CORROSION SCIENCE SECTION
Effect of Scribing Modes on Corrosion Test Results
H.K. Yasuda, C.M. Reddy, Q.S. Yu,* J.E. Deffeyes,** G.P. Bierwagen, and L. He***
ABSTRACT
A Prohesion salt spray corrosion test was carried out with
32 primer-coated AA2024-T3 (UNS A92024) test panels with
four different kinds of scribes (eight test panels each). The
scribing width and depth showed little effect on the test re-
sults. The extent of damage to the interface between the
primer and the substrate alloy produced the greatest influ-
ence on the test results. The concurrent electrochemical im-
pedance spectroscopy (EIS) measurement with Prohesion salt
spray showed that the sharp drop of the impedance modulus
at low frequency ( | Z |0.1Hz) for the samples scribed with a spin-
ning cutter tip started much earlier during the Prohesion ex-
posure than for samples scribed without spinning the cutter
tip. There was very little difference observed on the imped-
ance modulus values of the samples with different scribe
depth and width. The consistent results between the
Prohesion test results and EIS data suggest that the concur-
rent EIS measurement with Prohesion salt spray may provide
additional information pertinent to the corrosion protection
mechanisms involved in the coating under examination.
KEY WORDS: aluminum alloys, E-coat, electrochemical
impedance spectroscopy, scribing effect
INTRODUCTION
It is a well-established practice to test corrosion re-
sistance of a coated panel by exposing a scribed coat-
Submitted for publication March 2000; in revised form, August
2000.
* Center for Surface Science and Plasma Technology, University of
Missouri–Columbia, Columbia, MO 65211.
** The Boeing Company, St. Louis, MO 63166.
*** Department of Polymers and Coatings, North Dakota State
University, Fargo, ND 58105.
0010-9312/01/000007/$5.00+$0.50/0
CORROSION–Vol. 57, No. 1 © 2001, NACE International
ing layer to a corrosive environment, such as salt
spray, for a prolonged period of time.1 Corrosion
resistance of the coating is evaluated qualitatively by
examining the corrosion that took place near the
scribed line. Such a method certainly provides an
estimate of the coating’s level of corrosion resistance;
however, this method does not yield information
concerning the mechanisms of corrosion protection.2
Corrosion resistance of a coated metal sheet
could be considered dependent on at least five fac-
tors:3-5 (1) salt intrusion resistance of the top surface
of a coating,6-7 (2) barrier characteristics with respect
to water, salt, and other corrosive chemicals,7-8 (3)
function of passivating agents (if any),7-8 (4) level of
coating adhesion to the substrate,2,9 and (5) the sur-
face state of oxides on which the coating is applied.3,10
All of these factors are important when consider-
ing corrosion resistance of a coating that remains
intact (i.e., undamaged coating). When the surface
of a coating is scribed (damaged), the main barrier
characteristics of a coating described in (1) and (2)
are bypassed. Then the major factors are reduced to
(3), (4), and (5). Under such a condition, the exposed
coating/metal interface becomes the major factor.
The role of passivating agents or corrosion inhibitors
is focused on the exposed metal surface and the
new metal surface that will be exposed by the
corrosion-induced delamination of the coating near
the scribed line.
The scribing process exposes not only the sub-
strate metal but also the coating/metal interface.
Once the coating/metal interface is exposed to a salt
solution, the nature and extent of coating adhesion
29
CORROSION SCIENCE SECTION
to the substrate metal becomes the most important
factor dictating the occurrence of corrosion. The
importance of the water-insensitive adhesion in cor-
rosion tests was investigated recently by means of
electrochemical impedance spectroscopy (EIS).11 EIS
could detect the microscopic delamination of coating
without artificially introduced defects. EIS study is
extended in the present investigation to explore the
nature of scribing, specifically the damage to the
coating/metal interface. For this purpose, a severe
scribing method was included to cause interfacial
damage. Questions arise: Does a wider scribing width
cause more corrosion? Is a deeper scribing depth
more damaging? With this background information
in mind, 32 sheets of AA2024-T3 (UNS A92024)(1)
were coated with an electrocoat (E-coat) under the
identical conditions of coating and curing, and they
