Corrosion-resistant

metallic coatings
We describe recent computational and experimental studies on the
corrosion properties of metallic coatings that can be tailored (tuned)
to deliver up to three corrosion-inhibiting functions to an underlying
substrate. Attributes are tuned by a selection of alloy compositions and
nanostructures, ideally in alloy systems that offer flexibility of choice
to optimize the corrosion-resisting properties. An amorphous Al-based
coating is tuned for corrosion protection by on-demand release of ionic
inhibitors to protect defects in the coating, by formation of an optimized
barrier to local corrosion in Cl– containing environments, as well as by
sacrificial cathodic prevention. Further progress in this field could lead
to the design of the next generation of adaptive or tunable coatings that
inhibit corrosion of underlying substrates.
F. Presuel-Moreno1, M. A. Jakab2, N. Tailleart3, M. Goldman4, and J. R. Scully3*
1 Florida Atlantic University, Boca Raton, FL 33431, USA,†
2 Southwest Research Institute, San Antonio, TX 78238-5166, USA†

3 Department of Materials Science and Engineering, University of Virginia, Charlottesville, VA 22904–2442, USA
4Constellation Power Company, Calvert Cliffs, MD 20657, USA†

*E-mail : jrs8d@virginia.edu
†Formerly at MSE, University of Virginia, VA, 22904-4246, USA

The epidermis–dermis–subcutaneous system is able both to resist
and repair damage and also regrow over a defect that exposes
underlying tissue. These are admirable qualities in biological
systems because these processes are repetitive, autonomous,
and can be triggered by damage without external intervention1.
In corrosion of metallic materials, dip, spray, chemically or
electrodeposited organic-based, metallic, and ceramic coatings are
often used to protect a substrate from corrosive damage2.
Natural passive films, artificially grown oxide layers (i.e. anodized
and sealed), and conversion coatings3–5 can also protect underlying
metals and alloys. Successful native passive films can form a protective
layer over many metals if the ingredients for passivation (i.e. alloying
elements) are present in high enough concentration in the underlying
alloy. The oxide quickly and automatically reforms to repair defects
in many environments. Conversion coatings and anodized layers rely
on the formation of a chemically engineered layer based both on

