235

Canadian Metallurgical Quarterly, Vol 39, No 2, pp 235-246, 2000

© Canadian Institute of Mining, Metallurgy and Petroleum
Published by Canadian Institute of Mining, Metallurgy and Petroleum
Printed in Canada. All rights reserved

PASSIVATION OF LASER-TREATED NICKEL ALUMINUM

BRONZE AS MEASURED BY ELECTROCHEMICAL
IMPEDANCE SPECTROSCOPY
R.D. KLASSEN1, C.V. HYATT2 and P.R. ROBERGE1
1
Royal Military College of Canada, Dept. Chem./Chem. Eng., Kingston, Ontario, Canada
2
Defense Research Establishment Atlantic, Dockyard Laboratory, Halifax, Nova Scotia, Canada

(Received April 1999; in revised form August 1999)

Abstract — Electrochemical impedance spectroscopy was used to assess the corrosion behavior of the
weld zones and surface conditions of a laser-clad nickel aluminum bronze immersed in a 3.5% neutral
saline solution. The zones and conditions examined included: (i) as-cast base material; (ii) laser-clad
material with the high temperature oxide from welding intact; (iii) polished laser-clad material and (iv)
specimens representative of just the as-deposited and reheated zones of the laser-clad surface. A pseudo
steady-state level of passivation was reached in all the samples within 40 hours. The reheated zone pas-
sivated more slowly than the as-deposited region and both weld zones passivated more quickly than the
base material. Electrochemical impedance data illustrated a transition during the passivation process of
the polished specimens that is consistent with the development of a film layer that restricted mass trans-
fer. The welding oxide from the laser treatment immediately behaved as a passivation film that was indis-
tinguishable from that which eventually develops on polished specimens.

Résumé — On a utilisé la spectroscopie à impédance électrochimique pour évaluer le comportement de

corrosion des zones de soudure et les conditions de surface d'un bronze de nickel et d'aluminium plaqué
au laser, immergé dans une solution neutre saline à 3.5%. Les zones et les conditions examinées
incluaient: (i) matériel de base brut de coulée, (ii) matériel plaqué au laser avec l'oxyde de haute
température provenant du soudage, toujours intact, (iii) matériel plaqué au laser, poli et (iv) spécimens
représentatifs de zones telles que déposées et de zones re-chauffées de la surface plaquée au laser. Tous
les échantillons ont atteint, en dedans de 40 heures, un niveau de passivation en régime pseudo-
permanent. La zone re-chauffée a été passivée plus lentement que la région telle que déposée et les deux
zones de soudure ont été passivées plus rapidement que le matériel de base. Les données d'impédance
électrochimique ont illustré une transition lors du procédé de passivation des spécimens polis qui est
consistante avec le développement d'une couche en film restreignant le transfert de masse. L'oxyde de
soudage provenant du traitement au laser s'est comporté immédiatement comme un film de passivation
indistinct de celui qui se développe éventuellement sur les spécimens polis.

INTRODUCTION improved, unaffected or degraded slightly depending on the

Laser cladding is a promising method for the fabrication,
repair and surface engineering of nickel aluminum bronze
(NAB) alloys. These alloys are used in marine engineering
and other applications because they are easily fabricated
and because they have excellent bulk and surface proper-
ties. In most applications, it is the surface properties that
limit the performance of these alloys. Recently, it has been
shown that laser cladding can improve the cavitation-ero-
sion, wear and corrosion-erosion resistance of nickel alu-
minum bronzes. General corrosion resistance has been
corrosion conditions, the surface condition, the alloy com-
position and the cladding conditions. This paper addresses
the complex issue of the general corrosion behavior of the
laser-clad surfaces of these alloys with a view towards
optimizing their properties.
Understanding the general corrosion resistance of these
alloys is complicated by the heterogeneous nature of clad
surfaces. The clad surface is made up of as-deposited areas
and reheated lines which consists of as-deposited material
that was reheated sufficiently by a subsequent pass such

