Smart Polymeric

Coatings—Recent Advances
W. FENG
Otto H. York Department of Chemical Engineering, New Jersey Institute of Technology,
Newark, NJ 07102

S. H. PATEL, M-Y. YOUNG

Polymer Processing Institute, New Jersey Institute of Technology, Newark, NJ 07102

J. L. ZUNINO III
U.S. Army Corrosion Office, Picatinny Arsenal, NJ 07806

M. XANTHOS
Otto H. York Department of Chemical Engineering, New Jersey Institute of Technology,
Newark, NJ 07102
Received: January 2, 2007
Revised: March 11, 2007

ABSTRACT: There is an ever-growing number of developments that aim to

bring novel functionalities to polymer-coating systems with nanotechnology
being one of them. This article will cover recent advances in the field of smart
polymeric structures that are used in protective coatings in terms of stimulus and
response, sensing mechanisms, and current or potential applications. Such
structures are commonly based on polymers modified through organic or
inorganic additives. Emphasis is placed on smart sensors used for detecting the
onset of corrosion on polymer coated ferrous and nonferrous substrates.
Examples of self-healing and repair through the action of microcapsules are also
presented.
C 2007 Wiley Periodicals, Inc. Adv Polym Techn 26: 1–13, 2007;

Published online in Wiley InterScience (www.interscience.wiley.com). DOI

10.1002/adv.20083

Correspondence to: M. Xanthos; e-mail: Xanthos@njit.edu.

Contract grant sponsor: U.S. Army Corrosion Office;
Picatinny, NJ through the Smart Coatings program at the
New Jersey Institute of Technology.

Advances in Polymer Technology, Vol. 26, No. 1, 1–13 (2007)

C 2007 Wiley Periodicals, Inc.
SMART POLYMERIC COATINGS
KEY WORDS: Additives, Coatings, Corrosion, Sensors, Smart materials,
Stimuli-sensitive polymers
Introduction
I ntelligent or smart materials, which may com-
bine the functions of sensor or actuator, rely on
their capabilities to respond to physical, chemical, or
mechanical stimuli by developing readable signals.
Changes in properties and structure, in response to
changes in the environment, are in many cases re-
versible. Responses may often actuate, in addition
to simple sensing, corrective action such as self-
mending or healing. Smart materials are expected
to be used not only as advanced functional mate-
rials but also as an integral part of complete smart
structures composed of various elements including
sensors, actuators, control algorithms, control hard-
ware, and structural members.1
The range of materials displaying some property,
which would allow them to be incorporated as sen-
sors or actuators in a smart structure, is almost lim-
itless and well documented.1,2 Clearly, it would be
beyond the scope of the present brief review to list all
common types of material response to every possi-
ble form of stimuli. Key technologies that have been
developed or are currently evaluated include shape
memory metal alloys and polymers, fiber optic sen-
sors, piezoelectric materials, electrochromic materi-
als, and electro-rheological and magneto-rheological
fluids. With respect to coatings, in addition to pro-
tective polymeric coatings for military and civilian
applications, intended uses of organic and inorganic
systems with smart functionality include

membranes for controlled drug release;

coatings with different adsorptive capacity for
proteins;

thermochromic, electrochromic, and gasochro-
mic smart windows; and

sensors for volatile organic compounds (VOC)
contaminants, land mines, radiation, and
chemical warfare gases.
There is an ever-growing number of develop-
ments that aim to bring novel functionalities to
polymer-coating systems with nanotechnology be-
ing one of them. Interdisciplinary materials research
at universities, research centers, start-up companies,
2 Advances in Polymer Technology
and established industrial R&D laboratories are
rapidly producing technologies with high potential
to convert otherwise conventional, “dumb” coating
systems into “intelligent” ones. The present brief
review concentrates on polymeric structures, which
in most cases are modified through organic or
inorganic additives and are used in polymer coat-
ings. Emphasis is placed on smart sensors used for
detecting the onset of corrosion on coated metallic
substrates.
Smart Polymer Coatings Based
on Color Response
For smart sensors based on color response, the
response may be visible color change, fluorescence,
or phosphorescence as a result of a variety of stimuli
that include

