ELSEVIER Materials Science and Engineering A190 (1995) 143-154

Evaluation of the stress corrosion cracking behaviour of

damage-tolerant A1-Li sheet using the slow strain rate testing technique

R. Braun
German Aerospace Research Establishment, Institute of Materials Research, Linder Hdhe,
D-51147 Cologne, Germany
Received 15 July 1993; in revised form 19 May 1994

Abstract

Slow strain rate tests were performed on longitudinal tensile specimens of 8090-T81 sheet under permanent immersion conditions
in various synthetic environments. Strain rates were in the range 10-7-10 4 s-t. Environmentally assisted cracking is observed in
aqueous chloride-carbonate-hydrogencarbonate solutions. Near neutral 3.5% NaC1 solution and also 3% NaCI solution with
hydrogen peroxide added do not promote stress corrosion cracking with 8090-T81 alloy sheet. The degradation of ductility found
with tensile specimens immersed in the latter corrosive environments is caused by localized corrosion independent of stress. Fracture
energy data obtained from slow strain rate tests in substitute ocean water reveal a large scatter. Again, the deterioration observed is not
related to stress corrosion cracking. Slow strain rate tests were also carried out with longitudinal tensile specimens of 2091-T8X and
2091 CPHK-T8X alloy sheet using an aqueous solution of 3% NaCI + 0.3% H202. For the alloy 2091 CPHK-T8X, similar results
were obtained to those with 8090-T81, whereas 2091-T8X sheet is prone to environment-induced cracking in the aqueous
chloride-peroxide solution.

Keywords: Stress; Corrosion; Cracking; Aluminium;Lithium; Strain

1. Introduction prone to stress corrosion cracking (SCC) [3]. By metal-

In the last decade, considerable effort has been
made to develop aluminium-lithium-based alloys
which are attractive for aircraft structures because of
their combined low density and high stiffness. Many
product forms of AI-Li alloys including plate, sheet
and extrusions have now attained commercial status
and are waiting for aerospace applications [1, 2].
Damage-tolerant sheet materials have a great potential
to be used in aircraft fuselage structures. High fracture
toughness and good fatigue performance are the essen-
tial characteristics. However, the environmental behav-
iour of the newly developed A1-Li alloys is also crucial
with regard to their substitution for conventional
aluminium alloys.
Sheet material of the alloy 2091-T8X, developed by
C6g6dur P6chiney, achieved properties equivalent to
those of 2024-T3 [1]. High damage tolerance and
isotropy of mechanical properties required a recrystal-
lized microstructure and an under-aged temper T8X
(12 h at 135 °C). However, sheets of 2091-T8X were
lurgical adjustments, SCC resistance was improved at
the slight expense of strength and toughness (CPHK
version) while the under-aged temper T8X was
retained [1]. Environment-induced cracking was also
observed with recrystallized 8090-T81 sheet
developed by British Alcan Aluminium [4-9].
To avoid long-term outdoor exposure tests in
marine, industrial or other natural environments,
accelerated tests are used to assess the SCC behaviour
of structural materials. With aluminium alloys alternate
immersion in 3.5% NaC1 solution according to ASTM
G44 is widely used as a synthetic environment. For
sheet materials bent-beam specimens are feasible and
their preparation is simple. Owing to the varying stress
through thickness, these specimens are considered to
have failed when a crack is detected on the convex
surface. However, the inspection of the surface is sub-
jective, and pitting or intergranular corrosion can inter-
fere with crack initiation; furthermore, corrosion
products can deposit on the surfaces, impeding their
examination. Hence other accelerated SCC testing

0921-5093/95/$9.50 © 1995 - Elsevier Science S.A. All rights reserved

SSDI 0921-5093 (94)09611 -Y
144 R. Braun / Materials, Science and Engineering Al90 (1995) 143-154

techniques have been developed applying more

objective failure criteria. These include the slow strain
rate (SSR) technique [10], the breaking load method
[11] and, more recently, the automated stress corrosion
ring (ASCOR) test [12]. Many investigations on
aluminium alloys have shown that the SSR technique
can provide results in accordance with service experi-
ence [13-18]. However, the synthetic environment to
be used with this testing technique is still an open
question. It has been demonstrated that neutral 3.5%
NaC1 solution is not appropriate [19-23]. Promising
synthetic environments found are substitute ocean
water and an aqueous solution of 3% NaCI + 0.3%
H202 [18, 22-24]. Whereas these environments
were mainly used with conventional 2XXX and 7XXX
series aluminium alloys, SCC investigations on lithium
bearing alloys are limited in these environments.
The aim of the present investigation was to study the
SCC behaviour of damage-tolerant A1-Li sheet
materials employing the slow strain rate technique.
This work was concentrated on alloy 8090-T81. To
assess the effectiveness of various synthetic environ-
ments used, results of SSR tests on the alloys 2091
CPHK-T8X and 2091-T8X are also reported.

