Accepted Manuscript

Title: Impact of a post-casting homogenization treatment on

the high-temperature oxidation resistance of a cu-ni-fe alloy

Authors: S. Jucken, E. Schaal, B. Tougas, B. Davis, D. Guay,

L. Roué

PII: S0010-938X(18)31509-9
DOI: https://doi.org/10.1016/j.corsci.2018.11.037
Reference: CS 7794

To appear in:

Received date: 16 August 2018

Revised date: 27 November 2018
Accepted date: 28 November 2018

Please cite this article as: Jucken S, Schaal E, Tougas B, Davis B, Guay
D, Roué L, Impact of a post-casting homogenization treatment on the high-
temperature oxidation resistance of a cu-ni-fe alloy, Corrosion Science (2018),
https://doi.org/10.1016/j.corsci.2018.11.037

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Impact of a post-casting homogenization treatment on the high-temperature

oxidation resistance of a Cu-Ni-Fe alloy

S. Juckena, E. Schaala, B. Tougasb, B. Davisc, D. Guaya, L. Rouéa,*

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a
INRS-Énergie Matériaux Télécommunication; 1650 Boulevard Lionel Boulet; Varennes,

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Québec, J3X 1S2, Canada

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b
Centre de Métallurgie du Québec (CMQ); 3095 Rue Westinghouse, Parc Industriel des

Hautes-Forges, Trois-Rivières, Québec, G9A 5E1, Canada

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c
Kingston Process Metallurgy Inc.; 759 Progress Avenue, Kingston, Ontario, K7M 6N6,

Canada N
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* Corresponding author. E-mail: roue@emt.inrs.ca (L. Roué).

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Highlights
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 Cu-Ni-Fe alloy can be homogenized with an appropriate post-casting heat-

treatment.
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 Homogenisation of Cu65Ni20Fe15 improves its high-temperature oxidation

resistance.
 The oxide scale consists of a CuO outer layer and a (NiO+Fe3O4)-rich inner layer.
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 There is no evidence of NiFe2O4 formation under the present oxidation

conditions.
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Abstract

Homogeneous Cu65Ni20Fe15 (wt.%) alloy, which is a promising anode material for zero-

carbon Al production, was successfully produced by casting followed by heat treatment

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at 1070C for 50 h. At 700C, the homogenization procedure increases the oxidation

resistance of the homogeneous Cu-Ni-Fe alloy, as confirmed by the decreased weight

gain (34% less after 20 h) and parabolic rate constant kp (by a factor of 2.5) compared to

the as-cast alloy. The oxide scale formed on the homogenized alloy is thinner, more

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compact and coherent, consisting of a CuO outer layer and a (NiO+Fe3O4)-rich inner

layer.

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Keywords: alloy; high temperature corrosion; SEM; XRD

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1. Introduction
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Over the past 20 years, the modernization of aluminum smelters and better control
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of the process have significantly improved the environmental performance of the primary
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Al industry [1]. Nevertheless, Al production is still a large emitter of greenhouse gases

(GHG) with 2 tons of CO2 equivalents emitted per ton of aluminum produced for the
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best performing Al smelters using GHG-free hydroelectricity [2]. The reason is that

current Al production technology uses carbon anodes that are consumed during the
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electrolysis of aluminum to form CO2 according to the overall reaction: Al2O3 + 3/2 C 

2 Al + 3/2 CO2. Moreover, CO2 emissions during the production of carbon anodes are
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also significant. Other GHGs can also be formed during electrolysis due to anode effects,

such as perfluorocarbons [1].

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A significant reduction in GHG emissions from Al smelters will only be able to

rely on the emergence of new technologies. The most effective solution would be to

replace carbon anodes with so-called inert anodes that emit O2 rather than CO2 according

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to the overall reaction: Al2O3  2 Al + 3/2 O2. Their advent would also lead to a

significant reduction in the operating and infrastructure costs of aluminum smelters by

preventing frequent anode lowering and replacement operations, by elimination of the

carbon anode production plant, and by allowing the development of more compact

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vertical electrode electrolysis cells [3]. It is therefore not surprising that the primary

aluminum industry places the development of inert anodes among its top priorities in

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R&D needs [4]. However, the design of inert anodes is a major challenge because of the

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severe conditions during the electrolysis of aluminum (cryolitic NaF-AlF3 medium at

960C) which require materials with excellent corrosion and thermal shock resistance as

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well as adequate electrochemical properties for Al electrolysis. To date, there is no inert
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anode fully meeting the requirements for Al production at the industrial scale. One must
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however note that Rio Tinto and Alcoa, two large Al producers, are recently announced
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the creation of a new joint venture, called Elysis, to scale up and commercialize the

world’s first carbon-free Al smelting technology using O2-evolving anodes [5].

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Inert anodes can be classified into 3 families depending on their composition,

namely metal, ceramic and cermet, with their specific advantages and drawbacks [6,7].
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Metal anodes have the advantage of having a high electrical conductivity, they are easy to

connect electrically, they have a good resistance to thermomechanical shocks and are
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easy to manufacture. However, most of the metals being soluble in the cryolitic medium,

their resistance to corrosion is based on the formation (in-situ or ex-situ) of a surface

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oxide layer that must remain sufficiently conductive, stable, dense and adherent during

prolonged Al electrolysis. Among the many metallic materials studied to date, Cu-Ni-Fe-

based alloys seem to be the most promising due to their ability to form a nickel ferrite

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(NiFe2O4) rich layer on the surface of the anode which is recognized for its low solubility

in the cryolite [8]. However, as-cast Cu-Ni-Fe alloys have a two-phase structure (a Cu-

rich phase and a Fe-Ni-rich phase) which has a detrimental effect on their resistance to

corrosion because the iron-rich phase produces corrosion tunnels in the alloy [9]. Single-

