Sie sind auf Seite 1von 14

Corrosion Science, 1968, Vol. 8, Pp. 55 to 65. Pergamon Press.

Printed in Great Britain

THE MECHANISM OF STRESS--CORROSION CRACKING


IN THE BRASS-AMMONIA SYSTEM*

MICHINORI TAKANO and SABURO SHIMODAIRA


The Research Institute for Iron, Steel and Other Metals, Tohoku University, Sendai, Japan

A b s t r a e t ~ T h e effect of corrosive environments, compositions of alloying elements and degree of


pre-strain on the stress-corrosion cracking of the brass-ammonia system, has been investigated and
the mechanism of intergranular cracking and of the transition from intergranular to transgranular
cracking have been discussed.
Intergranular cracking arises from the formation of thick and large cuprous oxide grains over slip
steps and the resulting locking of the movement of dislocations.
The transition from intergranular to transgranular cracking depends on the mechanical properties
of the surface film produced in a corrosive environment.
The mechanism of the stress-corrosion cracking has been explained on the basis of the film
theory.

R~sumA---On a ~tudi6 l'effet exercd sur la corrosion sous tension du syst~me laiton-ammoniaque par
l'environment corrosif, la composition d'gl6ments d'alliages et le degrg de raise en tension; on a
discut6 le mgcanisme de la corrosion intergranulaire et de la transition de la corrosion intergranulaire
transgranulaire.
Une corrosion intergranulaire rdsulte de la formation de grains dpais et grands d'oxyde cuivreux
sur des bandes de glissement, et de l'obstacle qui en rgsulte sur le mouvement de dislocations.
La transition de la corrosion de la forme intergranulaire ~ la forme transgranulaire dgpend des
proprigtds mdcaniques du film superficiel produit darts un milieu corrodant.
Le mdcanisme de la corrosion sous tension a gt6 expliqud sur la base de la th$orie du film.

Zusammenfassung--Der Einflul3 der korrodierenden L6sung, der Zusammensetzung der Legierung


und der angewendeten mechanischen Spannung auf die Spannungskorrosion yon Messing in
Ammoniak wurde untersucht, und der Mechanismus des interkristallinen Bruchs und des Crbergangs
zu transkristallinem Bruch wird diskutiert. Der interkristalline Bruch entsteht, wenn sich dicke und
grobl3 Kupferoxydk6rner auf Gleitstufen bilden und damit die Bewegung von Versetzungen blockieren.
Der CJbergang zu transkristallinem Bruch wird beeinflul3t durch die mechanischen Eigenschaften des
gebildeten Oberfl~chenfilmes. Der Ablauf der Spannungsril3korrosion wird auf der Grundlage der
Deckschicht-Theorie erkliirt.

Pe~epaT - - I4cc~eaoBaHo B~HAH~e Koppos~OnHbIX cpe~, n p a p o a ~ ~erHpymm~x O~eMeHTOB


n cTeneHH npe~BapHTe~bHoro HanpA~eaHa Ha HopposHOHHOe pacTpec~4BaH~e no~ Hanpa-
h~enHeM CHCTeM JIaTyHL-aMMHaK; o 6 c y ~ e H MexaHH3M Meh~KpHcTa~THOrO pacTpecKHBaHHa
nepexo~ OWMe~RpHcTa~J~HTHOrO K TpaHc~pHcTa~HTHOMy pacTpecKtmaHHm.
Me~RpHcTa~HTHOe pacTpecK~naHHe np0Hcxo~HT I~3-3a oSpa3oBa~Ma n~0vH,-~x H 5 0 ~ m H X
3epeH ORHCH Me/In no nJIOCI~OCTI:IM CHOJIb;t~eHHH, qTO B~3HBaeT TOpMOmeHHe ~BHH~eHH~

IIepexo~ oT Me~i~p~tc~aJ~J~;~THOrO g TpaHc~pHcTa~THOMy p a c T p e c ~ B a ~ m HBJIneTCH


~yHK~He~ OV MexaHaqecsHx CBOI~CTBno~epxHOCTHOt~ n~eH~H, oSpaayeMo~ B goppos~OHHOfZ
cpe~Ie. Mexa~HaM ~opp03~OHHOrO pacTpeCgHBaH~a ~0~ HanpameH~eM o6~ac~aeTc~ Ha
OCHO~e n~eHOqHOi~ weopHm
*Manuscript received 17 February 1967; received in revised form 12 July 1967.
55
56 IVhci-nNolu T A g ~ o and SABUROSHIMODAIRA

