Microcapsules for Self-Healing Coatings

Joshua Christian Nathanael

U1320096D, Aerospace Engineering, Nanyang Technological University, Singapore

Abstract
Among many possible ways to create self healing material, one of them is by
embedding microcapsules containing healing agents into a polymer matrix. When the
matrix is damaged, the microcapsules are damaged and the healing agents leak out and
fill in the damage. They harden through chemical reaction and heal the damage. High
reactivity of hexamethylene diisocyanate (HDI) with water is utilized as healing agent,
and it is encapsulated into microcapsules by interfacial polymerization between
methylene diphenyl diisocyanate (MDI)-based prepolymer and tetraethylenepentamine.
The microcapsules are then integrated with a polymer matrix to create a coating with self
healing property. When the coating is damaged, the released HDI should react with water
in the environment and it should harden and heal the damage, and therefore the coating
achieve self-healing property. Conditions in preparation of the microcapsules and
properties of their results are monitored to determine the condition that gives the most
effective microcapsules.

Introduction
Without looking too hard, it can be seen that nature has the unique ability to mend
itself from damage. Firstly, taking the closest example, humans can recover from wound
and damage that they experience. When experiencing a bone fracture, humans only need
to wait for some time, be patient and still, and the bone that was once broken will be
recovered. And when humans get injured and bled, substances in the blood are released
and create blood clot which will close the wound and prevent from further blood loss.
Other than humans, some trees, when their bark is wounded, secrete resin which will
harden and cover the wound, and some animals, geckos for example, can self-mutilate for
self-defense and the part that was once gone will grow back.
 In contrast, materials that are used in life do not have such ability. Once damage
comes, it stays there until more damage is taken and eventually the materials break down.
This is because living beings have substances inside them which will react systematically
upon an event and enable them to do things, such as healing from an injury. On the other
hand, materials do not have the substances and the complexity that would create a
mechanism to heal itself as living beings do, and they can only be as they are, without
reaction to change from their state after damage occurs.
The development of materials, as van der Zwagg (2007) explained, has been
progressing along the concept of damage prevention, where materials are developed such
that they can take more load without having a damage, and once damage is initiated, it
takes longer time and more load until the material fails to bear anymore load. But damage
is inevitable and the material must be checked periodically to determine whether it calls
for repair and cost.
Meanwhile, an alternative concept to that is damage management, where the
initiation of damage is not problematic and the material is developed such that the
damage can be healed autonomously once it is initiated. This concept becomes the basis
of the field of self healing materials, where it is not impossible to impose such
complexity into a material that will create the autonomous healing process within that
material.
Van der Zwagg (2007) explained that to achieve that and create a self healing
material, the material is developed such that:
- it contains matter that is mobile enough to fill in any defect, and that will
harden and bond the surfaces together, such that the material doesn’t lose its
function
- it can sense damage and start the self-healing process when necessary
- the surfaces due to damage stay and are fixed in close contact while the
healing is in process
Ever since the study on self-healing material started in 1994 and 1996 by Dry, and
took off in 2001 by White et al. (all cited by van der Zwagg, 2007), it has developed
different ways to achieve self-healing property, One of the first ways, done by White et
al. in 2001, is by embedding microcapsules containing healing agent and catalyst
separately into a polymer matrix so that when the matrix is damaged, the microcapsules
are also damaged. The healing agent and catalysts leak out, fill in the damage, and
eventually harden and heal the damage. This technique has been one of the most efficient
and widely used approaches in self-healing materials development (Huang & Yang,
2011).
In developing self-healing material with microcapsules, the healing agent
contained in them needs to have long shelf life, low monomer viscosity and volatility,
rapid polymerization at ambient conditions, and low shrinkage upon polymerization
(Andersson, Keller, Moore, Sottos & White, 2007). These requirements ensure that the
healing agent’s durability upon idleness and its mobility to travel on time to the damage
site before quickly polymerizing and not shrinking to heal the damage.
The microcapsules themselves also have requirements to meet as they serve as a
trigger for the self-healing process to start when the microcapsules are broken and the
healing agent leaks out. The microcapsules need to have high interfacial bond strength to
the surrounding polymer matrix and moderate walls strength, so that when the polymer
matrix is damaged, the microcapsules are also ruptured at the same time, rather than
cracked up prematurely or not at all. The capsules must also prevent leakage and
diffusion of their content during idleness, and their size and morphology also influence
how they rupture and release their content (Andersson et al., 2007).
Different substances have been encapsulated and dispersed in polymer matrix,
among them are dicyclopentadiene in poly(urea-formaldehyde) microcapsules with
bis(tricyclohexylphosphine)benzylideneruthenium(IV)di-chloride (Grubb’s catalyst)
(done several times as cited by Andersson et al., 2007) or Tungsten hexachloride catalyst
(done by Rule in 2005, as cited by Andersson et al., 2007) in epoxy matrix, hydroxy end-
functionalized poly(dimethylsiloxane) (HOPDMS) and poly(diethoxy siloxane) (PDES)
with a di-n-butyltin dilaurate (DBTL) catalyst in polyurethane microcapsules, dispersed
in vinyl ester matrix (done Cho et al. in 2006, as cited by Andersson et al., 2007).
Polymer matrices, dispersed with microcapsules containing such substances, have
successfully shown self-healing property upon damage in these studies.
This time around, hexamethylene diisocyanate (HDI) is to be encapsulated by
interfacial polymerization of methylene diphenyl diisocyanate (MDI)-based prepolymer
and tetraethylenepentamine in oil-in-water emulsion. These microcapsules will be
dispersed into an epoxy matrix to create self-healing coating. HDI is reactive enough
when exposed to moisture or water and it does not need catalyst as previous examples
demonstrate, but its reactivity could have been a problem in encapsulation process
(Huang & Yang, 2011). But the interfacial polymerization of other substances that are
more reactive prevents HDI from being exhausted from reaction with water and therefore
encapsulation of HDI is possible.

