Culpan & Rose: Corrosion o/Cast Nickel Aluminium Bronze in Sea Water 161

5 Ni 5 F~ o Ni OFc

1000 1000

u
o ~
uJ
uJ
a:
800 a: 800
:>
~~ ~:>~
a: a;
uJ uJ
a+{J +1e+12 Q.
~ 600
.•.a
~
~
uJ
Ie ~
uJ

~ Clot" 12
400
1,
400
8 9 10 12 8 9 10 II 12

WEIGHT PERCENTAGE WEIGHT PERCENTAGE

ALUMINIUM ALUMINIUM

(a) (b)

Fig. 1 (aJ Vertical section of the Cu-Al-Ni-Fe system at 5% Ni,

5% Fe
(bJ Binary Cu-Al system
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Cast Nickel Aluminium Bronze

Development of microstructure
A vertical section of the copper, aluminium, nickel, iron
equilibrium diagram, from the work of Cook, Fentiman &
Davies,8 is shown in Fig. 1, together with the copper aluminium
binary system. Compared with the binary system the principal
difference is the presence of the " phase, which absorbs
aluminium from the matrix, and hence extends the apparent
range of the a field. Thus, under equilibrium conditions, ~ is not
retained below 6000e unless the aluminium content exceeds
11%, compared with 9·4% in the binary system. The "
precipitation in the a matrix considerably increases the
mechanical strength and at the same time the reduction in
ductility is not as marked as would occur if ~ had been formed
in a binary alloy to give equivalent strength. This is the most
outstanding advantage which alloys of this type have over other
aluminium bronzes. The absence of ~ also avoids any danger of
eutectoid formation unless the aluminium content exceeds 11%.
According to earlier work 3,9 nickel aluminium bronze
solidifies with an all 13 structure, from which " and some a are
precipitated on cooling to about 900oe. The K particles formed
at this stage are coarse and rounded and often take the form of
rosettes. Below about 900 e the remaining ~ is transformed to a
0
finely divided mass of a and Ie, with the" frequently being of a
lamellar form. Further cooling to room temperature, if
sufficiently slow, results in a further precipitation of fine "
within the a. grains. More recent work has shown that the "
phase can exist in a number of forms depending on its
composition and morphology. Weill-Couly & ArnaudlO have
identified various forms of " that are evident in cast nickel
aluminium bronze, as shown in Fig. 2. Using electron probe
microanalysis they obtained an indication of the chemical
composition of some of the phases. These were identified as
follows:
Fig. 2 Typical as cast microstructure of nickel aluminium bronze
showing constituent phases xl ,000
The present authors have recently carried out an investi-
gation into the development of microstructure in as cast and
heat treated nickel aluminium bronze. II The analyses of the
phases present were carried out using energy dispersive analysis
techniques with a scanning electron microscope (SEM) for bulk
specimens and a scanning transmission electron microscope
(STEM) for extraction replica and thin foil specimens. With
these instruments the spot size for analysis is about 20 nm.
Quantitative analyses were carried out using the Nazirl2
technique for bulk specimens and the Cliff & Lorimer 13
technique for electron transmitting specimens. Aspects of this
work relevant to the corrosion behaviour of as cast and heat
treated alloys are briefly summarised below.
It was shown that the phase changes that occur during
solidification of a nickel aluminium bronze are substantially the
same as those described earlier. The breakdown of the ~
phase occurs at the 0./13 interface with the lamellar eutectoid
growing at right angles to the interface. It is probable that the
rosette KI phase can cause nucleation of KIII around its
perimeter which may explain the dark etching band surrounding
the leI particles seen in as cast microstructures. This is shown

