SBO project NAPROM

Challenges for self-healing

coatings on metals
VUB – UGent – UA – Flamac

Herman Terryn
Research Group Electrochemical and Surface Engineering
Departement Materials and Chemistry
Vrije Universiteit Brussel
hterryn@vub.ac.be
 Introduction – NAPROM
Multiple action corrosion protection Coating

Metal

1. Self-healing coating
Metal
2. Encapsulated corrosion inhibitors

Metal
3. Leaching out of corrosion inhibitors

Metal

4. Defect closure by self-healing of polymer Metal

 Consortium in NAPROM

Self-healing polymer and supramolecular design and synthesis by

Inhibitor expertise PCR, UGent (F. Du Prez) and SC, UGent (R. Hoogenboom)
support at SURF
(support TU-Delft )
Bulk and coating thermomechanical analysis by
FYSC, VUB (B. Van Mele, G. Van Assche)
1 µm ?
Coating morphology, chemical and interface
50 nm -5 µm
analysis by SURF, VUB (H. Terryn, I. De Graeve)
Electron microscopy support for coating analysis by
EMAT, UA (S. Van Tendeloo, A. Abakumov)
metal

Polymer self-healing mechanism by

Co-operative active
SURF, VUB and FYSC, VUB

Inhibitor mechanism by SURF, VUB

} protection property
analysis by SURF and
FYSC

Accelerated screening method for active corrosion

protection by SURF, VUB (A. Hubin) and Flamac (J. Paul)
 Self-healing Coating
Polyester- urethane acrylate coating
=
“Shape Recovery” Polymer
Nano phase separated high Tg polymer (dark zones)
and polyester segments (light zones)

combining extreme toughness with the ability to

recover from mechanical damage by heating

Semi-crystalline PCL=Polycaprolactone soft phases, Tg 50-60 °C

 Self-healing polymer

Fresh coating 2 scratches Healed coating

Major defect Stepwise healing Closed defect

 Metal

Self-Healing - SEM

>50°C
<1min
 Impedance Spectroscopy
Coating with Flexible Spacers

Virgin coating
Coating healed for the
second time
Healed coating

Coating scratched again

after healing
Scratched coating
 Metal

SVET Analysis of Self-Healing

In 0,05M NaCl Before healing After healing
 Spectroscopic
techniques such as
EDX and EELS
provide elemental
information, making
the localization of
Interface SH coating-galvanised steel elements available,
furthering the
understanding of the
sample.

The steel polymer

interface. EELS
elemental mapping
reveals the location
of the various
components: the
polymer (indicated
by the carbon signal)
fills up a indentation
in the oxidized zinc
surface.
 Inhibitor MERCAPTO-BENZOTHIAZOL
Encapsulation
Porous nanocapsules Layered Double Hydroxides (LDH)

+MBT

SEM EDX

SEM
40 nm
TEM
10µm
 Metal

Leaching out
Surface Enhanced Raman Spectroscopy

LDH+MBT on AgProbe
SiNC+MBT on AgProbe
Blank AgProbe

H. Verbrugge
 NSH-coating without inhibitors
In-situ SVET mapping above two micro-drill defects

High currents after 4 hr of immersion

 Metal

NSH-coating with LDH + MBT

In-situ SVET mapping above two micro-drill defects

No corrosion detectable after 4 hr of immersion

 MF
1st generation of Melamine Protective outer
Formaldehyde (MF) capsules barrier shell
~ 90% plasticizer content plasticizer

Scale bar 100 µm Scale bar: 10 µm

Robust microcapsules Very Thin Shells

< 5µm
 Accelerated screening of aging
phenomena of coatings (Flamac)
• Methods for determining aging properties and associated methods for
accelerated testing of aging phenomena in the field of the high throughput
development of coatings (Flamac)

• Early stage detection of coating defects

• Current status:
o High-throughput accelerated ageing platform evaluated
 Application of micro- and macro-
scratches
Methodology developed for applying controlled
micro-scratch (cfr. ICON project SHREC WP 5)
– Micro-scratches1:
– order of magnitude:
– 10 μm wide, 5 μm deep