14 OCTOBER 2008 | VOLUME 11 | NUMBER 10 ISSN:1369 7021 © Elsevier Ltd 2008

 Corrosion-resistant metallic coatings
the oxidation of elements in the metal as well as on incorporation of
selected species in a pretreatment bath to reinforce the natural oxide.
Controlled additions of specific molecules to the conversion coating
bath are required and these can seldom be applied in the field.
Corrosion protection by passive films and
coatings
Passive films, conversion coatings, and metallic and organic coatings
confer corrosion protection via a variety of mechanisms, including
formation of barriers to the penetration of corrodants; high ionic
resistivity in surface layers to minimize electrochemical reactions
under the coating at the metal–coating interface; active corrosion
inhibition where an inhibitor is stored, released, and delivered to a
defect; and sacrificial cathodic protection. Chromate systems possess
this active corrosion inhibition property6 but are being phased out due
to their high toxicity and carcinogenicity7. Oxides may also exhibit
ion-selective permeability, as well as a desirable potential and/or pH
of zero charge to limit detrimental anion (Cl–) adsorption and ingress8.
Enhanced adhesion, control of the liquid chemistry at the metal–
coating interface and superhydrophobic properties9,10 may also operate
in many exciting new systems.
Active corrosion inhibition
Traditionally, metallic coatings serve only one or two functions.
For example, Zn has excellent corrosion resistance and functions
as a sacrificial anode11. Zn galvanizing provides sacrificial cathodic
protection and acts as a barrier12 but does not usually supply inhibitor
ions. The release of Zn ions during the sacrificial protection of
galvanized steels11,13 only provides a small additional benefit compared
to galvanic protection provided by the potential driving force. Metallic
coatings used to protect Al alloys14,15 consist of a thin layer of nearly
pure Al mechanically bonded to standard precipitation age-hardened
Al alloys. The coating sacrificially cathodically protects the Al alloy
substrate (a beneficial form of galvanic corrosion) but does not provide
active corrosion inhibition. Galvanic throwing power is limited because
the roll-bonded cladding16 has a limited electrochemical driving force
for protection. The open circuit potential (OCP) of AlcladTM alloys
is only ~80–100 mV below that of the structural substrate, such as
AA 2024-T317, and their pitting potentials (Epit) are actually below
that of underlying structural Al alloys. The consequential virtual
non-polarizability enables cathodic protection of the aerospace alloy
but also ensures a high self-corrosion rate and considerable anodic
inefficiency.
Long-range corrosion protection of coating
defects
In the case of a coating containing active corrosion inhibitors or
passivators that are stored, released, and transported, defects such
as a scratch in the coating may be protected over long distances
REVIEW
(i.e. possess a chemical throwing power) due to concentration
(e.g. chemical potential) gradient-driven random transport from
inhibitor-rich regions to unprotected sites. Sacrificial cathodic
protection (i.e. galvanic throwing power) may also operate over long
distances. The distance over which protection can be afforded is
a function of the electrochemical properties of both the sacrificial
anode and the unprotected site as well as the geometry and ionic
conductivity of the ionic phase (often a thin electrolyte exposed to the
atmosphere) over the coating. The electric field in the ionic solution
established by the potential driving force difference between the
anodic and cathodic half cell potentials facilitates long-range cathodic
polarization. Such long-range functionality is superior to that of
biological systems where an internal circulatory system is required to
repair damaged sites1,18. Similarly, self-healing of mechanical damage
in man-made materials requires locally distributed microcapsules,
or encased composites containing gels or monomeric polymers and
catalysts spaced at a short distance from defects1,19–22. The monomer
cannot be easily supplied over long distances to repair damage sites.
One vision for new coatings with multiple,
tunable functions
Unfortunately, existing corrosion protecting metallic coatings cannot
provide active corrosion inhibitors to protect defects via transport of
the inhibitor through the liquid corrosive phase. Moreover, corrosion
properties are rarely tunable. For instance, the behavior of metallic
claddings is often fixed by rather inflexible limits on compositions and
microstructures. Therefore, there are few user-adjustable parameters
available to tune cathodic protection to mitigate certain localized
corrosion processes triggered above certain potential thresholds
(e.g. pitting, stress corrosion, exfoliation at high potentials, or H
embrittlement at very negative potentials). In addition, cathodic
protection, active chemical inhibition, as well as the presence of a local
corrosion barrier, are desired simultaneously. The addition of inhibitors
is a particular challenge for metallic materials. While sacrificial and
barrier attributes can be adjusted somewhat by changing composition
or structure, inhibitors can rarely be added to a solid. Moreover,
inhibitors, stored in the solid state, must be released as a liquid-soluble
molecular or ionic species to enable transport through the liquid
corrosive phase to a defect. In contrast, sparingly soluble inhibiting
pigments can readily be added to organic coatings and released by
chemical dissolution. An added challenge for both organic and metallic
coatings is the desire to trigger inhibitor release on-demand so that the
stored inhibitor is used only when it is needed.
We will now discuss some recent computational and experimental
studies where several corrosion-protecting functions are achieved
simultaneously in a single metallic coating. The desired properties
include active corrosion inhibitor supplied on demand to enable
corrosion inhibition and/or autonomous repair. Sacrificial anode-based
cathodic protection and barrier properties can also be tailored to
OCTOBER 2008 | VOLUME 11 | NUMBER 10 15
REVIEW Corrosion-resistant metallic coatings

Fig. 1 Schematic of a structural high-strength precipitation age-hardened alloy (in this case AA 2024-T351, a Al–Cu–Mg alloy) protected against corrosion by a
system comprising a Al–Co–Ce metallic coating, an organic primer, and an organic topcoat. The corrosive environment is the layer of aqueous electrolyte on top
of the coating. The structural alloy is a polycrystalline alloy with Cu-rich coarse constituent particles labeled ‘IMC’ (for intermetallic compounds), grain boundaries
and fine nanoscale, precipitates. Several macroscopic defects are shown. They include a coating with a scratch through to this substrate alloy, and a scratch through
the organic coating. Ideally the metallic coating (a) functions as a barrier to corrosion, (b) delivers corrosion inhibitors indicated as released Ce3+ in the case of the
Al–Co–Ce coating, and (c) serves as a sacrificial anode to deliver cathodic protection (indicated by electrons, e–). Other enhancements include a graded coating
composition and mixed metallic phases potentially optimized to enhance bonding and ductility on the inner layer to serve as a barrier to corrosion on the outer
layers as well as to place the interface in compression to suppress fatigue of the substrate. Inhibitors released from the coating system can inhibit both anodic pits
(local corrosion attack) as well as strong cathodic reactions at Cu-rich IMC. Inhibitors and cathodic protection (electrons, e–) can inhibit pitting as well as more
advanced forms of attack such as intergranular corrosion. (Courtesy of King A. University of Virginia)

