ACCELERATED CORROSION AND ADHESION ASSESSMENTS OF CARC

PREPARED ALUMINUM ALLOY 2139-T8 USING THREE VARIOUS

PRETREATMENT METHODS AND TWO DIFFERENT PRIMER COATINGS

Brian E. Placzankis and Elizabeth A. Charleton

U.S. Army Research Laboratory, (RDRL-WMM-C)
4600 Deercreek Loop
Aberdeen Proving Ground, MD 21005-5066

Amy L. Fowler
U.S. Naval Air Warfare Center
NAVAIR, Code 4.3.4.2
48066 Shaw Road, Bldg. 2188
Patuxent River, MD 20670-1906

ABSTRACT

Aluminum alloy 2139-T81 panels of 0.25” thickness were machined from 1.0” rolled plate and
coated in accordance with Chemical Agent Resistant Coating (CARC) specifications2 for evaluation
using three different pretreatment conditions. The pretreatment conditions were abrasive blasted, a
chromium free pretreatment (CFP), and a commercial trivalent chromium pretreatment (TCP). The
pretreatment conditions were evaluated using two different primers, MIL-DTL-0053022C3 and MIL-
PRF-23377J4 Class N. Both sets of primer panels were then topcoated using the polymeric bead based
MIL-DTL-530395 Type II. Additionally, limited evaluations were performed using MIL-PRF-227506
interior coating. Corrosion resistance was evaluated under GM 9540P7 and ASTM B 1178 neutral salt
fog (NSF) methods. Adhesion was assessed under dry conditions using the ASTM D 45419 pull-off test
method and under wet conditions in accordance with ASTM D3359A10. Prior to coating, conversion
coated surfaces were compared for uniformity and color versus identically prepared AA2024-T311 and
AA2519-T8712 samples to determine whether or not the alloy differences would warrant modifications
to current pretreatment processes.

Keywords: Corrosion, Aluminum, Armor, 2139-T8, Cyclic, GM 9540P, Salt fog, Adhesion, Pull-off

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 INTRODUCTION

Current U.S. Army and Marine Corps vehicle deployments require improved survivability and
lightweight armor designs to maintain mission performance. Historically, armor alloys such as
AA5083-H13113 then followed by ever-stronger alloys such as AA7039-T6414, and AA2519-T87 have
been used in armor systems such as the M113, the M2 Bradley, and the USMC Expeditionary Fighting
Vehicle (EFV) in accordance with their corresponding Military Specifications. The ever-increasing
threat levels in current operations have driven development and qualification15 of new or improved
aluminum alloys for armor applications such as AA5059-H13116 and AA2139-T8. These improved
alloys provide improved ballistic protection versus armor piercing threats and can also derive lighter
weight hull designs from their increased yield and tensile strengths. The corrosion resistance for the
newer alloys can vary significantly depending on the main alloying chemistry. Little or no accelerated
corrosion characterization or long-term atmospheric exposure data exists for these materials when fully
coated. A recent U.S. Army study characterized the performance of AA5059-H13117 for accelerated
corrosion and adhesion when coated with a typical CARC based Army coating system. While that paper
represented a good start, additional studies are still needed to characterize other alloys new to armor
such as 6061-T618 and 2139-T8 that will be increasingly used in future systems. This study will focus
on AA2139-T8 and will include accelerated corrosion and adhesion evaluations of both U.S. Army and
Marine Corps CARC coating systems.
Unlike strain hardened 5000 series armor aluminums such as AA5083, AA5059, or AA5456,
AA2139 derives its strength through precipitation hardening incorporating particles rich in copper,
silver, and manganese. The development of aluminum alloy 2139 originally arose from a NASA funded
investigation to develop and improve the processing of aerospace aluminum alloys19. The goal of the
study was to engineer a high strength, high fracture toughness 2xxx alloy in an artificially aged
condition (T6 or T8 temper) for damage tolerant applications with durability properties comparable to
those occurring from alloys undergoing a naturally aged and cold working process (the T3 temper) 20.
Cho and Bes20 noted that the strengthening phases in typical 2xxx series aluminum alloys are nucleated
heterogeneously; and when such alloys are artificially aged to obtain their maximum strength, the
precipitates tend to nucleate at dislocations, sub-grain and to grain boundaries. Such grain boundary
precipitation can limit the damage tolerance capabilities of an alloy since it can result in the
intergranular failure of the material21. Conversely, 7xxx alloys rely on homogenous nucleation of the
precipitates which result in high strength, high fracture toughness materials without cold work, but can
be prone to stress corrosion cracking in the high strength (T6) temper21. Noting the work of Polmear22,23
who discovered alloying utilizing small amounts of magnesium (Mg) and silver (Ag) promoted
enhanced strengthening due to precipitates known as the ! phase, Cho and Bes 20 developed an
aluminum-copper-magnesium-manganese alloy of enhanced strength and fracture toughness. Cho24
noted that the ! precipitate forms homogeneously within the grains on the <111> plane21 and Nie et al.25
noted that plate-like precipitates on this plane have a greater impact on the strengthening of aluminum
alloys than precipitates on other planes. Since the ! phase precipitates homogeneously nucleate without
relying on grain boundaries or dislocation sites, aluminum 2139 is less prone to intergranular fracture
after artificial aging as compared to other 2xxx series alloys. In addition, the homogeneous nucleation
of the precipitate allows for a more uniform distribution of the precipitate throughout the alloy.
Therefore, the alloy does not rely on a large amount of cold work to achieve maximum strengthening.
This allows for the processing of thick plates without degradation in strength. As such, “2139 has the
precipitation strengthening characteristics of a 7xxx alloy system while having the benefits of a 2xxx
alloy system” 24 and was issued U.S Patent No. 7,229,5081. Alcan Rolled Products produces the
aluminum alloy 2139 at its Ravenswood, West Virginia, facility, which is capable of rolling plate from

