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Smart Coatings Getting Smarter
Dr. Ing. Patricia Geelen – Feb 19, 2021

TAGS: Smart Coatings

What are Functional Coatings?

Smart Coatings Versus Functional Coatings
Smart Coatings – Fields of Application
Commercialization of Smart Coatings

What are Functional Coatings?

In the field of coating technology, many coatings have been developed over decades of re‐
search, leading to high-quality coatings which have:

Good adhesion
Mechanical properties, and
Other important functions which are defined by the final application and use.

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Example of Water Droplet on Superhydrophobic Coating

However, next to good mechanical and chemical properties additional functionalities have
been introduced to further increase the added value of these coatings. Well-known examples
of such functions, just to name a few are - Anti-reflection, Anti-fingerprint, Corrosion protec‐
tion, Superhydrophobicity, etc.

Let's understand when a functional coating is smart and the key considerations while designing smart coating ap‐
plications.

Smart Coatings Versus Functional Coatings

Next to functional coatings, the term smart coating is often misused. The question remains: when is a functional
coating also smart?

Even though there is no fixed definition of when a coating is smart, the consensus is that the smart coating has the
added functionality that it actively reacts to an external or internal trigger, whereas the functional coating is a pas‐
sive layer which is insensitive to environmental conditions.

Stimuli - Response to External or Internal Factors

As it was mentioned before, smart coatings react to

an external or internal stimulus. The main cate‐
gories that may induce the response of the smart
coating include:

1. UV Light
2. Temperature
3. pH
4. Moisture
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5. Damage
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Capture fresh ideas and gain insights into next concepts for your functional coat‐
ings by reviewing Smart Coatings trends in our exclusive innovation round-up.
The new materials, latest commercial launches, promising concepts, & innova‐
tions can be a game-changer for you as well, if you act quick. Join today »

Chemical Conversion Coating

In the specific case of corrosion protection, chemical conversion can be used as the smart function within the
paint or coating. These chemical conversion coatings contain inorganic compounds which rely on the principle of
the dissolve – reprecipitation effect in local defects.

In the figure below, we can see the principle of a chemical conversion coating. The active protection of the magne‐
sium alloy takes place in 4 stages:

1. The dissolution of magnesium (and evolution of hydrogen gas at the AlMn particles)
2. The formation of magnesium phosphate
3. The nucleus formation of calcium phosphate and zinc phosphate, and finally
4. The growth of the crystalline deposit, giving again protection to the magnesium alloy.

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1
Working Principle of Chemical Conversion Coatings
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Chemical conversion coatings have the important advantages of having excellent mechanical-stability and the sim‐
ple preparation method of the coatings. Their limitation lies in the low-efficiency self-healing performance, which
limits their application in certain ways.

Self-healing Paint and Coatings

The self-healing paint and coatings can be designed

using various approaches, such as:

Encapsulation of active ingredients

Reversible crosslinks
Controlled/dynamic release
Active leaching or shape memory

Amongst these approaches, encapsulation and re‐

versible crosslinks are explained below.

Encapsulation

Self-healing paint and coatings contain capsules which are loaded with active repair agents, which can transform
the coating from a barrier role to an active role. The stimuli can occur either internal or external, such as:

Ion release
pH increase
Dynamic bonds, and
Shape memory effect

Besides microcapsules, hollow tubes are being used as the carrier for the active materials, such as fibers or capil‐
laries.

Schematic of the Self-protection Process: Paint Coating Having Microcapsules with Self-healing Protecting Paint on Carbon Steel2

Compared with chemical conversion coatings, encapsulation coatings rely more on the functions of the coating
materials and intelligent designs; this makes for the encapsulation coatings having a more complex preparation
process but poses a higher efficiency and controllability. Currently, research focuses on the encapsulation of ions,
inhibitors, nanoparticles, and nano/microcapsules.