INTRODUCTION
THE MECHANISMof stress-corrosion cracking has been widely studied and discussed by
many investigators, but many factors are involved in the cracking process and the
influence of these factors is very complicated and no well-defined elucidation of the
mechanism has been given heretofore.
It is well known that in the brass-ammonia system the form of the cracking,
intergranular or transgranular, depends on the corrosive environment,1-4 composition
of alloying elements 5-7 and degree of work. s,9 Therefore, this system is of particular
interest in relation to the mechanism of stress-corrosion cracking. It is our view that
the existence of the characteristic black oxide layer, the tarnish, produced in a corrosive
environment is essential to intergranular stress-corrosion cracking in this system. It
has been emphasized by previous electrochemical studies that cupric complex ions
Cu(NHs)~'+ play a major role in intergranular cracking.l.a.4,1°, u However, the fact
that the micro-corrosion behaviour of alloys deformed plastically under stress cannot
be directly determined makes it impossible to clearly define the mechanism of cracking.
The film rupture theory which ascribes the mechanism to the formation of a surface
film in a corrosive environment and its subsequent breakdown under stress has been
developed by Logan, x2 Forty and Humble 1~ and McEvily and Bond, ~4 but none of
them have fully explained the processes involved from the initiation of micro-stress-
corrosion to the propagation of cracks.
The present work was carried out to investigate the effects of corrosive environ-
ments, compositions of alloying elements and degree of pre-strain on stress-corrosion
cracking in the brass-ammonia system, using thin foil or bulk specimens. The
mechanism of intergranular cracking and of the transition from intergranular to
transgranular cracking have been discussed from the standpoint of crystal structure.
Following the previous work, x5 this paper is intended to describe at full length the
mechanism of intergranular stress-corrosion cracking of a-brass, with emphasis on
the film theory.

EXPERIMENTAL
The chemical compositions of the brasses are listed in Table 1.
The thin foil specimens (cold-rolled to 0.1 mm) were I00 × 5 × 0-1 mm and were
wrapped in thin foils of the same composition and annealed at 600°C in vacuum. They
were then electrolytically polished in 200 cm s of phosphoric acid + 80 g of chromic
acid at 90°C. The deformation of the electropolished thin foil specimens in various
corrosive environments was performed in the same way as that described previously.Is

TABLE 1. CHEMICAL COMPOSITIONS OF "IF.ST ALLOYS

Test alloys Cu Zn Pb F¢ AI

10Zn-Cu brass 90.51 R 0-004 0.012


20Zn-Cu brass 79.58 R 0.007 0.005
30Zn-Cu brass 70.02 R 0.006 0.003
40Zn-Cu brass 60.18 R 0-005 0.003
0.86Al-brass 79.04 R 0"86
1.97Al-brass 78.54 R 1'97
The mechanismof stress--corrosioncrackingin the brass-ammoniasystem 57

Specimens for the stress--corrosion cracking tests, and for the observation of the
stress--corrosion behaviour by the replica technique, were 60 × 7 × 1.2 ram. They
were packed in carbon powder to prevent dezincification, annealed for 1 h at 600°C,
and were then stressed by the three-point bend-beam system with a constant deforma-
tion. Tests were carried out in 0.05 M CuSO4 q- 0.5 M (NH4)zSO4, which is thesame
composition as that used by Mattsson, t and also in ammonia vapour. The pH value of
the solution was adjusted to 2.0, 7-4 or I0.0 by addition of sulphuric acid or ammonia.
In order to give the pre-strain to the specimens an Instron tensile test machine
(Type T'I'-CM-L) was used and each specimen was deformed by 2, 5, 10 or 15 per
cent in tension, respectively. In order to investigate how the initial micro-attacked
trenches extend at crystallographic defects, stress-corrosion tests of the annealed bulk
specimens by the three-point bend-beam system were carried out, and the corrosion
behaviour of the same specimens exposed for various times in the corrodent was
examined by the replica technique. All the specimens used were annealed and electro-
polished prior to the experiment. The average grain size was about 5 i~m and the
electropolished specimen surface prior to the experiment did not show any irregularity
under various magnifications. At 5, 30, 60 and 120 min after the start of stress-
corrosion tests, each specimen was removed temporarily from a given corrosive
environment and the corrosion behaviour of the specimen surface was examined.