2. Experimental

The 1.6 mm thick 8090-T81 sheet was supplied by

British Alcan Aluminium. The microstructure was
recrystallized with grains elongated in the rolling
direction particularly in the sheet centre (Fig. l(a)). The
alloys 2091 and 2091 CPHK were supplied by
C~g6dur P~chiney as 1.6 mm thick sheet material in an
as-quenched and stretched condition. Both alloys were
aged 12 h at 135 °C to T8X temper. Whereas alloy
2091-T8X reveals a fully recrystallized microstructure
with nearly equiaxed grains (Fig. l(b)), 2091 CPHK-
T8X exhibits a more flattened grain structure and a
partially recrystallized layer in the centre of the sheet
(Fig. l(c)). The chemical compositions and longitudinal
tensile properties of the A1-Li alloys investigated are Fig. 1. Etched metallographic sections (S-T plane) of the alloys
investigated:(a) 8090-T81; (b) 2091-T8X; (c) 2091 CPHK-T8X.
given in Tables 1 and 2, respectively.
Flat tensile specimens with 16 mm gauge length and
a cross-section of 10 mm 2 were machined with the
loading axis along the longitudinal direction of the ranged from 10 -7 to 10 -4 S - l . To assess the SCC
sheet. Slow strain rate (SSR) tests were performed behaviour of the materials investigated, the fracture
under permanent immersion conditions in the follow- energy, which is the area beneath the stress-strain
ing aerated corrosive media at free corrosion potential: curve, was used. Environment-induced cracking results
near neutral 3.5% NaC1 solution (pH=6.5), an in a reduction of the fracture energy compared with
aqueous solution of 3% NaC1 + 0.3% H202 reference values determined in an inert environment
(pH = 6.0), an aqueous solution of 0.5 M NaCI + 0.1 M (dry laboratory air obtained by embedding the speci-
LiCI + 0.05 M N a H C O 3 + 0.05 M N a 2 C O 3 (pH = 9.7) mens in Mg(C104) 2 powder). Because specimens can
and substitute ocean water without heavy metals also be degraded by corrosion independent of applied
according to ASTM Dl141 (pH=8.2). Strain rates stress, e.g. by pitting, intergranular corrosion or hydro-
 R. Braun / Materials, Science and Engineering AlgO (1995) 143-154 145

Table 1 60
Chemical composition in wt.% of the AI-Li sheet material used
as given by the producers 50

Alloy Li Cu Mg Zr Fe Si B 40

8090-T81 2.42 1.14 0.83 0.06 0.05 0.02 30

2091-T8X 2.00 2.00 1 . 4 0 0.07 0.04 0.03 ua
• 00
2091 CPHK-T8K 1.95 2.00 1.24 0.09 0.05 0.05 iI
20
<>
<> • OO inert environment
10 o• • 3% NaCI + 0.3% H202
• o~
Table 2 o pre-exposure
Longitudinal tensile properties of 1.6 mm thick AI-Li sheet 0 I , I I , J I i I I I

materiaP I0-7 10-6 10-5 10-4

(a) Strain R a t e , s -I
Alloy 0.2% proof Tensile Fracture
stress strength elongation
(MPa) (MPa) (%) 60

8090-T81 333_+5 443_+6 11.3+_0.9 T SO

2091-T8X 358_+5 474+_10 17.6+1.8
2091CPHK-T8X 350_+5 445+6 12.0-+1.1

aThe mean and the estimate of the standard deviation were 3o

calculated from the data for slow strain rate tests performed in
an inert environment. } 2o
• ~ inert environment
10 • 3% NaCI + 0.3% H202
pre-exposure
gen absorption during exposure in aggressive environ- I , I I , I I ~ I I I

10-7 10-6 10-5 10 -4

ments, pre-exposure tests have to be carried out.
Unstressed specimens were permanently immersed in (b) Strain R a t e , s-I

the corrosive media. T h e exposure periods corre-

sponded to the immersion times of the specimens 100
during the SSR tests. After pre-exposure the specimens
T
were rinsed in distilled water, dried in warm air, stored B 80
for 15 min in a vacuum chamber at a pressure of 0.4 Pa
and then tensile tested in an inert environment at the 60 inert enviroqment
same strain rate as in the corrosive m~dia (to be more t.u • 3% NaCI + 0.3% H202
precise: at the strain rate gf, the SSR test in a corrosive 40 O pre-exposure
4?•
medium takes a time t~. Specimens are immersed for
the time 6 in the same corrosive medium without 20
4~
applied stress and, after pre-exposure, tensile tested at
d) •
the strain rate gf in an inert environment). M o r e details 0 ~ . , .•, • * , . J , i
10 -7 10 -6 10 -s 10 -4
of the SSR testing technique are described elsewhere
[21]. (c) Strain R a t e , s -1

