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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 229042442, 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 epidermisdermissubcutaneous system is able both to resist

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Natural passive films, artificially grown oxide layers (i.e. anodized

and repair damage and also regrow over a defect that exposes

and sealed), and conversion coatings35 can also protect underlying

underlying tissue. These are admirable qualities in biological

metals and alloys. Successful native passive films can form a protective

systems because these processes are repetitive, autonomous,

layer over many metals if the ingredients for passivation (i.e. alloying

and can be triggered by damage without external intervention1.

elements) are present in high enough concentration in the underlying

In corrosion of metallic materials, dip, spray, chemically or

alloy. The oxide quickly and automatically reforms to repair defects

electrodeposited organic-based, metallic, and ceramic coatings are

in many environments. Conversion coatings and anodized layers rely

often used to protect a substrate from corrosive damage2.

on the formation of a chemically engineered layer based both on

OCTOBER 2008 | VOLUME 11 | NUMBER 10

ISSN:1369 7021 Elsevier Ltd 2008


Open access under CC BY-NC-ND license.

Corrosion-resistant metallic coatings

REVIEW

the oxidation of elements in the metal as well as on incorporation of

(i.e. possess a chemical throwing power) due to concentration

selected species in a pretreatment bath to reinforce the natural oxide.

(e.g. chemical potential) gradient-driven random transport from

Controlled additions of specific molecules to the conversion coating

inhibitor-rich regions to unprotected sites. Sacrificial cathodic

bath are required and these can seldom be applied in the field.

protection (i.e. galvanic throwing power) may also operate over long
distances. The distance over which protection can be afforded is

Corrosion protection by passive films and


coatings

a function of the electrochemical properties of both the sacrificial

Passive films, conversion coatings, and metallic and organic coatings

conductivity of the ionic phase (often a thin electrolyte exposed to the

confer corrosion protection via a variety of mechanisms, including

atmosphere) over the coating. The electric field in the ionic solution

formation of barriers to the penetration of corrodants; high ionic

established by the potential driving force difference between the

resistivity in surface layers to minimize electrochemical reactions

anodic and cathodic half cell potentials facilitates long-range cathodic

under the coating at the metalcoating interface; active corrosion

polarization. Such long-range functionality is superior to that of

inhibition where an inhibitor is stored, released, and delivered to a

biological systems where an internal circulatory system is required to

defect; and sacrificial cathodic protection. Chromate systems possess

repair damaged sites1,18. Similarly, self-healing of mechanical damage

this active corrosion inhibition

property6

but are being phased out due

to their high toxicity and carcinogenicity7. Oxides may also exhibit

anode and the unprotected site as well as the geometry and ionic

in man-made materials requires locally distributed microcapsules,


or encased composites containing gels or monomeric polymers and

ion-selective permeability, as well as a desirable potential and/or pH

catalysts spaced at a short distance from defects1,1922. The monomer

of zero charge to limit detrimental anion (Cl) adsorption and ingress8.

cannot be easily supplied over long distances to repair damage sites.

Enhanced adhesion, control of the liquid chemistry at the metal


coating interface and superhydrophobic properties9,10 may also operate
in many exciting new systems.

One vision for new coatings with multiple,


tunable functions
Unfortunately, existing corrosion protecting metallic coatings cannot

Active corrosion inhibition

provide active corrosion inhibitors to protect defects via transport of

Traditionally, metallic coatings serve only one or two functions.