pH change,

redox reactions,

the presence of heavy metals,

sorption of chemicals,

radiation,

mechanical action,

temperature changes, and

electrical current.
Table I summarizes the characteristics of selected
polymeric coatings described in the literature as hav-
ing smart functionality. Information is presented on
type of stimulus and response, sensor type, sensing
mechanism, and types of existing or potential ap-
plications. The smart functionality may be imparted
by functional additives (colorants) that are added
separately into the coating prior to its application
on a given substrate (systems 1–4, 6–8); examples of
such applications include corrosion detection, self-
healing, surface decontamination, radiation detec-
tion. Smart functionality may also be built into the
polymeric structure (systems 5, 9, 10). Examples
include
(a) Acrylic polymers with long crystal-
lizable hydrocarbon side chains that
DOI 10.1002/adv
 TABLE I
Smart Polymeric Coatings Containing Functional Colorants
System Stimulus Response Sensor Type Sensing Mechanism Application References

1 pH change Color pH indicators Ionic form of different Corrosion detection 3

color
2 Oxidation Fluorescence Fluorescein, Schiff Redox Corrosion detection 4

Advances in Polymer Technology

bases reaction-fluorescent
oxidized form
3 Sorption, diffusion Fluorescence Fluorescence probes Decrease fluorescence Follow degradation 5
(increase free of coating
volume)
4 Mechanical action Capsule U/F capsules with film Healing: film or CaCO3 Self-healing; crack 6
rupture-healing, former, or Ca(OH)2 formation—Crack detection

DOI 10.1002/adv
color change or marker dye sensing: dye release
5 UV light, γ-rays Color Diacetylenes Polymerization Radiation detection 7
6 Light, temperature Color Photochromic dyes, Structural transitions Battery tester, printing 8–12
Thermochromic inks, miscellaneous
pigments, LCP coatings
and dyes
7 Heavy metal, Color change Colorimetric dye Colored metal complex Strippable coatings for 13,14
radioactive surface
contamination decontamination
8 TNT, nerve gas Quenching Fluorescent polymer TNT binds to receptors Location of land mines; 15
presence fluorescence fiber, reactive sensor on chromophores, sensor for chemical
reducing signal; warfare gas
nerve gas reacting
with sensor
9 Temperature Color change Side-chain Reversible crystalline H2 O barrier controlling 16
crystallizable polymer to amorphous seed germination
10 Oxidation Optical absorbance, Conducting polymer Switch between Sensors, actuators, 17
miscellaneous films (Pani, Ppy, Pth) charged and corrosion resistance
properties neutral states
SMART POLYMERIC COATINGS