protect various substrates in a range of environments. Moreover, the
electric field created by the galvanic couple between the coating and
the substrate can be manipulated to augment transport of inhibitors
over large distances. To demonstrate this possibility we discuss a
specific nanoengineered, spray-applied, amorphous metallic alloy
(Fig. 1) that illustrates some of the mitigation strategies and functions
desired and achievable using a nanoengineered metallic coating such
as a corrosion-inhibiting system. The challenges and issues involved in
achieving these functions are highlighted.
Materials and fabrication of tunable
amorphous metallic coatings
The challenges of tailoring the properties of metallic coatings compared
to polymer-based coatings are numerous. In the case of polymers,
a micrometer- or nanometer-scale composite can be created by
mixing in the liquid state, and thus with great flexibility, a monomer,
resin, filler, solvent, etc., and a phase encapsulating the inhibitor
(e.g. strontium chromate pigment) in a slurry that is then reacted in
various ways and solidified in a rigid state below the polymer glass
transition temperature, Tg. In contrast, metallic coatings are often
applied at high temperatures and involve delivering a liquid metal via
either a hot dip or spray process. Such heating may adversely alter
the microstructure of the underlying alloy. Physical and chemical
vapor deposition, pulsed thermal spray (PTS), cold spray (CS), and
mechanical cladding are alternative methods to avoid excessive
temperatures. Numerous nonequilibrium alloying techniques may also
be employed to add beneficial alloying elements in significant enough
concentrations to have a major impact on properties. Corrosion barrier
properties can be improved by several routes. Minimizing structural
defects such as intermetallic and metalloid phases and optimization
of certain compositions in solid solution both usually significantly
improve corrosion ‘barrier’ properties. Therefore, methods to produce
supersaturated solid solutions which lack intermetallic and metalloid
phases are highly desired. By using metallic glasses, metallic elements
may be added or mixed in a soluble liquid solution with improved,
although not unlimited, flexibility, and then solidified and trapped
below Tg to achieve chemically homogeneous solid solutions. Moreover,
active corrosion inhibitors might be supplied if some of the added
alloying elements can function in this capacity. Amongst the possible
replacements for Cr(VI)23–27, transition metal (TM) and rare-earth (RE)
metal ions (Co2+, MoO42– and Ce3+) are possible choices to inhibit
localized corrosion of Al alloys23–25 and steels26–27. These elements
also can be alloyed to form Al-based metallic glasses. RE metal ions
may serve as inhibitors if they can be incorporated and released by
a chemical or electrochemical process. Alloying a crystalline metal
with these elements is traditionally difficult because of their limited

16 OCTOBER 2008 | VOLUME 11 | NUMBER 10

 Corrosion-resistant metallic coatings
solubility in the solid state28. This problem can be overcome by using
a glassy alloy that dissolves these alloying elements in solid solution.
Indeed, certain Al–TM and Al–refractory metal alloys29,30 can exhibit
enhanced local corrosion barrier24 and sacrificial anode-based cathodic
protection qualities31,32. The Al–RE–TM alloy series is of particular
interest because of its good glass-forming abilities33,34, high strength,
low density, and superior corrosion properties35–37.
In fact, a new amorphous Al–Co–Ce alloy system was recently
synthesized38–40 as an environmentally compliant metal coating with
multiple corrosion protection functionalities41–43. The notion of a
multifunctional metallic coating need not be restricted to Al–TM–RE
and there are likely to be many alloys that can be designed following
these general strategies. The goal was to simultaneously provide a
corrosion barrier, sacrificial anode-based cathodic protection42,44, or
prevention44 as well as active corrosion protection (e.g. contain and
deliver a supply of inhibiting cations that can be released to suppress
corrosion) to minimize corrosion at coating defects that expose the
underlying structural alloy45–47. Fig. 1 highlights this overall strategy.
Cathodic protection abilities may also be optimized by lowering the
OCP of the coating relative to the underlying substrate. For instance,
the OCP of the Al–Co–Ce alloy can be lowered as much as 750 mV
below that of AA 2024-T3 depending on the alloy composition and
solution pH41,48–50. Amorphous Al alloys also have the ability to store
beneficial alloying elements in solid solution. For instance, the selected
transition and RE metals (e.g. Ni, Fe, Co, Ce, Y, Gd) added as alloying
elements improve amorphicity in concentrations up to about 15 at.%.
Co, Ni, or Fe improve the resistance of Al to local corrosion, while
Ce3+, Y3+, and Gd3+ are good corrosion inhibitors when added as salt
in aqueous solutions40,51. The amorphous alloy can be formed over a
Fig. 2 Map of Al–Co–Ce alloy compositions that yield amorphous, amorphous/
crystalline, and crystalline nanostructures in the Al–Co–Ce alloy system
based on the at.% Co and Ce present in solid solution Al. The map shown was
produced at a high cooling rate and results may differ at different cooling
rates. The crystal structures were determined by both X-ray diffraction and
transmission electron microscopy analysis.(Reproduced with permission from.
© 2007 J. Electrochem. Soc.)
REVIEW
wide range of Co and Ce compositions, as seen in Fig. 238. The alloy’s
amorphous state is very stable.
High-velocity oxygen-fuel spray (HVOF), CS and PTS methods
are possible deposition methods to apply such coatings. PTS utilizes
high heating and large quenching rates, which allows for either
amorphous or crystalline powder feedstock material (Fig. 3) to develop
an amorphous or nanocrystalline coating on a substrate material.
The structure of the feedstock material tends to dictate the resulting
structure of the coating. The coating powder and deposited layer
are shown in Fig. 4a–d. The feedstock powder is often supplied as a
controlled particle size distribution ranging from 0.5 to 20 µm, although
larger powder sizes can be attempted (Fig. 4a). PTS is distinguished
by rapid particle acceleration and heating, a minimal residence time
within a high enthalpy environment, and rapid particle quenching
upon interaction with the target substrate52,53. The quenching rate
for particles less than 20 µm in size can be as high as 106 K/s54. Also
notable is that naturally aging precipitation age-hardened aerospace
alloys, such as the AA 2024-T3 substrates, do not exceed 60 ºC during
the coating process54. Reduced substrate thermal loading enables short
stand-off coating capability that, from an application standpoint, is
desirable because it allows for localized repairs of the coating where
a physical defect exists exposing the underlying structural alloy and
gives the capability for coating complex geometries55. The pulsed spray
stream rasters over the surface of the substrate in such a way that the
resulting spray-applied coating is actually a built-up series of layers.
PTS and HVOF coatings have the advantage of accepting the feedstock
powder for these alloys in either crystalline or amorphous forms, as the
feedstock particles can melt mid-process as long as powders are small.
The HVOF process has a large quench rate, similar to that of the PTS
Fig. 3 X-ray diffration patterns for the Al88Co10Ce2 feedstock powder, an as-
deposited PTS coating, and an amorphous Al84Co7.5Ce8.5 melt-spun ribbon
(MSR) indicating an amorphous structure in the MSR but the presence of Al
face-centered cubic nanocrystals in both the sprayed coating and powder
feedstock. (Reproduced with permission from. © 2007 J. Electrochem. Soc.)
OCTOBER 2008 | VOLUME 11 | NUMBER 10 17
REVIEW Corrosion-resistant metallic coatings

