Laser surface treatment to

improve the surface corrosion

properties of nickel-aluminum
bronze

20

R. Cottam1,2, M. Brandt2,3
Swinburne University of Technology, Melbourne, VIC, Australia; 2Defence Materials
Technology Centre, Melbourne, VIC, Australia; 3RMIT University, Melbourne, VIC, Australia
1

20.1

Introduction

Nickel-aluminum bronze (NAB) is a copper-based alloy that has additions of

between 9 and 12 wt.% Al, and up to 5 wt.% of Fe and Ni, depending on the
application. This class of alloys have an excellent combination of strength and corrosion resistance and, as such, have found extensive maritime applications such as
ship propellers and valves that handle sea water. While their corrosion behavior is
good for the level of strength, there has nevertheless been ongoing research to
improve it via several surface engineering methods. This has included laser cladding
[1], friction stir processing [24], laser surface alloying [5], and laser surface
melting [6]. While all of these treatment techniques have shown an improvement
in mainly the cavitation corrosion behavior, the stagnant sea water corrosion resistance has suffered. This can be attributed to the formation of the Widmanstatten
morphology of the microstructure due to the processing. It is also known that the
kIII phase present in the as-cast NAB microstructure promotes selective phase
corrosion and is responsible for a deterioration in its stagnant sea water corrosion
properties [7].
The above-mentioned surface treatments generally involve a phase change and the
formation of the detrimental Widmanstatten morphology. Another approach that
offers greater potential for improving the NABs corrosion properties because of
its composition and microstructure is the solid-state heat treatment. Our results show
that solid-state heat treatment using a laser can be effective in producing a microstructure that is free from the Widmanstatten morphology, and free from the kIII and, as
such, shows an improvement in not only the cavitation corrosion behavior but also
electrochemical corrosion behavior, which is linked to the behavior of the alloy in
stagnate sea water. This chapter details the development of the solid-state approach,
laser-processing parameters used, characterization of the processed NAB surface, and
its subsequent corrosion performance.
Laser Surface Engineering. http://dx.doi.org/10.1016/B978-1-78242-074-3.00020-9
Copyright 2015 Elsevier Ltd. All rights reserved.

470

20.2

Laser Surface Engineering

Solid-state laser treatment and development

of laser-processing parameters

As the phase diagram shown in Figure 20.1, NAB alloys that have between 9% and
12% aluminum at elevated temperatures form two phases, a and b. The a phase is an
fcc phase and the b is a bcc phase. Then, upon slow cooling the b phase transforms to
a + kIII. This reaction is the eutectoid reaction of NAB where the kIII forms a lamella
structure. At high cooling rates, this reaction does not take place and martensite or
the Widmanstatten morphology microstructure forms. The eutectoid reaction can
also take place in reverse and, as such, the kIII precipitate is dissolved and the b
phase forms. Therefore, with the right processing parameters it is possible to dissolve
the kIII phase and cool at a rate that the Widmanstatten morphology microstructure
does not form and the kIII is not precipitated. In this case, both elements of the NAB
microstructure that are responsible for the poor corrosion performance can be eliminated with the right heating and cooling conditions. The reverse eutectoid reaction is
diffusion dependant and the nature of the reaction is analogous to the perlite austenitization reaction in low-carbon steels [8]. Therefore, a two-phase diffusion model
was employed to determine the kinetics of the reaction. This is detailed in the next
section.

1200
L
1040
T
1000
e
m
p 910
e
r
800
a
t
u
r
600
e

+
+

++
400
4

8
8.5

12

16

10.8

wt.% Aluminum

Figure 20.1 NAB phase diagram for increasing aluminum content, where the iron and nickel
contents are 5 wt.%.

Laser surface treatment to improve the surface corrosion properties of nickel-aluminum bronze

km Lamella

km Lamella

471

910 C

Figure 20.2 The reverse reaction for the NAB eutectoid reaction.