Before testing, the specimens were ultrasonically
cleaned in ethanol and degreased in acetone vapour.
Specimens which were dynamically strained in 3.5%
NaC1 solution were additionally cleaned in an alkaline
solution of 10 g 1-~ Turco 4215 N C (Turco Chemie,
Hamburg, Germany) and then pickled in an aqueous
solution of 150 cm 3 1-~ H2SO 4 ( 9 6 % ) + 7 5 g 1-]
Na2Cr204"H20 at 60 °C for 15 min.
Fracture surfaces were examined by scanning
electron microscopy. Prior to examination, the fracture
surfaces were cleaned using an aqueous solution of
chromic and phosphoric acids as r e c o m m e n d e d in
A S T M Standard Practice G 1 for aluminium alloys.
Fig. 2. Fracture energy vs. strain rate curves for the alloys (a)
8090-T81, (b) 2091 CPHK-T8X and (c) 2091-T8X. Specimens
were dynamically strained in an aqueous solution of 3%
NaCl+0.3% H202. Data for pre-exposed specimens are
included.
3. Results
Results of the SSR tests performed in an aqueous
solution of 3% NaC1 + 0.3% H 2 0 2 a r e plotted in Fig. 2.
In the chloride-peroxide solution, the fracture energy
of the three A I - L i alloys studied decreases with de-
146 R. Braun / Materials, Science and Engineering AlgO (1995) 143-154
creasing strain rate. For the alloys 8090-T81 and 2091
CPHK-T8X, the reduction of fracture energy is not
caused by stress corrosion cracking. As proved by pre-
exposure tests, the degradation is related to corrosion
independent of stress. Fractographic examinations of
the fracture surfaces of pre-exposed 8090-T81 and
2091 CPHK-T8X specimens reveal pitting and inter-
granular corrosion on the edges (Fig. 3). For short pre-
exposure length, the grain boundary attack is narrow
(Fig. 4(a)), whereas with increasing exposure times
fissures broadened owing to progressive dissolution of
the grains (Fig. 4(b)). Because pre-exposed specimens
are tensile tested in an inert environment, the corrosive
attack observed on their fracture surfaces occurred
during the pre-exposure. Intergranular corrosion is
also observed in the metallographic sections of pre-
exposed specimens which were not tensile tested (Fig.
5(a)). Therefore, a highly localized dissolution of the
grain boundaries causes the brittle appearance of inter-
Fig. 3. Scanning electron fractographs of (a) 8090-T81 and (b)
2091 CPHK-T8X specimens which were pre-exposed for 12 h
in 3% NaCI + 0.3% H202 and subsequently tensile tested in an
inert environment.
granular fracture observed on the fracture surfaces of
specimens which have been pre-exposed in the
chloride-peroxide solution for relatively short periods
(Fig. 5(b)).
For the alloy 2091-T8X, the degradation of the
specimens cannot be completely associated with corro-
sion independent of stress. In the strain rate range from
2 x 10 -6 to 2 x 10 -5 s 1 stress corrosion cracking
seems to contribute to the reduction of fracture energy
(Fig. 2(c)). The occurrence of stress corrosion cracking
for 2091-T8X alloy is supported by fractography. The
fracture surfaces of dynamically strained SCC speci-
mens reveal intergranular fracture (Fig. 6). The dissolu-
tion of the grain boundaries observed at higher
magnifications (Fig. 6(b)) probably results from a post-
fracture attack in the very corrosive chloride-peroxide
solution. In contrast to the alloys 8090-T81 and 2091
Fig. 4. Scanning electron fractographs of 8090-T81 specimens
which were pre-exposed for (a) 0.75 and (b) 98 h in an aqueous
solution of 3% NaCl+0.3% H202 and subsequently tensile
tested in an inert environment. Note the higher magnification in
(a).
 R. Braun / Materials, Science and Engineering A190 (1995) 143-154 147

........... 7 : - ) , ~--~,- • . -,- • , ~ ? --'2+ +--

. . . . . .. .. . . . .. .. . . . .. . . .) , , . . , ~- - , 0,1ram - ~

(a) ...... ++-~+: -<+" c~+f+C._.?_Y'--.+~-+"-~, . . . .

Fig. 5. (a) Metallographic section (T-S plane) and (b) scanning Fig. 6. Scanning electron fractographs of a 2091-T8X specimen
electron fractograph of 8090-T81 specimens which were pre- which was dynamically strained in an aqueous solution of 3%
exposed for 3 h in 3% N a C l + 0 . 3 % H202. Specimen (b) was NaC1 + 0.3% H 2 0 ~ at a strain rate of 2 × 1 0 -6 s - i.
tensile tested in an inert environment after pre-exposure (the
upper margin of the fractograph corresponds to the edge of the
fracture surface).
Furthermore, no degradation was observed with
degreased specimens which were dynamically strained
CPHK-T8X, however, the proportion of intergranular in 3.5% NaCI solution. As shown by metallography, the
fracture is significantly greater than the area on the pickling treatment itself does not attack grain
fracture surfaces of corresponding pre-exposed speci- boundaries. Therefore, neither the surface treatment
mens showing pitting and intergranular corrosion. nor the corrosive environment alone causes the reduc-
With increasing pre-exposure length, the degradation tion of fracture energy illustrated in Fig. 8. Both
of specimens becomes more severe. At a strain rate of pickling and immersion jointly promote corrosion,
3 x 10 -7 s - I , the pre-exposed and the dynamically resulting in deterioration in ductility.
strained SCC specimens exhibit the same deterioration As shown by pre-exposure tests, the degradation
(Fig. 7). of specimens dynamically strained in 3.5% NaC1
Fig. 8 shows results of SSR tests with 8090-T81 solution is primarily caused by corrosion independent
sheet using 3.5% NaCI solution. Specimens strained in of stress. The fracture energy vs. strain rate shows a
the corrosive environment as well as pre-exposed slight minimum at 3 x 10-6 s- t. It might be related to a
specimens were pickled in chromatic-sulfuric acid strain rate-induced degradation, because the reduction
prior to testing. The surface condition had no influence of fracture energy is more severe for the SCC speci-
on tensile properties when the SSR tests were con- mens at this strain rate compared with the pre-exposed
ducted in an inert environment, e.g. similar values of specimens. On the fracture surface of pre-exposed
the fracture energy were obtained using pickled speci- specimens, intergranular corrosion is observed. Again,
mens and specimens which were only degreased. the grain boundary attack is narrow for specimens with
148 R. Braun / Materials, Science and Engineering A190 (1995) 143-154

; . ° . .