3
SMART POLYMERIC COATINGS

can act as temperature-activated crys-
tallinity/permeability switches. In a typical
application involving seed germination with
soil temperature below about 13◦ C, the seed
coating is crystalline, provides a barrier
to moisture, and prevents germination; at
higher temperatures, the amorphous coating
structure enhances permeation and allows
germination.21
(b) Conductive forms of polypyrrole, polythio-
phene, and polyaniline undergo property
changes during reversible redox and pH
switching reactions; properties include color,
electrical conductivity, permeability, density,
and charge density. Such polymers can be used
in corrosion protection coatings for steel, stain-
less steel, aluminum, and copper. The conduct-
ing polymer anodically protects the metal, en-
couraging the formation of a passivating oxide
layer.17
Colorants may be simple dyes or pigments as
shown for systems 1–8 in Table I, or more complex
hybrid, multicomponent colorants based on inor-
ganic substrates coated with inorganic or organic
additives that provide specific effects or offer a po-
tential for smart functionality (Table II). Figure 1
shows the structure of a TiO2 coated mica special
pearlescent pigment.
Some recent research efforts toward the devel-
opment of smart materials have been bioinspired.
Color and color changes due to environmental
changes may be considered as functional proper-
ties of certain living organisms. For certain birds,
fish, snakes, and butterflies, color and apparent color
are due to pigments but also to iridescence (creative
interference) because of overlapping carbohydrate
scales giving the appearance of different color; the
effects depend on the angle of viewing, wavelength,
and the medium refractive index. For chameleons,
there is a control of the extent of surface exposure of
layers of colored or reflecting cells. For certain squids
and octopi, change of volume (and apparent color) of
sacs containing pigments may occur through muscle
contraction and relaxation.22
An example of a bioinspired intelligent system
is a N-isopropyl acrylamide gel loaded with car-
bon black. Through temperature changes, the sys-
tem undergoes reversible volume changes and, as
a result, changes in polymer chain conformations;
at the lowest critical solution temperature (LCST) of
31◦ C, these changes affect apparent color. Potential
applications for such system include smart windows
and camouflage.23,24
Smart Polymer Coatings Based
on Noncolor Response
Numerous polymeric coatings based on noncolor
response have been described in the literature as
having smart functionality. Table III summarizes the
characteristics of selected intelligent polymeric coat-
ings based on stimulus, response, sensor type, sens-
ing mechanisms, and types of existing or potential
applications. The smart functionality may be im-
parted by functional additives added separately into
the coating prior to its application on a given sub-
strate or be built in the polymeric structure. Exam-
ples include self-healing of cracks in coatings (sys-
tem 1), selective absorption of gaseous pollutants
(system 2), modification of absorptive characteristics
of coatings on biomaterials (systems 3 and 4), tem-
porary protective coatings that can be removed on
demand through dissolution in appropriate reagents
(system 5), and monitoring durability of coatings
through dielectric sensors (system 6). Durability of
polymeric systems containing glass fiber reinforce-
ment can also be monitored by incorporating fiber
optic sensors that respond in real time to excessive
strains imposed upon the structure during manufac-
turing and actual use.32

TABLE II
Multicomponent Colorants with Potential for "Smart Functionality"
Effect Material Reference

Pearlescence, interference effect
Electrical conductivity, magnetism,
IR reflective, laser sensitive
Electroluminescence
Color
Mica substrate based pigments (TiO2 , FeTiO3 , Fe3 O4 , Cr2 O3 ) 18
Oxide coated mica substrate (Sn, Sb, Fe, Ti oxides) 18
Nanoclay substrate coated with emissive polymer 19
Bentonite coated with cationic dyes—pulp colorant 20

4 Advances in Polymer Technology DOI 10.1002/adv

 SMART POLYMERIC COATINGS

FIGURE 1. Hybrid special effects pigments consisting of TiO2 coating deposited on mica flakes. Reproduced with
permission from Wiley-VCH.18

TABLE III
Smart Polymeric Coatings Based on Noncolor Response
Sensing
System Stimulus Response Sensor Type Mechanism Application Reference

1 Mechanical action Capsule U/F capsules DCPD- Crack 25

rupture-healing containing catalyzed self-healing
DCPD polymeriza- of coatings
tion
2 Gases; HC’s, Selective PP copolymer, Match Coating on 26,27
ammonia, absorption PC, acrylics solubility quartz crystal
acetaldehyde parameters resonator,
electronic
nose
3 Light Surface Azobenzene Cis–trans iso- Coating with 28
wettability derivatives merization reversible
absorptive
capacity for
biological
agents
4 Temperature Hydrophilicity/ N -isopropyl LCST31◦ C Coating on 29
hydrophobicity acrylamide (transition biomaterials
from random (nonprotein
coil to absorptive or
dehydrated) protein
retentive)
5 Neutralizing Dissolution Carboxylated Water soluble Temporary 30
agents (NH3 , copolymer neutralized protective
(NH4 )2 CO3 ) form coatings
6 Aging Mechanical Frequency Dielectric Monitor 31
deterioration properties, dependent sensing of durability of
water dielectric molecular coatings
resistance measure- mobility
ment
sensor