2
1.0” (nominal) to 6.125” thick to date and is noted that thicker plates are possible. In addition, 2139
plates below 1.00” were added and are currently being rolled from ingots. Aluminum alloy 2139 is
registered at the Aluminum Association, comparisons of mechanical properties and chemical
composition between AA2139-T8 and other current qualified aluminum armor alloys26 are shown in
Tables 1 and 2.

TABLE 1: CHEMICAL COMPOSITION REQUIREMENTS FOR QUALIFIED MILITARY

SPECIFICATION ALUMINUM ARMOR ALLOYS (%)AND 2139 (%)12,13,14,16,18,20,26,27

TABLE 2: MINIMUM MECHANICAL REQUIREMENTS FOR MILITARY SPECIFICATION

ALUMINUM ARMOR ALLOYS AND 2139-T8 WITH DENSITIES12,13,14,16,18,20,26,27

*5456-H131 Mechanicals are greater than 5083-H131 and will be updated in upcoming MIL-DTL-46027 revision

The enhanced precipitation hardening in the AA2139 produces a significantly improved ballistic
material as noted by Cheeseman and Gooch et al.27 and this improved ballistic performance is plotted in
Figure 1.

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 Figure 1 – Strength and Ballistic Performance of 1” thick AA2139-T9 plate27

When compared versus existing current military specified armors, the AA2139-T8 still exhibits
significant pitting in corrosive environments similar to other armors such as AA251928. Images of
pitting comparisons between unprotected AA2519-T87 and AA2139-T8 under NSF and GM 9540P
cyclic corrosion are provided in Figures 2-5. It is thus imperative for this particular alloy to have the
best coating system possible to preserve the integrity of the armor substrate.

Figure 2: Bare and Untreated AA2139-T8 After Neutral Salt Fog

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Figure 3: Bare and Untreated AA2139-T8 After GM 9540P Cyclic Corrosion

Figure 4: Bare and Untreated AA2519-T8 After Neutral Salt Fog

Figure 5: Bare and Untreated AA2519-T8 After GM 9540P Cyclic Corrosion

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 EXPERIMENTAL PROCEDURE

The purpose of this study was to verify the corrosion durability of the AA2139 alloy when
coated with U.S. Army and USMC variations of CARC coating systems most likely to be used at
original equipment manufacturer (OEM) production facilities, and to determine what differences or
unforeseen issues may exist when AA2139 is used. The focus areas for these evaluations include
ASTM B 117 neutral salt fog corrosion, GM 9540P cyclic corrosion, ASTM D 4541 pull-off adhesion,
and ASTM D 3359A wet adhesion. Test panels measuring 4” x 6” x 0.25” thickness were machined and
water jet cut from 1.0” rolled plate. The one inch thick 4” x 6” “blanks” were bisected via saw and then
milled on the interior surface to the final 0.25” thickness. Based upon feedback from Program Manager
Heavy Brigade Combat Team29 (PM-HBCT), BAE Systems, General Dynamics Land Systems (GDLS),
and Program Manager Expeditionary Fighting Vehicle (PM EFV), a coatings matrix based upon likely
production line scenarios was devised. The matrix consisted of three different surface preparations:
abrasive blast, chromium free pretreatment (CFP), and trivalent chromium pretreatment (TCP).
Abrasive blast test panels were prepared using 60 grit aluminum oxide blast media producing a
consistent surface profile of 1.5 mils. Alodine 520030 was used for the CFP test panels and Metalast
TCP-HF31 was used for the TCP test panels. The Metalast pretreatment is a variant of the NAVAIR
developed TCP formulation and fully complies with both MIL-DTL-5541F32 and MIL-DTL-81706B33
as a type II hexavalent chrome free variation. In addition, it is listed on the MIL-DTL-81706B Qualified
Products List34 (QPL).
Prior to applying the conversion coating, bare fasteners were incorporated in a select number of
test panels in order to examine accelerated galvanic corrosion effects. Three types of fasteners were
used: aluminum (AA2024-T4 slot round head machine screws), stainless steel (316 stainless hex head
machine screws), and titanium (Ti-6Al-4V hex head machine screws). Table 3 lists the coating
configurations used for the AA2139 panels with the mounted fasteners.