CANADIAN METALLURGICAL QUARTERLY

236 R.D. KLASSEN, C.V. HYATT and P.R. ROBERGE
that some metallurgical transformation occurs. Additionally
on some parts of the clad surface, prior welding oxide may
remain. To define a study on the corrosion behavior of
laser-clad nickel aluminum bronzes it is useful to consider
the following: (i) the nature of the as-cast alloy; (ii) the
nature of the as-deposited and reheated microstructures and
(iii) the results of corrosion studies on as-cast and laser-clad
NAB.
Although the development of cast microstructures in
these alloys has been extensively studied [1], complete
phase diagrams have not been constructed. When cast, the
alloy solidifies as a high temperature β phase sometimes
with intermetallic particles (κI) that precipitate directly
from the melt. On cooling, the high temperature β phase
transforms first to a FCC solid solution with globular κII
(iron rich with a Fe3Al structure) regions and then to a cou-
pled eutectoid of α and κIII (nickel rich lamellar and grain
boundary phase) phases. At lower temperatures, fine iron
rich precipitates again with a Fe3Al structure form the non-
eutectoid α regions. The last β to transform forms β*
(retained β), which for some alloys has been identified as a
3R martensite that is rich in nickel, iron and aluminum.
This phase, for other alloys, has been postulated to be an
optically unresolvable α plus γ2 eutectoid which causes
poor corrosion behavior in aluminum bronzes.
The as-cast corrosion behavior of these materials is
interesting in a number of ways. Historically the most sig-
nificant problem has been the preferential attack of the
retained β phase leading to dealloying [2-3]. It has been
shown that this phase can become anodic to the rest of the
casting [4]. Dealloying can be eliminated or reduced by
controlling the levels of manganese, aluminum and nickel.
Structure also plays a role in dealloying with martensites
being more susceptible because of their defect which is a
rich structure [5]. In contrast, at least initially, the nickel-
rich κIII phase is reported to be more noble than the sur-
rounding α matrix and corrosion around it occurs by the
local attack of the α leaving the κIII proud [6-8]. In crevices,
preferential attack initially occurs this way until the pH
drops and then a reversal of the corrosion cell occurs with
the κIII phase becoming anodic to the α phase [8]. Both heat
treatments and composition control have been attempted to
break up or avoid a continuous κIII network that clearly is
undesirable regardless of precise mechanism. Corrosion
behaviour in seawater is time dependent and requires a
month or more for a steady state condition to be established
in natural seawater [3]. Applied potentials can strongly
affect the nature of the corrosion films and the passivation
behavior [9]. At large electronegative potentials, growth of
a calcareous film slows mass transport. After seawater
immersion, complex copper chlorides are often found in
the outer parts of the corrosion deposit [6]. A recent study
of samples in both simulated seawater and sodium chloride
solutions, employing both electrochemical and surface ana-
lytical methods, provided several interesting results [10].
CANADIAN METALLURGICAL QUARTERLY
First, in contrast to a previous hypothesis that the passiva-
tion layer was aluminum doped Cu2O, Ref. [10] showed
that the passivation layer, formed during anodic polariza-
tion, contains a thin (~9 nm) disordered layer of aluminum
oxide which presumably limits the rate of reaction by
restricting ionic transport. After 164 hours of exposure to
stirred synthetic seawater, Auger spectroscopy on the cor-
rosion layer revealed it to be enriched in copper oxide at the
outer surface and to contain aluminum, magnesium, copper
and iron oxides (nickel could not be measured) and negli-
gible chlorides. The absence of chlorides was attributed to
the presence of Mg in the simulated seawater. In a com-
panion paper to Ref. [10], again using synthetic seawater,
sulfides were reported to interfere with the development
and reformation of the aluminum oxide layer and led to the
incorporation of copper sulfides in the corrosion product
layer [11]. This in turn has been shown to lead to localized
corrosion and increased corrosion rates. There has also
been speculation that the aluminum oxide film is highly
sensitive to pH and that especially under conditions of low
pH the aluminum oxide film may be less stable. In another
study, the occurrence of copper chlorides in real seawater,
but not in synthetic seawater, is probably due to the organ-
ic films and compounds present in real seawater that tend
to absorb copper chlorides heavily [12].
The as-deposited and reheated microstructures in nick-
el aluminum bronze clad with a consumable of composition
Cu-9.0Al-4.6Ni-3.9Fe-1.2Mn have been studied in detail
[13]. Briefly, at heat inputs below about 64 J/mm the as-
deposited material is predominately 9-R martensite with a
high density of fine precipitates. As heat input increases, in
addition to the martensite and precipitates, increasing
amounts of Widmanstätten and grain boundary α phases
form. At all heat inputs above about 47 J/mm, the reheated
zone consists of a mixture of martensites, precipitates and
Widmanstätten and grain boundary α phases [14-15]. As
heat input increases the volume fraction of the α phases
also increases. This work also showed that the as-deposited
and reheated zone microstructures are sensitive to compo-
sition as well as to heat input.
Corrosion studies on laser-clad nickel aluminum
bronzes have been reported by a number of workers.
Reductions in de-aluminification of an aluminum bronze
by laser surface melting have been reported [16].
Significant reductions in the corrosion rate of DGS 348
nickel in a 3.5% NaCl solution was made possible by laser
surface melting [17]. Ref. [17] also showed that passivation
time was much shorter for the surface melted material
whether or not the high temperature oxide was present.
Specimens with the high temperature oxide layer intact
were shown to exhibit different passivation kinetics than
clad material polished to remove this layer prior to immer-
sion. Potentiodynamic experiments in simulated cooling
water containing chlorides showed the corrosion resistance
of nickel aluminum bronze could be improved by electron
 PASSIVATION OF LASER-TREATED NICKEL ALUMINUM BRONZE 237