Advances in Polymer Technology DOI 10.1002/adv 5

SMART POLYMERIC COATINGS
Corrosion Detection
GENERAL
Corrosion occurs within both industrial and do-
mestic environments, and corrosion of a metal sur-
face increases significantly as the structure ages.
Structural defects from corrosion can cause fail-
ure. As a result, detection of corrosion at the ear-
liest stages is an important step toward improving
safety and reducing cost. Many different sensors and
techniques are being developed to detect corrosion.
Methods that are currently used to detect corro-
sion include X-ray,33 ultrasound,34 optical,35 flash
thermography,36 and electrochemical impendance
spectroscopy.37
The use of smart materials for corrosion-sensing
purposes relies on a material undergoing a transfor-
mation through its interaction with the corrosive en-
vironment. It is such transformations that can poten-
tially be used for indicating and detecting corrosion
damage. Ideally, the sensing function could be inte-
grated with additional actuation and control func-
tions designed to protect metals from corrosion and
to control corrosion damage. A recent example of
a smart nonpolymeric coating is an amorphous Al-
Co-Ce alloy applied on structural aluminum alloys.
The pH change accompanying corrosion prompts
dissolution of the coating and release of corrosion-
inhibiting ions that migrate to the critical site. When
corrosion stops, the pH returns to normal and the
dissolution of the coating returns to low levels.38 In
another example, pH changes for metals exposed in
corrosive media may be measured by a novel local
ion concentration technique. Using a miniaturized
pH sensor and reference electrode, a significant in-
crease in alkalinity (up to pH 12) was detected in
a scribe of a coating, 5 h after immersion in NaCl
solution.39
Additional examples related to the use of con-
ductive coatings for corrosion inhibition by repassi-
vating the metal substrate involve the use of mod-
ified polyanilines containing anionic inhibitors as
dopants that are released through polarization of a
polymer–polymer blend whose one component is a
conductive polymer.40 Related references are

Epoxy, polyester, or crosslinked polyvinyl
alcohol coatings containing polyaniline or
polypyrrole have been shown to increase the
corrosion resistance of aluminum alloys sev-
eral fold; this is possibly due to interactions of
6 Advances in Polymer Technology
the conductive polymer with either the alu-
minum surface or functional groups of the
binder.41

A polymethyl methacrylate coating containing
anion-doped polyaniline and applied on iron,
first releases anions through polyaniline re-
duction; the doping anions form a passivating
complex with iron cations that act as a physi-
cal protective barrier for aggressive corrosive
ions.42
CORROSION-SENSING COATINGS
A variety of corrosion resistant or protective poly-
meric coatings and paints have been described in the
literature as having smart functionality. Some exam-
ples have been shown in Tables I and III. Additional
smart-coating principles, relevant or potentially rel-
evant to corrosion sensing that are described below
include the following:

Paint systems containing color-changing com-
pounds, responding to pH changes that result
from corrosion processes.

Changes of coating compounds from nonfluo-
rescent to fluorescent states, upon oxidation or
complexing with metal cations.

Release of color dyes containing anticorrosive
additives from embedded microcapsules filled
with dye and additive following mechanical
damage of the capsule coating.

Use of pigments that absorb corrosive chem-
icals or release corrosion inhibiting chem-
icals “on demand” with or without color
changes.
Compounds, which show fluorescence in the ul-
traviolet to near infrared region, have been investi-
gated for their corrosion-sensing capabilities when
subjected to the effects of temperature, pH, reduc-
tion, and reoxidation behavior. For corrosion sens-
ing, the chemical should fluoresce only when ei-
ther oxidized or when reacting with the corroding
species. Compounds such as fluorescein, Morin or
Schiff bases, oxines and hydroxyquinolines, were
found to fluoresce with aluminum ions and dur-
ing oxidation in air when incorporated into primer
paint coatings for aluminum alloys. Fluorescent
dyes were applied to microelectronic test vehicles to
detect pH changes associated with corrosion of Al
or Au metallization under an applied bias in a hu-
mid environment.43 Fluorescing and color-changing
DOI 10.1002/adv