were divided into four groups of different scribing
modes. Four groups of scribed samples, in which
the only difference was the mode of scribing, were
exposed to Prohesion† salt spray testing in two
different locations. The coating of the slightly inferior
adhesion was used intentionally to magnify the
interfacial aspect. Results thus obtained are shown
in this paper.
EXPERIMENTAL PROCEDURES
Aluminum Alloy Panels and Surface Cleaning
The Al alloy panels (7.62 cm by 15.24 cm by
0.081 cm) used for the present study were AA2024-
T3 (2024 specifications are [wt%]: 0.5 Si, 0.5 Fe,
3.8 to 4.9 Cu, 0.3 to 0.9 Mn, 1.2 to 1.8 Mg, 0.1 Cr,
0.25 Zn, 0.15 Ti, 0.15 other, and remainder Al12)
procured from Q-Panel Lab Products.
The AA2024-T3 panels were first cleaned by
acetone (CH3COCH3) wiping with Kimwipes† to re-
move the ink marks and loose organic matter from
the surfaces. The chemical cleaning of the Al alloy
panels was performed by following the method pro-
vided by The Boeing Company. Alkaline solution of
Turco 4215S† was prepared and used per McDonnell
Douglas Process Specification PS 12030. Alkaline
cleaning of the panels was conducted by immersion
in an alkaline bath at 65°C (150°F) for ~ 25 min, or
until each panel became water-break free when
rinsed with deionized (DI) water; they were then
thoroughly rinsed with DI water.
Application of Primer
Electrodeposition of the E-coat (ED6650) was
carried out in a 1-gal E-coat bath at 90°F (32°C)
using the substrate as the cathode and a stainless
steel strip (3.81 cm by 25.4 cm) as the anode. A
(1)
UNS numbers are listed in Metals and Alloys in the Unified
Numbering System, published by the Society of Automotive
Engineers (SAE) and cosponsored by ASTM.
†
Trade name.
30
direct current (DC) power source with variable volt-
age facility was used for the electrodeposition. Elec-
trodeposition was carried out at 200 V for 2 min. The
electrocoated panels were then rinsed with DI water
to wash the undeposited E-coat from the surface.
Panels were dried in air for 30 min and cured in an
oven for 20 min at 325°F (163°C). After baking, the
thickness of cured E-coat was ~ 25 µm as measured
using an Elcometer† 355 with a nonferrous probe.
Scribing Procedures
Panels were scribed using a computerized
engraver, model Vanguard Unica†, with a cutter
42-037-000 Diamond Graver†. It was noted that the
cutter had the tip geometry shown in the schematic
diagram in Figure 1.
Two depths (0.02 in. [~ 0.05 cm] and 0.04 in.
[~ 0.10 cm]) of scribes were made using the cutter in
stationary or spinning modes. Because of the cutting
head geometry, a deeper cut yields a wider scribe
line. To distinguish the difference between scribe
modes, the scribe made in stationary mode (horizon-
tal dragging of the tip across the panel surface) was
defined as V-shaped, and the scribe made with a
spinning cutter tip was defined as U-shaped. The V
or U shape definition identifies different scribes, not
the real scribe shapes.
The scribe depth was controlled by adjusting the
depth increment of each scribe and the number of
scribes. Initially, the cutter position was zeroed on to
the panel surface to be scribed, and then panels were
scribed in increments of 0.25 mm (0.01 in.).
Prohesion Salt Spray
The scribed samples were divided into two
groups according to respective scribing modes, and
one group of samples was sent to Boeing and another
group to North Dakota State University (NDSU) for
Prohesion salt spray testing. Both labs carried out
testing according to the procedure described in ASTM
G85, A5.1 This test is performed with an electrolyte
solution (dilute Harrison’s solution) of 0.05% sodium
chloride (NaCl) and 0.35% ammonium sulfate
([NH4]2SO4) by mass. The duration of the test was
~ 12 weeks (2,000 h), which is the standard practice
followed at Boeing. The wet/dry cycle consists of a
1-h fog followed by a 1-h dry-off. The fog temperature
during the fog period is maintained at 25°C. The pH
of the collected solution is within the range of 5.0
and 5.4. The dry-off temperature throughout the ex-
posure zone is maintained at 35 ± 1.5°C. The dry-off
is achieved by purging with fresh air, such that
within .75 h all visible moisture is dried off of the
specimens. The condensate rate is maintained within
1 mL/h to 2 mL/h. ASTM G85, A5 does not mention
condensate rate, but these recommendations are
from the manufacturer of both labs’ test chambers,
Q-Lab Products.
CORROSION–JANUARY 2001
 CORROSION SCIENCE SECTION

