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Opportunities and challenges in smart coatings manufacturing

Conference Paper · January 2015

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Abdel Salam Hamdy Makhlouf

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Opportunities and Challenges in Smart Coatings Manufacturing

Prof. Dr. Abdel Salam Makhlouf

RGV STAR Professor: Manufacturing Engineering Department
College of Engineering and Computer Science
University of Texas-Pan American, USA
 Smart coating technologies

What is meant by “Smart

Coatings”

Smart coating is one of the hottest

topics in materials science and
surface engineering.

A smart coating is defined as one that

changes its properties automatically
in response to an environmental
stimulus.
Self healing of a skin wound
(Reproduced from P. Martin, Science, 75 1997, P. 276, [13])
 Smart coating technologies

Examples of Smart Coatings

• Self-healing coatings
• Self-cleaning coatings
• Multifunctional coatings
• Bio-inspired coatings
• Nano-bio-coatings
• ..etc
Smart Coatings Approaches

Where we are?
 Smart Self-healing Coatings

Smart Self-healing Coatings

For

Advanced Magnesium Alloys

AV31A-T6,
AZ31 HP-O,
and Rare-earth Mg alloys
 Self-healing stannate coatings for AV31A-T6
Stannate coated AV31A-T6 after seven days in NaCl

Blank Alkaline Acidic

Alkaline/Acidic Directly Treated

 Self-healing stannate coatings for AV31A-T6
A one-step stannate coated AV31A-T6 after 7days in NaCl

7900

6900

5900

4900
-Z"/ ohm

AZ91D+Stannate
3900

2900

1900
AZ91D

900
AV31A-T6 AV31A-T6 + Stannate
-100
0 2000 4000 6000 8000 10000 12000 14000
Z'/ ohm
A.S. Hamdy, B. Marx, D. P. Butt and P. Callahan, “Self-healing stannate based conversion coatings for magnesium alloys”, US Patent, number to be assigned
Self-healing stannate coatings for AV31A-T6
Rates of H2 Evolution
Mg + 2 H2O = Mg(OH)2 +H2
4,00

Volume (ml/cm2)
3,00

2,00

1,00

0,00
0,00 50,00 100,00 150,00 200,00 250,00 300,00
Time (hours)
Corrosion Rate
Alloy Hydrogen Evolution Salt spray test
µ m/yr µ m/yr

AZ91D 727 254

AV31A-T6 770 558
AZ91D+Tin Coating 240 160
AV31A-T6 +Tin Coating 284 192
 Vanadia coatings for AZ31 HP-O alloy
Strategy

Organic Top Coat Organic Top Coat

Chromate Conversion Coating Vanadia Conversion Coating

Metallic Substrate Metallic Substrate

A schematic representation (not to scale) showing (a) the two layers of a conventional toxic chromate-
containing corrosion protection system and (b) the two layer vanadium oxide coating technology in the
system being developed by the MPI team.
 Vanadia coatings for AZ31 HP-O alloy
One-step Vanadia coatings after seven days in NaCl

Macro-images after seven days of immersion in NaCl

solution
 Vanadia coatings for AZ31 HP-O alloy
One-step Vanadia coatings after seven days in NaCl

The autonomic healing concept

EIS and SEM-EDS after seven days of immersion in NaCl solution
A. S. Hamdy, et al "Assessment of a one-step intelligent self-healing vanadia protective coatings for magnesium alloys in
corrosive media”, J. Electrochimica Acta, 56 (2011) 2493
 Vanadia coatings for AZ31 HP-O alloy
One-step Vanadia coatings after seven days in NaCl

The autonomic
healing
performance

A. S. Hamdy, et al “Smart self-healing anti-corrosion vanadia coating for magnesium alloys”, Progress in Organic Coatings,
doi:10.1016/j.porgcoat.2011.05.011
 Smart Self-healing Coatings

Smart Self-healing Coatings

For

AA2024 Aluminum Alloys

 Self-healing vanadia coatings for AA2024
alloys

as polished
V 10 @ pH 7
50000 V 30 @ pH 7
V 50 @ pH 7

40000

30000
-Z' [ohm]

Macro-images after seven days 20000

of immersion in NaCl solution

10000

0
0 10000 20000 30000 40000 50000 60000

Z' [ohm]
 Self-healing vanadia coatings for AA2024
alloys

SEM-EDS after seven days of immersion in NaCl solution

Other Smart Coatings Approaches

LBL Ti-oxide
coatings based
coatings

Anodizing
coatings

Nano-/ Micro
capsule based
coatings
 How to Design
Smart Self-healing Coatings?

The main components in smart coatings

1. Corrosion Inhibitor suitable for the materials to be protected

2. Coatings matrix (mostly organic coatings)
3. Containers or Reservoirs to store the corrosion inhibitor
 Should be sensitive to external stimuli such as pH, magnetic field, temperature)
 Should not react with the corrosion inhibitor
 Should not react with the coating matrix
 Should be stable during the working conditions (temperature, pH etc)
 How to Design
Smart Self-healing Coatings?

Anodizing coatings

SEM micrograph of Ti Oxide self healing coatings.

 Smart Self-healing Coatings

LBL methods of constructing films of polyelectrolytes,

inorganic polyions or composite multilayer films
 Smart Self-healing Coatings

Capsule based self-healing materials

B.J. Blaiszik et al., Annu. Rev. Mater. Res. 2010. 40:179–211
 Smart Self-healing Coatings

Self-healing using capsules based coatings

B.J. Blaiszik et al., Annu. Rev. Mater. Res. 2010. 40:179–211

 Smart Self-healing Coatings

Synthesis of capsules

Luz M. Calle, in A.S. Hamdy (Ed.), “Handbook of Smart Coatings for Corrosion Protection”,
Woodhead Publishing Limited, UK, in press.
 Smart Self-healing Coatings

Inhibitor-loading of capsules

Luz M. Calle, in A.S. Hamdy (Ed.), “Handbook of Smart Coatings for Corrosion Protection”,
Woodhead Publishing Limited, UK, in press.
Self-healing coatings for Steels

Luz M. Calle, in A.S. Hamdy (Ed.), “Handbook of Smart Coatings for Corrosion
Protection”, Woodhead Publishing Limited, UK, in press.
 Smart Self-healing Coatings

The self-healing mechanism

B.J. Blaiszik et al., Annu. Rev. Mater. Res. 2010. 40:179–211
 Smart Self-healing Coatings

Vascular based self-healing materials

B.J. Blaiszik et al., Annu. Rev. Mater. Res. 2010. 40:179–211
Smart Self-healing Coatings

Intrinsic based self-healing materials

 Smart Self-healing Coatings

Self-healing using capsules based coatings

Luz M. Calle, in A.S. Hamdy (Ed.), “Handbook of Smart Coatings for Corrosion Protection”,
Woodhead Publishing Limited, UK, 2014.
Mechanism
 Smart Self-healing Coatings

Challenges with the current self-

healing coating technologies

1. Multi-step (8-12).

2. Expensive raw materials and chemicals.

3. Some of them are not environmentally friendly.

4. Can affect negatively the adhesion performance and wear resistance of

the coating to the substrate.

5. Some of them are not suitable for large surface areas.

6. The healing efficiency is unknown at low temperature > 0°C (freezing of

inhibitors) or > 40°C where swelling or micro-cracks due to partial
inhibitor evaporation.
 Limitations: Smart Self-healing Coatings

Damage modes in polymer composites

B.J. Blaiszik et al., Annu. Rev. Mater. Res. 2010. 40:179–211

 For more details!

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