FIGURE 2. Fluorescent materials for corrosion detection on alloy surfaces.45 [Color figure can be viewed in the online
issue, which is available at www.interscience.wiley.com.]
dyes also have been applied to Al after corrosion to
identify the location of the hydrous aluminum ox-
ide corrosion product [44]. Johnson and Agarwala4
incorporated into paint different chemicals that flu-
oresce upon oxidation or upon complexation with
metal cations formed by the corrosion process. This
is shown in Fig. 245 , for an epoxy coating containing
fluorescein on aluminum panels, the area experienc-
ing corrosion fluoresces under UV light. These stud-
ies show the potential of fluorescent compounds as
early warning corrosion sensors; large surface areas,
such as aluminum alloys used in aircraft, coated with
epoxy-containing fluorescent probes can be scanned
with light of suitable wavelength to determine the
onset of corrosion.46
In addition to compounds that change their
optical signature when they undergo redox (re-
duction/oxidation) behavior, there exist a vari-
ety of compounds that change color as a result
of pH changes. Zhang and Frankel3 and Frankel
et al.47 used different color change or fluorescing
compounds, which are sensitive to the increase in
local pH associated with the cathodic reaction
O2 + 2H2 O + 4e− → 4OH−
accompanying the anodic reaction that forms hy-
drous aluminum oxide corrosion product. Figure 3
contains a schematic of an experimental painted lap
joint setup for detecting crevice corrosion on alu-
minum panels (Fig. 3a) and results on panels coated
with acrylic paints containing pH indicators after
immersion in 1 M NaCl solution for a period of
Advances in Polymer Technology DOI 10.1002/adv
SMART POLYMERIC COATINGS
time (Fig. 3b); color change in the coating indicated
the occurrence of localized corrosion. In another
approach,48 pH sensitive dyes have been encapsu-
lated in a polymeric shell susceptible to degradation
at the alkaline pH accompanying cathodic corrosion.
The released dyes serve as corrosion indicators at the
localized corrosion sites.
Fiber-optic arrays have been evaluated for cor-
rosion sensing of uncoated or coated aeronautic
structures.49−51 The imaging fiber’s distal face, con-
taining an immobilized pH-sensitive fluorescent dye
or coated with coatings containing pH-sensitive
dyes, was used for visualizing remote corrosion
sites. By measuring local chemical concentrations at
these sites, the results were applied to real-time cor-
rosion such as galvanic and crevice corrosion and
pitting. In a particular arrangement, applicable to
coated surfaces, tapped Bragg gratings of different
Bragg periods are spaced along the fiber to refract
a narrow bandwidth component of a broad beam
light pulse transmitted through the fiber. Figure 4
shows a cut-away view of a lap joint with one tapped
Bragg grating in a longitudinal segment of the op-
tical fiber sensor.52 The sensing compound #18 that
coats the optical fiber is a corrosion responsive chem-
ical acting through color change or fluorescence,
e.g., 1,10-phenanthroline for steel and fluorescein
for aluminum. Because of corrosion, the compound
reflects the refracted components and their ampli-
tudes are detected and displayed for each narrow
bandwidth.
More recently, anion-exchanging hydrotalcite53
and cation-exchanging bentonite54 clays, both
7
SMART POLYMERIC COATINGS

FIGURE 3. (a) Experimental setup for determining crevice corrosion onset through color changes in painted lap joint.
Reprinted with permission from Zhang and Frankel.3 (b) Photographs of color change of two pH sensing coating on Al
5454 substrate following immersion in 1.0 M NaCl solution. Left: phenolphthalein paint after 8 days, Right: Bromothymol
paint after 13 days. Reprinted with permission from Zhang and Frankel.3 © NACE International 1999. [Color figure can be
viewed in the online issue, which is available at www.interscience.wiley.com.]