(a) (b)

(c) (d)

Fig. 4 (a) Conventional secondary electron imaging (LEI) scanning electron microscopy (SEM) image of the Al88Co10Ce2 feedstock powder used for spray-applied
coatings. (b) LEI cross-sectional SEM image of an as-deposited PTS coating showing good adhesion with AA 2024-T351 (Al–Cu–Mg alloy). (c) LEI SEM image of
cross-sectioned and polished PTS coating showing pulse-deposited layers and level of porosity. (d) Confocal scanning laser microscropy (CSLM) image of an-
deposited PTS coating surface showing inherent roughness. (Reproduced with permission from. © 2007 J. Electrochem. Soc.)

process56. High-density samples with favorable corrosion properties

can be achieved57–63. The CS process utilizes the plastic deformation of
the sprayed, solid, feedstock particles on impact with the substrate to
achieve a uniform coating55. The spray event occurs below the melting
point of the spray materials, so less microstructural change and less
oxidation should occur55. Numerous metallic coatings have also been
deposited by these methods64–70.
Al–Co–Ce alloy coatings have been produced by both HVOF and
PTS with thicknesses ranging from 75 to 600 µm often with good
adhesion and low porosity. In some studies these have been compared
to melt-spun ribbon (MSR) alloys produced by the traditional method
of streaming the molten alloy on to a spinning copper wheel to enable
rapid quench rates.

Tunable barrier properties in multifunctional
amorphous Al–TM–RE coatings
Coatings which act as barriers to corrosion are commonly used and
date back to the use of noble decorative and corrosion-resistant
metallic coatings71. However, as in the case of sacrificial cathodic
protection, barrier properties are often fixed by rather inflexible alloy
compositions and structures. Porosity in coatings is often minimized by
increasing coating thickness.
The advanced processing methods discussed above enable new
coating compositions which break out of old constraints on alloy
Fig. 5 Comparison of E–log(i) curves for an as-deposited PTS Al–Co–Ce coating
to the same coating with a hole drilled which exposes the AA 2024-T351
substrate. Data for AA 2024-T351 and a Al87Co7Ce6 MSR are also presented.
Tests were performed in deaerated 0.006 M NaCl solution at a neutral pH and
enable determination of pitting potential, Epit, repassivation potential, Erp, and
open circuit potential, OCP. The higher pitting potential indicates a greater
resistance to pitting. A more negative OCP than AA 2024-T3 indicates that the
sprayed coating can cathodically protect the AA 2024-T3 alloy at scratches.
The total area tested was 0.238 cm2, the area of the exposed substrate/drilled
hole was 2 × 10–3 cm2. These results show that a PTS Al–Co–Ce alloy coating
exhibits a much great pitting potential than the AA 2024-T3 substrate in the
absence of an intentional defect. (Reproduced with permission from. © 2007 J.
Electrochem. Soc.)

