SELF HEALING OF POLYMERIC COMPOSITES

ABSTRACT

Inspired by biological system, in which damage triggers an autonomic healing response a

new class of polymeric composite materials was developed which begins to repair itself
as soon as crack forms. Self healing polymeric composite has the potential to defend
against material failure, it greatly improves product safety and reliability ultimately
extends product life time. Polymeric matrix, microcapsules containing healing agent and
catalyst are the major components of the self healing polymeric composites. These new
classes of materials find applications in the field of biomedical, paint and coatings,
sporting equipments, automobiles, aircraft and aerospace.

Key words: self healing polymers, healing agent, microcapsules

INTRODUCTION:

Composite materials are macroscopic combinations of two or more materials. In which

each constituents retain their identity. The basic constituents of Polymeric Matrix
composites (PMCs) are :( 1) Matrix made up of polymers and (2) Reinforcing agents
(particles, fibers etc.).

Inspired by biological system, in which damage triggers an autonomic healing

response a new class of polymeric composite materials was developed which begins to
repair itself as soon as crack forms. These self healing polymeric composites have
potential to defend against structural failure and greatly improve product safety and
reliability leads to extend product lifetime. Self-healing is accomplished by incorporating
a microencapsulated healing agent and a catalytic chemical trigger within a polymer
matrix. When the material is damaged, the microcapsules rupture and release the healing
agent into the damaged region through capillary action. As the healing agent contacts the
catalyst, polymerization is initiated and the damage is repaired.[1]
GENERAL MECHANISM:
Constituents of Self- Healing PMC:
The main constituents of a self-healing polymeric matrix composite (SHPMC) are shown
as:

Fig. 1: Constituents of self healing polymeric composite

Matrix: The matrix is made up of a polymers either thermoplasts or thermo sets.

Healing Agent: The healing agent is a fluid in the form of encapsulated tiny bubbles that
are spread throughout the composite material.
Microcapsule: This contains the healing agent and separates the catalyst and healing
agent.

Catalyst: The catalyst triggers the polymerization process and usually is Grubbs’
catalyst. The function of catalyst is to enable the healing agent to heal the composite
material. Catalyst and healing agent are separated until they are required to seal a crack.
[2]
Concept of Autonomic Healing:
The figure below illustrates the autonomic healing concept. The healing is accomplished
by incorporating a microencapsulated healing and a catalytic chemical trigger within an
epoxy matrix. An approaching crack ruptures embedded microcapsules, releasing healing
agent into the crack plane through capillary action. Polymerization of the healing agent is
triggered by contact with the embedded catalyst, bonding the crack faces. [2]

Fig. 2: The autonomic healing concept

Case Study – Self Healing Epoxy Composite:

Matrix: The matrix is epoxy matrix. The epoxy matrix composite was prepared by
mixing 100 parts epoxide with 12 parts DETA (diethylenetriamine) curing agent. Self-
healing epoxy specimens were prepared by mixing 2.5 wt% Grubbs’ catalyst and 10 wt%
microcapsules with the resin mixture described above. The resin was then poured into
silicone rubber moulds and cured for 24 hours at room temperature, followed by post
curing at 400C for 24 hrs.
Healing Agent – (DCPD): The healing agent is dicyclopentadiene (DCPD). It is a low
viscosity (.736cP @ 21oC) hydrocarbon monomer. [2]

Figure 3: Structure of DCPD

Chemistry of Self-Healing:

Completion of self-healing process requires a suitable chemistry to polymerize the

healing agent in the fracture plane. We identified the living ring-opening metathesis
polymerization (ROMP) as meeting the diverse set of requirements of the self-healing
system, which includes long shell life, low monomer viscosity and volatility, rapid
ambient conditions; and low shrinkage upon polymerization. The ROMP reaction
invokes the use of a transition metal catalyst (Grubbs’ catalyst) that shows high
metathesis activity while being tolerant of a wide range of functional groups as well as
oxygen and water. The reaction polymerizes dicyclopentadiene (DCPD) at room
temperature in several minutes to yield a tough and highly cross-linked polymer network.

The characteristics of this reaction are: (1) Fast reaction time, (2) High monomer to
catalyst loading 10000:1 and (3) Minimal volume shrinkage. [2]
 Fig. 4: Chemistry of self healing
Preparation of Microcapsules:
Microcapsules are prepared by in-situ polymerization, which is also referred as Micro
encapsulation, which is described as under:
In a 600ml beaker, urea (7 gm) is dissolved followed by resorcinol (0.5 gm)
and ammonium chloride (0.5 gm) in water (150 ml). A 5 wt% solution of ethylene-
Maleicanhydride copolymer (100 ml) is added to the reaction mixture and the pH of the
reaction mixture was adjusted to 3.5 using 10% NaOH solution. The reaction mixture
was agitated at 45 RPM and to this stirred solution 60 ml of dicyclopentadiene was added
to achieve an average droplet size of 200 m. To the agitated emulsion 37%
formaldehyde (0.23 ml, 18.91gm) solution was added and then the temperature of the
reaction mixture was raised to 50oC and maintained for 2 hours. After 2 hours, 200 ml of
water was added to the reaction mixture. After 4 hours the reaction mixture was cooled to
room temperature and the microcapsules were separated. The microcapsule slurry was
diluted with additional 200 ml water and washed with water. The capsules were isolated
by vacuum filtration, and dried. The yield was 80%. Their average size was 220m. [2]