RESULTS
Stress-corrosion cracking tests
Tests for both annealed and pre-strained bulk specimens of each brass were carried
out in Mattsson's solutions and in ammonia vapour, and the corrosion products on
the specimen surface after the test were examined by electron diffraction. Generally,
with increasing pre-strain, the failure time decreased and the number of cracks
increased, and the specimens which suffered intergranular cracking were covered with
a black oxide layer. The results of stress-corrosion tests are summarized in Table 2.
30% Zn-Cu alloy in Mattsson's solution at pH 2-0 and 10.0 did not fail within
the test periods of 7 and 5 days, respectively. 10Yo Zn-Cu alloy and two kin:Is of
Al-brass also did not fail within 12 days. With the 40% Zn-Cu alloys pre-strained
above 5 per cent, both intergranular and transgranular cracks were observed. In the
other cracked specimens, however, the difference in the form of cracking with the
degree of pre-strain was not recognized, but only intergranular cracking was observed.
All the specimens tested in ammonia vapour failed rapidly; in particular two kinds
of Al-brass failed within 2 h. The difference in the form of cracking with the degree of
pre-strain was not observed, but intergranular and transgranular cracks were observed
in 10--30 % Zn-Cu alloys and in 40 Yo Zn-Cu alloy respectively, and both intergranular
and transgranular cracks were observed in two kinds of Al-brass: intergranular
cracking was predominant in 0"86~o Al-brass, and transgranular cracking in
1.97 % M-brass.
The surface films after the test consisted mainly of cuprous oxide CuzO and were
independent of the corrosive environments, susceptibility and form of cracking.

Stress-corrosion behaviour of thin foil specimens


From the results obtained by the stress-corrosion test, it is evident that the
58 MICHINORI TAKANO a n d SABURO SHIMODAIRA

TABLE 2. RESULTS OF STRESS--CORROSION CRACKING TESTS OF BULK SPECIMENS

Mattsson's Solution Ammonia vapour


Specimens
Surface Pre- Surface
Annealed Pre-strained " film Annealed strained film
10~. Zn---Cu pH 7.4 NC NC I I Cu~O, Cu
20~. Zn--Cu pH 7"4 I I CutO, Cu I I Cu20, Cu
pH 2-0 NC
30 ~. Zn-Cu pH 7"4 I I Cu~O, Cu I I Cu~O
pH 10"0 NC
I for2~o
40~0 Zn-Cu pH 7"4 I I + T for 5~o Cu20 T T Cu~O

0.86 AI-
brass pH 7.4 NC NC Cu20, Cu I -t- T I q- T Cu20, Cu
1.97 AI-
brass pH 7.4 NC NC Cu~O, Cu I + T I + T Cu20, Cu
NC: No cracking.
I: Intergranular cracking.
T: Transgranular cracking.

susceptibility and the form of cracking depend on the corrosive environments, degree
of pre-stain and composition. In order to examine these differences microscopically,
the stress-corrosion behaviour of the thin foil specimens was observed by transmission
electron microscopy. The annealed materials used as the thin foil specimens were
deformed in various corrosive environments.
The micro-stress-corrosion behaviour of 30 ~o Z n - C u alloy in Mattsson's solution
at p H 2-0, 7.4 or I0.0 and of 40% Z n - C u alloy in the same solution at p H 7.4 is
shown in Fig. 1. These micrographs show the micro-corrosion trenches nucleated
along the slip steps which were produced by dislocation movements on the restricted
slip planes under stress. In addition, preferential dissolution was also observed at the
dislocation ends, twin boundaries and grain boundaries, but predominantly at slip
steps. The above experiment was performed under the condition in which inter-
granular cracking occurred easily in the solution at p H 7.4 and also that in which the
cracking occurred with difficulty in the solution at p H 2.0 or I0.0. Although there was
no difference in the mode of initiation of micro-attacks, the nucleated micro-attacks
in the former condition tended to extend immediately over the brass surface. The
typical examples of the surface-extended corrosion traces in 30 ~o Z n - C u alloy and
40 ~o Z n - C u alloy at p H 7.4 are shown in Fig. 2. The selected area diffraction pattern
obtained from the preferential corroded region in 30~o Z n - C u alloy is shown in
Fig. 3. In this ease the corrosion products in the preferentially attacked region consisted
of Cu and Cu20, and the oxide developed epitaxially on the dezincified copper metal.
Zn and ZnO were not detected in the corroded thin foil specimen, and two straight
lines which can be considered as the slip traces produced in the original brass specimen
are visible in the extended films of Cu20 and Cu.
The mechanismof stress--corrosioncracking in the brass-ammoniasystem 59