20.2.1 Modeling of the reverse eutectoid reaction

During a reverse eutectoid reaction, the alloying elements that are precipitated, which
for NAB are aluminum and nickel, are dissolved and their diffusion away from its
precipitate form coincides with the growth of the new phase, which for NAB is the
b phase, as shown by the schematic in Figure 20.2.
The kinetics of the reaction is governed by the diffusivity of aluminum in copper
and the movement of the a/b interface, which is given by the difference in
composition between the a and b phases at the interface, also known as the partition
coefficient. The calculation of this rate allows a dwell time to be calculated for laserprocessing parameter of laser-traversing speed, which eliminates the need for a trial
and error determination of laser-processing parameters.
The two-phase diffusion problem involves solving its partial differential equations
as shown in Equations (20.1)(20.2):



@c 1 @ m
@c

x Da c
@t xm @x
@x

(20.1)


@c 1 @ m
@c
m
x Db c
@t x @x
@x

(20.2)

where c is the concentration of the diffusing element (wt.%), x is the position in

meters, D is the diffusivity in meter square per second, t is the time in seconds,
and m 0 for planar geometry, m 1 for cylindrical geometry, and m 2 for spherical
geometry. The interface mass balance and its velocity is given by Equation (20.3):


cab  cba

 
 
 @y
@c
@c
Db
 Da
@t
@x
@x

(20.3)

where @y
@t is the interface velocity in meter per second, cab is the a-phase side of the
partition concentration, and cba is the b-phase side of the partition concentration.
There are several methods to solve the two-phase diffusion problem including the

472

Laser Surface Engineering

finite element method [9], the finite volume method [10], and the finite difference
method [8]. In this work, the finite difference scheme of Karlsson and Larsson [11]
was employed to solve the diffusion equations, due to its relative simplicity to
implement.
The boundary conditions used were as follows. The concentration of the a-phase
initially was 7.2 wt.% Al and was taken from the microprobe analysis of Hasan et al.
[12]. The concentration of the b-phase was 50% because the kIII precipitate is equal
parts nickel and aluminum. The partition concentrations used were 8.5 wt.% Al for cab
and 10.8 wt.% Al for cba, Figure 20.1. The spacing of the kIII lamellae in the a-matrix
was taken from a scanning electron microscope (SEM) image of the alloy used in the
investigation, Figure 20.2. The kIII thickness was taken as 0.75 mm and the spacing
between them as 1.25 mm for the larger spaced lamellae, which would take longer
to transform.
The results of the calculation are shown in the reverse time-temperaturetransformation diagram of Figure 20.3. The kinetics of the transformation of the
boundary condition used in the model ranges from 0.2 to 0.75 s. The diffusion of
aluminum in copper is quite fast; even though it is a substitution-based process (as
opposed to an interstitial process) the diffusion rates at temperature are comparable
with carbon in iron.

20.2.2 Modeling of the laser heating of NAB

The objective of modeling the heating behavior of NAB is to develop a relationship
between the three main processing parameters of laser heating, namely, spot size,
1040
1030
1020

Temperature (C)

1010
1000
990
980
970
960
950
940
930
920
910
0.01

0.1
Time (s)
50%Trans

100%Trans

Figure 20.3 Reverse time-temperature-transformation diagram for as-cast NAB for the
a + kIII ! b reaction.

Laser surface treatment to improve the surface corrosion properties of nickel-aluminum bronze

473

traversing speed, and power. Using the analytical heating model of Komanduri and
Hou [13], the relationship between these variables was determined with NAB as
the substrate material. The model and its associated equations are as follows:
T x, y, z

