SELF-HEALING

MATERIALS

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
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

Self-Healing Materials

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 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 bonds
e) after the healing of the damage the previously
mobile material is immobilised again, resulting in
restored mechanical properties

http://www.autonomicmaterials.com/technology/

Self-Healing Methods

Material Design

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.

Moore, J. et al. Adv. Funct. Mater. 2010, 20, 1721

Restoration of Conductivity with TTF-TCNQ ChargeTransfer Salts

Conductive healing agent is generated upon mechanical damage.
Two core solutions travel by capillary action to the relevant
damage site before forming the conductive salt.
The major advantage of this approach is greater mobility of
precursor solutions compared to suspensions of conductive
particles.

Tetrathiafulvalene Tetracyanoquinodimethane
tetrathiafulvalenetetracyanoquinodimethane

Non-conducting Non-conducting

Conducting

Moore, J. et al. Adv. Funct. Mater. 2010, 20, 1721

Microcapsule Synthesis
TTF and TCNQ were individually
incorporated into microcapsule cores
as saturated solutions in chlorobenzene
(PhCl), ethyl phenylacetate (EPA), and
phenyl acetate (PA).
Poly(urea-formaldehyde) (PUF)
coreshell microcapsules were
prepared using an in situ
emulsification polymerization in an
oil-in-water suspension.

Electron impact mass spectra of the

dried microcapsule core solutions
confirmed the presence of TTF and
TCNQ in the microcapsules.

Figure 1. Optical microscope images from A) an attempt

to encapsulate crystalline TTF-TCNQ salt in PA, B) MCs
containing powdered TTF-TCNQ salt suspended in PA;
inset: ruptured MCs containing powdered TTFTCNQ salt
in PA, C) TTF-PA MCs, and D) TCNQ-PA MCs. All scale bars
are 200mm.

Moore, J. et al. Adv. Funct. Mater. 2010, 20, 1721

Microencapsulation by in-situ Polymerization

Microencapsulation of DCPD utilizing acidcatalyzed in situ polymerization of urea with
formaldehyde to form capsule wall.

Brown, E. et al.; J. Microencapsulation, 2003, vol. 20, no. 6, 719730

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 chargetransfer salt formation.
Moore, J. et al. Adv. Funct. Mater. 2010, 20, 1721

Restoration of Conductivity by TTF-TCNQ

Charge-Transfer Salt

Figure 7. IV measurements of analytes on glass slides

measured between two tungsten probe tips spaced
approximately 100mm apart for neat ruptured TTF-PA,
TCNQ-PA, and TTF-PA:TCNQPA in a 1:1 ratio (wt%)
Moore, J. et al. Adv. Funct. Mater. 2010, 20, 1721
microcapsules.

Optimization of Precursor Concentration

Moore, J. et al. Adv. Funct. Mater. 2010, 20, 1721

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.

Hansen, C. et al. Adv. Mater. 2009, 21, 15.

Two fugitive organic inks possess similar

viscoelastic behavior, but different temperaturedependent phase change responses.

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, 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, 15.

Coaxial Electrospinning of Self-Healing Coatings

Healing agent encapsulated in a bead-on-string structure
and electrospun onto a substrate.

Advantages

Park, J. et al. Adv. Mater.

2010, 22, 496499

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, 496499

CoreShell Bead-on-String Structures

Figure. SEM images of a) the coreshell bead-on-string morphology and b) healing agent released from the
capsules when ruptured by mechanical scribing. 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.
d) TEM image of as-spun bean-on-fiber core/sheath structure.

Park, J. et al. Adv. Mater.

2010, 22, 496499

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, 496499

Self-Healing by Polymerization

Figure. 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.

Figure 2. Control and self-healing coating samples that were stored under ambient
conditions for 2 months after 5 days salt water immersion.

Park, J. et al. Adv. Mater.

2010, 22, 496499.c

Nanoscale Shape-Memory Alloys for

Ultrahigh Mechanical Damping
Nanoscale Pillars of shape-memory alloys exhibit
mechanical damping greater than any bulk material.

San Juan, J. et al. Nature Nanotech., Vol. 4, 2009.

Dissipation of mechanical energy by reversible

transformation between Austenite and Martensite
due to stress.

San Juan, J. et al. Nature Nanotech., Vol. 4, 2009.

Size Effect of Cu-Al-Ni Nanopillars

Figure. SEM image of CuAlNi pillar, mean

diameter of 900 nm.

Cu-Al-Ni pillars were produced

by focused ion beam (FIB)
micromachining of surface
sections of Cu-Al-Ni crystals.
San Juan, J. et al. Nature Nanotech., Vol. 4, 2009.

(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

Comparison of High Damping Materials

Merit index = E1/2 W/Wmax

W dissipated energy per stress-release cycle
W- maximum stored energy per unit volume
E Youngs modulus
San Juan, J. et al. Nature Nanotech., Vol. 4, 2009.

What is Next ?

Go Nano !