the inhibitor through the liquid corrosive phase. Moreover, corrosion

For example, Zn has excellent corrosion resistance and functions

properties are rarely tunable. For instance, the behavior of metallic

as a sacrificial anode11. Zn galvanizing provides sacrificial cathodic

claddings is often fixed by rather inflexible limits on compositions and

protection and acts as a

barrier12

but does not usually supply inhibitor

microstructures. Therefore, there are few user-adjustable parameters

ions. The release of Zn ions during the sacrificial protection of

available to tune cathodic protection to mitigate certain localized

galvanized steels11,13 only provides a small additional benefit compared

corrosion processes triggered above certain potential thresholds

to galvanic protection provided by the potential driving force. Metallic

(e.g. pitting, stress corrosion, exfoliation at high potentials, or H

coatings used to protect Al

alloys14,15

consist of a thin layer of nearly

embrittlement at very negative potentials). In addition, cathodic

pure Al mechanically bonded to standard precipitation age-hardened

protection, active chemical inhibition, as well as the presence of a local

Al alloys. The coating sacrificially cathodically protects the Al alloy

corrosion barrier, are desired simultaneously. The addition of inhibitors

substrate (a beneficial form of galvanic corrosion) but does not provide

is a particular challenge for metallic materials. While sacrificial and

active corrosion inhibition. Galvanic throwing power is limited because

barrier attributes can be adjusted somewhat by changing composition

the roll-bonded cladding16 has a limited electrochemical driving force

or structure, inhibitors can rarely be added to a solid. Moreover,

for protection. The open circuit potential (OCP) of AlcladTM alloys

inhibitors, stored in the solid state, must be released as a liquid-soluble

is only ~80100 mV below that of the structural substrate, such as

molecular or ionic species to enable transport through the liquid

AA

2024-T317,

and their pitting potentials (Epit) are actually below

corrosive phase to a defect. In contrast, sparingly soluble inhibiting

that of underlying structural Al alloys. The consequential virtual

pigments can readily be added to organic coatings and released by

non-polarizability enables cathodic protection of the aerospace alloy

chemical dissolution. An added challenge for both organic and metallic

but also ensures a high self-corrosion rate and considerable anodic

coatings is the desire to trigger inhibitor release on-demand so that the

inefficiency.

stored inhibitor is used only when it is needed.

Long-range corrosion protection of coating


defects

studies where several corrosion-protecting functions are achieved

In the case of a coating containing active corrosion inhibitors or

include active corrosion inhibitor supplied on demand to enable

passivators that are stored, released, and transported, defects such

corrosion inhibition and/or autonomous repair. Sacrificial anode-based

as a scratch in the coating may be protected over long distances

cathodic protection and barrier properties can also be tailored to

We will now discuss some recent computational and experimental


simultaneously in a single metallic coating. The desired properties

OCTOBER 2008 | VOLUME 11 | NUMBER 10

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Corrosion-resistant metallic coatings

Fig. 1 Schematic of a structural high-strength precipitation age-hardened alloy (in this case AA 2024-T351, a AlCuMg alloy) protected against corrosion by a
system comprising a AlCoCe 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
AlCoCe 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

vapor deposition, pulsed thermal spray (PTS), cold spray (CS), and

electric field created by the galvanic couple between the coating and

mechanical cladding are alternative methods to avoid excessive

the substrate can be manipulated to augment transport of inhibitors

temperatures. Numerous nonequilibrium alloying techniques may also

over large distances. To demonstrate this possibility we discuss a

be employed to add beneficial alloying elements in significant enough

specific nanoengineered, spray-applied, amorphous metallic alloy

concentrations to have a major impact on properties. Corrosion barrier

(Fig. 1) that illustrates some of the mitigation strategies and functions

properties can be improved by several routes. Minimizing structural

desired and achievable using a nanoengineered metallic coating such

defects such as intermetallic and metalloid phases and optimization

as a corrosion-inhibiting system. The challenges and issues involved in

of certain compositions in solid solution both usually significantly

achieving these functions are highlighted.

improve corrosion barrier properties. Therefore, methods to produce


supersaturated solid solutions which lack intermetallic and metalloid

16

Materials and fabrication of tunable


amorphous metallic coatings

phases are highly desired. By using metallic glasses, metallic elements

The challenges of tailoring the properties of metallic coatings compared

although not unlimited, flexibility, and then solidified and trapped

to polymer-based coatings are numerous. In the case of polymers,

below Tg to achieve chemically homogeneous solid solutions. Moreover,

a micrometer- or nanometer-scale composite can be created by

active corrosion inhibitors might be supplied if some of the added

mixing in the liquid state, and thus with great flexibility, a monomer,

alloying elements can function in this capacity. Amongst the possible

resin, filler, solvent, etc., and a phase encapsulating the inhibitor

replacements for Cr(VI)2327, transition metal (TM) and rare-earth (RE)