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Reversible Crosslinks

Another way to create self-healing properties is by the incorporation of reversible crosslinks in the coating matrix,
also called covalent adaptable networks (CANs). Suitable mechanisms for this include:

Diels-Alder/ Retro Diels-Alder

Ring-opening metathesis polymerization using DCPD
Schiff base (imine) bonds
Reversible hydrazone bonds
Oxime bonds
Disulfide bonds

These covalently crosslinked networks are formed such that triggerable, reversible chemical structures persist
throughout the polymer matrix. These reversible covalent bonds can be triggered through:

Molecular triggers
Light or other incident radiation, or
Temperature changes

Upon application of this stimulus, rather than causing a temporary shape change, the CAN structure responds by
permanently adjusting its structure.

SEM Image of Self-healing Coating with DA Reversible Crosslinking3

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All of the reversible crosslinking reactions described are within the chemical linkage category. The other category
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which can be used for reversible crosslinking is the physical linkage category. Examples of reversible physical link‐
ages are:

Hydrogen bonding
Host-guest interactions (such as Cyclodextrins), or
Electrostatic/ionic interactions

However, the coatings typically have inferior mechanical properties due to the lack of covalent crosslinks. The
choice of self-healing mechanism depends on the matrix composition, trigger and overall product requirements.

Smart Coatings – Fields of Application

Anti-scaling

In industrial environments, scale formation is a key problem. The most effective method for the protection of
pipes and metal is the use of (smart) coatings. Next to functionalities such as (super) hydrophobicity and corrosion
protection, gradual and dynamical leaching of scale inhibitors causing chelating and prevent further scale
formation/deposition4.

Limescale Formation in Water Pipes

Related Read: Sol-Gel Based Nanotechnology Solutions for Advanced Smart and Functional Coatings

Corrosion Protection

In the case of corrosion protection, the conventional coatings are of very high quality but in certain complex ser‐
vice environments, the damage will inevitably occur. In these cases, smart coatings or self-healing properties5 en‐
hance the lifetime and provide long-term protection of the protected substrate.

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Example of Corroded Surface
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An important class of smart coatings, in the field of corrosion protection, are the chemical conversion coatings as
described above. Next to this, many coatings are described in the literature which makes use of encapsulated cor‐
rosion inhibitors which leach out and repair upon inflicted damage or other suitable triggers, such as pH change6.

Automotive Coatings

In order to enhance the lifetime of automotive coatings and improve the aesthetic appearance, enhanced scratch
resistance and scratch repair are major drivers towards the development of self-healing or self-repairing topcoats.

To improve scratch resistance, fillers and nanoparticles play a major role in increasing this next to the hardness.
However, there is a maximum amount of fillers which can be used which when exceeded the mechanical proper‐
ties will deteriorate and appearance will be affected.

To further improve the scratch resistance, several pathways towards self-healing and self-repair are described.
Partial replacement of covalent bonds by physical linkages, to provide dynamic chain movement for thermal heal‐
ing treatments at high temperature7, is one of them. And the second one is the use of micro/nanocapsules which
will actively repair the damage.

Self-repairing Paint by Nissan

Anti-microbial Coatings

For many years, antimicrobial coatings have been a field of attention. To provide antimicrobial properties to the
coating, 4 different categories can be used:

1. Inorganic and metal-based: Silver and copper are the most used metals. Despite their effectiveness, there
are concerns regarding their toxicity over a period of time due to leaching. Also, the long-term dosage ef‐
fects are not well reported.
2. Organo-compounds: A very popular solution is the use of organo-silanes. They provide (super) hydrophobic
properties to the surface incapable of hosting any colonization properties. Zwitterions are also very efficient
due to their response behavior, enabling both antibacterial properties and antifouling properties to the
surface.
3. Nanomaterials: Due to their extraordinary properties and behavior, nanoparticles are utilized.
4. Anti-microbial peptides: These can be attached to the surface chemically or by physical attachment.