As stated already, both intergranular cracking and transgranular cracking took


place in 30 ~o Zn-Cu and 40 ~o Zn-Cu alloys in ammonia vapour, respectively. The
stress--corrosion behaviour of these thin foil brass specimens in this corrodent are
shown in Fig. 4. In the two specimens there is no difference in the initiation of micro-
attacks as shown in Figs. 4 (a) and (b), and only the slip steps are preferentially
corroded. In 30 ~o Zn-Cu alloy which cracked intergranularly in this corrodent, the
formation of the surface-extended corrosion as seen in Mattsson's solution at pH 7.4
(see Fig. 2) was not observed in 3 min of stress-corrosion. This difference of micro-
corrosion behaviour in the Mattsson's solution at pH 7.4 and in ammonia vapour will
be discussed later.

Stress-corrosion behaviour of bulk spechnens


The characteristics of stress--corrosion cracking of the bulk specimens depended
remarkably on the corrosive environments and compositions of alloying elements as
seen in Table 2. The nucleation of the micro-stress-corrosion trenches of the thin foil
specimens was independent of the susceptibility and the form of cracking, and took
place predominantly at the disclocation ends, twin boundaries and grain boundaries,
particularly at fresh slip steps. In the experiment of the thin foil specimens, however,
only the initial stage of micro-attacks could be revealed. The earlier reported trans-
mission micrographs (Figs. I and 2) were prepared from the annealed specimens which
plastically deformed, and in this section the corrosion behaviour of the annealed
bulk specimens which plastically deformed by the three-point bend-beam system was
examined by the replica technique.
Figure 5 shows the stress-corrosion behaviour of 30~o Zn-Cu alloy in Mattsson's
solution at pH 2.0, 7.4 and I0.0. Figure 5 (a) and (b) are the micrographs obtained
after 5 and 120 min, respectively. Figure 5 (a) shows the following characteristics:
(a) at pH 2.0 corrosion is so slow that the corrosion trenches along the slip traces are
seen, (b) at pH 7.4 the corrosion morphology extends over the bulk surface cor-
responding to the surface-extended micro-attacks as shown in Fig. 2 (a), and (c) at
pH 10-0 the corrosion rate is very high, and the original surface topography of the
bulk specimen has already disappeared, followed by the occurrence of general
corrosion. The following characterislics can be seen from Fig. 5 (b): (a) at pH 2.0
the surface corrosion morphology in Fig. 5 (a) still remains, suggesting that the stress-
corrosion cracking of brass in this solution is difficult to occur, (b) at pH 7.4 the
corrosion morphology within the grains as shown in Fig. 5 (a) does not appear, but
the grain boundaries are significantly corroded, indicating the appearance of inter-
granular cracking, (c) at pH 10.0 corrosion is much more severe than that after the
5 min period of exposure.
The stress-corrosion behaviour of 30 ~o Zn- and 40 ~o Zn-Cu alloys and 1.97 YoAI-
brass in ammonia vapour are shown in Figs. 6 (a), (b) and (c), respectively. Figure 6
represents the corrosion morphology of the specimen surface obtained after 5 and
120 min (upper 5 min, lower 120 min). After 5 min, corrosion along the slip traces is
seen in 30 ~o Zn-Cu alloy, but the tendency toward general corrosion has already
been seen in 40~o Zn-Cu alloy and in 1-97Yo Al-brass. After 120 min, corrosion
proceeds significantly at grain boundaries in 30~o Zn-Cu alloy, suggesting the
initiation of intergranular cracking. However, the morphology of corrosion in
60 Mxcr~mOR1TAKANOand SASUROSHIIdODAIRA

40 ~o Zn-Cu alloy and in 1"97~o Al-brass shows extremely irregular roughness, and
the nucleation of micro-fracture in the grains of 40 ~o Zn-Cu alloy is observed.