,; .v

-- "7 ] : '0"~: ':: .... o

- f , "2,

I °'1ram I
• °

Fig. 7. Scanning electron fractographs of 2091-T8X specimens
which were (a) dynamically strained in an aqueous solution of
3% NaCl+0.3% H202 at a strain rate of 3x 10 -7 s -1 and (b)
pre-exposed for 40 h in 3% NaCl+0.3% H202 and sub-
sequently tensile tested in an inert environment at a strain rate of
3x10-Ts-%
Fig. 9. (a) Metallographic section (T-S plane) and (b) scanning
electron fractograph of pickled 8090-T81 specimens which were
pre-exposed for 8 h in 3.5% NaCI. Specimen (b) was tensile
tested in an inert environment after pre-exposure (the left margin
of the fractograph corresponds to the edge of the fracture
surface).

60
a short exposure length and b e c o m e s m o r e severe with
5O
? longer immersion time periods. Metallographic
E sections of p r e - e x p o s e d but not tensile tested speci-
40
mens reveal intergranular corrosion attack which
# correlates with the d e p t h of intergranular fracture
w 30
observed on the fracture surfaces of specimens which
~ 20 were tensile tested after p r e - e x p o s u r e (Fig. 9). T h e
fracture surfaces of specimens dynamically strained in
10
t
• • 3.5% NaCI 3.5% NaC1 solution are similar to those of pre-exposed
<> pre-exposure specimens.
10 -7 1 0 -6 10 -s 1 0 -4
Fig. 10 shows the fracture energy vs. strain rate for
8090-T81 specimens dynamically strained in the
Strain Rate , s- l
aqueous solution of 0.5 M NaCI + 0.1 M LiCI + 0.05 M
Fig. 8. Fracture energy vs. strain rate for 8090-T81 alloy sheet. N a H C O 3 + 0 . 0 5 M NazCO3. T h e fracture energy
Tensile specimens were dynamically strained in an inert environ- decreases at strain rates below 5 x 10 -7 s -1. Pre-
ment and in aqueous 3.5% NaC1 solution. Data for pre-exposed
specimens are included. Specimens strained in 3.5% NaC1 exposure in this corrosive environment does not result
solution and pre-exposed specimens were pickled prior to in degradation of tensile properties. Therefore, the
testing. SSR technique indicates environment-assisted cracking
 R. Braun / Materials, Science and Engineering A190 (1995) 143-154 149

60 of alloy 8090-T81 in aqueous chloride-carbonate

solutions. Fractographic examinations corroborate
50 ~ ~ e • SCC failure, showing regions of intergranular fracture
T

40
• (Fig. 1 l(a)). The slight dissolution of the grain bound-
aries observed at higher magnifications probably
30 results from a post-fracture attack (Fig. l l(b)). The
taJ
o) inert environment
fracture surfaces of the pre-exposed specimens reveal a
v qbo complete transgranular ductile fracture. No corrosive
20 • 0.5 M NaCI + 0.1 M LiCI
v
n~ + carbonate-bicarbonate attack is found. The effect of lithium ions is also shown
pre-exposure
10 ~7 0.6 M NaCI + in Fig. 10. Without the addition of lithium ions to the
carbonate-bicarbonate bulk electrolyte, the reduction of fracture energy is
0 ~ ~ shifted to slower strain rates. A certain amount of
10 -7 10 - 6 10 -5 10 -4
lithium ions dissolved during immersion seems to be
Strain R a t e , s -1
required to promote stress corrosion cracking. Again,
Fig. 10. Fracture energy vs. strain rate for 8090-T81 alloy sheet. the pre-exposed specimens are not deteriorated.
Specimens were dynamically strained in aqueous chloride-
carbonate-hydrogencarbonate solutions. Data for pre-exposed
As shown in Fig. 12, fracture energy data evaluated
specimens are included. from SSR tests in substitute ocean water display a large
scatter at strain rates below 10-6 s- 1. A similar scatter
is found with pre-exposed specimens. The degradation
of specimens does not result from stress corrosion
cracking, as demonstrated by pre-exposure tests. On
the fracture surfaces of pre-exposed specimens, inter-
granular corrosion and pitting are observed. With
increasing pre-exposure length, the corrosion attack
becomes more severe (Fig. 13). Near the transition to
ductile fracture, grain boundaries partially dissolved
are observed (Fig. 14). Fractographic examinations of
specimens dynamically strained in substitute ocean
water reveal intergranular corrosion and pitting as well
(Fig. 15(a)). However, near the transition to overload
fracture, intergranular fracture with brittle appearance
is also observed for specimens tensile tested at inter-
mediate strain rates (Fig. 15(b)). It is difficult to resolve
whether these brittle fracture surfaces are caused by a
very fine intergranular corrosion attack or by stress
corrosion cracking.

6O

50
T

~ 4o )E

~ 3o
<>
~ 20
• <> v
• | ~ inert environment
10 | • substitute ocean water
0 (> pre-exposure