beam surface melting with the improvement being depen-
dent upon welding heat input. Electropolishing in acidified
NaCl solutions has been shown to allow the martensitic
regions of laser-clad welds on nickel aluminum bronze to
be preferentially etched away [18]. Potentiodynamic corro-
sion experiments using natural seawater showed laser-clad
surfaces produced with 68 and 390 J/mm were more resis-
tant to corrosion than the base material. Ref. [18] also
showed that the higher heat input material is more suscep-
tible to pitting under some conditions and that the lower
heat input material is superior to the higher heat input mate-
rial. Long term corrosion experiments in flowing and stag-
nant seawater, with and without coupling to more noble
metals, showed that particularly in reheated zones the
martensites were attacked more than the surrounding
Widmanstätten and grain boundary α. These experiments,
though showing the cladding was generally an improve-
ment over an equivalent base casting, showed that pitting
was more likely to occur under crevices and in the as-
deposited material, except in the highest heat input speci-
mens where corrosion also occurred in the reheated zones.
The work also led to speculation that prior welding oxide
may have played a role in the development of pitting by
acting as a crevice. Other work showed corrosion potential
is dependant on both composition and heat input at fixed
composition [19-20].
The foregoing discussion reveals that the corrosion of
laser-clad nickel aluminum bronzes in seawater depends on
heat input, surface composition, applied potential, the
nature of the environment and the presence of prior weld-
ing oxide. It also shows the reheated zone may behave dif-
ferently than the as-deposited material. Based on studies on
cast material, passivation behavior and the nature of corro-
sion films usually depend on pH, the type of testing solu-
tion (saline, simulated seawater or real seawater) and the
potential. The application of laser-clad NAB materials
could be made more certain if the following phenomena
were examined: (i) the corrosion behavior of the as-deposited
and reheated zones; (ii) the corrosion behavior of material
with and without a prior oxide layer from welding; (iii) the
nature of the high temperature oxide film and (iv) the effect
of heat input on the corrosion behavior of both zones.
and a relatively high heat input was applied in the laser
cladding process. In all cases, electrochemical impedance
spectroscopy (EIS) was used to make the corrosion mea-
surements because the response can be fitted to a physical
model of the surface and the low applied voltage (10 mV)
minimizes any surface changes due to the measurement
itself.
MODELING OF THE ELECTROCHEMICAL
IMPEDANCE SPECTROSCOPY DATA
The main result of an EIS measurement is an estimate of
the polarization resistance of the metal-solution interface,
Rp which is inversely proportional to the corrosion rate. The
electrochemical impedance measurements were interpreted
by fitting the data to analogues of electrical circuits, as is
customary. Variations of two circuit types were applied: (i)
mixed kinetic and diffusion control (MKD) and (ii) filmed
metal. The MKD circuit is shown in Figure 1 and consists
of a solution resistance, a polarization resistance, a diffu-
sion resistance and a constant phase element. The solution
resistance (Rs) is the resistance between the reference elec-
trode and the sample. The diffusion resistance element (W),
known as the Warburg impedance, is due to the influence of
diffusion of the oxidants and reductants on the overall reac-
tion rate. The inverse of the polarization resistance (1/Rp) is
directly proportional to the corrosion current according to
the Butler-Volmer equation for small perturbations of the
potential from the open circuit potential. Theoretically, the
double-layer capacitance at the interface between an elec-

This paper describes experiments that were undertaken

to provide insight into the first two of the above uncertain-
ties. The fine scale of the reheated and as-deposited zones
complicated corrosion rate measurements. A masking tech-
nique to allow just the as-deposited material to be studied
was developed and applied. To examine the reheated zone,
simulated reheated material was produced using clad mate-
rial and a weld thermal simulation device (Gleeble) [19].
This technique is particularly effective for these alloys
because the reheated zones are somewhat insensitive to
heat input. To examine the effect of welding oxide, both
polished and as-clad specimens were studied. The compo- Fig. 1. Electrical circuit analogues for mixed kinetic and diffusion control
sition of the cladding wire was the same for each specimen (MKD) and a filmed circuit.