Evaluation of Test Results

After completing test cycles in Prohesion salt
spray, the panels were rinsed with distilled water and
visual observations were made. Then, the panels
were subjected to a commercial paint stripper solu-
tion (Turco-5469†) to strip off the E-coat on the
scribed surface to expose the corrosion effect under-
neath the E-coat film and away from the scribe.

Concurrent EIS Measurement

and Prohesion Salt Spray
Samples tested at NDSU were examined concur-
rently with EIS measurement during the regular
Prohesion exposure period. During the 2,000-h
(83.3-day, 12-week) Prohesion exposure, the tested
panels were taken out of the chamber once a week, FIGURE 1. Schematic of the scribing cutter 42-037-000 Diamond
and the EIS measurements were performed on the Graver tip at 50X magnification.
unscribed parts of the scribed panels. The electro-
chemical measurements were taken over ~ 1 h, and
during this time the scribed area was exposed to lab
ambient conditions. EIS measurements were per-
formed in dilute Harrison solution (0.05% NaCl and
0.35% [NH4]2SO4 aqueous solution) using a Gamry†
potentiostat controlled by Gamry CMS 100† software.
Measurements were taken from 0.1 Hz to 5 kHz with
a 10-mV sign wave potential. Ten points were col-
lected per decade. The reference and counter elec-
trodes were a saturated calomel electrode (SCE) and
a platinum electrode, respectively. Figure 2 shows
the schematic of the sampling for EIS measurement
of scribed panels at NDSU. The circle between
the scribe lines is the sampling area for the EIS
measurements.

RESULTS AND DISCUSSION
Optical Microscopic Study
Figure 3 shows the optical microscopic pictures
of the four different scribes at 50X magnification.
As seen in Figure 3, flat scribes were produced by
stationary mode (designated as V-shaped), with
horizontal dragging of the cutter tip across the
panel surface. In contrast, spinning tracks were
clearly observed in the scribes made in spinning
mode (designated as U-shaped). Spinning left burrs
in the scribes and also produced wider scribes.
Since they exposed more surface area, the burrs
in the scribe may have had more chance to initiate
corrosion.
It should be noted that the V-shaped scribe
(stationary mode) is very similar to the knife-edge cut
of ASTM methods D1654 and D335913-14 in prepara-
tion of painted specimens for corrosion and adhesion
tests. Since the ASTM scribing methods are largely
dependent on individual operators, the scribing by an
automated engraver machine, as used in this work,
may have provided a more consistent and uniform
cut through the coatings on metallic substrates.
FIGURE 2. Schematic of the sampling for EIS measurement of
scribed panels.
Prohesion Salt Spray Test Results
Figure 4 shows the typical pictures of Prohesion-
tested sheets with different scribes and depths. From
the visual examination of the tested panels, a general
conclusion can be made that the U-shaped scribe
resulted in much more corrosion through the corro-
sion test, but the scribe depth had very little effect
on the corrosion test results. Consistent corrosion
test results also were obtained with the samples
tested at NDSU.
As a result of the cutting head geometry, as
shown in Figure 1, increasing scribe depth also in-
creased scribe width. Consequently, a general con-
clusion could be that scribing width and scribing
depth has little effect on corrosion test results. The
most striking difference in the corrosion results was
caused by the different modes of scribing. In a sim-
plified view, the V-shaped scribe caused the least
corrosion and the U-shaped scribe caused severe
corrosion.

CORROSION–Vol. 57, No. 1 31

CORROSION SCIENCE SECTION

V (0.02 in.) U (0.02 in.) V (0.04 in.) U (0.04 in.)

FIGURE 3. Optical microscopic pictures of the four different scribes at 50X magnification.

V (0.02 in.) U (0.02 in.) V (0.04 in.) U (0.04 in.)

FIGURE 4. Scanned picture of Prohesion salt spray-tested samples with different scribe types and depths. Tested at
Boeing with E-coat removed after test.