10 -7 10 -6 10 -5 10 -4

Fig. 11. Scanning electron fractographs of a 8090-T81 specimen
which was dynamically strained in an aqueous solution of 0.5 M
N a C l + 0 . 1 M L i C l + 0 . 0 5 M N a H C O 3 + 0 . 0 5 M Na2CO 3 at a
strain rate of 1.3 x l 0 -7 s- 1.
Strain R a t e , s -1
Fig. 12. Fracture energy vs. strain rate for 8090-T81 alloy sheet.
Specimens were dynamically strained in substitute ocean water.
Data for pre-exposed specimens are included.
150 R. Braun / Materials, Science and Engineering A l gO (1995) 143-154
Fig. 13. Scanning electron fractographs of 8090-T81 specimens
which were pre-exposed for (a) 36 and (b) 70 h in substitute
ocean water and subsequently tensile tested in an inert environ-
ment.
4. Discussion
Under permanent immersion conditions, neutral
3.5% NaCI solution does not promote environmentally
assisted cracking in A1-Li alloys. However, stress
corrosion cracking does occur under alternate
immersion conditions in 3.5% NaCl solution [25-27].
In near neutral 3.5% NaC1 solution, sharp cracks
cannot be sustained because the environment within
the fissures is too aggressive, causing crack blunting
[28, 29]. Under alternate immersion conditions, how-
ever, cathodic reactions take place more and more
within the fissures during the drying cycle. Owing to the
removal of external cathodic sides and to the dissolu-
tion of lithium, the fissure electrolyte becomes alkaline.
Adsorption of atmospheric carbon dioxide results in a
local environment providing a critical balance between
active dissolution and passivation. Therefore, cracks
Fig. 14. Scanning electron fractographs of a 8090-T81 specimen
which was pre-exposed for 70 h in substitute ocean water and
subsequently tensile tested in an inert environment at a strain
rate of 3.5 x 1 0 - 7 s - I. Dissolution of grain boundaries is shown
at (a) nearly final and (b)initial stages.
initiate and propagate [27, 29]. In a recent study on
alloy 2090, two key features for stress corrosion crack-
ing were proposed: stress-assisted anodic dissolution of
active precipitates at the crack tip and the formation of
passive films along crack walls [30].
The present results are in agreement with this pro-
posed SCC mechanism. Whereas in alternate immer-
sion tests damage tolerant AI-Li alloy sheet is found to
be prone to stress corrosion cracking [4-9, 12], SSR
tests in neutral 3.5% NaC1 solution indicate no
environmentally assisted cracking [8, 19, 31]. A surface
finish effect is observed in accelerated SCC tests with
A1-Li alloys. In alternate immerson tests, an acid
pickling treatment reduces the time-to-failure lives of
8090-T62 specimens compared with those of
degreased specimens [6]. Besides shorter time-to-
failure lives, Gray et al. [9] found also a reduction of the
 R. Braun / Materials, Science and Engineering A190 (1995) 143-154
Fig. 15. Scanning electron fractographs of 8090-T81 specimens
which were dynamically strained in substitute ocean water at
strain rates of(a) 2.5 × 10 -v and (b) 7 × 10 -7 s-i.
threshold stress associated with a mild de-oxidizing
treatment. Under permanent immersion conditions,
pickling sensitized specimens to intergranular
corrosion when they are immersed in 3.5% NaCI
solution. In tensile tests after exposure, intergranular
fissures may act as stress raisers leading to premature
fracture. As supported by fractography, the fissures
produced by intergranular corrosion are relatively
narrow in the initial stage, leading to high stress con-
centration at their roots. With time they blunt by disso-
lution of the matrix. Reduced stress concentrations at
these broadened defects can result in a recovery of
ductility or in a diminution of degradation with increas-
ing immersion time periods. Intergranular fissures
formed during straining cause a more severe loss of
ductility than that determined with specimens which
are tensile tested after pre-exposure. Therefore, the
slight minimum of the fracture energy shown in Fig. 8
for dynamically strained SCC specimens is probably
not related to stress corrosion cracking but to fissures
151
caused by intergranular corrosion which are very fine
at the initial stage.
As reported in the literature, environmental
degradation of A1-Li alloys can also result from
hydrogen embrittlement [32-35]. A1-Li-Cu alloys
were found to be susceptible to this type of environ-
ment-induced cracking correlated with the presence of
the hardening phase TI [32]. For damage-tolerant
8090 sheet in the underaged temper T62, hydrogen is
postulated to be involved in the SCC mechanism [35].
Hydrogen embrittlement associated with pre-exposure
was found for 2091-TSX sheet and A1-Li-Cu-Zr
alloys, indicated by a change in fracture mode and by a
recovery of ductility when a full heat treatment was
given to specimens after pre-exposure, respectively [3,
32]. Therefore, the degradation of the specimens
observed in the present work might also be attributed
to joint effects of hydrogen and intergranular corro-
sion. The influence of hydrogen has not been studied in
this work. Cathodic charging experiments with simul-
taneous straining or with subsequent tensile testing are
usually performed to investigate hydrogen effects.
However, as pointed out by Stoudt et al. [36] in a recent