modified through the incorporation of specific
ions, were used in organic coatings for corro-
sion protection and sensing. It was shown that
a change in crystalline structure identified by X-
FIGURE 4. Cut-away view of lap-joint with one tapped
Bragg grating in a longitudinal segment of the optical fiber
sensor. The sensing compound (18) coating the optical
fiber is a corrosion responsive chemical acting through
color change or fluorescence.52
ray diffraction could be detected as a result of an
ion exchange reaction accompanying corrosion. As
shown in Fig. 5, the coatings with a decavanadate-
modified hydrotalcite (HT-V) show better protection
in the salt spray test than the unmodified coating.
Figure 6 (left) compares the X-ray diffraction pat-
terns of epoxy containing HT-V deposited on alu-
minum before and after exposure in a 0.5 M NaCl
solution for 450 h. Figure 6 (right) shows that the
profound changes in the diffraction pattern of the
exposed coatings are the result of an ion exchange
reaction leading to the formation of HT-Cl and
the release of corrosion-inhibiting decavanadate.
Vanadate release may be triggered at specific pH or
by a sudden decrease in electrochemical potential for
novel coatings based on the biopolymer chitosan.55
In another approach,56 corrosion inhibitors attached
to nanopaticles that are embedded in epoxy primers
are released upon the development of alkalinity at
the onset of corrosion and migrate to arrest corrosion
at the steel/coating interface.

8 Advances in Polymer Technology DOI 10.1002/adv

 SMART POLYMERIC COATINGS

FIGURE 5. Optical macrographs of 2024-T3 coupons coated with PVA with and without HT-V inhibitors before and after
exposure to ASTM B117 salt spray. Reproduced with permission from Progress in Organic Coatings, 47.53 [Color figure
can be viewed in the online issue, which is available at www.interscience.wiley.com.]

Polymeric coatings containing aligned imper-
meable platelets of high-aspect ratio, or additives
reactive toward corrosive liquids, can significantly
reduce permeability of liquids and vapors versus
the unmodified polymers.57,58 This permeability re-
duction has been shown to impart barrier properties
and inhibit corrosion of aluminum substrates coated
with epoxy filled with mica flakes as a result of in-
creased tortuosity.59 The use of cationic (e.g., mont-
morillonite) or anionic (e.g., hydrotalcite) nanoclays
after exfoliation and planar orientation of the indi-
vidual lamellae would also be expected to provide
barrier properties. The presence of reactive sites on
these clays could also offer the option of using them
as carriers for pH responsive, color changing sens-
ing additives such as ionizable dyes; such dyes have
been used successfully for doping other inorganics
such as mesostructured silica.60
The evaluation of nanoclays modified with pH
sensitive colorants as sensors for onset of corrosion
of polymer coated aluminum and ferrous substrates
is part of a broad recent research program aiming
at developing smart coating systems for military
materiel with unique properties such as self-repair,
selective removal, corrosion resistance, and sensing
capabilities.61 Preliminary data62−65 indicate that it is
possible to produce nanoclay based, well-dispersed,
functional colorants for corrosion sensing and
barrier improvement where the colorant is strongly
bound to the clay, at concentrations as low as 1 wt%

FIGURE 6. X-ray diffraction patterns from HT-V dispersed in epoxy resin and exposed to aerated 0.5 M NaCl solution
for 450 h. Reproduced with permission from Buchheit et al.53 [Color figure can be viewed in the online issue, which is
available at www.interscience.wiley.com.]