18 OCTOBER 2008 | VOLUME 11 | NUMBER 10

 Corrosion-resistant metallic coatings
Fig. 6 Relationship between the repassivation potential, ERP, and alloy content
in solid solution (Co at.% and Ce at.%). The relationship shown is plotted
from polynomial expressions developed from Scheffé polynomials based
on tests conducted on amorphous MSR of various Al–Co–Ce alloys in 0.6 M
NaCl solution at neutral pH. The ERP of the Al–Co–Ce alloy is compared to
AA 2024-T3 and high-purity Al. These results show that the repassivation
potential and thus barrier resistance to pitting can be controlled by controlling
the alloying content in solid solution.
composition. In one study of an Al–Co–Ce alloy, three parameters
were obtained from E–I plots (tests performed in NaCl) (Fig. 5) to
characterize corrosion properties over a flexible range of compositions.
These were the OCP, the pitting potential, Epit, and the repassivation
potential, Erp. Epit and Erp are indicators of the pitting resistance,
while OCP helps forecast the galvanic corrosion behavior of an alloy
(e.g. potential driving force for sacrificial cathodic protection when
coupled to a substrate). Various regression models suitable for use with
alloys where the composition is constrained to 100% were explored
and two examples are shown in Figs. 6 and 744. Plots include possible
substrate structural materials (AA 2024-T3, Aermet 100® steel, etc.).
The influence of Co on the OCP is based on Co’s effect on the cathodic
kinetics of Al–Co–Ce alloys. By increasing the reaction rate for both
the O reduction reaction (ORR) and the H evolution reaction (HER),
additions of Co in solid solution results in a higher OCP. The decrease
in OCP associated with the addition of Ce is most likely due to the
suppression of the ORR by Ce. The positive influence of Co on Erp is
due to the decreased hydrolysis product of this cation72, probably
resulting in a less aggressive pit environment and reduced anodic
dissolution rates of a Al–Co solid solution. A complex trend with Co
was seen. A parabolic shape also described the effect of Al and Ce
on Erp. These three elemental behaviors, when considered together,
describe a complex balance where Co and Ce reduce the aggressiveness
of the pit solution: Co lowers the dissolution rate while Al aids oxide
REVIEW
Fig. 7 Predicted values of the open circuit potential (OCP) for the solid solution
Al–Co–Ce alloy system over a range of solid solution Co at.% and Ce at.%
contents, utilizing a Scheffé model with two inverse terms, demonstrating the
range of OCP possible within the Al–Co–Ce alloy system. These OCP values are
compared to AA2024-T3 and Aermet 100® OCP values. These are alloys the
Al–Co–Ce alloy might be designed to protect. The more negative OCP of the
Al–Co–Ce alloy compared to AA 2024-T3 and Aermet 100 confirms not only
the feasibility of this material to serve as a sacrificial anode but shows that the
driving force for cathodic protection can be tuned. The calculated values were
based on tests conducted on amorphous MSR of various Al–Co–Ce alloys in 0.6
M NaCl solution deaerated, at neutral pH.
formation in an aggressive acidic solution. Therefore, optimization
of alloying elements produces the highest Erp values, with a complex
dependency of Erp on alloy content. To optimize the composition so as
to provide a barrier with the highest resistance to localized corrosion,
Co amounts should be relatively high (6-8 at.%), and Ce contents
moderately low (3-5 at.%) in this particular alloy.
Tunable sacrificial anode-based cathodic
protection in Al–TM–RE coatings
Sacrificial anode-based cathodic protection when two or more metals
are galvanically coupled is a potent electrochemical protection
method12. A coating that can polarize an exposed substrate material
just a few hundred millivolts below its OCP can lower its corrosion
rate by a factor of 100 or more. It is often more useful to polarize
many structural materials that corrode by local corrosion mechanisms
such as pitting or intergranular corrosion above some critical threshold
potential (i.e. Epit) to levels below this threshold potential. This is
accomplished by engineering a galvanic couple potential below Epit or
Erp. This is called cathodic prevention. Unfortunately, the governing
properties needed to optimize cathodic protection or prevention
(material-dependent OCP, and electrochemical current–potential
characteristics) have previously only been optimized through trial and
error. Moreover, parameters such as OCP are often rather inflexible
due to the limited choices of alloy composition and structure available.
OCTOBER 2008 | VOLUME 11 | NUMBER 10 19
REVIEW Corrosion-resistant metallic coatings