TABLE 3: COATING CONFIGURATION MATRIX FOR FASTENER SPECIMENS

The general configuration in regards to bolt and screw positioning on the AA2139 specimens
configured with fasteners is provided in Figure 6.

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Figure 6: AA2139 Galvanic Corrosion Panel Configuration (a) Front with coated fasteners and (b) Back
with exposed fasteners, Red Arrows Point to Titanium Fasteners, Yellow Arrows to Stainless Steel, and
Green Arrows to AA2024.

All conversion coating test panels were hand-cleaned using MEK and then cleaned using a non-
silicated, non-chromated, mildly alkaline aluminum cleaner, for 5 minutes at 120 ºF. The panels were
then etched using a 20% phosphoric acid etch bath at 140 ºF for 30 seconds followed by a non-
chromated ferrous sulfate/nitric acid based desmutter for 10 seconds at ambient conditions. The CFP
was spray applied for 1 minute at ambient conditions and TCP (25%) was spray applied for 5 minutes at
90 ºF. All test panels were given a final deionized water rinse following completion of conversion
coating application. The process flow diagram used for CFP and TCP is illustrated in Figure 7.

7
 Figure 7: AA2139 Test Panel Conversion Coating Processing Flowchart

All of the primer and topcoats used were manufactured by Hentzen35. The primers consisted of
solvent based MIL-DTL-0053022, MIL-P-22750 (seafoam green) interior coating, and MIL-DTL-23377
Class N. The topcoat was 1 lb/gal volatile organic compound (VOC) 686 tan pigmented topcoat
formulation compliant with the new class of Type II low VOC and polymeric bead flattened topcoats
described under MIL-DTL-53039B. When the coatings were applied, additional care was taken to apply
these systems to the original exterior rolled surface of the test panel and not to the interior surface
exposed during machining operations.
The MIL-DTL-0053022 primers formed the basis of the Army coating systems and were
targeted at 1.5 mils dry film thickness (DFT). For the USMC coating system the MIL-DTL-23377N
primer was used and targeted for 0.8 to 1.2 mils. The actual thickness of MIL-DTL-23377N applied
was ultimately thicker due to an issue with the eddy current gage that produced a reading that was lower
than the actual thickness. When the measurement error was detected, the MIL-DTL-23377N primed
panel coating thicknesses were re-measured and determined to be 2.0 mils thick. The MIL-DTL-53039
topcoat thicknesses for the Army and USMC systems were applied to the 1.8 mil minimum thickness in
accordance with the specification. For the USMC interior coating system, only one pretreatment (TCP)
was used. The primer for this system was the MIL-DTL-23377N applied identically to the exterior
panels followed by application of MIL-PRF-22750 interior epoxy as a topcoat at a minimum thickness
of 1.7 mils. Per standard production procedures, coating thicknesses on the abrasive blast panels were
adjusted upwards to accommodate the 1.5 mil abrasive blast profile.
After 1 week of cure time, 5 replicates each of test panels for neutral salt fog (ASTM B 117) and
cyclic accelerated corrosion (GM 9540P) were scribed with an “X” using a carbide tipped hardened steel
scribe and placed into their respective chambers. A Harshaw Model 22 test chamber was used for NSF
testing and an Attotech Model CCT-NC-20 was used for cyclic testing. The NSF operating parameters
were in accordance with ASTM B 117, 95ºF with saturated humidity and atomized fog of 5% NaCl
solution. The cyclic accelerated corrosion test was in accordance with GM 9540P consisting of 18
separate stages including the following: saltwater spray, humidity, drying, ambient, and heated drying.
The environmental conditions and duration of each stage for one complete cycle are provided in Table 4.