Advances in Polymer Technology DOI 10.1002/adv 9

SMART POLYMERIC COATINGS
FIGURE 7. Accelerated corrosion testing in salt fog spray chamber (two layer structures—tape protected exposed area)
of scribed aluminum panels. From left to right: 0, 96, 432 h.65 [Color figure can be viewed in the online issue, which is
available at www.interscience.wiley.com.]
(based on clay). Furthermore, it is possible to de-
tect development of localized alkalinity as a result
of corrosion of metallic panels coated with acrylic,
polyurethane, or epoxy paints through color changes
as a function of time. Detection of onset of corrosion
strongly depends on the initial color of the modified
polymer paint. Figure 7 shows results of accelerated
corrosion testing (ASTM B117) of aluminum pan-
els coated with two paint layers. The bottom layer
with poor protective capacity consists of a liquid
acrylic coating containing a colorant-modified nan-
oclay, whereas the top layer is a clear crosslinked
acrylic powder with excellent protection character-
istics. Development of blue color as a result of the
increasing alkalinity accompanying corrosion at the
scribed area is evident.
Self-healing Coatings
Microcapsules containing a small amount of
“healing agent” that will be released by crack
propagation or other triggering mechanism have
been incorporated into polymeric coatings. This
process has been used for self-healing in polymer
composites through release of a polymerizable heal-
10
ing agent that would bridge cracks after reaction
with appropriate catalysts as shown in Fig. 8.25
A self-repair approach applicable to cementitious
matrices involves cracking of hollow repair fibers
and timed release of chemicals that seal matrix
microcracks.66 A biomimetic approach to perform
self-repair by a bleeding action of filled hollow fibers
has been described by Pang and Bond.67 The addi-
tion of a fluorescent die enhances damage visibility
in the reinforced plastics structure. A similar pro-
cess has been used with acrylic coatings applied on
deteriorated lead-based paints. Figure 9 shows mi-
crocapsules containing film formers that suppress
the release of lead dust. If corrosion-resistant addi-
tives were encapsulated into the microcapsules, the
same process could also be used for corrosion protec-
tion or detection. Polymeric capsules could also be
degraded by the high alkalinity accompanying cor-
rosion, thus, delivering healing agents to terminate
corrosion at its early stage.48
It should be noted that color development
through capsule rupture and subsequent chemical
reaction of its colorless acid sensitive dye contents
has been used over the years in carbonless carbon
paper. In a three-part form, the released dye solu-
tion is transferred from the bottom surfaces of the
first and second sheets to the top surfaces of the
second and third sheets, respectively, where it reacts
Advances in Polymer Technology DOI 10.1002/adv

FIGURE 8. A microencapsulated healing agent is
embedded in a structural composite matrix containing a
catalyst capable of polymerizing the healing agent. (a)
Cracks form in the matrix wherever damage occurs; (b)
the crack ruptures the microcapsules, releasing the
healing agent into the crack plane through capillary
action; (c) the healing agent contacts the catalyst,
triggering polymerization that bonds the crack faces
closed. Reprinted with permission from Macmillan
Publishers LTD: Nature, 2001.25 [Color figure can be
viewed in the online issue, which is available at
www.interscience.wiley.com.]
FIGURE 9. Left: Urea/formaldehyde microcapsules filled with polybutene; center: microcapsules release healant when
damaged; right: urea/formaldehyde microcapsules (60 µm) in acrylic latex topcoat.6 [Color figure can be viewed in the
online issue, which is available at www.interscience.wiley.com.]
Advances in Polymer Technology DOI 10.1002/adv
SMART POLYMERIC COATINGS
with an acidic clay or resin coating to form an image
as a result of a change of pH or oxidation. Figure 10
shows a typical three-part carbonless copy paper
system.68
Concluding Remarks
Significant work is underway toward the tran-
sition of smart polymeric coatings from labora-
tory curiosities toward the identification of ap-
plications that would eventually lead to their
commercialization. These efforts will be facilitated
by increased interaction between academia and in-
dustry, focus on market applications, and a coherent
technical and funding strategy from national gov-
ernments. Primary areas that are to benefit from
such efforts appear to be transportation, aerospace,
military, and self-healing composites. Examples of
areas of continuing active and innovative research
efforts are conductive polymers, molecular surface
design, use of ionic liquids in functional coatings,
photolatent colors enabling coloration on demand,
polymer brushes from immiscible polymer blends
attached on substrates to create surface gradients,
smart biocoatings for decontamination, or coatings
that protect materials from biofouling. Challenges
in more advanced research areas that could pos-
sibly reach fast commercialization are (a) the un-
derstanding of the corrosion protection mechanism
11
SMART POLYMERIC COATINGS
FIGURE 10. Three-part carbonless paper system.68
imparted by conducting polymers, (b) the advance-
ment of micro- nanoencapsulation as a means to im-
part self-healing, or depaint-on-demand functionali-
ties in thin polymeric coatings, and (c) the limitations
of corrosion-sensing color-based systems in real
commercial products that contain color-interfering
pigments.
Acknowledgments
The assistance of Ms. G. Chouzouri, Dr. S. Kim,
Mr. N. Patel, and Mr. K. Park with early experimental
results of the work conducted at New Jersey Institute
of Technology, Newark, NJ, is much appreciated.
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