(e.g. strontium chromate pigment) in a slurry that is then reacted in

metal ions (Co2+, MoO42 and Ce3+) are possible choices to inhibit

may be added or mixed in a soluble liquid solution with improved,

various ways and solidified in a rigid state below the polymer glass

localized corrosion of Al alloys2325 and steels2627. These elements

transition temperature, Tg. In contrast, metallic coatings are often

also can be alloyed to form Al-based metallic glasses. RE metal ions

applied at high temperatures and involve delivering a liquid metal via

may serve as inhibitors if they can be incorporated and released by

either a hot dip or spray process. Such heating may adversely alter

a chemical or electrochemical process. Alloying a crystalline metal

the microstructure of the underlying alloy. Physical and chemical

with these elements is traditionally difficult because of their limited

OCTOBER 2008 | VOLUME 11 | NUMBER 10

Corrosion-resistant metallic coatings

REVIEW

solubility in the solid state28. This problem can be overcome by using

wide range of Co and Ce compositions, as seen in Fig. 238. The alloys

a glassy alloy that dissolves these alloying elements in solid solution.

amorphous state is very stable.

Indeed, certain AlTM and Alrefractory metal alloys29,30 can exhibit

High-velocity oxygen-fuel spray (HVOF), CS and PTS methods

enhanced local corrosion barrier24 and sacrificial anode-based cathodic

are possible deposition methods to apply such coatings. PTS utilizes

protection qualities31,32. The AlRETM alloy series is of particular

high heating and large quenching rates, which allows for either

interest because of its good glass-forming abilities33,34, high strength,

amorphous or crystalline powder feedstock material (Fig. 3) to develop

low density, and superior corrosion

properties3537.

In fact, a new amorphous AlCoCe alloy system was recently

an amorphous or nanocrystalline coating on a substrate material.


The structure of the feedstock material tends to dictate the resulting

synthesized3840 as an environmentally compliant metal coating with

structure of the coating. The coating powder and deposited layer

multiple corrosion protection functionalities4143. The notion of a

are shown in Fig. 4ad. The feedstock powder is often supplied as a

multifunctional metallic coating need not be restricted to AlTMRE

controlled particle size distribution ranging from 0.5 to 20 m, although

and there are likely to be many alloys that can be designed following

larger powder sizes can be attempted (Fig. 4a). PTS is distinguished

these general strategies. The goal was to simultaneously provide a

by rapid particle acceleration and heating, a minimal residence time

corrosion barrier, sacrificial anode-based cathodic protection42,44, or

within a high enthalpy environment, and rapid particle quenching

prevention44

upon interaction with the target substrate52,53. The quenching rate

as well as active corrosion protection (e.g. contain and

deliver a supply of inhibiting cations that can be released to suppress

for particles less than 20 m in size can be as high as 106 K/s54. Also

corrosion) to minimize corrosion at coating defects that expose the

notable is that naturally aging precipitation age-hardened aerospace

underlying structural alloy4547. Fig. 1 highlights this overall strategy.

alloys, such as the AA 2024-T3 substrates, do not exceed 60 C during

Cathodic protection abilities may also be optimized by lowering the

the coating process54. Reduced substrate thermal loading enables short

OCP of the coating relative to the underlying substrate. For instance,

stand-off coating capability that, from an application standpoint, is

the OCP of the AlCoCe alloy can be lowered as much as 750 mV

desirable because it allows for localized repairs of the coating where

below that of AA 2024-T3 depending on the alloy composition and

a physical defect exists exposing the underlying structural alloy and

solution

pH41,4850.

Amorphous Al alloys also have the ability to store

gives the capability for coating complex geometries55. The pulsed spray

beneficial alloying elements in solid solution. For instance, the selected

stream rasters over the surface of the substrate in such a way that the

transition and RE metals (e.g. Ni, Fe, Co, Ce, Y, Gd) added as alloying

resulting spray-applied coating is actually a built-up series of layers.

elements improve amorphicity in concentrations up to about 15 at.%.

PTS and HVOF coatings have the advantage of accepting the feedstock

Co, Ni, or Fe improve the resistance of Al to local corrosion, while

powder for these alloys in either crystalline or amorphous forms, as the

Ce3+, Y3+, and Gd3+ are good corrosion inhibitors when added as salt

feedstock particles can melt mid-process as long as powders are small.

in aqueous solutions40,51. The amorphous alloy can be formed over a

The HVOF process has a large quench rate, similar to that of the PTS

Fig. 2 Map of AlCoCe alloy compositions that yield amorphous, amorphous/


crystalline, and crystalline nanostructures in the AlCoCe 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.)