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Antimicrobial Coatings (L), Zwitter Ion Function in Smart Antibacterial Coatings (R)8

Commercialization of Smart Coatings

The class of smart coatings has become embedded in the research towards the functionality of coatings in many
fields and even more applications. Due to the intensive research, following the exponential growth in academic
publications, companies such as PPG, Croda and AkzoNobel have commercialized smart coatings, such as:

Self-healing vehicle refinish coatings

Smart anti-fingerprint coatings, and
Antimicrobial coatings, amongst others

Challenges that remain to be the focus in the development of these smart coatings are:

1. Economic viability
2. Ease of production
3. Lifetime or durability of the coating

For self-healing coatings, it is no doubt that active materials and coating designs are the core parts of the coat‐
ings. However, currently, the utilization efficiency of active materials is relatively low. Therefore, novel and efficient
active materials and intelligent coating designs need to be explored in further studies.

» Follow Our Exclusive Channel for All the Latest Industry Developments in Smart Coatings

Main Considerations While Designing Smart Coatings

In addition, it is also vital to evaluate how the basic properties of polymer coatings are affected by the introduc‐
tion of these smart functionalities. Naturally, the smart function may not have a negative effect on the main (me‐
chanical) properties of the coating.

Other considerations which need to be made when designing a smart coating are:

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Costs of raw materials

Availability of raw material in commercial volumes
Added benefit of the smart functionality with respect to the
Coating lifetime
Substrate protection
Added value
Health and safety issues
Efficiency of the smart functionality
Durability of the smart functionality

The main balance will still be finding the optimum between the price of the raw materials used and the added
benefit over the “standard” functional coating.

Capture fresh ideas and gain insights into next concepts for your functional coatings by review‐
ing Smart Coatings trends in our exclusive innovation round-up. The new materials, latest
commercial launches, promising concepts, & innovations can be a game-changer for you as
well, if you act quick. Join today!

References

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11/9/22, 10:57 AM Smart Coatings Getting Smarter

1. Zeng, R., Zhang, F., Lan, Z., Cui, H. and Han, E., 2014. Corrosion resistance of calcium-modified zinc phosphate conversion
coatings on magnesium–aluminum alloys. Corrosion Science, 88, pp.452-459.
2. Koh, E., Kim, N., Shin, J. and Kim, Y., 2014. Polyurethane microcapsules for self-healing paint coatings. RSC Adv., 4(31),
pp.16214-16223.
3. Zhang, F., Ju, P., Pan, M., Zhang, D., Huang, Y., Li, G. and Li, X., 2018. Self-healing mechanisms in smart protective coatings: A
review. Corrosion Science, 144, pp.74-88.
4. Zhu, Y., Li, H., Zhu, M., Wang, H. and Li, Z., 2021. Dynamic and active antiscaling via scale inhibitor pre-stored superhy‐
drophobic coating. Chemical Engineering Journal, 403, p.126467.
5. Zhang, D., Peng, F. and Liu, X., 2021. Protection of magnesium alloys: From physical barrier coating to smart self-healing
coating. Journal of Alloys and Compounds, 853, p.157010.
6. Chen, L., Yu, Z., Yin, D. and Cao, K., 2020. Preparation and anticorrosion properties of BTA@HNTs-GO nanocomposite smart
coatings. Composite Interfaces, 28(1), pp.1-16.
7. Yari, H., Mohseni, M. and Messori, M., 2016. A scratch resistant yet healable automotive clearcoat containing hyper‐
branched polymer and POSS nanostructures. RSC Advances, 6(79), pp.76028-76041.
8. Li, X., Wu, B., Chen, H., Nan, K., Jin, Y., Sun, L. and Wang, B., 2018. Recent developments in smart antibacterial surfaces to
inhibit biofilm formation and bacterial infections. Journal of Materials Chemistry B, 6(26), pp.4274-4292.

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