"I a globular or rosette form of composition, 69% Fe,

more clearly in Fig. 3 where the continuity between the lamellar
form of KIll and the surrounding band is evident. In a normal as
13% Cu, 13% Ni, 6% AI. cast structure there would be present a, K I, "u, "III and "IV,
"II and "III a globular and lamellar form of composition, with possibly some retained ~. A summary of the chemical
26-43% Fe, 13-20~!;) Cu, 23-34% Ni, 18-20% AI. composition of these phases is shown in Table I.
KIV a fine precipitate within the a grains, thought to be Heat treated microstructures
iron rich.
Heat treatment of the as cast nickel aluminium bronze at
is thought to be based on Fe3AI and KIll based on
"I temperatures under 8300e did not produce any changes in the
NiAI-FeAI. This work, to determine the chemical composition major phases present, except that any retained 13 was
of the K phases, was done using electron microprobe analysis transformed to Q +K. There was, however, a significant increase
which, due to a relatively large electron beam spot size, is in the amount of fine precipitate present within the a grains of
unlikely to analyse the very fine precipitates without consider- heat treated specimens, shown in Fig. 4, which follows treatment
able interference from the adjacent a matrix. at 675°c for 6 h. Closer examination of this precipitate has

Br. Corros. J., 1979, Vol. 14, No.3

 162 Culpan & Rose: Corrosion o/Cast Nickel Aluminium Bronze in Sea Water

V)
M N •....•
I I I ~+1 I
;:3
U +1 +1 +1
00 ~ ~
M ~ M M

Z I I I +1
I
+1 +1 +1
C';S
0
M :! V)
M ;;;
.~ V) \0 -.:t M
0..
+1 +1 +1 +1
~ I
(I)

~ I I I
(I)

.•......•• -.:t M r- 0
M \0 N -.:t
::E
~ •....• -.:t M N
f--
C/)
I:
6 6 0 0

::E I I I +1 I
.-.-+1 .-v:+1 .-+1
.-
~ "?

I on N -.:t N
I +1 +1
+1 +1
~ I I I I Fig. 3 Rosette Kl phase surrounded by lamellar KIll x3,300
~ :! r-
N
r-
•....•
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-.:t -.:t -.:t \0

+1 +1 +1 +1
I
;:3
QJ u I I I
=
N \0 M \0 M
00 N N N
0
r. V) V)
"J:) N -.:t

E Z +1 I I +1 +1 +1 I I
=
-.:t 00
M
.. \0
·S
.-+1
N N
;§
"s I:
V) V) 00

=
"i
:.a
f--
~
(I)

~ I I +1
~
+1
N
+1
0
I I
~~
.•......•• M N \0
N
::E
~ ~
-
"S f--
M M
~ ~
C/) I:
0 6 0 0
~~ ::E +1 I I +1 +1 +1 I I
.5
~ 00
0 .- .- .-
"? "? "?

=~
UJ -.:t -.:t
...:l N -.:t
co +1 +1
~
QJ
+1 I I +1 I
~ ~
I
~
QJ N
r. 00 0\
c.. N

~
~~
QJ -.:t
+1 ~
V) V) -.:t .-+1
..c +1
.-
+1 +1
;:3
~
\0
~
c...c..
U V) N

0
V)
00
00
~ N
\0
N ~
~
";j
"i
~
=~ Z
.-"'+1!" v:
M
+1
~
+1
N
+1
•....•
+1 .-
N
-.:t
N
M r- N
Heat treated at 675°cfor 6 h; air cooled x330
V)
V)
•....• -.:t Fig.4
"i N M
~ N

"s
QJ
...::.::
"3
r-
..c N r- M
6
-.:t

.-
o:l +1 "? +1 +1 +1
U .•......••
~
Q)
+1
\0 V)

::E r- V) N N
N M

~
C/)
N V) M N
N
\0

•....• \0 M
-.:t
6 0
M
0 •....•
I:
::E +1
~
.-
C? 6
+1
+1 0
+1
+1
v: .- .- "?