Fig. 3 X-ray diffration patterns for the Al88Co10Ce2 feedstock powder, an asdeposited 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

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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 (AlCuMg 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 andeposited PTS coating surface showing inherent roughness. (Reproduced with permission from. 2007 J. Electrochem. Soc.)

process56. High-density samples with favorable corrosion properties


can be achieved5763. 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 methods6470.
AlCoCe alloy coatings have been produced by both HVOF and
PTS with thicknesses ranging from 75 to 600 m 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 AlTMRE 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

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OCTOBER 2008 | VOLUME 11 | NUMBER 10

Fig. 5 Comparison of Elog(i) curves for an as-deposited PTS AlCoCe 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 2 103 cm2. These results show that a PTS AlCoCe 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.)

Corrosion-resistant metallic coatings

REVIEW

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 Scheff polynomials based
on tests conducted on amorphous MSR of various AlCoCe alloys in 0.6 M
NaCl solution at neutral pH. The ERP of the AlCoCe 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.

Fig. 7 Predicted values of the open circuit potential (OCP) for the solid solution
AlCoCe alloy system over a range of solid solution Co at.% and Ce at.%
contents, utilizing a Scheff model with two inverse terms, demonstrating the
range of OCP possible within the AlCoCe alloy system. These OCP values are
compared to AA2024-T3 and Aermet 100 OCP values. These are alloys the
AlCoCe alloy might be designed to protect. The more negative OCP of the
AlCoCe 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 AlCoCe alloys in 0.6
M NaCl solution deaerated, at neutral pH.

composition. In one study of an AlCoCe alloy, three parameters

formation in an aggressive acidic solution. Therefore, optimization

were obtained from EI plots (tests performed in NaCl) (Fig. 5) to

of alloying elements produces the highest Erp values, with a complex

characterize corrosion properties over a flexible range of compositions.

dependency of Erp on alloy content. To optimize the composition so as

These were the OCP, the pitting potential, Epit, and the repassivation

to provide a barrier with the highest resistance to localized corrosion,

potential, Erp. Epit and Erp are indicators of the pitting resistance,

Co amounts should be relatively high (6-8 at.%), and Ce contents

while OCP helps forecast the galvanic corrosion behavior of an alloy

moderately low (3-5 at.%) in this particular alloy.

(e.g. potential driving force for sacrificial cathodic protection when


alloys where the composition is constrained to 100% were explored

Tunable sacrificial anode-based cathodic


protection in AlTMRE coatings

and two examples are shown in Figs. 6 and 744. Plots include possible

Sacrificial anode-based cathodic protection when two or more metals

substrate structural materials (AA 2024-T3, Aermet 100 steel, etc.).

are galvanically coupled is a potent electrochemical protection

The influence of Co on the OCP is based on Cos effect on the cathodic

method12. A coating that can polarize an exposed substrate material

kinetics of AlCoCe alloys. By increasing the reaction rate for both

just a few hundred millivolts below its OCP can lower its corrosion

the O reduction reaction (ORR) and the H evolution reaction (HER),

rate by a factor of 100 or more. It is often more useful to polarize

additions of Co in solid solution results in a higher OCP. The decrease

many structural materials that corrode by local corrosion mechanisms

in OCP associated with the addition of Ce is most likely due to the

such as pitting or intergranular corrosion above some critical threshold

suppression of the ORR by Ce. The positive influence of Co on Erp is

potential (i.e. Epit) to levels below this threshold potential. This is

coupled to a substrate). Various regression models suitable for use with

due to the decreased hydrolysis product of this

cation72,

probably

accomplished by engineering a galvanic couple potential below Epit or

resulting in a less aggressive pit environment and reduced anodic

Erp. This is called cathodic prevention. Unfortunately, the governing

dissolution rates of a AlCo solid solution. A complex trend with Co

properties needed to optimize cathodic protection or prevention

was seen. A parabolic shape also described the effect of Al and Ce

(material-dependent OCP, and electrochemical currentpotential

on Erp. These three elemental behaviors, when considered together,

characteristics) have previously only been optimized through trial and

describe a complex balance where Co and Ce reduce the aggressiveness

error. Moreover, parameters such as OCP are often rather inflexible

of the pit solution: Co lowers the dissolution rate while Al aids oxide

due to the limited choices of alloy composition and structure available.