Extreme cathodic potentials are not desired because ‘overprotection’
can lead to adverse side effects such as H embrittlement, alkaline
attack, and paint blistering. Therefore, tunable cathodic protection is a
highly desired capability.
The flexibility in OCP achieved by selecting particular compositions
of the Al–Co–Ce alloy system (Fig. 7) is extremely beneficial, as it
enables application of varying degrees of cathodic protection. By
choosing an Al–Co–Ce composition with relatively low Co (3-5
at.%) and low Ce levels (3–5 at.%) a sacrificial anode material can
be produced with a moderately low OCP value, to avoid cathodic
overprotection. An example is Al90Co5Ce5. The unique combination
of OCP values more negative than pure Aermet 100 ® or AA 2024-T3
along with an enhancement of barrier properties in the coating makes
this amorphous Al–Co–Ce alloy particularly well suited to serve as
a protective coating material. The enhanced resistance to localized
corrosion offered by this alloy results in greater Faradiac efficiency for
the sacrificial material, extending the theoretical lifetime of protection
compared to the Al–Zn and Al–Mg alloys used as Al alloy cladding
materials.
The sacrificial anode-based cathodic protection attributes sought
have been recently investigated by computational methods42,45,73–75
focusing on galvanic couples between a metallic coating and
exposed substrate under atmospheric conditions73. Fig. 8a shows
how atmospheric exposure (a thin electrolyte layer) of a structural
Al alloy covered by a metallic coating with a scratch at the center of
the sample Fig. 1) was modeled. A metric of the cathodic throwing
power of the sacrificially anodic Al–Co–Ce alloy was taken as the
galvanic couple potential distribution along the horizontal axis
of Fig. 8a and its proximity relative to the OCP of the Al–Co–Ce
coating and the AA 2024-T3 Epit. A figure of merit used is ∆E, given
as (Epit 2024 – Ecouple), where Ecouple is the interfacial galvanic couple
potential at the centerline of the scratch, CL (Fig. 8b). Effective cathodic
prevention design maximizes ∆E. The maximum ∆E that can be
achieved during galvanic coupling is termed ∆Emax and is defined by
Epit2024 – Eocp of the Al–Co–Ce alloy.
Fig. 9 shows the extent of polarization given by the parameter ∆E
obtained for a variety of situations as a function of scratch width at
a fixed sample length. The parameter ∆E is shown as the ordinate for
each case, with the value of ∆E at S = 0 being the theoretical ∆Emax
(i.e. Epit-2024 – EOCP, AlCoCe). The theoretical limit is approached for
small scratches. A greater extent of protection can be achieved when
the Cl– concentration is low. The potential distribution model predicts
that substantial sacrificial cathodic prevention of an AA 2024-T3
scratch could be achieved with a nanoengineered alloy coating.
The extent of the sacrificial cathodic protection provided by the
Al–Co–Ce alloys is a function of pH, Cl– concentration, the cathodic
kinetics on the AA 2024-T3, and the Co content of the metallic
coating. The metallic coating provides the best protection (i.e. largest
cathodic polarization of the scratch) when it is tailored to contain a
low Co content, and is exposed to either high or low pH solutions
of low Cl– concentration. Finally, the combination of chemical and
electrochemical protection predicted by computational modeling
has been verified via experiments involving defects machined into
PTS Al–Co–Ce alloys over AA 2024-T3. Corrosion protection is indeed

(a) (b)

Fig. 8 (a) Schematic of the geometry associated with the galvanic coupling modeled between an Al–Co–Ce alloy coating (left) and AA 2024-T3 substrate (right)
exposed as a scratch in a thin electrolyte (e.g. corrosive solution) of thickness δ. Symmetry considerations allow solution of half of the scratch (S) exposing AA
2024-T3 by applying a zero flux boundary at CL. The half-scratch length, S, was varied from 500 to 5000 µm in width while the total length of the coating–scratch
system was held constant at 1 cm. The JO = 0 boundary condition reflects the physical situation at the right end of a specimen. This system was used to conduct
finite element modeling of the galvanic protection provided by the Al–Co–Ce coating to the AA 2024-T3 scratch. (b) In this plot the galvanic couple potential
based on material properties, electrolyte characteristics, and physical geometry is plotted as a function of horizontal position along the coating/scratch surface of
Fig. 8a, showing the effect of scratch length (indicated at far right) on the galvanic couple potential achieved. The scratch is located on the right-hand side. Model
parameters: variable S, Co ~ 3–5 at %, idl on AA 2024-T3 of 1.6 A/m2, in solution of pH 3 and 0.05 M Cl–. The vertical line indicates the position of the interface
between metallic coating and substrate for the 5000 µm scratch. The dotted horizontal line indicates Epit of AA 2024-T3. Any galvanic couple potential below this
line indicates successful cathodic prevention. Thus, for this situation scratches 500–2500 µm in halfwidth are protected, while half-scratch widths of 5000 and 3500
µm are not protected against pitting near the centerline of the scratch at the far right. This is because the throwing power of the coating is inadequate to drive the
potential below Epit. (Reproduced with permission from © 2007 J. Electrochem. Soc.)