Methodology
1. Creating the Microcapsules
First of all steps, oil phase and water phase are created. Oil phase is made by
mixing HDI with a fixed mass of MDI-based prepolymer and the water phase is
surfactant solution in a beaker which is suspended in water bath. The temperature of the
water bath can be controlled by a programmable hot plate, and the solution is agitated
with a mixer. After preparing both phases, oil phase is put into the water phase under
agitation to create a stable emulsion system, which will be heated with increasing
temperature.
The surfactant in the solution and the agitation ensures that the droplets of the oil
phase in the water phase become a stable emulsion system and they don’t combine into
bigger droplets. Then solution of tetraethylenepentamine is added drop by drop into the
emulsion system to react with MDI-based prepolymer from the oil phase. The two are
situated in different phases such that they polymerize at the interface of the two phases
and form shells around the droplets containing the oil phase. The reaction between MDI-
based prepolymer with tetraethylenepentamine are much more reactive and occur faster
than reaction between HDI and water at the interface. Therefore the formation of
microcapsules encapsulating HDI is possible. After a period of time, the shells become
the newly formed microcapsules and they are filtered and washed with distilled water for
several times, and they are dried for 48 hours before analysis.
Batches of microcapsules are created and each batch is created in different
conditions, such as different temperature, agitation rate, duration of reaction between
MDI-based prepolymer and tetraethylenepentamine, surfactant solution concentration and
mass of HDI. Each batch will be analyzed as each condition will produce microcapsules
with different properties, and therefore an optimal condition can be determined to create
the most effective microcapsules.

2. Analyzing the Microcapsules

Aspects that will be analyzed for each batch of microcapsules are yield
percentage, thermal property, core content, chemical structure, morphology, shell
thickness, size, reactivity and environmental stability. These aspects are dependent to the
condition of preparation of microcapsules and they determine the effectiveness of the
microcapsules.
Yield percentage is determined by taking the ratio of total mass of obtained
microcapsules to the total mass of chemicals (HDI, MDI-based prepolymer and
tetraethylenepentamine) used in preparing the microcapsules. The ratio will show how
much microcapsules are gained and how much the chemicals are wasted for a certain
condition, and therefore high yield percentage is preferable.
The microcapsules’ thermal property is analyzed using thermogravimetric
analysis (TGA), where the mass of complete microcapsules and the mass the capsules’
shells (each is analyzed separately) is monitored while being in an environment with
increasing temperature. It will give a graph, plotting mass against temperature, and also a
graph of its derivative of mass loss. This will show how the microcapsules can withstand
heat and start to decompose at certain temperature. The core fraction is estimated by
comparing width of peaks from the graph of derivative of mass loss with temperature.
The core fraction shows how much core content contained in the microcapsules
compared to one complete capsule.
The microcapsules’ chemical structure is analyzed using Fourier Transform
Infrared Spectroscopy (FTIR), where the complete microcapsules, the capsules’ shells,
the capsule’s core content and chemicals involved in (HDI and MDI-based prepolymer)
are tested by radiating infrared radiation with various wavelengths. Each object absorbs
radiations of certain wavelengths and FTIR gives unique transmittance spectrum with
signature peaks for each object. Comparing signature peaks from one object with another,
the chemical structure of microcapsules and what each of its part is made of can be
determined.
Morphology of the microcapsules can be determined by using scanning electron
microscopy and the size and shell thickness of microcapsules are determined by taking
measurements from a number of samples from each batch. Measurements from each
batch will give average size and average shell thickness, along with the distribution. As
pointed out earlier, the size and morphology of the microcapsules influence how they
rupture and release its content for the self-healing process.
Reactivity of the core content is checked by taking some microcapsules and
crushing them to obtain the core content. Ethylenediamine is added to some of the core
content to see whether the core content is reactive, and the rest of the core content is
exposed to open environment to see whether it can react to moisture in the environment.
Microcapsules are also tested by putting them in aqueous solution. After a period
of time, some are analyzed with thermogravimetric analysis to determine their core
fraction, while the rest are crushed to observe using scanning electron microscopy how
the immersion in water affect the microcapsules. Additionally, microcapsules are put into
exposure to open air environment with room temperature for long period of time, and
how much core content left is examined to determine their shelf life.