CANADIAN METALLURGICAL QUARTERLY

238 R.D. KLASSEN, C.V. HYATT and P.R. ROBERGE

Table I – Compositions and dimensions of the NAB samples.

Alloy Designation Thickness Specimen Composition

(UNS) mm Cu Al Ni Fe Mn

Substrate for clad C95800 – 9.2 4.7 3.4 0.77

Gleeble specimen
Alloy D C95800 25 81 9.1 4.4 4.1 1.1
Wire CuNiAl 0.25 80.8 9.0 4.6 3.9 1.2

Table II. Cladding conditions.

Specimen Laser Travel Wire Dia., Defocus, Number Shielding Heat

Power, W Speed mm/s mm mm of Layers Gas Input, J/mm
Alloy D 5000 17 0.25 10.2 2 Argon 294
Gleeble 3300 21 0.25 10.2 1 Argon 150

trode and its surrounding electrolyte should be modeled as
a capacitor. However, in working systems, this is usually
best modeled as a mathematically flexible capacitor called
a constant phase element (C.P.E.), which has two parame-
ters, Q and an exponent n. In the upper limit where the
exponent n is unity, the value of 1/Q corresponds to capac-
itance. Similarly, where n is 1/2, 1/Q corresponds to a
Warburg parameter and where n is zero, 1/Q corresponds to
a resistor. The circuit model for a painted metal or a metal
with a film layer is also shown in Figure 1. The film layer
is modeled as a resistance, Rf, that is in series with the
polarization resistance at the metal surface and the solution
resistance. The capacitance of the film is modeled as either
a capacitor or a C.P.E. and is usually much smaller than a
typical double layer capacitance.
EXPERIMENTAL
Materials
The composition of the base materials, alloy D and the
Gleeble specimen and the welding wire given in Table I and
the cladding conditions are given in Table II. As shown in
Table II, different cladding conditions were used to produce
the specimens for corrosion studies (alloy D) and the spec-
imens for subsequent processing using the Gleeble method
to produce simulated reheated zone material. In the latter
method, a Gleeble 2000 simulator was used to heat by elec-
trical resistance and then cool (by water mist quenching)
bars (10 x 10 x 70 mm) machined from the laser clad weld-
ment. The laser-clad surface was left intact on one face of
the bar. By control of the heat flow from and to the jaws
that held the specimen, the maximum temperature was
reached across a uniform but narrow cross-section of the
bar. The thermal history of this part of the bar was mea-
sured with a thermocouple. Based on previous experience,
the combination of cladding and thermal simulation vari-
ables used produced a microstructure that is representative
of the reheated zone of a 300 J/mm clad specimen.
Each specimen, approximately 1 by 1 by 2 cm, was pre-
pared by attaching a screw to the unclad side before encas-
ing the connection and sample in a cylindrical mould of
epoxy. Sample surfaces were then polished with 240-, 400-
and 600-grit paper and then with cloths saturated with
1.0µm and then 0.2µm alumina particles. The edge of the
sample was coated with a silicone rubber paste (Dow
Corning, 1890 protective coating) which was found to pre-
vent crevice corrosion for at least one week.
In order to examine the area of interest on the Gleeble-
simulated reheated zones and the as-deposited zones, it was
necessary to mask the unwanted areas. On the Gleeble
specimen, a band on the reheated clad surface, less than
1mm wide and wholly in the zone of known and uniform
thermal history, was masked off. On the as-deposited spec-
imen it was necessary to first identify the as-deposited
regions metallographically. This was done by etching, on
each side of the area of interest, parts of the clad surface,
which were eventually to be masked off, with an etchant
made up of 5 g FeCl2, 15 ml HCl and 60 ml ethanol for
about 10 s. This ‘macro-etch’ revealed the reheated and as-
deposited zones on the specimens. Drawing imaginary
lines out from the boundary between the reheated and as-

CANADIAN METALLURGICAL QUARTERLY

 PASSIVATION OF LASER-TREATED NICKEL ALUMINUM BRONZE 239

Several of the samples were immersed for approximately

ten weeks in 3.5% saline in order to visualize longer term
effects on the surface topography.