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 TABLE 4: GM 9540P CYCLIC CORROSION TEST DETAILS
Interval Description Time (min) Temperature (±3C)
1 Ramp to Salt Mist 15 25
2 Salt Mist Cycle 1 25
3 Dry Cycle 15 30
4 Ramp to Salt Mist 70 25
5 Salt Mist Cycle 1 25
6 Dry Cycle 15 30
7 Ramp to Salt Mist 70 25
8 Salt Mist Cycle 1 25
9 Dry Cycle 15 30
10 Ramp to Salt Mist 70 25
11 Salt Mist Cycle 1 25
12 Dry Cycle 15 30
13 Ramp to Humidity 15 49
14 Humidity Cycle 480 49
15 Ramp to Dry 15 60
16 Dry Cycle 480 60
17 Ramp to Ambient 15 25
18 Ambient Cycle 480 25

The standard test solution consisting of a mixture of 0.9% NaCl, 0.1% CaCl2, and 0.25%
NaHCO3 was used. In addition the cyclic chamber was calibrated with standard steel mass loss
calibration coupons as described in the GM 9540P test specification. Uncoated 1.5” x 1.5” x 0.25”
2139-T8 and AA2519-T87 test panels were added as controls to assess and compare the relative inherent
corrosion resistance of the unprotected alloys.
In order to quantify the corrosion, all panels were numerically rated for scribe corrosion
creepback damage at scheduled intervals in accordance with method ASTM D 1654.36 The NSF panels
were rated initially at 200 hours, 3 weeks (504 hours), and then every three weeks henceforth until 1000
hours. The cyclic panels were rated at 10 cycle intervals. To facilitate easier viewing of the data, color
codes were assigned to the tables based upon ranges of the ASTM D 1654 ratings. Table 5 depicts the
ASTM D 1654 rating parameters and also defines the colors and their respective rating ranges.

TABLE 5: EVALUATION AND COLOR CODING OF SCRIBED COATED SPECIMENS

SUBJECTED TO CORROSIVE ENVIRONMENTS (ASTM D 1654)

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In cases where blistering occurred in regions away from the scribe, cross-hatching was assigned to the
color coded data cells in the data tables. Accompanying images were obtained via 600 dpi digital
flatbed scans at recurring inspection intervals of 504 hours for NSF and every 20 cycles for cyclic.
Wet adhesion was performed in accordance with Method 6301 of Federal Test Method Standard
14137 and rated in accordance with ASTM D 3359A. Previous studies17,38 on similar systems had
indicated good performance from the conversion coatings used in this study, therefore a more rigorous
form of the wet adhesion procedure was chosen. In this procedure, two replicates of each coating
system were immersed in deionized water undisturbed for 1 week at 150ºF. After one week, the panels
each were removed from the bath, patted dry with a lint-free wipe, then scribed and tested for wet tape
adhesion using diagonal incisions in addition to the normal parallel scratches to form two connecting
“V” intersections. The specimens’ surfaces and the corresponding adhesive sides of the removed tape
were examined to determine the extent of coating removal using the rating system for from ASTM D
3359A is described in Table 6.

TABLE 6: WET ADHESION RATING – METHOD ASTM D 3359A

Rating Description of Coating After Tape Removal
Method A - Wet Adhesion
5* No peeling or removal. (*Passes Military Performance Criteria)
4 Trace peeling or removal along scribes.
3 Jagged removal along scribes up to 1/16 in. (1.6 mm) on either side.
2 Jagged removal along most of the scribes up to 1/8 in. (3.2 mm) on either side.
1 Removal from most of the area between the scribes under the tape.
0 Removal beyond the area of the scribes.

The immersion specimens were of sufficient area to enable two measurements per panel for a total of
four measurements per coating system.
Pull-off adhesion measurements assessing the adhesion performance of the primer to surface
preparation and/or pretreatments were performed in accordance with ASTM D 4541. The MIL-DTL-
53039 topcoat was not included in this evaluation after it was found in previous studies17 to possess a
cohesive strength that was substantially lower than the bond strength of the primer to the pretreatment
and substrate interfaces. An Elcometer Model 108 Hydraulic Adhesion Test Equipment (HATE) was
used for this procedure. In addition to being a more quantitative test method, pull-off adhesion is also
less prone to inevitable human influences in testing such as variations in pressure applied during
scribing as well as interpretation and perception of results. For the pull-off adhesion test, a loading
fixture commonly referred to as a “dolly” is secured normal to the coating surface using an adhesive.
For pull-off data to be valid, the specimen substrate must be of sufficient thickness to ensure that the
coaxial load applied during the removal stage does not distort the substrate material and cause a bulging
or “trampoline effect.” If a thin specimen is used, the resultant bulge causes the coating to radially peel
away outwards from the center instead of being uniformly pulled away in pure tension. Thus, the use of
a thinner substrate results in significantly lower and erroneous readings than for identically prepared
specimens at greater substrate thickness. At 0.25 inches, all of the AA2139-T8 armor panels evaluated
had adequate thickness for valid pull-off test results. For this study, a higher performance thermal
setting polyamide-epoxy known as FM®1000 by Cytec39 was used after performance of cyanoacrylate-
based adhesives was found inadequate. Coating failure tensions (in psi) were recorded with
accompanying failure modes characterized. For measurements where adhesion measurements exceeded
the 3500 psi maximum range of the instrument, the readings were recorded as >3500 psi. In order to

10
capture a statistically meaningful numerical assessment of coating adhesion, a minimum of 30 pull-off
data points were collected for each of the coating configurations. A cross-sectional diagram of the pull-
off test apparatus with dolly is illustrated in Figure 8 with laboratory conditions for adhesive bonding to
the coatings listed in Table 7.