20 OCTOBER 2008 | VOLUME 11 | NUMBER 10

 Corrosion-resistant metallic coatings REVIEW

However, slow release only when needed is often desired. Conducting

Fig. 9 Cathodic polarization obtained with AlcladTM compared to the
Al–Co–Ce metallic coating expressed as the potential difference, ∆E, between
Epit and the galvanic couple potential at the center of the scratch (x = 1 cm;
at C-line of Fig. 8a) attained for different scratch widths at a fixed half sample
length of 1 cm. The theoretical ∆Emax for AlcladTM and the other coatings
are shown on the ordinate at S = 0. The potential difference between the Epit
of AA2024-T3 and the galvanic couple potential at x = 1 cm are shown in
the plot for each half-scratch width. Boundary conditions for the AlcladTM
used: ipass=0.002 A/m2, EpitAlclad 45 mV below Epit2024. The conditions
include 0.05 M Cl– and a pH of 3, with idl = 0.4 A/m2 for the various alloys
compositions. The results indicate that the Al–Co–Ce coating protects better
than AlcladTM as indicated by the larger ∆E. This suggests that the Al–Co–Ce
coating can protect bigger scratches by cathodic prevention. Moreover, a low
Co content (i.e. 0–1 > 3–5% Co > 7–9% Co ) in the Al–Co–Ce alloy helps to
protect AA2024-T3 to a greater extent. (Reproduced with permission from ©
2007 J. Electrochem. Soc.)
provided in experiments when the PTS coating is electrically coupled to
the AA 2024-T3 substrate.
On-demand active-corrosion inhibition based
on tunable Al–TM–RE alloy coatings
Controlled-release technologies are often used to supply chemicals
at given rates76,77. Release often occurs upon contact with solution.
electroactive polymers are one means to provide controlled drug
delivery77. In corrosion protection, triggered or on-demand release
of inhibitor ions is also very important. Conductive polymers have
recently been utilized as reservoirs for corrosion inhibitors whose
triggered release occurs by galvanic reduction or ion exchange78–82.
Amorphous Al–Co–Ce alloys enable pH-controlled release of corrosion-
inhibiting ions from a metallic coating. The pH change that triggers
release is a consequence of the chemistry changes brought about by
corrosion itself43. Therefore, on-demand release occurs as a result of
exposure to corrosive species when corrosion initiates, for instance,
pH. ‘Turning off’ inhibitor release also occurs when the pH returns
to near-neutral and changes the local pH of the solution over the
coating. For a metal coating to behave like a pigmented paint that
can supply active corrosion inhibitors, several attributes are desired83.
The coating must store enough inhibitor to supply the critical inhibitor
concentration once released. The aqueous solution formed over the
metal surface must accumulate enough inhibitor to achieve the critical
inhibitor concentration, Ccrit, needed to stop corrosion in reasonable
time periods. This necessitates a high inhibitor capacity in the alloy
and a finite release rate. The Ccrit must be lower than the saturation
concentration of the inhibitor ion in the solution. The Ccrit in a given
electrolyte volume must be low enough so that the alloy can readily
release enough ions to achieve it without completely depleting the
inhibitor capacity83.
Al–Co–Ce alloys releasing Ce3+ meet these requirements. The
inhibitor is stored in the alloy and in its air-formed oxide layer in
valence states that are useful for corrosion inhibition. Inhibitors are
released by pH-dependent chemical dissolution of the oxide or direct
oxidation of the metal23–25 (Fig. 10). Ce and Co oxides are highly
soluble at low pH, insoluble under neutral, and partially soluble under
alkaline conditions (Fig. 11) 13,84. Thus, a pH change can be exploited
to trigger Co2+ and Ce3+ release. A pH change occurs during corrosion

Fig. 10 Schematic illustration of Al–Co–Ce coating (dark grey) on AA2024-T3 with a defect exposing the AA2024-T3 substrate. The less noble coating has been
tuned to possess an OCP more negative (–) than the underlying structural alloy. Consequently, cationic inhibitors released from the dissolving coating can be
transported to the defect by both migration as well as diffusion, while anionic species are transported in the opposite direction. A coating could also be engineered
to enable anionic transport by migration to the scratch as long as the polarity was reversed. This could be accomplished by tailoring the coating composition and
structure to create a coating with a potential greater than that of the scratch. The behavior shown has been confirmed for both MSR and spray-applied coatings.