DISCUSSION
In the present experiments the 30 ~o Zn-Cu alloy in Mattsson's solution at pH 2-0
and 10.0 did not fail. In particular, in the solution at pH 10.0 the specimens were
severely corroded and their thickness was rapidly decreased by corrosion, so stressing
could not be applied to the specimens. Mattsson1 has recently reported the electro-
chemical reactions of 37~o Zn-Cu alloy in the solution and found transgranular
cracking in the solution having high pH values. The observed corrosion behaviour in
the solution at each pH value in this experiment, generally, agree with his results.
The micro-attacked trenches were very evident along the slip steps in the grains
as shown in Figs. 1 and 4. The occurrence of these micro-trenches by a combined
action of stress and corrosion suggests the nucleation of stress corrosion. Similar
micro-corrosion behaviour, however, was observed even in the case of high stress-
corrosion cracking resistance?9 The nucleation and propagation of stress-corrosion,
therefore, cannot be elucidated according to the same mechanism. Previously, the
authors reported x9that in austenitic stainless steels the mechanisms of nucleation amd
propagation of stress-corrosion cracking were different from each other.
Tromans and Nutting2° have reported that the preferential attacks of the thin foil
30~o Zn-Cu alloy in Mattsson's solution (pH 7.3) occur at grain boundaries and at
individual dislocations adjacent to grain boundaries, and these micro-attacks are
associated directly with intergranular micro-cracking. RSnnquist21 has also demon-
strated that the micro-attacks occur at grain boundaries under a small stress and at
slip steps in the grain under a large stress. In this experiment, however, the nucleation
of stress-corrosion was not associated with the susceptibility and the form of cracking,
and took place remarkably at the fresh slip steps. This fact agrees well with the results
of the previous report? 9 The surface film consisted mainly of cuprous oxide in all
cases, being independent of the susceptibility and the form of cracking.
Whether the nucleated micro-corrosion trenches continuously proceed to cracking
or cease to extend will be determined by the competition between passivation due to
the action of H~O or dissolved oxygen and activation due to the breakdown of the
film by the action of ammonia or other anions, rather than by the chemical com-
positions of surface films. Forty and Humble, x3 Pickering and Swarm, 1~and Hoar and
Bookeris reported that the corrosion product on a brass surface in various ammonia
environments consisted of small platelet cuprous oxide. In our work, under the
condition which induced intergranular cracking, the cuprous oxide developed
epitaxially on the dezincified copper metal and existed in the form of grains as large
as ,,- 1 lain (Figs. 2 and 3). The oxide, which nucleated on the slip steps, would act as
the cathode to the brass substrate and extend over the brass surface by the electro-
chemical reaction. For 30 ~o Zn-Cu alloy intergranularly cracked in ammonia vapour,
the micro-attacked trenches which occurred on the slip steps at the initial stage did
not extend so fast as that in Mattsson's solution, because at the initial stage the
electrochemical reaction in vapour could not proceed as fast as that in aqueous solution.
This agrees with the result of the stress--corrosion behaviour of the bulk specimens
examined by the replica technique. Comparing Fig. 5 (Mattsson's solution, pH 7.4)
FIG. 1. Preferential micro-attacks obtained in deformed thin foil specinaens in
Mattsson's solution for 3 min.
(a) 30 Zn-Cu brass (pR 2.0).
(b) 30 Zn-Cu brass (pFI 7.4).
(c) 30 Zn--Cu brass (pH 10.0).
(d) 40 Zn-Cu brass (pFI 7-4).

FIG. 2. Typical examples of surface extended corrosion obtained in deformed thin foil
specimens in Mattsson's solution (pH 7"4) for 3 min.
(a) 30 Zn-Cu brass, (b) 40 Zn-Cu brass.
II (~i 3) Cu

. (ooz)C~
20

"~o e#
-II .Cu
lilt { )c.zo
10d
(M

4' ms

g
o

FIG. 3. Selected area diffraction pattern from preferential corroded region obtained in
deformed thin foil 30 Z n - C u brass in Mattsson's solution (pH 7.4) for 3 min.

FIG. 4. Preferential micro-attacks at slip steps obtained in deformed thin foil specimens
in ammonia vapour.
(a) 30 Zn-Cu brass, (b) 40 Z n - C u brass.
FiG. 5. Stress-corrosion behaviour of 30 Z n - C u brass in Mattsson's solution at pH
values of 2.0, 7.4 and 100.
Ca) Exposure time 5 min, (b) Exposure time 120 rain.