Figure 8: Pull-Off Hydraulic Adhesion Test (ASTM D 4541)

TABLE 7: LABORATORY CONDITIONS FOR PULL-OFF ADHESION ASTM D 4541

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 RESULTS

Processing and Coating Application

An additional goal of this study was to assess the AA2139 alloy from a processing standpoint
with the ultimate goal of production in mind. The abrasive blast and conversion coating process steps
were found to be most similar to AA5059 and AA2519 from a processing standpoint. For the Metalast
TCP-HF there was even the added bonus of a more distinct color change to the substrate produced by
the conversion coating. The Metalast TCP-HF formed a significantly darker blue gray coating with
more of a matte appearance exhibiting less light reflectance on AA2139 vs. AA2519. This was similar
to the appearance differences noted in a previous study17 between AA5059 and AA5083 and is visible in
Figure 9.

(a) (b) (c) (d)

Figure 9: Metalast TCP-HF Color Change on (a) AA2139, (b) AA2519, (c) AA5059, and (d) AA5083

This more obvious color change is advantageous for production lines from a quality control standpoint
and will directly translate to improved assurance of complete conversion coating coverage prior to
application of the primer.

Wet Adhesion

As outlined in the procedure, a much more rigorous form of wet adhesion testing was
conducted. With the exception of the Army coating system prepared by abrasive blasting, there was no
removal whatsoever of coating from any of the conversion coated panels after a full 7 days of immersion
in deionized water at 150 ºF when the tape was removed. All of these panels were assigned a rating of
5A, a perfect rating, which is fully compliant with the performance level set for military applications.
Although it was very minute, the abrasive blast prepared Army panels had coating removal at the sharp
vertices of the incisions and clearly performed worse than all of the other coating systems. While they

12
were certainly still rated a 5A according to the strictest interpretation of ASTM D 3359A they were
clearly and consistently still worse than all of the other coating systems. The wet adhesion data are
listed in Table 8, and representative scans of the results including the visible removal on the abrasive
blasted Army coating system are presented in Figures 10 - 16.

TABLE 8: EXTENDED WET ADHESION RESULTS FOR COATED AA2139-T8 AT 150ºF

Figure 10: Representative Scan of Army CARC System over NCP Treated 2139 After One Week
Deionized Water Immersion at 150 ºF Showing Surface Incisions and corresponding test tape back
sides, all rated at 5A per ASTM D 3359A.

13
 Figure 11: Representative Scan of Army CARC System over TCP Treated 2139 After One Week
Deionized Water Immersion at 150 ºF Showing Surface Incisions and corresponding test tape back
sides, all rated at 5A per ASTM D 3359A.

Figure 12: Representative Scan of Army CARC System over Grit Blast Processed 2139 After One Week
Deionized Water Immersion at 150 ºF Showing Surface Incisions and corresponding test tape back
sides, showing some removal at sharp vertices but still all rated at 5A per ASTM D 3359A.

14
Figure 13: Representative Scan of USMC CARC System over NCP Treated 2139 After One Week
Deionized Water Immersion at 150 ºF Showing Surface
Incisions and corresponding test tape back sides, all rated at 5A per ASTM D 3359A.

Figure 14: Representative Scan of USMC CARC System over TCP Treated 2139 After One Week
Deionized Water Immersion at 150 ºF Showing Surface
Incisions and corresponding test tape back sides, all rated at 5A per ASTM D 3359A.

15
 Figure 15: Representative Scan of USMC CARC System over Grit Blast Processed 2139 After One
Week Deionized Water Immersion at 150 ºF Showing Surface
Incisions and corresponding test tape back sides, all rated at 5A per ASTM D 3359A.

Figure 16: Representative Scan of USMC Interior CARC System over TCP Treated 2139 After One
Week Deionized Water Immersion at 150 ºF Showing Surface
Incisions and corresponding test tape back sides, all rated at 5A per ASTM D 3359A.