3. Microcapsules in Coatings
The microcapsules are put the test by integrating them into a polymer matrix to
create a self-healing coating. The microcapsules are mixed well with the epoxy resin,
before mixing with a curing agent that will harden the epoxy resin. Before it hardens, the
mixture is spread onto a clean, polished steel substrate to create a coating with certain
thickness. When the mixture hardens and becomes the steel’s coating, it is scratched and
put into a salt solution. For comparison, a coating without the microcapsules is made onto
another steel substrate and becomes a control specimen. It is also scratched and put into
the salt solution.
The steel from control specimen will experience corrosion for its coating is
damaged and the steel substrate is exposed to the salt solution which causes the
corrosion. Meanwhile, the corrosion on the steel substrate with its coating integrated with
microcapsules will determine whether the coating has self-healing property. Upon
scratching, the microcapsules should release its content and fill in the damage. When
immersed into the salt solution, the content in the damage site should react with water
from the solution, harden in that damaged part of the coating, protect the steel substrate
from exposure to the salt solution and therefore prevents corrosion. If the coating
succeeds in protecting the steel from corrosion even after damage from scratching, then
the coating has achieved self-healing property.

Applications and Limitations

Coatings in everyday life have two primary functions: protection and decoration.
The coating has a decorative function as it is the outermost part of a substrate and it can
give the substrate a certain look which covers many aspects such as gloss and reflection,
surface waviness, color perception, transparency, cleanability, etc. The coating also has
protective function as it protects the substrate it covers from external influences such as
light, humidity, air, fungi, bacteria, dirt, chemicals, mechanical damage, and the like (van
Benthem, Ming & de With, 2007).
Integrating microcapsules containing healing agent into coatings produces self-
healing coatings which are able to heal damage such as scratches and cracks. This special
property makes such coatings more durable than ordinary coatings, and therefore the
decorative and protective functions can last longer. Moreover the ability to heal damages
autonomously can reduce the maintenance cost and no money needs to be spent to repair
small damages as they are healed autonomously before they grow worse and the coating
fails to protect the substrate beneath.
Creating microcapsules to store healing agents and integrate them in a material
has been one of the most efficient and widely used approaches in self-healing materials
development (Huang and Yang, 2011). And it is expected that the development of self
healing materials will continue to progress as they are able to fulfill these societal needs:
1. All applications for which repair is intrinsically very costly but the demands
on reliability are very high (wind farms at sea, underground pipe systems, etc.)
2. All applications where a long term performance has to be guaranteed (tunnels
and large infrastructural works, etc.)
 3. All applications where a very high reliability is required (aircraft, nuclear
storage systems, etc.)
4. All applications where a high surface quality is highly appreciated (cars,
optical systems, windows in public transport, etc.) (van der Zwaag, 2007)
Despite its potential application, using microcapsules to create self-healing
coatings implies that it cannot do self-healing for multiple times as the healing agent
available in the material may run out. Moreover, the size of the microcapsules (50 μm
and above) will only allow possible applications in relatively thick coatings to
accommodate the microcapsules. In addition, the hollow spaces (in the order of μm), left
behind because of the diffusion of the healing agent, would become new spots with stress
concentration (van Benthem et al., 2007).
Polymer matrices are also subject to degradation even without deforming damage,
such as organic polymers are sensitive to weathering and ageing under the influence of
moisture, UV radiation, and oxygen from the air, progressing degrading processes such as
photolysis, photooxidation, and hydrolysis are inevitable. The healing agent in
microcapsules may be able to heal scratches and cracks but it cannot protect the polymer
matrix from degradation due to those influences and reactions. Damages caused by
thermo-oxidative degradation (burning) and reactions with aggressive chemicals are also
beyond the ability of self-healing with microcapsules (van Benthem et al., 2007).

Conclusion
Embedding microcapsules containing healing agent into a polymer matrix may be
one of the most efficient approaches in creating a self-healing material, but it is not the
only way that has been developed since the study of self-healing material began more
than a decade ago. Some other means that have been developed to produce self-healing
material are fracture and reformation of the molecular bonds (Chen et al. in 2002 made
use of thermally reversible chemical bonds along a covalent polymer backbone via retro-
Diels-Alder reactions in furan–maleimide-based polymers to create re-mendable polymer
as cited by van der Zwaag, 2007). Another way is by creating within the material a
microvascular network containing healing agent that can be replenished from a source
within, which makes possible healing of damage multiple times as done by Toohey et al.
in 2007 (as cited by van der Zwaag, 2007). Various studies have also been conducted to
impose self-healing property in concrete materials (Li & Yang, 2007). Therefore, there
are still many possibilities to be realized, not just to improve microencapsulation
technique, but also to invent new methods in creating self-healing material that will be
applicable in our practice someday.

References
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