FIo. 6. Stress~orrosion behaviour of (a) 30 Z n - C u brass, (b) 40 Z n - C u brass, and


(c) 1.97 AI-brass in ammonia vapour. Upper 5 rain. Lower 120 min.
The mechanism of stress--corrosion cracking in the brass-ammonia system 61

TABL~ 3. RELATIONBzrw~E~ THE PROPERTY


OF SURFACE FILM AND THE FORM OF CRACKING
(~ 37 Zn-Cu Brass. CuSO4 + (NH4)~SO4 (0-05 g/l Cu + 1M NFIa)

pH Surface Crack
4 Brown-red T
4"7 Brown-red I, T
5"2- 5"5 Interference colour T
6.3- 6.6 Black I, T
6'7- 7'3 Black I
9.4-11.2 Dark stain T

Reference 1.

(ii) 30 Zn-Cu Brass. Ammonia Solution

Solution Surface Crack

IM or 5M NH4OH + CuSO4 Visible film I


Visually bare T
1 or 5M NI-I4OH + CuCl~ Visible film T
Visually bare T
I or 5M NH4OH + Cu(NO~)~ Visually bare T
Filmed surface N C

Reference 2.

(iii) 30 Zn--Cu Brass. 15N Ammonia Solution + Cu, pH > 13

Cu Content
(g/l) Surface Crack

0.5 No visible film N C


0.5-1-5 Brown film, loosely I, T
1.5-3.25 No visible film I, T
3-25 Tarnish I

Reference 3.

(iv) 30 Zn--Cu Brass. 0.04M Cu + I'5M Total Ammonia

pH Surface Crack

5 Copper c31our T, I
6--7.5 Blue-black tarnish I
8 Blue-black tarnish I

Reference 4.

(v) 30 Zn-Cu Brass. 5 %, 25 ~o Nt-140H + 0-5 y. (NH,),CrO,

Surface Crack
Grey translucent T
Interference colour T
No visible corrosion T

Reference 22.
62 MICmNORI TAKANOand SABUROSmMODAIRA

and Fig. 6 (ammonia vapour) for 30 YoZn-Cu alloy, a remarkable difference in stress-
corrosion behaviour can be seen after 5 min of the stress--corrosion test, i.e. the former
showed the surface-extended corrosion and the later corrosion traces along the slip
lines. However, the corrosion remarkably penetrated into grain boundaries in both
cases after 120 min, suggesting the occurrence of intergranular cracking.
When transgranular cracking occurred, the nucleated micro-trenches on the slip
steps neither extended over the specimen surface nor formed the thick Cu20 oxide of
large grain size as seen in Fig. 7 (Mattsson observed transgranular cracking at
pH 10.0) and Fig. 4 (b), and the appearance of the specimen surface was not smooth,
but showed a topography of general corrosion as seen in Figs. 5 and 6. Recently,
there are many investigations1-4. 22 about the relation between the properties of the
surface films and the form of cracking. Those results are summarized in Table 3.
Excepting the results obtained in the solution containing CI- ions, Table 3 indicates
the occurrence of transgranular cracking when the surface films in the ammonia
environment are not thick.
From the experiments and considerations mentioned above, it is apparent that the
mechanical properties of surface films (grain size, thickness, porosity, hardness and
strength, etc.) play an important role in the process of stress--corrosion cracking.
From the viewpoint of the role of the surface films, the following hypotheses are
proposed for the mechanism of intergranular stress-corrosion cracking of Cu-Zn
alloys in the ammonia environment.
(1) The fresh coarse slip steps produced by the movement of dislocations under
stress in the corrodent are preferentially corroded resulting in the micro-attacked
trenches; these micro-attacked regions consist of the surface films of Cu20-Cu layers
(Fig. 7 (a)).
(2) Cu~O-Cu films developed on the slip steps act as the cathode to the brass
substrate and accelerate the electrochemical reaction. As the specimen surface is very
rapidly corroded, the Cu20-Cu films extend immediately over the brass surface. These
surface-extended films develop epitaxially to the brass substrate on the original slip
steps, forming thick and large grains, so that the movement of dislocations on the slip
plane below those films is blocked. On the other hand, the other slip steps could be
newly formed in the uncorroded region, and these new slip steps would exhibit the
same behaviour as shown in Fig. 7 (a) (Fig. 7 (b)).
(3) The brass surface is covered with thick Cu20-Cu films of large grain size. At
this stage the slip steps in the grains cannot develop, because the movement of the
dislocations on the emergent slip planes are almost blocked by the surface films. On
the other hand, dislocations, vacancies and impurities are present in grain boundaries,
and unde stress the grain boundaries are slipped by the movement of dislocations and
are disturbed by the interaction of the dislocations and vacancies with the impurities.
Furthermore, the surface films on the grain boundaries involve many defects and the
diffusion of the corrodent to the tip of micro-crevices, so that the chemical reaction
in the grain boundaries are intensified and the local corrosion is accelerated. The path
of stress--corrosion cracking thus changes from the slip steps in the grain to the grain
boundaries (Fig. 7 (c)).
As the surface film produced in the corrodents responsible for transgranular
cracking was not so thick nor so large in grain size as that in the case of intergranular
The mechanism of stress--corrosion cracking in the brass-ammonia system 63