Post Test Examination

Post test examination was done by optical and scanning
electron microscopy on both specimen surfaces and on sec-
tioned, polished and etched specimens. Only metallograph-
ic data was collected for the longer term exposure periods.

RESULTS AND DISCUSSION

Post Test Metallographic Examination

The unpolished (laser-treated) specimen appeared the same
before and after immersion. A micrograph of this specimen
Fig. 2. Test cell for electrochemical impedance measurements. after 1922 hours of immersion is shown in Figure 3. The
lines of reheated zones are clearly visible as low smooth
ridges and the as-deposited zones appear to have a rough-
deposited zones allowed an area of approximately 2mm by
ness height of about 1 µm. The increase in surface area of
10mm to be identified and masked off.
the unpolished specimen due to its greater roughness com-
pared to the polished specimens is negligible. After about
Apparatus
60 hours of immersion, the reheated zone lines on the pol-
The test cell used to obtain impedance data is shown in ished (laser-treated) specimen were visible to the naked
Figure 2. The test solution (3.5% w/v NaCl) was made from eye. After 1608 hours of immersion, approximately 30 % of
reagent grade NaCl and deionized water. The pH of the the re-heated area appears to be corroded in discontinuous
saline was from 6.4 to 7.1 and so was clearly in the neutral patches which is in contrast to the continuous reheated lines
range. The counter electrode was a cylinder of porous in Figure 3. Thus, part of the reheated zone appeared to be
graphite and the reference electrode was a standard calomel more susceptible to attack than other regions of the reheat-
electrode (SCE) that was placed in a Luggin capillary. The ed zone and the as-deposited region. After 60 hours of
tip of the Luggin capillary was located about 3 mm per- immersion, the base alloy specimen was also featureless.
pendicular from the outside edge of the sample. Air was However, after 1488 hours of immersion, visualization of
supplied to the cell via a pipette in such a way as to main- two metallurgical phases is possible as shown in the SEM
tain the cell solution near the sample in an aerated quies- micrograph in Figure 4. Both the Gleeble and as-deposited
cent state. All experiments were at room temperature which
was 21° to 23°C. Reheated zone Reheated zone
As deposited zone
Measurements
The EIS measurements were made with the FAS1
Femptostat manufactured by Gamry Instruments, Inc. The
frequency range was from 0.01 to 100,000 Hz and each
sweep required about thirty minutes. The lowest frequency
was a compromise between obtaining more points at the
low end and minimizing the total time required for a sweep
because of the changing nature of the passivation film. The
open circuit voltage was determined after a delay of 100s at
the beginning of each run. After immersion each specimen
was measured every 2.5 hours for a total immersion time of
about 60 hours. Each of the data sets was fitted to a circuit
that included an inductor in series with the solution resis-
tance element. The fitted value of this inductor was consis-
tently about 6 µH. The influence of the inductor was in the
high frequency end of the frequency spectrum and is
thought to be an artifactual effect due to not using a capac- Fig. 3. Scanning electron micrograph of laser-clad, unpolished specimen
itively coupled low impedance reference element as rec- after an immersion period of 1922 hours. The reheated zones lines and
ommended by the manufacturer of the EIS hardware. as-deposited zones are clearly evident.