It is important to recognize that the major differ-
ence in the two types of scribing lay in the extent of
damage caused to the coating/metal interface. Scrib-
ing with the spinning cutter head could cause exten-
sive damage to the coating/metal interface, and the
striking difference found between the V-shaped
scribe and the U-shaped scribe could be translated
into the extent of damage to the interface. Signifi-
cantly, one out of four samples showed opposite cor-
rosion test results, as if the sample had been
mislabeled. This means that the damage to the inter-
face was not a sole function of the scribing mode. It
simply means that the spinning head has a greater
probability of inflicting severe damage.
Concurrent EIS Measurement
EIS technique has been well-demonstrated to be
an efficient method in evaluating organic coating sys-
tems on metallic substrates.15-16 Recently, Katayama,
et al., have applied this technique to investigate the

32 CORROSION–JANUARY 2001
 CORROSION SCIENCE SECTION

degradation of an organic-coated stainless steel with

a macroscopic line defect.16 Their EIS data correlated
well with the actual delaminated area of the coating
system. In this study, EIS measurement conducted
concurrently with Prohesion salt spray testing was
used to examine the scribing effects on the corrosion
test results.
Figure 5 shows the dependence of impedance on
different scribing modes. It was noted that the sharp
drop of impedance modulus at low frequency
(|Z|0.1Hz) for 0.02-in. and 0.04-in. U-shaped samples
started after 14 days of exposure in the Prohesion
chamber. The sharp drop of impedance modulus at
low frequency (|Z|0.1Hz) indicated a coating system
failure, which also was evidenced by the onset of a
second time constant suggesting partial delamination
of the coating. In contrast, there was very little FIGURE 5. The impedance modulus at low frequency (|Z|0.1Hz)
gradual drop of the (|Z|0.1Hz) for 0.02-in. and 0.04-in. dependence on the scribe types and depths and the exposure time
V-shaped samples. The V-shaped scribed samples in the Prohesion salt spray corrosion test chamber.
did not start a large impedance modulus drop for a
long period of exposure time until after 70 days in
the Prohesion test chamber.
In samples with varying scribe depth, the
0.04-in. V-shaped samples with deeper scribe depth
showed slightly better corrosion resistance than the
0.02-in. V-shaped samples at the early stage of expo-
sure. With prolonged exposure, there was little differ-
ence in their performance. The 0.02-in. and 0.04-in.
U-shaped samples showed no significant difference
in their corrosion resistance during the entire
Prohesion test period.
Results of the concurrent EIS measurement are FIGURE 6. Pathways of corrosive chemicals to the site of EIS
consistent with Prohesion test results shown above. measurement.
The earlier failure of the coating system caused by
partial delamination at the interface resulted in
severe corrosion on the U-shaped scribed panels. attributed to the rapid transport by means of Path-
The concurrent EIS measurement reveals the impor- way A in the case of U-shaped scribes because of the
tance of lateral diffusion of salts initiating from extensive interface damage, which resulted in the
the damaged interface. This situation could be ex- earlier failure of the coating systems with partial
plained by Figure 6, which schematically depicts the delamination of the coating. Even in this case, the
pathways of electrolyte to the sampling site of EIS scribing depth and width had little effect. This means
measurement. that the severe damage to the coating/substrate in-
Since the same primer with controllable coating terface caused by the scribing process could have
thickness and characteristics was used, the different had the largest influence on the outcome of
scribe modes could not have had any effect on Path- Prohesion salt spray test results. The interfacial
ways B and C in Figure 6. If Pathway B or C had damage was considered to be a function of adhesive
been dominant, the difference in scribing modes strength of coating to substrate alloy. Good adhesion
would not have influenced the EIS impedance values might have minimized the interfacial damage. With-
as a function of the immersion time. In the case of out tenacious, water-insensitive adhesion of a coat-
V-shaped scribes (with minimal interface damage), it ing layer to the substrate metal, the propagation of
is likely that C might have been the dominant path- the interfacial damage could not be inhibited.11
way, and the difference in the scribing depth and The influence of scribing itself on the outcome of
width might have had little effect. corrosion test results is significant in establishing a
The most significant factor that can be seen in test method. Obtaining test results of narrow distri-
Figure 5 is the difference in the critical time at which bution is probably the main target of standardizing a
the impedance modulus values started to drop test method. However, from the viewpoint of predict-
sharply: 14 days for the U-shaped scribe and 70 days ing the best performance of a set of coated samples,
for the V-shaped scribe. This large difference can be it would be better to apply the most severe conditions