Catalyst:

The catalyst used is Grubbs’ catalyst. It is a stable transition metal catalyst used to initiate
a living polymerization (developed in the mid 1990’s by Robert Grubbs at Caltech). The
catalyst remains active even after triggering polymerization. Hence when additional
cracking occurs, the catalyst crystals continue to trigger polymerization, allowing
multiple healing to occur. [2]

APPLICATIONS:
1. Paints and Adhesives :
A new group of nontoxic , corrosion resistant self healing PMC replaced
chromates which have been used commercially as an anticorrosive constituent of
many paints and adhesives. As soon as the surface is scuffed the coating starts self
repairing.[3]

2. Medical Field:
 Self healing bandages: Small tissue sample is taken from a patient and a culture
is grown from the cells in laboratory. These cells are then placed on a membrane
made from a medical grade self healing PMC. This membrane is treated with a
special cell friendly coating which enables skin cells to attach and grow with it. It
is serve best to heal diabetic ulcers and other slow healing wounds.

 For healing of bone and cartilage: A new class of biocompatible self healing
PMCS act as scaffolding when it is placed inside a severe fracture or in the small
cavities using laser beams. The main advantage is that it maintains its strength and
eliminate problem of weaker and more porous bones and necessity of future
surgeries.

 Dental applications: Bioactive self healing PMCs containing amorphous calcium

phosphates are used as filler for teeth and applied by root canal therapy. This can
eventually cause teeth to repair their own small cavities. [4]

3. Electronics:
New class of self healing PMCs are used to design electrodes of capacitors, so
whenever short circuit cause damage to the dielectric layer these electrodes will
vaporize and heal that areas thus continue functioning of the capacitor. [5]

4. Self Healing Fuel Tanks:

Fuel tanks in military planes and helicopters which currently used several layers
of heavy rubber for protection. Self healing PMCs developed from surlyn and
ethylene-methacrylic acid copolymer which are self healed against bullet‘s attack.
It is also fuel resisting so long lasting and prevents leakage of fuel by bullets
strike.

5. Air Crafts and Space Applications :

 A clear and crack free air craft windows are developed by coating it with water
repellant self healing PMCs, it is also flexible enough to accommodate changes in
shape that a window undergoes without itself crazing or coming unstuck. [5]

ADVANTAGES AND LIMITATIONS:

ADVANTAGES:
 Addition of microcapsules and reinforcing agents strengthens the material.. [4]
 Such materials will increase the product safety, reliability.
 Self-healing polymers increase the life of thermosetting plastics by as much as 2-3
times.
 Requires less maintenance.
 These polymers will eliminate the deleterious effects of environmentally assisted
degradation such as moisture swelling and stress corrosion cracking.
 Self-healing polymers are used where it is not possible to repair the material once
it has been put into use and in any plastic subject to micro cracking.
 This polymeric composite recovers 70-90% of its original fracture toughness.

LIMITATIONS:
 It is necessary to obtain optimum size of microcapsules according to
characteristics of matrix material and different loading conditions.
 Microcapsules are not capable of multiple healing.
 The catalyst is expensive, but it’s cost will be compensate when a longer lifetime .
 less maintenance of product is obtained. [6]

CONCLUSION:
Self healing polymeric composites are efficient and will eliminate deleterious
effects of mechanical or environmental degradation of materials. This new class
of polymeric composites continues to gaining acceptance. Further research and
technological advancements will extend it’s usefulness in structural and
aerospace applications.

REFERENCES:
  N.R.Sottos & E.N.Brown, “Microcapsules induced toughening in a Self healing
polymeric
 composites”, Journal of Material Science, 39, Pg.1703 -10, 2004.
 S.R.White & N.R.Sottos & E.N.Brown, ”Autonomic healing of polymer
composites”, Letters to
 the Nature, 409, Pg.794 -97, Feb.2001.
 http://www.uri.edu.
 http://www.sciencedaily.com.
 http://www.csiro.au.
 E.N.Brown, N. R. Scottos & S.R. White, “Fracture Testing of Self healing
 polymeric composites”, Experimental Mechanics: An International Journal, 2001.

Document By
SANTOSH BHARADWAJ REDDY
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