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Corrosion-resistant metallic coatings

Extreme cathodic potentials are not desired because overprotection

galvanic couple potential distribution along the horizontal axis

can lead to adverse side effects such as H embrittlement, alkaline

of Fig. 8a and its proximity relative to the OCP of the AlCoCe

attack, and paint blistering. Therefore, tunable cathodic protection is a

coating and the AA 2024-T3 Epit. A figure of merit used is E, given

highly desired capability.

as (Epit 2024 Ecouple), where Ecouple is the interfacial galvanic couple

The flexibility in OCP achieved by selecting particular compositions


of the AlCoCe alloy system (Fig. 7) is extremely beneficial, as it

potential at the centerline of the scratch, CL (Fig. 8b). Effective cathodic


prevention design maximizes E. The maximum E that can be

enables application of varying degrees of cathodic protection. By

achieved during galvanic coupling is termed Emax and is defined by

choosing an AlCoCe composition with relatively low Co (3-5

Epit2024 Eocp of the AlCoCe alloy.


Fig. 9 shows the extent of polarization given by the parameter E

at.%) and low Ce levels (35 at.%) a sacrificial anode material can
be produced with a moderately low OCP value, to avoid cathodic

obtained for a variety of situations as a function of scratch width at

overprotection. An example is Al90Co5Ce5. The unique combination

a fixed sample length. The parameter E is shown as the ordinate for

of OCP values more negative than pure Aermet 100 or AA 2024-T3

each case, with the value of E at S = 0 being the theoretical Emax

along with an enhancement of barrier properties in the coating makes

(i.e. Epit-2024 EOCP, AlCoCe). The theoretical limit is approached for

this amorphous AlCoCe alloy particularly well suited to serve as

small scratches. A greater extent of protection can be achieved when

a protective coating material. The enhanced resistance to localized

the Cl concentration is low. The potential distribution model predicts

corrosion offered by this alloy results in greater Faradiac efficiency for

that substantial sacrificial cathodic prevention of an AA 2024-T3

the sacrificial material, extending the theoretical lifetime of protection

scratch could be achieved with a nanoengineered alloy coating.

compared to the AlZn and AlMg alloys used as Al alloy cladding

The extent of the sacrificial cathodic protection provided by the

materials.

AlCoCe alloys is a function of pH, Cl concentration, the cathodic

The sacrificial anode-based cathodic protection attributes sought

kinetics on the AA 2024-T3, and the Co content of the metallic

have been recently investigated by computational methods42,45,7375

coating. The metallic coating provides the best protection (i.e. largest

focusing on galvanic couples between a metallic coating and

cathodic polarization of the scratch) when it is tailored to contain a

exposed substrate under atmospheric

conditions73.

Fig. 8a shows

low Co content, and is exposed to either high or low pH solutions

how atmospheric exposure (a thin electrolyte layer) of a structural

of low Cl concentration. Finally, the combination of chemical and

Al alloy covered by a metallic coating with a scratch at the center of

electrochemical protection predicted by computational modeling

the sample Fig. 1) was modeled. A metric of the cathodic throwing

has been verified via experiments involving defects machined into

power of the sacrificially anodic AlCoCe alloy was taken as the

PTS AlCoCe 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 AlCoCe alloy coating (left) and AA 2024-T3 substrate (right)
exposed as a scratch in a thin electrolyte (e.g. corrosive solution) of thickness . 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 m in width while the total length of the coatingscratch
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 AlCoCe 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 ~ 35 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 m 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 5002500 m in halfwidth are protected, while half-scratch widths of 5000 and 3500
m 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.)

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


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 exchange7882.
Amorphous AlCoCe alloys enable pH-controlled release of corrosioninhibiting 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

Fig. 9 Cathodic polarization obtained with AlcladTM compared to the


AlCoCe 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 AlCoCe coating protects better
than AlcladTM as indicated by the larger E. This suggests that the AlCoCe
coating can protect bigger scratches by cathodic prevention. Moreover, a low
Co content (i.e. 01 > 35% Co > 79% Co ) in the AlCoCe alloy helps to
protect AA2024-T3 to a greater extent. (Reproduced with permission from
2007 J. Electrochem. Soc.)

time periods. This necessitates a high inhibitor capacity in the alloy

provided in experiments when the PTS coating is electrically coupled to

inhibitor is stored in the alloy and in its air-formed oxide layer in

the AA 2024-T3 substrate.