OCTOBER 2008 | VOLUME 11 | NUMBER 10 21

REVIEW Corrosion-resistant metallic coatings
Fig. 11 Effect of pH of a NaCl solution on the release rate of Al3+, Co2+, and
Ce3+ ions from an amorphous Al87Co8.7Ce4.3 MSR alloy in comparison to
high-purity Al. This plot illustrates that a shift in the electrolyte pH from the
near-neutral range typical of a benign solution to either the acidic or alkaline
range of a corrosive solution would help trigger the release of Ce cations (as
well as Al). This plot illustrates a mechanism for triggered release where the
environmental stimulus is the pH change.
which releases metal cations that hydrolyze to produce H+ at anodic
sites. High cathodic reactions at cathodic sites often increase the pH.
Therefore, when a metal is scratched and a galvanic couple forms
between the coating and newly exposed substrate, the pH will drop
over the anodic coating and rise at the cathodic scratch site. pH-
dependent release rates were found for Al–Co–Ce–(Mo) alloys41
(Fig. 11). The inhibitor ions released diffuse and then migrate towards
the damage site, reach Ccrit and suppress corrosion (Fig. 10). When
corrosion of the structural alloy stops, the pH of the environment
returns to neutral and Ce3+ is subsequently released at much lower
rate.
Computational studies42,45,73–75, have also been used to study
inhibitor release from such metallic substrates. Studies of inhibitor
release, transport, and achievement of Ccrit were conducted with and
without migration through the electrolyte phase. Migration-based
transport of Ce3+ to the scratch occurs due to the potential difference
established between the OCPs of AA 2024-T3 and the Al–Co–Ce
metallic coating. The time needed to reach Ccrit over the scratch was
determined, accounting for both transport processes as well as the
effect of temporal and position varying local release rates. Fig. 12
shows how the released Ce3+ profile develops with time and position in
one example. Migration aids Ce transport (for OCPAlCoCe < OCPAA2024),
explaining the uphill transport of Ce3+. The Ccrit,Ce is reached at the
coating–scratch interface at various times for different scratch lengths.
Accumulation was limited by ionic transport.
In summary, corrosion inhibition of a AA 2024-T351 scratch can
be achieved with ions released from a metallic coating. Experimental
exposure of AA 2024-T3 in a corrosive solution near an electrically
isolated Al87Co7Ce6 alloy confirmed computational modeling. The
Ce3+ supplied significantly decreased the maximum corrosion pit sizes
22 OCTOBER 2008 | VOLUME 11 | NUMBER 10
Fig. 12 Computational model calculations of Ce3+ profiles in the electrolyte
phases (see Fig. 8a) with time and position over an Al–Co–Ce coating (left)
with exposed AA 2024-T3 substrate alloy (right). The plot indicates that Ce3+
can build up over the AA 2024-T3 on the right and even continues to build up
against the concentration gradient. This is due to the migration of Ce3+ in the
electric field formed in the electrolyte. The greater Ce3+ concentration near
the interface is due to slightly elevated release at high pH as indicated in Fig.
11. Computational results shown are for the selected case of initial solution
pH 6, 0.05 M Cl–, S = 1500 µm and slow ORR kinetics on the metallic coating
and AA2024-T3 (right). The vertical line indicates the position of the scratch
with the coating at the left and exposed AA 2024-T3 on the right as depicted
in Fig. 8a. (Reproduced with permission from. © 2007 J. Electrochem. Soc.)
on the AA 2024-T3 surface below a critical size43. This is important in
aerospace structural materials, such as fuselage and wing skins, because
large corrosion pits above approximately 110 µm greatly reduce fatigue
life85,86.
Summary
A multifunctional amorphous alloy has been described that possesses
three corrosion protection abilities when deployed as a coating over
structural alloys. The coating (i) functions as a local corrosion barrier,
(ii) serves as a sacrificial anode, and (iii) supplies soluble ions used as
corrosion inhibitors by engineering metallurgical and electrochemical
properties. The alloy system described is just one example of many
exciting new possibilities in metallic coatings enabled by the progress
in amorphous and nanocrystalline alloy development, as well as novel
synthesis and coating deposition methods. In the case presented,
excellent inherent resistance to corrosion is achieved through
structural amorphicity and choice of composition to optimize corrosion
functions. For instance, tunable electrochemical and chemical throwing
powers to achieve long-range protection of substrate defects can be
achieved. These concepts are generic and other alloys can in principle
be developed to optimize these functions. Such alloys can also be
manipulated to enable transport of inhibiting cations by both migration
and diffusion. Inhibitor release can be triggered on-demand.
Acknowledgments
A Multi-University Research Initiative (Grant No. F49602–01–1–0352)
entitled ‘The Development of an Environmentally Compliant Multifunctional
 Corrosion-resistant metallic coatings
Coating for Aerospace Applications using Molecular and NanoEngineering
Methods’ initially supported this work under the direction of Jennifer Gresham,
at air force office of scientific research (AFOSR). Coating development was
supported by AFOSR under Robert Manz and Jennifer Gresham in collaboration
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