CANADIAN METALLURGICAL QUARTERLY

240 R.D. KLASSEN, C.V. HYATT and P.R. ROBERGE
Fig. 4. Scanning electron micrograph of polished base specimen (not
laser-clad) after an immersion period of 1488 hours.
Base metal
Fig. 5. Micrograph of a cross-section of polished, laser-clad specimen.
The as-deposited (AD), reheated zone (RHZ) and base metal zones are
labelled.
specimens after 1177 and 1608 hours of immersion, respec-
tively, were smooth and featureless when examined in the
SEM at 100X.
A micrograph of a cross-section of the polished speci-
men is shown in Figure 5. The as-deposited (AD), the
reheated (RHZ) and base metal zones are visible with the
former two zones being of principal interest. Both consist
of light etching Widmanstättan and grain boundary α and
dark etching martensite. Within the dark etching phases,
particularly in the reheated zone, some eutectoid β decom-
position probably also formed, based on TEM studies of
lower heat input welds [14-15].
CANADIAN METALLURGICAL QUARTERLY
Cross-sections of the polished as-deposited, unpolished
as-deposited, Gleeble and base casting specimens are
shown as SEM micrographs in Figures 6a, 6b, 6c and 6d,
respectively. No measurable differential attack on the pol-
ished as-deposited material on the polished specimens is
evident (Fig. 6a). No conclusions about the corrosion of the
unpolished as-deposited specimen could be drawn because
of their prior surface roughness (Fig 6b). The reheated
material on the simulated reheated zone material (Gleeble)
specimen showed preferential attack of the dark etching
martensite phase (Fig. 6c). Attack of the light-etching α
phase, adjacent to the κII and κIII phases was noticed in the
base casting material (Fig. 6d).
Electrochemical impedance spectroscopy
The inverse of the area-specific polarization resistance
(1/Rp.area) is shown for each specimen as a function of
immersion time in Figure 7. Representative impedance
spectra for the five specimens are presented as Bode plots
in Figures 8 to 12 and the fitted parameters for these sets
are listed in Table 3. The parameters for the C.P.E. element
are a flexible capacitor, Q and an exponent n. Since the
C.P.E. is only a true capacitor where the exponent n is unity,
the value of 1/Q is listed as “µF/cm2” with quotations as a
reminder that this is not a straightforward capacitance.
The passivation pattern illustrated in Figure 7 is consis-
tent, with one exception, with that reported by Ref. [17] for
the laser-treated specimens as measured by linear polariza-
tion resistance. They found that the corrosion rate for a pol-
ished laser-treated NAB was similar to that for an unpol-
ished laser-treated NAB, i.e. a relatively flat pattern. In this
work, the corrosion rate for the polished laser-treated spec-
imen decreased sharply to the steady state range within the
first 3 hours. There are at least two possible explanations
for this difference. One possibility is that the high initial
rate within this time frame was missed by Ref. [17]. A sec-
ond possibility is that the specimen used by Ref. [17] was
truly different, either because it was produced at a much
lower heat input of 1-2 J/mm or because of composition
differences (the exact composition was not reported).
The corrosion rate of each of the polished specimens
decreased at different rates within the first 40 hours to
roughly the same steady rate. For each specimen, the steady
state is not perfect as indicated by other measurements
beyond 50 hours. This is likely due to a sequence of film
breakdown/re-passivation events for small discrete patches
on the specimen. Thus over a long period of time; i.e.
longer than 50 hours, the kinetics of passivation becomes
influential. Specimens that passivate faster will experience
less corrosion in the long run because the small-scale film
breakdowns will recover faster.
As is evident in Figure 7 the polished laser-treated spec-
imen clearly passivates faster than the polished specimen
 PASSIVATION OF LASER-TREATED NICKEL ALUMINUM BRONZE 241

a b

c d
Fig. 6. Micrograph of the cross-section of four specimens: (a) as-deposited region of polished, laser-clad sample, (b) as-deposited region of un-polished,
laser-clad sample; (c) Gleeble sample and (d) base metal.

that was not laser treated. This is consistent with other
observations that laser treatment of NAB reduces the cor-
rosion rate. It is also clear from Figure 7 that the as-deposit-
ed zone passivates faster than the reheated zone based on
the result for the simulated reheated zone (Gleeble). This
result is consistent with the behavior of the long term cor-
rosion specimen (Fig. 6c) which shows that the dark etch-
ing martensite phase was attacked more than the light etch-
ing α phase. This observation is also consistent with the
observations by Ref. [18] that the martensitic regions of the
reheated zone of laser-treated NAB were more susceptible
to dissolution via electropolishing in an acidified saline
solution.
There is a suggestion of a two-stage passivation process
in Figure 7 for the polished laser-treated specimen. The
first drop in corrosion rate occurred after about three hours
and a second lesser drop occurred after about twelve hours.
These times correspond closely with the transition times
observed for the as-deposited and simulated reheated zone
(Gleeble) specimens. The scale of the changes, with the
first one being larger at 1 kohm-1cm-2 and the second one
being smaller at 0.1 kohm-1cm-2, is consistent with earlier
passivation of a larger area followed by later passivation of
a smaller area. There are two possible mechanisms for this
two-stage passivation behavior. The first possibility is that
the as-deposited region and perhaps part of the reheated