Pull-off Adhesion

As in the wet adhesion results, the pull-off adhesion performance was also exceptional. All of the
readings taken for the Army primer system using either CFP or TCP pretreatments exceeded the 3500
psi limit of the pull-off instrument and were simply listed as >3500psi. In addition, the vast majority
(27/31) of the pull-off measurements for the abrasive blast prepared Army primer panels also exceeded
the 3500 psi limit. There was significantly more variability in adhesion readings for the USMC
prepared coating specimens. While there were still many pull-off readings in excess of 3500 psi, the
majority of measurements were lower than the typical 3500 psi Army specimen readings. This
discrepancy was most likely due to mechanical limitations of the MIL-PRF-23377J Class N primer
versus the MIL-DTL-0053022C primer. While indeed lower, these adhesion readings were still
excellent and never fell below 2000 psi. All pull-off adhesion data with pull-off failure modes are listed

16
in Tables 9-14.
TABLES 9 AND 10: PULL-OFF RESULTS CFP AND TCP FOR ARMY PRIMER

TABLES 11 AND 12: PULL-OFF RESULTS FOR ABRASIVE BLAST ARMY AND USMC

17
 TABLES 13 AND 14: PULL-OFF RESULTS CFP AND TCP FOR USMC PRIMER

Accelerated Corrosion

When compared with previous studies with similar coatings and surface pretreatments on
similarly corrosion prone AA2219,40,41 the AA2139 panels exposed to neutral salt fog (NSF) and cyclic
corrosion testing generally noted similar to better creepback ratings performance at the same exposure
durations. The creepback growth was from blistering with the blisters themselves all forming locally at
the edge of the scribes with a compact round geometry. With the exception of the Army abrasive blast
and the USMC interior epoxy coated specimens, the NSF exposed panels performed very well through
504 hours. Though performing worse versus the other preparations, the Army abrasive panels were
initially rated higher though 216 hours and still marginally higher at 504 hours versus previous data on
identically prepared AA505917 panels. This positive trend ended at 1008 hours and all 5 Army prepared
abrasive blast panels creepback measurements extended past 3mm dropping the ratings to 5, lower than
for similar specimens using the AA5059 alloy. Similarly, there was major creepback growth between
504 to 1008 hours for all of the other treatments with many of the panels ratings dropping from as high
as 9 all the way down to 6. Interestingly the Army prepared TCP panels that showed minor blisters
away from the scribe in early readings appeared to have stabilized at 1008 hours with respect to
creepback and blisters. With the exception of one panel, all previously detected blisters flattened and
were undetectable at 1008 hours. In addition, these panels had the lowest creepback distances and rated
7s with one 6 in all 5 replicates. The USMC prepared panels that seemed superior through 504 hours
were no better than the Army prepared panels by 1008 hours. With the exception of the Army prepared
panels, the TCP was no better at 1008 hours than the other processes with ratings of 6 across all 5
replicates of the USMC prepared panels. The abrasive blasted USMC coated panels initially fared much

18
better than the Army abrasive blast specimens with consistent “9” ratings across all 5 replicates as late
as 504 hours but similar to the other panels had dropped back to “6” ratings by the 1008 hour
measurement interval. The MIL-PRF-22750F interior epoxy prepared panels began strong with ratings
of “9” at 216 hours but rapidly dropped in creepback performance ratings of “6” across all replicates by
504 hours in spite of their TCP pretreatment. It must be noted that the NSF data for the MIL-PRF-
22750F interior epoxy topcoated panels lags the other specimens by 504 hours due to a measurement
error where the panels were not returned to the chamber with the rest of the matrix after they were
scanned. These panels will be run for the additional time and results will be reported in a later study
with longer-term accelerated exposure data for all of the systems. Figure 17 shows a scan of one of the
Army abrasive blast replicates with a 5X magnification of the round blisters.

(a) (b)
Figure 17: (a) Army Abrasive Blast Panel at 1008 Hours NSF With Round Creepback
Blister, Rated at ASTM D 1654 “5”, (b) Magnified 5X.

The order of performance after 1008 hours was: the Army coating system with TCP, a 3 way tie
between all of the USMC coating systems, Army with CFP, and Army abrasive blasted. The USMC
prepared panels with the interior epoxy topcoat were 504 hours behind but rated worst when they were
compared versus the other systems at 504 hours. The creepback performance ratings for the NSF
exposures of coated AA2139 through 1008 hours are tabulated in Table 15.

