microencapsulation, 2003, vol. 20, no. 6, 719–730
  10. 10. Damage and Formation of Charge-Transfer Salt Figure. Microcapsules crushed between two glass slides: A) 50mg PAMCs; B) 50mg TTF-PA MCs; C) 50mg TCNQ-PA MCs; D) 50mg each TTFPA and TCNQ-PA MCs. When mixtures of TTF and TCNQ microcapsules were ruptured, a dark-brown color was immediately observed, indicative of the TTF-TCNQ charge- transfer salt formation. IR spectroscopy was used to verify charge-transfer salt formation. Moore, J. et al. Adv. Funct. Mater. 2010, 20, 1721–1727.
  11. 11. Restoration of Conductivity by TTF-TCNQ Charge-Transfer SaltFigure 7. I–V measurements of analytes on glass slidesmeasured between two tungsten probe tips spacedapproximately 100mm apart for neat ruptured TTF-PA, TCNQ-PA, and TTF-PA:TCNQPA in a 1:1 ratio (wt%) microcapsules. Moore, J. et al. Adv. Funct. Mater. 2010, 20, 1721–1727.
  12. 12. Optimization of Precursor Concentration Moore, J. et al. Adv. Funct. Mater. 2010, 20, 1721–1727.
  13. 13. Self-Healing Materials with Interpenetrating MicrovascularNetworks Key advances in direct-write assembly: Two fugitive organic inks possess similarHealing strategy mimics viscoelastic behavior, but different temperature-human skin, in which a minor dependent phase change responses.cut triggers blood flow fromthe capillary network in theunderlying dermal layer tothe wound site. Hansen, C. et al. Adv. Mater. 2009, 21, 1–5.
  14. 14. 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, 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, C. et al. Adv. Mater. 2009, 21, 1–5.
  15. 15. Repeated Repair Cycles Once a crack contacts the microvascular network, epoxy resin and hardener wick into the crack plane due to capillary forces. Healing Efficiency Hansen, C. et al. Adv. Mater. 2009, 21, 1–5.
  16. 16. Coaxial Electrospinning of Self-Healing CoatingsHealing agent encapsulated in a bead-on-string structureand electrospun onto a substrate. Advantages Park, J. et al. Adv. Mater. 2010, 22, 496–499
  17. 17. 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, J. et al. Adv. Mater. 2010, 22, 496–499
  18. 18. Core–Shell Bead-on-String StructuresFigure. SEM images of a) the core–shell bead-on-string morphology and b) healing agent released from thecapsules when ruptured by mechanical scribing. c) Fluorescent optical microscopic image of sequentially spun Park, J. et al. Adv. Mater.Rhodamine B (red) doped part A polysiloxane precursor capsules and Coumarin 6 (green) doped part B capsules. 2010, 22, 496–499d) TEM image of as-spun bean-on-fiber core/sheath structure.
  19. 19. Self-Healing after Microcapsule Rupture Self-healing by polycondensation of hydroxyl-terminated PDMS and PDES crosslinker catalyzed by organotin. Park, J. et al. Adv. Mater. 2010, 22, 496–499
  20. 20. Self-Healing by PolymerizationFigure. SEM images of scribed region of the self-healing sample after healing a) 458crosssection and b) top view of the scribed region on a steel substrate. Figure 2. Control and self-healing coating samples that were stored under ambient Park, J. et al. Adv. Mater. conditions for 2 months after 5 days salt water immersion. 2010, 22, 496–499.c
  21. 21. Nanoscale Shape-Memory Alloys for Ultrahigh Mechanical DampingNanoscale Pillars of shape-memory alloys exhibitmechanical damping greater than any bulk material. San Juan, J. et al. Nature Nanotech., Vol. 4, 2009.
  22. 22. Dissipation of mechanical energy by reversibletransformation between Austenite and Martensitedue to stress. San Juan, J. et al. Nature Nanotech., Vol. 4, 2009.
  23. 23. Size Effect of Cu-Al-Ni Nanopillars Figure. SEM image of Cu–Al–Ni pillar, mean diameter of 900 nm.Cu-Al-Ni pillars were produced (1) Stabilization of austenite byby focused ion beam (FIB) elimination of martensite nucleationmicromachining of surface sitessections of Cu-Al-Ni crystals. (2) Stabilization of martensite by small pillars that relieve elastic energySan Juan, J. et al. Nature Nanotech., Vol. 4, 2009. at the surface by crossing the entire specimen
  24. 24. 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, J. et al. Nature Nanotech., Vol. 4, 2009.
  25. 25. What is Next ?Go Nano !

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