valence states that are useful for corrosion inhibition. Inhibitors are

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
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.
AlCoCe alloys releasing Ce3+ meet these requirements. The

released by pH-dependent chemical dissolution of the oxide or direct

On-demand active-corrosion inhibition based


on tunable AlTMRE alloy coatings

soluble at low pH, insoluble under neutral, and partially soluble under

Controlled-release technologies are often used to supply chemicals

alkaline conditions (Fig. 11) 13,84. Thus, a pH change can be exploited

at given rates76,77. Release often occurs upon contact with solution.

to trigger Co2+ and Ce3+ release. A pH change occurs during corrosion

oxidation of the metal2325 (Fig. 10). Ce and Co oxides are highly

Fig. 10 Schematic illustration of AlCoCe 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

Therefore, when a metal is scratched and a galvanic couple forms

Fig. 12 Computational model calculations of Ce3+ profiles in the electrolyte


phases (see Fig. 8a) with time and position over an AlCoCe 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 m 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.)

between the coating and newly exposed substrate, the pH will drop

on the AA 2024-T3 surface below a critical size43. This is important in

over the anodic coating and rise at the cathodic scratch site. pH-

aerospace structural materials, such as fuselage and wing skins, because

dependent release rates were found for AlCoCe(Mo) alloys41

large corrosion pits above approximately 110 m greatly reduce fatigue

(Fig. 11). The inhibitor ions released diffuse and then migrate towards

life85,86.

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.

the damage site, reach Ccrit and suppress corrosion (Fig. 10). When
corrosion of the structural alloy stops, the pH of the environment

Summary

returns to neutral and Ce3+ is subsequently released at much lower

A multifunctional amorphous alloy has been described that possesses

rate.

three corrosion protection abilities when deployed as a coating over

Computational

studies42,45,7375,

have also been used to study

structural alloys. The coating (i) functions as a local corrosion barrier,

inhibitor release from such metallic substrates. Studies of inhibitor

(ii) serves as a sacrificial anode, and (iii) supplies soluble ions used as

release, transport, and achievement of Ccrit were conducted with and

corrosion inhibitors by engineering metallurgical and electrochemical

without migration through the electrolyte phase. Migration-based

properties. The alloy system described is just one example of many

transport of

Ce3+

to the scratch occurs due to the potential difference

exciting new possibilities in metallic coatings enabled by the progress

established between the OCPs of AA 2024-T3 and the AlCoCe

in amorphous and nanocrystalline alloy development, as well as novel

metallic coating. The time needed to reach Ccrit over the scratch was

synthesis and coating deposition methods. In the case presented,

determined, accounting for both transport processes as well as the

excellent inherent resistance to corrosion is achieved through

effect of temporal and position varying local release rates. Fig. 12

structural amorphicity and choice of composition to optimize corrosion

shows how the released Ce3+ profile develops with time and position in

functions. For instance, tunable electrochemical and chemical throwing

one example. Migration aids Ce transport (for OCPAlCoCe < OCPAA2024),

powers to achieve long-range protection of substrate defects can be

explaining the uphill transport of Ce3+. The Ccrit,Ce is reached at the

achieved. These concepts are generic and other alloys can in principle

coatingscratch interface at various times for different scratch lengths.

be developed to optimize these functions. Such alloys can also be

Accumulation was limited by ionic transport.

manipulated to enable transport of inhibiting cations by both migration

In summary, corrosion inhibition of a AA 2024-T351 scratch can

and diffusion. Inhibitor release can be triggered on-demand.

be achieved with ions released from a metallic coating. Experimental


exposure of AA 2024-T3 in a corrosive solution near an electrically

Acknowledgments

isolated Al87Co7Ce6 alloy confirmed computational modeling. The

A Multi-University Research Initiative (Grant No. F496020110352)


entitled The Development of an Environmentally Compliant Multifunctional

Ce3+ supplied significantly decreased the maximum corrosion pit sizes

22

OCTOBER 2008 | VOLUME 11 | NUMBER 10

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

REVIEW

with Enigmatics, Inc. and SAIC. In particular, the support and insight of Ben
Gauthier and Schmuel Eidelman is greatly appreciated. Additional financial
support was provided by the National Science Foundation DMR-NSF-0504983
under the direction of Harsh D. Chopra.

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