Grain
Grain boundary
boundary Amonia Slip step
/ aqueous
solution

(a)
Brass

(b)

(c)

FIG. 7. Schematic representation of intergranular stress-corrosion cracking of brass in


ammonia aqueous solution.
(a) Showing the preferential micro-attack at slip step.
(b) Micro-attack begins to extend over the brass surface and the movement of dis-
locations at coarse slip plane is locked by Cu20 and Cu layers.
(e) After brass surface is covered with these layers, crack propagates along grain
boundaries.

cracking, such a film would not so strongly block the development of the slip steps
created by the movement of the dislocations. Therefore, the nucleated micro-attacked
trenches along the slip steps within the grains continuously grew up into trans-
granular cracking. In this case, the surface films are ruptured by the increased shear
stress associated with the development of slip steps as shown by the surface topography
of the micro-fracture of 40 ~o Z n - C u alloy (Fig. 6).
Whether the alloys in which the dislocations are distributed in a planar arrange-
ment fail by intergranular or transgranular cracking could be determined by the
relative values of the amount of shear stress at the tip of the dislocation pile-up and
the strength of the surface films formed in a corrosive environment; that is, if the n
dislocations pile up against the brass surface, the amount of shear stress acting on the
surface films is equal to n~', where ~ is the shear stress. Now denoting the strength of
the surface films as F, the development of slip steps would be obstructed and inter-
granular cracking occurs for F > n~r; for F < nr, transgranular cracking may be
preferred. Whether or not the surface films produced in the corrodent are ruptured by
the development of steps would depend on the thickness, porosity, grain size, degree
64 MICI-ffNORITAKANO and SABURO SHIMODAIRA

of pre-strain of brass substrate and the coherence of surface films to the brass sub-
strate, etc. These factors would also depend on the corrodent, composition of alloying
elements and amounts of stress.
Transgranular cracking thus propagates by the corrosion of the fresh slip steps
developed under plastic deformation, and the surface films produced are mechanically
ruptured by the shear stress at the growing steps, facilitating the diffusion of the
corrodent to the tip of microcracks. The mechanism of stress-corrosion cracking in
other homogeneous alloys may be explained according to the above-mentioned film
theory.
Very few of the numerous micro-trenches nucleated on the slip steps in the early
stage grow up into cracks. This fact can be explained as follows: the stress-corrosion
cracking occurs in the corrosive environment where the influence of passivators is
stronger than that of activators, and therefore repassivation in the slip steps usually
prevails as corrosion progresses. Furthermore, the stress field in the alloys is micro-
scopically non-uniform. Under these conditions, the corrosion rates of the micro-
trenches into the interior of the alloy would become different from one another with
the lapse of time. At the tip of the most deeply corroded regions on the slip planes, a
microscopic stress concentration occurs, and the movement of dislocations on these
slip planes is further activated and the fresh slip planes are easily exposed to the
corrodent. Passivators such as dissolved oxygen would also find difficulty in diffusing
into the micro-crevices. The corrosion of these slip planes, therefore, is accelerated
and cracks are formed. Then the corrosion would penetrate not only along the same
slip planes but also along the adjacent slip planes, branching off at the planes of cross-
slip. The segregation of solute atoms (impurity atoms) should also play an important
role in the penetration of the corrosion.
The above explanation is concerned with the transgranular cracking when the
applied stress is large enough to rupture the surface films. Even if the applied stress
is not sufficient to rupture the surface film, a crack may develop at the base of a
corrosion pit since here slip is presumably not hindered by the presence of a surface
film. There appears to be a close relationship between pitting and stress-corrosion.