report, tests under controlled potentials cannot be used
to study the SCC mechanism for aluminium alloys.
Whereas neutral 3.5% NaC1 solution is not con-
ducive to environmentally assisted cracking, peroxide
additions to aqueous chloride solutions readily
promote stress corrosion cracking in highly sensitive
microstructures under permanent immersion condi-
tions. This is supported by recent investigations on
2024 and 7 4 7 5 alloy plate [22, 23]. SSR tests in the
chloride-peroxide solution clearly demonstrate the
low SCC resistance of 2024-T351 and 7475-T651 in
the short transverse direction. As found in the present
work, SCC failure does not occur in this synthetic
environment with less susceptible alloys. Whereas the
SSR testing technique indicates stress corrosion crack-
ing with the sensitive alloy 2091-T8X, environment-
induced cracking is not observed for the more resistant
2091 CPHK-T8X and 8090-T81 alloy sheet. This may
be attributed to crack blunting. If stress corrosion
crack growth is reduced in less sensitive microstruc-
tures, the aqueous chloride-peroxide solution is too
aggressive to sustain sharp cracks. This assumption is
also supported by the results of the SSR test with alloy
2091-T8X at the slowest strain rate applied. At
3 x 10 v s ~ the pre-exposed and the dynamically
strained SCC specimens of the latter alloy exhibit the
same degradation of fracture energy and their fracture
surfaces are equally attacked by intergranular
corrosion (Fig. 7). Applying very low strain rates, crack
initiation and/or propagation are too slow to prevent
crack wall dissolution forming broad fissures, and
environmentally assisted cracking can no longer be
152 R. Braun / Materials, Science and Engineering A190 (1995) 143-154
retained. Thus, with more resistant alloys the influence
of the aqueous chloride-peroxide solution may be
similar to that of neutral 3.5% NaC1 solution, which is
too aggressive to permit stress corrosion cracking even
in very sensitive aluminium alloys.
Under permanent immersion conditions, passivation
in chloride solutions can be provided by the addition of
carbonates and hydrogencarbonates [28]. As indicated
by the SSR testing technique, an aqueous solution of
0.5 M NaCI + 0.1 M LiCI + 0.05 M NaHCO3 + 0.05 M
Na2CO 3 promotes stress corrosion cracking with
8090-T81 sheet (Fig. 10) and also with 2091 CPHK-
T8X and 2091-T8X sheet [20]. These results are
in agreement with those of other studies showing
that alkaline chloride-carbonate-hydrogencarbonate
solutions are conducive to environmentally assisted
cracking for AI-Li alloys [27, 28, 29, 37]. Intergranular
corrosion is observed on the fracture surfaces of SCC
specimens of damage-tolerant AI-Li sheet which were
dynamically strained in the aqueous solution of
0.5 M NaCI + 0.1 M LiC1 + 0.05 M NaHCO 3 + 0.05 M
Na2CO 3. In contrast, pre-exposure in this environment
does not result in degradation. This may be caused by
variations in the local chemistry of the electrolyte
within cracks in comparison with the bulk solution. As
found by Holroyd and co-workers [25, 28] for the alloy
8090-T651, the pH inside an artificial crevice changes
with time and is controlled by lithium ions in solution.
Owing to variations of the anion concentration with
crack depth, the grain boundary breakdown potential
may be changed within the cracks compared with that
in the bulk electrolyte.
The amounts of chloride in 3.5% NaC1 solution and
substitute ocean water are similar; however, the latter
synthetic environment also contains carbonate and
sulphate ions. Both species induce stress corrosion
cracking with AI-Li alloy 8090 in the peak-aged
temper [29]. Using substitute ocean water, the SSR
testing technique indicates the low short transverse
SCC resistance of plate materials of the alloys 2014-
T651, 2024-T351, 7475-T651 and 2091-T8X51 as
well as the high resistance of 7475-T7351 [19, 22, 23,
38]. With AI-Li sheet, environment-induced cracking
is observed for alloy 2091-T8X [20], whereas SCC
sensitivity is not indicated for the alloys 8090-T81 (Fig.
12) and 2091 CPHK-T8X [20]. Similarly to aqueous
chloride-peroxide solutions, substitute ocean water
does not seem to promote stress corrosion cracking
with alloys revealing an intermediate resistance.
The fracture energy data plotted in Fig. 12 display a
large scatter for both pre-exposed specimens as well as
specimens dynamically strained in substitute ocean
water. Therefore, the scatter is not associated with
incubation effects of stress corrosion cracking. A
similar scatter in fracture energy data was found with
long transverse tensile specimens of 2091 CPHK-T8X
sheet and 2091-T8X51 plate which were dynamically
strained in substitute ocean water [19, 20]. As reported
by Dexter [39], artificial seawaters are just as change-
able as is natural seawater, not producing less variable
results in laboratory tests than those found with natural
seawater. The pH of artificial seawaters is controlled by
the dissolved gases nitrogen, oxygen and carbon
dioxide [39]. The scatter of fracture energy data may be
attributed to changes of the pH value and other
properties in substitute ocean water. Furthermore, it