CANADIAN METALLURGICAL QUARTERLY

242 R.D. KLASSEN, C.V. HYATT and P.R. ROBERGE

Fig. 8. Bode diagram of the EIS of the polished base alloy D (not laser-
clad) after 5 hours and after 27.8 hours. See Table III for the fitted parameters
for each data set. Round dots are for the 5 hour data set and diamonds are
for the 27.8 hour data set.
Fig. 7. Plot of the inverse of polarization resistance with immersion time.
The data sets with 1/Rp below the line were evaluated with a film circuit.

zone, passivates first and then the balance of the reheated

zone, which is of smaller surface area than the as-deposit-
ed material, passivates second. Another possibility is that
the relatively larger volume of α phase passivates first fol-
lowed by some, or all, of the relatively smaller volume
fractions of martensite. With the current data, it is difficult
to be certain; however, based on the cross-sections of the
long term corrosion specimens, it is likely that it is the
martensitic portion of the reheated zones which is slowest
to passivate. The probable reason for the preferential attack
of the martensitic zone in the reheated zone is that the cycle
of Widmanstätten coarsening and enrichment of the β
phase during reheating, followed by transformation of the
enriched β to martensite on cooling, creates larger compo-
sition differences than in the as-deposited region. Fig. 9. Bode diagram of the EIS of the Gleeble specimen after 9.2 and
24.6 hours. See Table III for the fitted parameters for each data set. Round
The passivation pattern of the unpolished sample is in dots are for the 9.2 hour data set and diamonds are for the 24.6 hour data set.
marked contrast to the polished samples. Apparently the
welding oxide provides an immediate level of corrosion
resistance that is similar to that which eventually develops
on the polished specimens. This similarity in passivation is
likely because both the high temperature oxide formed dur-
ing welding and the post weld cooling cycle and the passi-
vation film seem to consist of aluminum oxide [11,21].

There was a qualitative change in the electrochemical

impedance spectra for each of the polished specimens at
different immersion times. Each could be reasonably fit to
the MKD circuit up to a certain immersion period that was
distinct for each specimen. After the transition, the imped-
ance spectrum was best fit to a version of the filmed metal
circuit. In Figure 7, all the runs above the dashed line were
best fit with the MKD circuit and all the runs below the
dashed line were best fit with a filmed metal circuit. In
Figures 8 to 12, representative data sets before and after the Fig. 10. Bode diagram of the EIS of the polished as-deposited specimen
transition are presented. The unpolished specimen was best after 1 and 23.5 hours. See Table III for the fitted parameters for each data
fit to a filmed metal circuit for all data sets. The filmed set. Round dots are for the 1 hour data set and diamonds are for the 23.5
metal circuit for the Gleeble, polished, laser-treated and as- hour data set.

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 PASSIVATION OF LASER-TREATED NICKEL ALUMINUM BRONZE 243

Table III. Parameters for the circuits fitted to the data shown in Figures 8 to 12.

Specimen Parameter Units Circuit

MKD Film
Gleeble Rs Ohms 12.3 ± 0.1 14.0 ± 0.3
Rp Kohm-cm2 0.96 ± 0.01 10.6 ± 0.6
W Ohm-cm2 82 ± 4 1700 ± 100
l/Qp “µF”/cm2 300 ± 6 153 ± 3
Np - 0.762 0.003
Rf Ohm-cm2 - 2±1
Cf µF/cm2 - 7.0 ± 1.4
Polished alloy D Rs Ohms 4.15 ± 0.04 4.78 ± 0.07
Rp Kohm-cm2 0.83 ± 0.01 8.65 ± 0.21
W Ohm-cm2 185 ± 5 237 ± 52
l/Qp “µF”/cm2 217 ± 4 183 ± 4
Np - 0.779 ± 0.003 0.770 ± 0.004
Rf Ohm-cm2 - 3.1 ± 0.4
Cf µF/cm2 - 11 ± 1
Polished, laser-clad, Rs Ohms 24.8 ± 0.3 23.0 ± 0.5
as-deposited alloy D Rp Kohm-cm2 1.93 ± 0.04 9.8 ± 0.4
W Ohm-cm2 110 ± 10 -
l/Qp “µF”/cm2 446 ± 6 55 ± 5
Np - 0.678 ± 0.002 0.944 ± 0.004
Rf Ohm-cm2 - 190 ± 20
Qf µF/cm2 - 467 ± 13
Nf - - 0.594 ± 0.003
Base alloy D, polished Rs Ohms 5.30 ± 0.05 7.73 ± 0.12
(not laser-treated) Rp Kohm-cm2 1.50 ± 0.03 6.45 ± 0.17
W Ohm-cm2 310 ± 10 440 ± 42
l/Qp “µF”/cm2 264 ± 7 179 ± 3
Np - 0.750 ± 0.002 0.755 ± 0.004
Rf Ohm-cm2 - 2.5 ± 0.4
Cf µF/cm2 - 9.3 ± 1.0
Unpolished, laser-clad, Rs Ohms 3.7 ± 0.4 6.3 ± 0.8
alloy D1 Rp Kohm-cm2 5.5 ± 0.2 11.8 ± 0.7
W Ohm-cm2 170 ± 43 470
l/Qp “µF”/cm2 56 ± 16 106 ± 3
Np - 0.58 ± 0.03 0.71 ± 0.02
l/Qf µF/cm2 82 ± 23 170 ± 53
Nf - 0.68 ± 0.05 0.58 ± 0.08