AQv
4lap2 =2r2L

ri rL , wv2 t=4a
r i 0,w0

eXV Br i

1 wu=4w
e
I 0 dwdri
w3=2

(20.4)

where T is the temperature rise at any position, x, y, z, in degree Celsius under the
laser beam; A is a constant given in Table 20.1, depending on the laser beam profile;
Q is the absorbed laser power in Watts; l is thermal conductivity in W m1oC1; a is
the thermal diffusivity of the medium in meter square per second; rL is the radius of
the laser in meters; ri is the radius of that integration segment in meters; B is a mathematical function that is determined by the laser beam profile given in Table 20.1;
v is the laser traversing speed in meter per second; and t is the time the laser is on for
in seconds.
Equations (20.5)(20.7) are used to define the other variables:
Rv
2a
q
R r 2i + X20 + y2 + z2
u

X0 x  vt

(20.5)
(20.6)
(20.7)

(x, y, z) are any position relative to the starting position in meters. I0 is calculated from
a function that has been defined mathematically in Ref. [14] and V v/2a.
This heating model was programmed in MATLAB and was used to construct the
theoretical processing map in Figure 20.5. Using a melting point of 1040  C, a thermal
diffusivity of 1.32  105 m2 s1, and a thermal conductivity of 37.7 W m1 oC1,
the laser power and traversing speed were varied to determine conditions where
the above-mentioned parameters produced a temperature of 1040  C (a locus of
points). Repeating this analysis for several laser spot sizes, a theoretical solid-state
processing map was produced in Figure 20.4. For each laser beam radius, the area
above the line represents too much power and, consequently, surface melting, while
the area below represents not enough heat and, consequently, a nonoptimized process.

Coefficients for beam profile used in analytical heating

model, Equation (20.1)

Table 20.1

Distribution

Normal
Bimodal
Uniform

9
4.3677
1

e3ri =rL
2
2
e3:947ri =rL 0:947 + e3:947ri =rL 0:947
1

474

Laser Surface Engineering

900

Absorbed laser power (W)

800

700

600

500

400

300

200
0

200
400
600
Laser traversing speed (mm min1)

800

3 mm Gaussian

5 mm Gaussian

4 mm Gaussian

6 mm Gaussian

7 mm Gaussian

Figure 20.4 Laser heating processing map for NAB for different laser spot dimensions. The
laser spot sizes are a radius dimension.

Due to the processing limitations of the equipment used to do the experiments, a laser
spot size of 4 mm radius with a processing traversing speed of 6 mm min1 and 780 W
of dialed power were used.

20.3

Experimental procedure

Laser processing of as-cast NAB with nominal composition Cu-8.5Al-5Ni-4.5Fe (wt.%)

was carried out with a fiber coupled, 3.5 kW Laserline diode laser. The beam was delivered via a 1-mm diameter optic fiber terminated with a 200 mm collimating and focussing optic attached to a Motoman UP20 robot (see Figure 20.5a). A processing speed of
6 mm min1 with a power setting of 780 W (taken from the map in Figure 20.4) and a
4 mm radius spot size was used. To maintain the ambient temperature of the substrate, a
water-cooled plate was placed under 6-mm thick NAB plate during processing. Initially,
a single track was trialed and then multitrack experiments were conducted with a 2-mm
intertrack spacing (see Figure 20.5b).

Laser surface treatment to improve the surface corrosion properties of nickel-aluminum bronze

475

Figure 20.5 Picture of laser processing of NAB; (a) laser set up and (b) treated plate.

20.4

Characterization of laser-processed microstructure

Several techniques were employed to characterize the laser-processed layer. These

included optical microscopy, SEM, neutron diffraction for residual stress measurements, and microhardness traverses. The SEM revealed that the results of the
processing had achieved the goal; the kIII phase of the as-cast NAB had been
dissolved and the formation of a Widmanstatten microstructure had been avoided
(see Figure 20.6). Figure 20.7 shows a macroshot of the treated area. The rough
surface of the treated area is believed to be connected with the change in volume
associated with dissolving the kIII precipitate and is not due to local melting. To
further understand the difference between a laser-melted and a laser-processed
structure, microhardness traverses were conducted (see Figure 20.8). From this graph
it is apparent that laser melting has a slightly harder microstructure than the laserprocessed microstructure.
Residual stress analysis was also conducted on the laser-melted and laserprocessed samples, and the results are shown in Figure 20.9. The residual stress analysis
was conducted using neutron diffraction at the Australian Nuclear Science and Technology Organisation (ANSTO). From the results of the analysis, it is apparent that the
tensile residual stress in the region of the laser-melted area is five times higher than the
laser-processed sample at the same region. This can be attributed to a steeper thermal
gradient in the laser-melted sample when compared with the processed sample. The