could also be associated with variable surface condi-
tions of the tensile specimens, which were only
degreased prior to immersion. This pre-treatment does
not eliminate surface heterogeneities associated with
rolling scales and, therefore, does not result in a
reproducible surface finish. Compared with the
chloride-peroxide solution, substitute ocean water is
not so conducive to general corrosion and pitting.
Therefore, variations in the surface condition might
have a more pronounced influence on the initiation of
intergranular corrosion in the latter environment.
To assess the applicability and the reliability of the
SSR testing technique, the results obtained have to be
compared with those of other established test methods.
In alternate immersion tests in 3.5% NaC1 solution, the
alloy 2091-T8X was found to be very sensitive to stress
corrosion cracking. A threshold stress below 100 MPa
was determined in rolling direction [3]. The other two
A1-Li alloy sheets are also prone to environmentally
assisted cracking. Long transverse threshold stresses
between 200 and 250 MPa were measured [1, 9].
Employing the SSR testing technique, neutral 3.5%
NaC1 solution cannot be used as a synthetic environ-
ment under permanent immersion conditions as
discussed above. Holroyd and Scamans [18] found that
an aqueous solution of 3% NaCI + 0.3% H202 is an
effective synthetic environment to determine the SCC
behaviour of aluminium alloys. This was corroborated
by SSR tests with sensitive alloys indicating their low
SCC resistance [22, 23]. Because the
chloride-peroxide solution is also highly conducive to
pitting and intergranular corrosion, pre-exposure tests
have to be carried out to confirm stress corrosion
failure. Using this synthetic environment, the SSR
testing technique is an appropriate screening test
method to discriminate among alloys with low and high
SCC resistance. For AI-Li alloys with moderate resis-
tance, the chloride-peroxide solution cannot be used.
For these alloys, the degradation of dynamically
strained specimens is caused by pitting and inter-
granular corrosion. Similar results are obtained
performing SSR tests in substitute ocean water.
Owing to the local chemistry within cracks and
fissures for AI-Li alloys, aqueous chloride solutions
 R. Braun / Materials, Science and Engineering A190 (1995) 143-154
with c a r b o n a t e - h y d r o g e n c a r b o n a t e additions seem to
be effective synthetic environments to investigate the
SCC behaviour of the latter alloys. T h e SSR testing
technique indicates environmentally assisted cracking
in this electrolyte with 8090-T81 sheet as well as with
2091 C P H K - T 8 X sheet [20]. However, further
investigations are needed to determine whether or not
accelerated SCC tests in c h l o r i d e - c a r b o n a t e -
hydrogencarbonate solutions can distinguish between
tempers or composition modifications causing
moderate or slight changes in the SCC behaviour. T h e
fracture energy vs. strain rate curves obtained for the
alloys 2 0 9 1 - T 8 X and 2091 C P H K - T 8 X are similar
[20]. A more p r o n o u n c e d effect is expected reflecting
the considerable improvement of the SCC resistance of
the C P H K version.
5. Conclusions
Using an aqueous solution of 3% N a C l + 0 . 3 %
H202, SSR tests indicate no SCC susceptibility for the
alloys 8090-T81 and 2091 CPHK-T8X. T h e reduction
of fracture energy is associated with localized corro-
sion independent of stress. For the alloy 2091-T8X,
stress corrosion cracking exacerbates the degradation
of fracture energy additionally to the loss observed in
pre-exposure tests.
U n d e r permanent immersion conditions, near
neutral 3.5% NaCI solution does not p r o m o t e stress
corrosion cracking even by applying dynamic straining.
Pickling sensitizes 8090-T81 specimens to inter-
granular corrosion when they are immersed in this
corrosive environment.
U n d e r dynamic straining conditions, an aqueous
solution of 0.5 M N a C I + 0 . 1 M L i C I + 0 . 0 5 M
N a H C O 3 + 0 . 0 5 M NazCO 3 is conducive to stress
corrosion cracking for damage-tolerant A1-Li alloy
sheet.
Using substitute ocean water, the SSR testing tech-
nique does not indicate sensitivity to environment-
induced cracking with 8090-T81 alloy sheet. A large
scatter in fracture energy data is observed when tests
are performed in this synthetic environment.
Acknowledgement
T h e author thanks Mr. U. Fuchs and W. Schrnau for
performing the SSR tests and acknowledges useful
discussions with Dr. H. Buhl. Metallographic and
photographic work carried out by Mrs. M. Alperth and
Mrs. U. Krebber, respectively, are appreciated.
153
References
[1] M. Doudeau, P. Meyer and D. Constant, A G A R D Confer-
ence Proceedings No. 444, New Light Alloys, Neuilly sur
Seine, 1989, paper 2.
[2] R. Grimes, M. A. Reynolds, A. P. Titchener, M. S. Greaves,
I. Strassheim and D. Warrington, in M. Peters and E-J.
Winkler (eds.), Aluminium-Lithium, DGM, Oberursel,
1992, p. 3.
[31 K. Welpmann, H. Buhl, R. Braun and M. Peters, in G.
Champier, B. Dubost, D. Miannay and L. Sabetay (eds.), 4th
International Aluminium Lithium Conference, Paris, Les
~ditions de Physique, Paris, 1987, p. C3-677.
[41 L. Schra and J. A. M. Boogers, NLR TR 88047L, National