CORROSION–Vol. 57, No. 1 33

CORROSION SCIENCE SECTION
even though it might result in large scattering. The
results shown in this study clearly indicate that the
interfacial damage is the most crucial factor in
scribed surface corrosion tests.
CONCLUSIONS
❖ Prohesion test results conducted at Boeing and
NDSU indicated that the scribe type had a significant
effect on the corrosion protection performance of the
samples, but the scribe depth and width had very
little influence on the corrosion performance of the
samples.
❖ Concurrent EIS measurement with Prohesion salt
spray showed that the sharp drop of impedance
modulus at low frequency (|Z|0.1Hz) for U-scribed
samples started much earlier during the Prohesion
exposure than for V-scribed samples. There was very
little difference observed on the impedance modulus
of the samples with different scribed depths. The
consistent results between Prohesion test results and
EIS data suggest that the concurrent EIS measure-
ment with Prohesion salt spray may provide addi-
tional information pertinent to the corrosion
protection mechanisms involved in the coating under
examination.
❖ The major factor causing the largest difference in
the corrosion protection performance of samples
tested in this study was the severity of damage in-
flicted on the interface between the primer and sub-
strate metal, which was observed by microscope
examination and concurrent EIS measurement and
Prohesion salt spray testing. Scribing by using a
spinning cutter tip did inflict severe damage to the
interface and thus provided a more severe test condi-
34
tion that could distinguish better coated systems. A
superior coated system should pass such a severe
scribing test.
ACKNOWLEDGMENTS
This study was supported by DARPA Contract
no. AF F33615-96-C-5055.
REFERENCES
1. ASTM G85-94, “Standard Practice for Modified Salt Spray (Fog)
Testing,” Annex 5 (West Conshohocken, PA: ASTM, 1994).
2. G.P. Bierwagen, Prog. Org. Coat. 28 (1996): p. 43.
3. C.M. Reddy, Q.S. Yu, C.E. Moffitt, D.M. Wieliczka, R. Johnson,
J.E. Deffeyes, H.K. Yasuda, Corrosion 56 (2000): p. 819.
4. Q.S. Yu, C.M. Reddy, C.E. Moffitt, D.M. Wieliczka, R. Johnson,
J.E. Deffeyes, H.K. Yasuda, Corrosion 56 (2000): p. 887.
5. C.E. Moffitt, C.M. Reddy, Q.S. Yu, D.M. Wieliczka, R. Johnson,
J.E. Deffeyes, H.K. Yasuda, Corrosion 56 (2000): p. 1,032.
6. S. Lee, “Effects of Plasma Polymer on the Multi-Stress Aging of
Organic Insulation and Proposed Degradation Mechanisms”
(Ph.D. Dissertation, University of Missouri-Columbia, 1995),
p. 149-188.
7. G.W. Walter, Corros. Sci. 26 (1986): p. 27.
8. H. Leidheiser, Jr., Corrosion 38 (1982): p. 376.
9. T.F. Wang, T.J. Lin, D.J. Yang, J.A. Antonelli, H.K. Yasuda,
Prog. Org. Coat. 28 (1996): p. 291.
10. H.K. Yasuda, T.F. Wang, D.L. Cho, T.J. Lin, J.A. Antonelli, Prog.
Org. Coat. 30 (1997): p. 31.
11. M. Chen, Q.S. Yu, C.M. Reddy, H.K. Yasuda, Corrosion 56
(2000): p. 709.
12. ASM Specialty Handbook: Aluminum and Aluminum Alloys
(Materials Park, OH: ASM International, 1993).
13. ASTM D1654, “Test Methods for Evaluation of Painted or
Coated Specimens Subjected to Corrosive Environments,”
Annual Book of ASTM Standards, vol. 06.01 (West
Conshohocken, PA: ASTM, 1994).
14. ASTM D3359, “Standard Test Method for Measuring Adhesion
by Tape Test,” Annual Book of ASTM Standards, vol. 06.01
(West Conshohocken, PA: ASTM, 1994).
15. G.P. Bierwagen, C. Jeffcoate, D.J. Mills, J. Li, S. Balbyshev,
D.E. Tallman, Prog. Org. Coat. 29 (1996): p. 21.
16. H. Katayama, K. Yagi, A. Nishikata, T. Tsuru, Electrochim. Acta
41 (1996): p. 1,093.
CORROSION–JANUARY 2001