1
The second EIS data set represented here for the immersion time of 24.2 hours was fit to a circuit with three R/C.P.E. circuits in series. However, the
parameters for the third pair are not listed

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244 R.D. KLASSEN, C.V. HYATT and P.R. ROBERGE
Fig. 11. Bode diagram of the EIS of the polished alloy D specimen after
0.3 and 25.7 hours. See Table III for the fitted parameters for each data
set. Round dots are for the 0.3 hour data set and diamonds are for the
25.7 hour data set.
Fig. 12. Bode diagram of the EIS of the un-polished alloy D specimen
after 4.5 and 24.2 hours. See Table III for the fitted parameters for each
data set. Round dots are for the 4.5 hour data set and diamonds are for the
24.2 hour data set.
deposited specimens were best fit with a capacitor in the
film sub-circuit. The values of the film capacitance
(7--11µF/cm2) are consistent with a thin layer of metal
oxide. A layer of pure aluminum oxide, 0.6 nm thick, cor-
responds to a capacitance of 10µF/cm2. This is in reason-
able agreement with the findings by Ref. [10] that a disor-
dered layer of aluminum oxide 9 nm thick was primarily
responsible for the corrosion resistance.
The Bode diagram for two of the data sets for the unpol-
ished laser-treated specimens is shown in Figure 12. The
filmed metal circuit with a C.P.E. element in the film was
fit to the early data set (4.5 hours). However, the later data
set (24.2 hours) was fit to a film circuit that included a third
resistance/C.P.E. sub-circuit. This model was able to follow
all the inflexions in the phase angle at the expense of an
increased uncertainty in the values of the third R/Q/n com-
CANADIAN METALLURGICAL QUARTERLY
bination. Therefore only the first two R/Q/n combinations
are listed in Table III.
In each specimen, there was an increase in the Warburg
impedance with immersion time. An increase in the mass
transfer resistance of the reductants is consistent with the
conclusions by Ref. [10] that the thin film of aluminum
oxide reduces the rate of ionic transfer of reductants from
the metal into solution.
Finally, the results shown here are for a laser cladding
applied with a relatively high energy input. It is expected
that the results for laser energy inputs lower than 700 J/mm
will be different and this will be the topic of a future study.
CONCLUSIONS
1. A pseudo-steady state of passivation was reached for
the specimens tested within about 40 hours of immersion in
a 3.5 % neutral saline solution. Due to the subsequent
sequence of local film breakdown and re-passivation, spec-
imens that passivate the fastest corrode the least over time.
2. For all specimens, EIS data supported the conclusions
from other work; i.e. that the passivation of NAB is due to
the development of a barrier film that increases the mass
transfer resistance of species involved in the corrosion
reaction.
3. The fitted capacitance of the barrier film is reasonably
consistent with aluminum oxide.
4. The laser-clad surface had a higher rate of passivation
than the base casting and thus, should show improved long-
term corrosion resistance.
5. The reheated zone of laser-clad NAB passivates more
slowly than the as-deposited region in a neutral saline solu-
tion which is consistent with an apparently two-stage pas-
sivation sequence.
6. The welding oxide of laser-clad NAB provides an
immediate degree of passivation that is similar to that
which eventually develops on polished specimens. Thus
there is no reason to believe that prior welding oxide will
function as a crevice.
ACKNOWLEDGEMENT
The Gleeble specimens were skillfully prepared by
Mr. M.W. Letts and Mr. J. Gianetto at the Materials
Technology Laboratory-CANMET in Ottawa, Ontario.
 PASSIVATION OF LASER-TREATED NICKEL ALUMINUM BRONZE 245

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