.- N
N
N
N
.-
.-+1
r:-
V) M \0 M

~
r:- +1 +1 +1 +1 \0
.-
0\

M
00
00
~ .- .-
0\ 00 0
N
N

::<
"'0

Q) (I)

~- -
en en
:::: ::: > :.a
C';S
..c:
p.,
tj c:o... ::< ::< ~ ::< '0
I-<
Q)
..c:
0.
C/)

Fig. 5 Heated treated at 675°cfor 6 h; air cooled x6,700

Dr. Corros. J., 1979, Vol. 14, No.3

 Culpan & Rose: Corrosion o/Cast Nickel Aluminium Bronze in Sea Water
Fig. 6 Structure of weld metal, heat affected zone and parent
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metal x43
Fig. 7 Selective phase attack adjacent to weld with associated crack;
as cast x53
shown that it is a mixture of two distinct forms, as in Fig. 5.
One type, usually spheroidal but on occasions closely
resembling tiny KI rosettes, was iron rich and was probably
connected with the KJVprecipitation found in as cast materials.
The second form (approximately 1,um x 0·1 ,urn), designated by
the authors as Kv, was cylindrical or lath shape and was rich in
nickel and aluminium. Above heat treatment temperatures of
'" 830°c the alloy can enter the P + a + K region. Heat
treatment in this region results in partial or complete spheroid-
isation of the K phase, depending on the heat treatment time.
The chemical analyses of Kv and the spheroidised K phase are
also shown in Table I.
Welding of nickel aluminium bronze
Nickel aluminium bronze was often arc welded using the
binary 10% aluminium filler metal to avoid problems with weld
cracking associated with a nickel aluminium bronze weld metal.
As discussed previously, such exposed binary alloy could be
susceptible to selective phase corrosion in an aggressive
Dr. Corros. J., 1979, Vol. 14, NO.3
163
Fig.8 Microstructure at corrosion interface; as cast x530
Fig.9 Microstructure at corrosion interface; as cast x3,300
environment, and therefore a deposit of nickel aluminium bronze
was normally overlaid on the binary weld metal. This
arrangement was successful providing that the outer layer
remained intact, but severe selective phase attack occurred when
the coating was damaged either in service or during the weld
grinding operation.
It has been shown 14 that the sub-solidus cracking of nickel
aluminium bronze welds is due to the low strength and very low
ductility of the weld metal at elevated temperatures. Impurities
such as lead, tin and bismuth have a detrimental effect on hot
ductility and, if these impurities are controlled, welding of nickel
aluminium bronze can be carried out with matching filler metal.
The structure of a matching nickel aluminium bronze weld is
shown in Fig. 6. Due to the rapid cooling the structure consists
of fine Widmanstatten a in a matrix of retained high
temperature P phase. Immediately adjacent to the weld fusion
zone, areas of a and lamellar K eutectoid have reverted to the 13
phase during welding, which on subsequent rapid cooling is
retained as martensitic 13. The a phase is essentially unchanged
in the HAZ.
 164 Culpan & Rose: Corrosion o/Cast Nickel Aluminium Bronze in Sea Water
Fig. 10 Corrosion attack adajcent to weld; heat treated at 830°c for
Downloaded by [Monash University Library] at 03:01 11 April 2016
2 hfollowing welding
The effect of heat treatment on niCkel aluminium bronze weld
metal is similar to that on parent metal. At temperatures above
600°c the retained ~ within the weld and HAZ is transformed to
a very fine dispersion of a and K, together with the fine dense
precipitation of Kv within the a grains of the HAZ. As the heat
treatment temperature is increased the I( within the weld metal
coarsens, with little change in the HAZ structure, until the
temperature exceeds 830°c, when a significant amount of ~ is
formed.
Corrosion Trials with Nickel Aluminium Bronze Castings
Experimental
Nickel aluminium bronze castings of composition, aluminium
9·5%, nickel 4·7%, iron 4·3%, manganese 1%, copper
remainder, were exposed to sea water in Portland Harbour for a
period of one year. The alloy was examined in four conditions:
(1) as cast,
(2) as cast and welded,
(3) as cast and heat treated,
(4) as cast, welded and heat treated.
Two heat treatments were used, 675°c for 6 h and 830°c for
2 h, in both cases followed by an air cool. In some cases perspex
strips were attached to areas of the castings to form artificial
crevices. Welding was carried out by the MIG process using
nickel aluminium bronze filler wire. Following sea water
exposure, selected areas were sectioned and examined by optical
and electron microscopy. Chemical analysis of the phases
present in the bronzes was carried out using energy dispersive
analysis techniques reported previously.u-13 Certain specimens
were observed in a Zeiss Electropolishing Microscope modified