476

Laser Surface Engineering

Figure 20.6 Scanning electron microscopy micrographs of NAB in the (a) as-cast condition
and (b) after laser heat treatment.

Figure 20.7 Macrostructure of the laser-processed NAB showing the overlapping tracks.

300

Hardness (Micro Vickers)

250

200

150

100

50

0
0

2
3
Position from surface (mm)

Laser processed

Laser melted

Figure 20.8 Micro Vickers hardness traverses of NAB both laser melted and laser processed.

Laser surface treatment to improve the surface corrosion properties of nickel-aluminum bronze

477

inflection of the laser-melted curve near the interface is as a result of the compressive
stress exerted by the martensitic transformation during cooling of this zone.
XRD of the laser-treated samples shows that the phase of the as-cast, laser melted,
and laser processed are all the same (see Figure 20.10). The shift in the peak position
150

Residual stress (MPa)

100

50

0
0

50

100

150

Position from surface (mm)

Laser melted

Laser processed

Interface

Figure 20.9 Residual stress analysis of NAB in the laser-melted and laser-processed state using
neutron diffraction.

(111)FCC

1200

800

(200)FCC

(111)FCC

Intensity (arb. units)

1000

600
400
200
0
40
As-cast

45

50
2q
Laser melted

55

60

Laser processed

Figure 20.10 XRD 2y scan of NAB in the as-cast, laser-melted and laser-heated states.

478

Laser Surface Engineering

for the laser-melted sample can be attributed to the Widmanstatten microstructure of

this material. This graph supports the notion that the laser processing merely dissolves
the kIII precipitate in the solid state.
The characterization shows that the laser-processed NAB is different microstructurally to both the as-cast and laser-melted condition. Hence, this microstructure is new to
the range of forms that NAB exhibits, which was the objective of the investigation.

20.5

Corrosion performance

The establishment of a new microstructure leads to an evaluation of its corrosion performance. For this investigation, this has included electrochemical corrosion performance, in the form of linear polarization and cavitation corrosion testing. These two
tests give an indication of the performance of this new material in the stagnant and
dynamic condition that most NAB parts experience in service.

20.5.1 Electrochemical corrosion

Three-electrode potentiostat testing was used to record polarization curves for
laser-heated and as-cast NAB specimens immersed in a 3.5% NaCl solution. Samples
were mounted in epoxy resin with an exposed area of 1 cm2 to the test solution. Prior
to testing, the electrochemical cell was purged with air for several minutes. Upon termination of purging, a 30-min initial circuit delay was imposed to ensure a stable test
environment. The potentiostat used was the Parstat 2273, which used the Powersuite
software to control and monitor the cell. Polarization curves were recorded at a sweep
rate of 0.166 mV/s. The results of the testing are shown in Figure 20.11.
It is apparent from this graph that the corrosion current of the laser-processed sample is lower than that of the as-cast substrate but the potential is higher for its maximum corrosion current density. This is evidence that the stagnant sea water
corrosion behavior of the laser-heated sample is superior. The origins of this improvement lie in the change in the microstructure brought about by the laser processing.
Essentially, the laser processing dissolved the kIII precipitate and more evenly redistributed the nickel and aluminum that the precipitate is composed of. Therefore, the
aluminum is more evenly distributed throughout the microstructure, which in turn promotes the formation of Al2O3 oxide, which is 11 times more stable than the Cu2O
oxide. The aluminum oxide film forms a highly impermeable layer that resists the
transportation of cuprous ions, hence reducing the corrosion rate [7].