1Visualised with microscope of nano-indentor

 Methodology to investigate the corrosion protection
given by a coating

Metals
Corrosion rate
Coating for
monitor device for
additional FAST AND
protection RELIABLE
ranking ZENSOR
+
EVALUATION Impedance to
+
Developing new coatings: METHOD understand damage ORP-EIS
Different formulations mechanism
Many conditions

ORP-EIS ZENSOR
Signal:
Sum of all single • Save time • Corrosion ranking
sines
• Trough • 2 electrode based device:
modelling evaluate corrosion activity
able to • Possibility of in-situ
understand monitoring
damage • User friendly
mechanism • Simplified setup but
Bode plot with info over noise levels
robust!
 Supramolecular self-healing materials –
concept and design
Design:
Charged ABA-type triblock copolymers Association of
+ + + +
charged end
+ + blocks
+ +
mixing
- - - -
- - - -
Charged CBC-type triblock copolymers
Charged phase
high Tg

 Network crosslinked by
supramolecular interactions

 Phase separated structure Uncharged

phase low Tg
Synthesis performed in UGent SC
Poster: A new class of supramolecular
thermoplastic elastomers for self-healing coatings
Lenny Voorhaar & Maria Mercedes Diaz
 Supramolecular self-healing materials –
thermal characterization

1.8
1.8
+ + + +
1.6
1.6
+ + + +
1.4
1.4

Heat capacity / J g -1 C-1

- - - - 1.2
1.2

- - - - 11 Tg 28°C

0.8
0.8
Tg generated by the
association of
0.6
0.6 charged end blocks!

0.4
0.4
-90
-90 -60
-60 -30
-30 0 30 60 90
T/ C 0 30 60 90
 Supramolecular self-healing materials –
thermal characterization
1.8

1.6

1.4 Tg 28°C

Heat capacity / J g -1 C-1

1.2
Tg -41°C
1

0.8

0.6

0.4
-80 -60 -40 -20 0 20 40 60 80
 The two Tg’s indicate phase separated T/ C

structure 10000 90

E'
E"
 DMA heating ramp shows the mechanical 1000
Delta
properties of the supramolecular network. 60
100

loss angle / °
E', E" / MPa
 Transitions the material undergoes are seen 10

by the drop in E’. 30

 The supramolecular interactions keep the

material from flowing even at 80°C. 0.1
-80 -60 -40 -20 0 20 40 60 80
0

T / °C
Poster: A new class of supramolecular
thermoplastic elastomers for self-healing coatings
Lenny Voorhaar & Maria Mercedes Diaz
 Supramolecular self-healing materials -
morphology

TEM micrograph

 OsO4 stains preferentially the charged

domains

 The different domains can be differentiated

in the morphology of the material

 The diffractogram gives evidence of

repeating structure and indicates distances d
(6-10nm)
Performed in EMAT-UA

Poster: A new class of supramolecular

thermoplastic elastomers for self-healing coatings
Lenny Voorhaar & Maria Mercedes Diaz
 Supramolecular self-healing materials -
morphology

Small Angle Neutron Scattering

(SANS)
10.0

 Repeating structure confirmed by SANS

I / cm-1
 Repeat distances d of 8-9nm are 1.0
observed.

2
d
qmax
0.1
0.01 0.1 1
q / Å-1

Performed in ISIS by Dr. Rogers

 Supramolecular self-healing materials –
self-healing
Concept:

Rupture Healing
Tamb T> 2nd Tg

↓scratch ~50μm wide Healing at 43°C

Healing after 20min.
T> 2nd Tg
 Supramolecular self-healing materials –
tuning network properties
2

1.8
• Changing the length of the end blocks allows
1.6
tuning network properties

Heat capacity / J g -1 C-1

1.4

+ + + + + + + + 1.2

1
+ + + + + + + +
0.8

- - - - - - - - 0.6

0.4

- - - - - - - - -80 -60 -40 -20

T/ C
0 20 40 60 80

10000

1000

100

E' / MPa
10 The length of the
charged blocks -> Tg
1 change and
mechanical properties
0.1
-80 -60 -40 -20 0 20 40 60 80
T / °C