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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
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and repair damage and also regrow over a defect that exposes
metals and alloys. Successful native passive films can form a protective
layer over many metals if the ingredients for passivation (i.e. alloying
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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
atmosphere) over the coating. The electric field in the ionic solution
property6
anode and the unprotected site as well as the geometry and ionic
barrier12
alloys14,15
AA
2024-T317,
inefficiency.
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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)
vapor deposition, pulsed thermal spray (PTS), cold spray (CS), and
electric field created by the galvanic couple between the coating and
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mixing in the liquid state, and thus with great flexibility, a monomer,
metal ions (Co2+, MoO42 and Ce3+) are possible choices to inhibit
various ways and solidified in a rigid state below the polymer glass
either a hot dip or spray process. Such heating may adversely alter
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high heating and large quenching rates, which allows for either
properties3537.
and there are likely to be many alloys that can be designed following
prevention44
for particles less than 20 m in size can be as high as 106 K/s54. Also
solution
pH41,4850.
gives the capability for coating complex geometries55. The pulsed spray
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
PTS and HVOF coatings have the advantage of accepting the feedstock
Ce3+, Y3+, and Gd3+ are good corrosion inhibitors when added as salt
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 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.)
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(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.)
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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.
These were the OCP, the pitting potential, Epit, and the repassivation
potential, Erp. Epit and Erp are indicators of the pitting resistance,
and two examples are shown in Figs. 6 and 744. Plots include possible
just a few hundred millivolts below its OCP can lower its corrosion
cation72,
probably
of the pit solution: Co lowers the dissolution rate while Al aids oxide
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at.%) and low Ce levels (35 at.%) a sacrificial anode material can
be produced with a moderately low OCP value, to avoid cathodic
materials.
coating. The metallic coating provides the best protection (i.e. largest
conditions73.
Fig. 8a shows
(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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valence states that are useful for corrosion inhibition. Inhibitors are
soluble at low pH, insoluble under neutral, and partially soluble under
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.
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between the coating and newly exposed substrate, the pH will drop
over the anodic coating and rise at the cathodic scratch site. pH-
(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.
the damage site, reach Ccrit and suppress corrosion (Fig. 10). When
corrosion of the structural alloy stops, the pH of the environment
Summary
rate.
Computational
studies42,45,7375,
(ii) serves as a sacrificial anode, and (iii) supplies soluble ions used as
transport of
Ce3+
metallic coating. The time needed to reach Ccrit over the scratch was
shows how the released Ce3+ profile develops with time and position in
achieved. These concepts are generic and other alloys can in principle
Acknowledgments
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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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