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TABLE 15: ASTM D 1654 CREEPBACK RATINGS FOR ASTM B 117 NSF ON COATED AA2139*

* Cross-hatching is used if blistering away from scribe occurs

Referring again to the previous studies on AA2219, as previously observed there was again
significantly more corrosion damage produced in GM 9540P on AA2139 versus damage levels typically
observed for coated 5000, 6000, and 7000 series aluminum alloys. Notable exceptions were the TCP
prepared panels for both the Army and the USMC prepared coating systems that were still performing
exceptionally well with ratings of “8” across all replicates at 50 cycles in contrast to the CFP and
abrasive blast prepared panels with mostly “5” and “6” ratings. Instead of the round blisters observed
under NSF, the creepback blistering damage was more filiform and much more evenly distributed along
the scribes. While these “5” and “6” readings were indeed lower versus typical values observed on
5000, 6000, or 7000 series alloys, even these ratings were better than the values observed in the previous
studies for similar exposure durations on AA2219. As of 50 cycles, the order of performance from best
to worst was the Army coating system with TCP, the USMC system with TCP, USMC with abrasive
blast, Army abrasive blast, Army with CFP, and USMC with CFP. Figure 18 compares one of the best
performing systems, an Army TCP processed panel with one of the worst, a USMC processed CFP one.
In addition Figure 18 includes a 4.5X zoom on a portion of the scribe with obvious filiform damage. The
complete creepback performance ratings for the cyclic exposures of coated AA2139 through 50 cycles
are listed in Table 16.

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 (a) (b) (c)
Figure 18: (a) Army TCP Panel at 50 Cycles Rated at ASTM D 1654 “8” (b) USMC CFP Panel at 50
Cycles (c) 4.5X Magnification of USMC CFP Panel at 50 Cycles with Filiform Creepback Blistering,
Rated at ASTM D 1654 “5”

TABLE 16: ASTM D 1654 CREEPBACK RATINGS FOR GM 9540P CYCLIC CORROSION

Accelerated Corrosion of Fasteners

For each galvanic panel with fasteners there were two sets for each fastener material. When
observations were taken the fastener set (bolt, washer, and nut) was referred to as “set a” for the top set

21
or “set b” for the lower set. Tables 17 lists the observations for NSF and cyclic exposures using a color
code scheme. The code system used “green” for no damage, “yellow” for blistering of the Army or
USMC CARC system in proximity to the fastener, and red for complete rupture of the coating system
and/or appearance of green copper based corrosion products from the AA2139 substrate indicating
galvanic corrosion attack.

TABLE 17: GALVANIC CORROSION RESULTS FOR NSF AT 1008 HOURS AND GM9540P
CYCLIC CORROSION AT 50 CYCLES

For the various fasteners mounted in the AA2139 there was far less galvanic corrosion damage
in the GM 9540P cyclic specimens than on the NSF sets. The only visible damage was some small
blisters around the titanium fasteners with one exception of a small blister on the back adjacent to a
stainless steel fastener set. The corrosion was significantly more extensive in NSF exposures, especially
on the specimen backs. For both NSF and cyclic exposures the majority of the corrosion occurred on
the backsides where there was significant uncoated surface area of the fasteners exposed. Normally,
backsides of panels are not evaluated in accelerated corrosion however the rapid galvanic corrosion of
the exposed titanium and stainless steel fastener substrates in NSF and their differences were worthy of
attention. For the specimen front sides, the screw and hex heads were well protected by the coating
system. The front side blistering that was detected at 1008 hours most likely originated from the back
side and had likely corroded along the fastener mounting holes to produce the blistering visible on the
fronts. Galvanic attack was most severe for the titanium fasteners followed by the stainless steel
fasteners. The coating showed very little or no damage around the AA2024 fasteners but there was
corrosion of the AA2024 fasteners indicating near equal or perhaps even anodic behavior of the AA2024
set versus the AA2139 substrate. A close-up of this corrosion of the AA2024 fasteners from panel
“GAL1” is shown in Figure 20. Figures 19 compares the relative amounts of corrosion between the
different fastener compositions at 1008 hours of NSF and resultant front side blistering from severe
galvanic corrosion of the titanium fasteners and also the corrosion of the AA2024 fasteners.

22
 (a) (b)

(c)
Figure 19: (a) Comparison of Galvanic Corrosion Between the Fasteners; AA2024 (left), Stainless Steel
(middle), and Titanium (right), (b) Magnified View of Front of Lower Titanium Fastener Set With
Blisters, and (c) Corrosion Damage of AA2024 Fasteners After 1008 Hours of NSF

DISCUSSION

The goal of this study was to evaluate the compatibility of the AA2139-T8 substrate with CARC
coating systems that are relevant to current and future Army and USMC weapon platforms. As
expected, the greater vulnerability to corrosion inherent to the AA2139 alloy produced more measurable
results relative to the same exposure intervals for previous studies on the less active 5000, 6000, and
even 7000 series aluminum alloys. One bright spot was the excellent performance of the TCP
pretreatment for both Army and USMC coating systems under GM 9540P cyclic corrosion. This