CONCLUSIONS
From the results of these experiments, the following conclusions can be obtained.
(1) The susceptibility and the form of stress-corrosion cracking in the brass-
ammonia system depend on the nature of the corrosive environment, the composition
of alloying elements and the degree of pre-strain. On the other hand, the nucleation of
the micro-stress corrosion trenches is independent of the susceptibility and the form of
cracking, and take place predominantly at the slip steps in all cases.
(2) Under the condition of susceptibility to intergranular cracking, thick cuprous
oxide of large grain size is formed over the slip steps. This surface film obstructs the
development of steps in the grains. In the grain boundaries the dislocations and
vacancies move considerably under stress, resulting in the formation of slipped regions,
and therefore the grain boundaries become chemically active and corrosion penetrates
along these boundaries.
(3) When the strength of the surface films is not so high as to obstruct the develop-
merit of steps created by the movement of the dislocations, the films are ruptured by
The mechanism of stress-corrosion cl'acking in the brass-ammonia system 65

shear stress and the corrosion along the slip planes proceeds, resulting in the occurrence
o f transgranular cracking.
(4) The transition from intergranular to transgranular cracking depends on the
mechanical properties o f the surface films produced in a corrosive environment,
(5) W h e n the applied stress is not so large as to rupture the surface films, the pits
nucleate and the node regions having no surface films are formed at the b o t t o m o f the
pits, where slip occurs easily, forming the nucleus in the initiation o f stress-corrosion
cracking.
(6) Transgranular cracking propagates by the corrosion o f fresh slip steps produced
at the tip o f the micro-fracture. The segregation o f solute atoms (impurity atoms) to
the slip planes which form the chemically active path plays an important role.
The mechanism o f stress--corrosion cracking o f ordinary homogeneous alloys can
be explained according to the above-mentioned film theory.

REFERENCES
1. E. MATrSSON,Electrochimica Acta 3, 279 (1961).
2. W. Lw~.s, Corrosion 21, 125 (1965).
3. E. N. Puon and A. R. C. W~STWOOD,Phil. Mag. 13, 167 (1966).
4. H. E. JOHNSONand J. L~A, Corrosion 22, 178 (1966).
5. M. E. WmTAr~R, Metallurgia Nov.-Dec., 21, 66 (1948).
6. A. K. LAnn~ and T. BAN~E, Corros. ScL 5, 731 (1965).
7. P. R. SwAn, Corrosion 19, 102 (1965).
8. W. D. ROBERTSONand A. S. TETELEMAN,Strengthening Mechanism in Solid, American Society of
Metals, Novelty, Ohio, p. 217 (1960).
9. Y. MURAr,.AMX,H. YOSHIDAand Y. IKAI,J. Japan Inst. Metals 1215 (1965).
10. F. C. At.THOr,Z. Metallk. 36, 177 (1944).
11. T. A. READ, J. B. REED and H. ROSENTrr.~, Symposium on the Stress Corrosion Cracking o f
Metals, p. 90, ASTM (1944).
12. H. L. LOGAN,J. Res. natn. Bur. Stand. 48, 99 (1952).
13. A. J. FORTYand P. HUMBLE,Phil. Mag. 8, 247 (1963).
14. A. J. McEVILYand A. P. BOND,J. electrochem. Soc. 112, 131 (1965).
15. M. TAKANOand S. SmMOD~RA, Trans. Japan bzst. Metals 7, 193 (1966).
16. M. TAKANOand S. SHIMOD~dRA,J. Japan Inst. Metals 29, 553 (1965).
17. H. W. PICIr.EmNGand P. R. SWANN,Corrosion 19, 373 (1963).
18. T. P. HOARand C. J. L. BOOKER,Corros. Sci. 5, 821 (1965).
19. M. TAKANOand S. ShUMOD~RA,Trans. Japan Inst. Metals 7, 186 (1966),
20. D. TRO~.NS and J. NtrrnNG, Corrosion 21, 143 (1965).
21. A. R6NNQtnST, 3rd Int. Congr. metallic Corros. p. 151, Moscow (1966).
22. W. LYNES, Corrosion 22, 113 (1966).