Aerospace Laboratory NLR, Amsterdam, 1988.
[51 U. Koch, Werkst. Korros., 41 (1990) 404.
[61 R. Holbein and A. Dembeck, Werkst. Korros., 42 (1991)
41.
[71 H. J. Kolkman and L. Schra, NLR TP 91399 L, National
Aerospace Laboratory NLR, Amsterdam, 1991.
[8] R. Braun, Werkst. Korros., 43(1992) 106.
[9] A. Gray, C. J. Newton and M. Alexander, in M. Peters and
P.-J. Winkler (eds.), Aluminium-Lithium, DGM,
Oberursel, 1992, p. 691.
[10] G. M. Ugiansky and J. H. Payer (eds.), Stress Corrosion
Cracking--The Slow Strain-Rate Technique, ASTM STP
665, American Society for Testing and Materials, Phila-
delphia, PA, 1979.
[11 ] R. J. Bucci, R. L. Brazill, D. O. Sprowls, B. M. Ponchel and
P. E. Bretz, in V. S. Goel (ed.), Corrosion Cracking Confer-
ence Proceedings, American Society for Metals, Metals
Park, OH, 1986, p. 267.
[12] L. Schra and E E Groep, J. Test. EvaL, 21 (1993) 44.
[13] H. F. de Jong, Corrosion, 34(1978) 32.
[14] G. M. Ugiansky, C. E. Johnson, D. S. Thompson and E. H.
Gillespie, in G. M. Ugiansky and J. H. Payer (eds.), Stress
Corroson Cracking--The Slow Strain-Rate Technique,
ASTM STP 665, American Society for Testing and
Materials, Philadelphia, 1979, p. 254.
[15] H. Buhl, in G. M. Ugiansky and J. H. Payer (eds.), Stress
Corrosion Cracking--The Slow Strain-Rate Technique,
ASTM STP 665, American Society for Testing and
Materials, Philadelphia, 1979, p. 333.
[16] S. Maitra, Corrosion, 37(1981) 98.
[17] H. Buhl and G. Mierke, Aluminium, 60 (1984) E704.
[18] N. J. H. Holroyd and G. M. Scamans, in S. W. Dean, E. N.
Pugh and G. M. Ugiansky (eds.), Environment-Sensitive
Fracture: Evaluation and Comparison of Test Methods,
ASTM STP 821, American Society for Testing and
Materials, Philadelphia, 1984, p. 202.
[19] R. Braun, in M. Peters and P.-J. Winkler (eds.),
Aluminium-Lithium, DGM, Oberursel, 1992, p. 697.
[20] R. Braun and H. Buhl, in M. Peters and P.-J. Winkler (eds.),
Aluminium-Lithium, DGM, Oberursel, 1992, p. 807.
[21] R. Braun and H. Buhl, in H. Buhl (ed.), Advanced Aero-
space Materials, Springer, Berlin, 1992, p. 296.
[22] R. Braun, Werkst. Korros., 44(1993) 73.
[23] R. Braun, in T. Magnin and J. M. Gras (eds.), Corro-
sion-Deformation Interactions CDI '92, Les [~ditions de
Physique, Paris, 1993, p. 163.
[24] H. F. de Jong and J. W. G. A. Berkelaar, Report LR-433.
Delft University of Technology, Delft, 1984.
[25] N.J.H. Holroyd, A. Gray, G. M. Scamans and R. Hermann,
in C. Baker, P. J. Gregson, S. J. Harris and C. J. Peel (eds.),
154 R. Braun / Materials,Science and Engineering A190 (1995) 143-154
Proceedings of the Third International Aluminium-Lithium
Conference, Institute of Metals, London, 1986, p. 310.
[26] G. Disson, M. Reboul and C. Fiaud, in T. H. Sanders, Jr.,
and E. A. Starke, Jr. (eds.), Proceedings of the Fifth Inter-
national Aluminium-Lithium Conference, Materials and
Component Engineering Publications, 1989, p. 1261.
[27] J.P. Moran and G. E. Stoner, in T. H. Sanders, Jr., and E. A.
Starke, Jr. (eds.), Proceedings of the Fifth International
Aluminium-Lithium Conference, Materials and Com-
ponent Engineering Publications, 1989, p. 1187.
[28] J. G. Craig, R. C. Newman, M. R. Jarrett and N. J. H.
Holroyd, in M. R. Louthan, R. P. McNitt and R. D. Sisson
(eds.), Environmental Degradation of Engineering Materials
III, Pennsylvania State University, 1987, p. 313.
[29] J. G. Craig, R. C. Newman, M. R. Jarrett and N. J. H.
Holroyd, in G. Champier, B. Dubost, D. Miannay and L.
Sabetay (eds.), 4th International Aluminium-Lithium Con-
ference, Paris, Les l~ditions de Physique, Paris, 1987,
p. C3-825.
[30] J. P. Moran, R. G. Buchheit and G. E. Stoner, in S. M.
Bruemmer, E. I. Meletis, R. H. Jones, W. W. Gerberich, E P.
Ford and R. W. Staehle (eds.), Parkins Symposium on
Fundamental Aspects of Stress Corrosion Cracking,
Minerals, Metals and Materials Society, Warrendale, PA,
1992,p. 159.
[31] R. Braun, Werkst. Korros., 41 (1990) 547.
[32] E.I. Meletis and W.-J. Huang, Mater. Sci. Eng., A148( 1991 )
197.
[33] E. I. Meletis, in S. M. Bruemmer, E. I. Meletis, R. H. Jones,
W. W. Gerberich, E E Ford and R. W. Staehle (eds.), Parkins
Symposium on Fundamental Aspects of Stress Corrosion
Cracking, Minerals, Metals and Materials Society, Warren-
dale, PA, 1992, p. 353.
[34] R. Balasubramaniam and D. J. Duquette, in S. M.
Bruemmer, E. I. Meletis, R. H. Jones, W. W. Gerberich, E E
Ford and R. W. Staehle (eds.), Parkins Symposium on
Fundamental Aspects of Stress Corrosion Cracking,
Minerals, Metals and Materials Society, Warrendale, PA,
1992, p. 131.
[35] R. Holbein, U. Herold-Schmidt and G. Ibe, in M. Peters and
P.-J. Winkler (eds.), Aluminium-Lithium, DGM,
Oberursel, 1992, p. 709.
[36] M. R. Stoudt, A. K. Vasudevan and R. E. Ricker, in V. S.
Agarwala and G. M. Ugiansky (eds.), New Methods for
Corrosion Testing of Aluminium Alloys, ASTM STP 1134,
American Society for Testing and Materials, Philadelphia,
1992, p. 196.
[37] R.E. Ricker, J. L. Fink and A. K. Vasudevan, Metall. Trans.
A, 2214 (1991)264.
[38] R. Braun, Werkst. Korros., 43(1992) 453.
[391 S. C. Dexter, in P. E. Francis and T. S. Lee (eds.), The Use of
Synthetic Environments for Corrosion Testing, ASTM STP
970, American Society for Testing and Materials, Phila-
delphia, 1988, p. 217.