23
performance was significantly better than it was under a previous study using an earlier version of the
same coating system on AA2219. Whether this improvement originates due to alloy differences,
technological evolution and maturing of the coating system, or a combination of both is unknown. What
can be stated is that the TCP pretreatment would be the preferable pretreatment process for optimum
corrosion resistance for this alloy irrespective of which primer type is used.
The correlation between the two accelerated corrosion methods was mixed. Of particular interest
is the apparent difference in limiting mechanisms between the NSF and the cyclic exposures. For the
first 500 hours in NSF, the corrosion (or lack of it) appeared to be more tied to the primer selection with
the MIL-PRF-23377J Class N prepared panels clearly performing better than Army primed counterparts.
Conversely, the cyclic exposures results appear to be much more conversion coating driven with TCP
treated panels performing much better through 50 cycles than CFP or abrasive blast prepared panels.
This relationship appeared to break down after 1000 hours when the MIL-PRF-23377J appeared to lose
much of its advantage versus the Army MIL-DTL-0053022C primer.
The galvanic corrosion sets using the fasteners behaved in a classic galvanic series manner with
the titanium hardware driving the most corrosion followed by the stainless steel sets and finally the
AA2024. The major differences in severity between NSF were likely due to the 100% wet time in NSF
versus the extensive drying intervals inherent to the GM 9540P procedure that inhibited the galvanic
reaction. The differences in galvanic potential between AA2139 and the fasteners are very significant,
between the titanium and stainless steel sets. As observed in this study and noted in a previous
NAVSEA study on AA2519, armor system hull designers will need to carefully consider their choice of
fastener materials as well as their configurations, especially if more noble fastener materials such as
stainless steel are selected.42 Figure 20 illustrates the extreme range in galvanic potential between
aluminum alloys, stainless steel, and titanium.

Figure 20: Galvanic Series Showing Approximately 0.7 - 1.0V Gap Between Aluminum (anodic)
vs. Stainless Steel and Titanium (cathodic) (ASTM G 82)43

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 As was obvious from the data, the timing of this study unfortunately means that this testing of
AA2139-T8 is still relatively early into its completion cycle with thousands more hours remaining to be
run in NSF as well as at least 80 more cycles of the cyclic exposure. Also, beachfront outdoor
exposures in Florida remain to be completed. Whether or not the initial mechanisms observed for
corrosion observed in each of the types of exposures used in this study will persist will need to be
revisited in a follow-on paper or technical report. Thus far into the study it does appear that the overall
best coating system for AA2139 is TCP treated with the MIL-PRF-23377J Class N primer. In addition,
the adhesion performance both wet and dry under pull-off conditions was excellent. In particular, the
wet adhesion performance across all replicates, even on abrasive blast without the conversion coating
was sufficient enough that Program Managers Offices (PMOs) such as the USMC Expeditionary
Fighting Vehicle can feel very confident in the robustness of the overall protective coating system
whether it uses the Army primer or the USMC preferred Navy primer. The CFP pretreatment while
quite useable on inherently corrosion resistant alloys such as AA5083, AA5059, or even AA6061 would
not be as applicable given the extensive pitting that AA2139 has in common with other 2000 series
alloys. The TCP is fully compliant as a Type II, hexavalent chromium free conversion coating under
MIL-DTL-5541. The previously referenced studies40,41 that also examined less corrosion resistant Al
alloys such as AA2024-T3, AA2219-T87, and 7075-T6 determined the performance of NAVAIR based
TCP variants to be greatest among any of the hexavalent chromium free conversion coatings. Similarly,
for this study TCP process is most recommended as a Cr+6 free conversion coating for use on 2000
series aluminum substrates such as AA2139. While AA2139 is improved in a number of areas including
ballistics and mechanical properties, similar precautions in regards to surface preparation and coatings
system selection used for AA2519 will ultimately also need to be taken to ensure the best protection for
AA2139.

CONCLUSIONS

1. AA2139-T8 did not display any negative compatibility problems with any of the CARC coating
components, processes, or the complete coating systems.
2. All coating systems provided superior wet and dry adhesion to the AA2139 substrate.
3. As observed in previous studies with 2000 series alloys, GM 9540P was significantly more
aggressive on coated AA2139 than on other aluminum alloys such as AA5083, AA5059,
AA6061, or AA7039 and behaved most similar to AA2219 and AA2519.
4. AA2139 is susceptible to galvanic attack from noble fastener materials such as titanium or
stainless steel under wet conditions. Extreme caution in fastener material selection and design
should be taken with this material.
5. The TCP pretreatment was superior to the CFP and abrasive blast processes, most notably in GM
9540P cyclic conditions and is recommended for AA2139-T8.

ACKNOWLEDGEMENTS

The authors wish to thank Drs. Bryan Cheeseman and Alex Cho of the U.S. Army Research
Laboratory for supplying the AA2139-T8 Plate. We also thank Thomas Braswell for the extensive
surface preparations and coating system applications necessary to prepare the test panel matrix.

25
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