to circulate sea water continuously across the surface of the
specimen. These were inspected following 24, 48 and 90 h
exposure.
Corrosion of as cast nickel aluminium bronze
In general, the surface corrosion of this material was confined
to slight attack of the a phase within the a + K eutectoid with the
deposition of a thin film of copper. A much more severe form of
attack was observed adjacent to the weld metal boundary shown
in Fig. 7. Here the penetration was greatest in the parent metal
just outside the heat affected zone. In this region there was a
band of selective phase corrosion and the consequential copper
deposition '" 1 mm wide parallel to the weld/parent metal
interface. In some cases the internal stress in the casting caused
the porous corroded area to crack. Using detailed optical
microscopy as shown in Fig. 8, which is taken at the edge of the
corroded region, it appears that the corrosion proceeds along the
lamellar KIII phase with the subsequent removal of most of the
grain boundary eutectoid. It can also be seen that the large KI
particles were rarely attacked and usually remained within the
corroded structure. The fine a / ~ weld structure was not
attacked. At the higher magnifications available with scanning
electron microscopy it was clear that the impression formed by
optical microscopy, that the KIll dissolved preferentially, was
not correct and, in fact, attack occurred by dissolution of the a
adjacent to the lamellar KIll with subsequent removal of the KIII.
This is shown in Fig. 9 at the edge of the corrosion region.
Castings which had been immersed with artificial crevices
were also examined. .l\round the crevice, the damage was
visually similar to that seen at the HAZ of welded specimens.
However, on sectioning and microscopical examination, it could
be seen that the surface attack was restricted to the few grains
adjacent to the surface. The attack appeared to proceed along
the a phase in the grain boundary eutectoid but, unlike the
corrosion adjacent to the HAZ, it did not penetrate appreciably
into the metal structure.
Corrosion of heat treated nickel aluminium bronze
Two heat treatment temperatures were used, namely 675°c
for 6 h and 830°c for 2 h. As discussed previously, the first
treatment does not change the basic microstructure of the alloy
except to form a dense precipitation of fine Kv within the a
grains. The second treatment produces a partial spheroidisation
of the K phase present, particularly the lamellar eutectoid phase.
With the lower temperature treatment crevice corrosion
behaviour was similar to that of the as cast material. The attack
took place along the a of the a + K eutectoid and was confined
to the surface grains of the metal. The change in corrosion
behaviour following heat treatment was much more significant
for the HAZ corrosion. In the case of the lower temperature
treatment there was very little attack in this region, although the
microstructure was similar to that exhibited in as cast structures
which show severe selective phase attack. The castings heat
treated at the higher temperature also show much improved
resistance to corrosion at the HAZ of welds, compared with as
cast material. It can be seen in Fig 10 that, although attack also
takes place by dissolution of the a adjacent to the grain
boundary K phase, such attack does not penetrate appreciably
as this phase is discontinuous. The higher temperature heat
treatment changes the weld microstructure in that the fine a / p
structure is transformed to a and globular K with areas of ~ at
grain boundaries. It was noted that, where the ~ formed a
continuous grain boundary phase in the weld, significant
corrosion occurred, again leaving areas of redeposited copper.
Corrosion of nickel aluminium bronze in flowing sea water
It was found that the optical microscope fitted to the
apparatus to examine the specimens in situ was unusable after
short exposure times due to the build up of corrosion products,
and to the limited magnification and depth of focus of the
microscope. The specimens were therefore removed after certain
time intervals, cleaned ultrasonically, and examined in the
scanning electron microscope. Fig. 11 shows the surface of the
as cast specimen and the specimen heat treated at 675°c,
following 90 h immersion. It can be seen that the corrosion
attack in the heat treated specimen is very uniform and does not
appear to be related to its metallurgical structure. The structure
is revealed in the as cast specimen which shows preferential
attack, particularly at the grain boundary eutectoid regions. This
is shown more clearly at higher magnifications as in Fig. 12. It
Br. Corros. J., 1979, Vol. 14, No.3