20.5.2 Cavitation erosion tests

Cavitation erosion testing was performed using an ultrasonic horn (Sonic VCX) with a
replaceable tip made from Ti-6Al-4V. Testing was conducted in 3.5% NaCl solution,
with the specimen held at a depth of 10 mm. The horn was operated at a frequency of
20 kHz and amplitude 50 mm, and the horn tip was 1 mm above the specimen. The

Laser surface treatment to improve the surface corrosion properties of nickel-aluminum bronze

479

0.1
0.05
0

Potential (V)

0.05
0.1
0.15
0.2
0.25
0.3
0.35
1E-08

0.0000001

0.000001

0.00001

0.0001

0.001

0.01

0.1

A/cm 2
Laser-processed

As-cast

Figure 20.11 Linear polarization curves for as-cast substrate and laser-heated NAB.

temperature was controlled using a coil to 25  2  C. Disc-shaped specimens

(12.8 mm diameter) were machined from NAB coupons. These were polished to
1200 grit with SiC paper prior to testing. Each specimen was cleaned with ethanol,
dried, and weighed before and after testing. The duration of each test was 6 h, and
weight loss was measured by interrupting testing at regular intervals (1, 3 and 6 h).
The results of the testing are shown in Figure 20.12.
It is apparent from these results that both laser-melted and laser-processed samples
are far superior to the as-cast and extruded materials. This shows that the laser-processed
material is not only superior in stagnant sea water but it also performs well when
exposed to cavitation. The fact that laser processed behavior is similar to laser melted
is of interest. Reference to the hardness of laser melted versus laser processed (see
Figure 20.7) shows that the melted sample is harder and, given that hardness and cavitation erosion resistance scale [15], it would be expected that the performance of the
laser-melted sample would be significantly superior. The reason that this is not the case
can be explained by the difference in the residual stress. The laser-melted sample has a
tensile residual stress level of 100 MPa (see Figure 20.8), which reduces the strength of
the material and evens up the difference in the strength between the two materials.

20.6

Conclusion

A new approach to improve the corrosion resistance of NAB at the surface by laser
processing has been developed. The technique produced a new type of microstructure for NAB, which has been developed by heating the surface with a laser near to

480

Laser Surface Engineering

0.04
0.035

Weight loss (g)

0.03
0.025
0.02
0.015
0.01
0.005
0
0

10

Time (H)
Laser processed
As-cast

Laser melted
Extruded

Figure 20.12 Cavitation erosion testing result for NAB in the laser-processed, as-cast,
extruded, and laser-melted conditions.

its melting point for a long enough period to dissolve the kIII phase in the solid state
and cooled at a rate where the Widmanstatten morphology microstructure is avoided.
The processing parameters required to do this were developed with the aid of
mathematical modeling of both the reverse phase transformation and laser heating.
The resulting microstructure exhibited a low residual stress, no significant increase
in hardness, and a crystal structure the same as the cast material. The corrosion
performance of the new microstructure showed improved electrochemical performance and cavitation erosion performance when compared with as-cast NAB, thus
proving the value of this new processing technique for extending the life of NAB
components.

Acknowledgments
This work has been conducted by funding from the Defence Materials Technology Centre, Program 2, Project 2.2 Surface Processing Technologies for Repair and Improved Performance of
Submarine and Surface Ship Components. The authors would like to acknowledge Brian
Dempster for conducting the laser-processing experiments and the valuable help of Dr Lenore
Pedrina of DSTO with corrosion testing. As well as for ANSTO and AINSE for providing neutron beam time through neutron proposal ID 2310 Residual stress analysis of laser-treated
nickel-aluminum bronze.

Laser surface treatment to improve the surface corrosion properties of nickel-aluminum bronze

481

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