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phase Cu-Ni-Fe alloys can be obtained over a large composition range by mechanical

alloying and the alloy composition Cu65Ni20Fe15 (wt%) was found to have good corrosion

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resistance in KF-AlF3 at 700°C [10-12]. The fabrication of large area electrodes from

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such materials, as required for industrial Al smelters, is challenging because the high

chemical homogeneity of the mechanically alloyed Cu-Ni-Fe powders must be conserved

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during the powder consolidation procedure. We have recently demonstrated that this

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homogeneity is retained during their consolidation by spark spray sintering (SPS) [13] or
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during their deposition on a substrate by cold spraying [14]. However, these
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methodologies are rather expensive and hardly scalable for the mass production of inert

anodes.
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In the present study, it is shown that monophased Cu65Ni20Fe15 alloy can be

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produced at large scale and low cost using an appropriate post-casting heat treatment.
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This procedure is inspired by the works of Gallino et al. showing that the miscibility gap

for the Cu-Fe-Ni system is experimentally smaller than the one predicted by
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thermodynamic calculations, and thus there exists a narrow window of temperatures in

which the Cux(Fe0.5Ni0.5)1-x alloys can be homogenized into a single phase [15,16]. The
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positive impact of the homogenization procedure on the high-temperature oxidation

resistance of Cu65Ni20Fe15 alloy is highlighted in the present study.

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2. Experimental

2.1. Casting of the alloy

The Cu65Ni20Fe15 (wt%) alloy was prepared from elemental Cu, Ni and Fe (+99%

purity) that were melted under air in a clay graphite crucible with an induction furnace,

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which allowed the production of 5 kg ingot per batch. To remove the dissolved oxygen

from the liquid metal, 0.1 wt% of Al was added to the melt and the produced aluminum

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oxide was removed manually from the liquid surface. The alloy was cast at 1425°C in

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three different molds, allowing for the study of the impact of the solidification (cooling)

rate on the alloy microstructure. The first casting was done in a cast iron mold which led

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to a fast solidification of the alloy (cooling rate 50C min-1). The second casting was
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done in a graphite mold, previously heated at 800°C for 2 h and wrapped in thermally
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insulating k-wool, which led to an intermediate solidification rate (cooling rate 15C
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min-1). The third casting was done in a ceramic investment casting mold, previously
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heated at 1000°C for 5 h, also wrapped in thermally insulating k-wool, resulting in a

slower solidification rate (cooling rate 5C min-1). The three molds were let to cool
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naturally under air after casting. The alloy composition determined by energy dispersive
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X-ray spectroscopy (EDX) was in accordance (within 1-2 wt%) with the nominal

Cu65Ni20Fe15 composition.
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2.2. Post-casting heat treatment

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The post-casting heat treatment was carried out on 1 cm thick samples in an

atmosphere-controlled furnace under 1 atm of Ar for different durations (from 10 to 50 h)

followed by water quenching. The temperature was fixed at 1070°C, as it lies inside the

5
homogenization temperature window of the alloy and under the melting temperature of

Cu, preventing the partial melting of the Cu-rich alloy phase [15,16]. A heat treatment

was also carried out in a hot isostatic press (HIP) in order to reduce the sample porosity

resulting from the solidification shrinkage upon alloy casting. This HIP treatment

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consisted of 2 h at 1070°C under 100 MPa Ar followed by 38 h at 1070°C under 1 atm

Ar.

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2.3. Characterization of the alloy

The resulting samples were polished and etched with an FeCl3 + HCl ethanol

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solution prior to observation with an optical microscope and were re-polished before

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observation with a Hitachi SU-3500 scanning electron microscope (SEM) combined with
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an EDX analyzer. Porosity of the samples was evaluated using Clemex software on five
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cross-section optical micrographs per sample (535 µm x 400 µm areas for each

micrograph).
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The crystalline structure of the alloy was determined by X-ray diffraction (XRD)
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using a Bruker D8 diffractometer with Cu Kα radiation. XRD data were analyzed using
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DIFFRAC.EVA software.
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2.4. Oxidation tests

The oxidation behavior of the alloy was investigated by thermogravimetric analysis

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(TGA) using a TA Instruments Q500 equipment. The oxidation temperature was fixed at

700C because Cu-Ni-Fe inert anodes are preferentially used for Al production in low

temperature (700°C) KF-AIF3 electrolyte 9-14. The mass variation of the samples were

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recorded for 20 h at 700°C under a 90 cm³ min-1 air flow. Additionally, SEM-EDX

observations of the oxide scale formed in a Thermolyne tubular furnace at 700°C under

100 cm³ min-1 Ar-20% O2 for 1, 10 and 20 h were undertaken by use of a Tescan Vega3

SEM after mounting the samples in an epoxy resin and polishing.

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3. Results and discussion

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3.1. Casting of the alloy

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Fig. 1a-c shows cross-section photographs of the alloy obtained with the three

different casting procedures. Large pores (ranging from ca. 0.1 to 7 mm in diam.) can be

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observed inside the alloy cast in the iron mold with a cooling rate of 50C min-1 (Fig.
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1a) and the graphite mold with a cooling rate of 15C min-1 (Fig. 1b). These large
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pores are due to the alloy solidification shrinkage, which is accentuated as the
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solidification (cooling) rate increases. Indeed, the alloy solidified at a slower cooling rate

(5C min-1) in the ceramic mold shows no apparent porosity (Fig. 1c).
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During solidification, chemical segregation occurs within the alloy, resulting in the

formation of Ni-Fe-rich dendrites embedded in a Cu-rich matrix 15,16. This dendritic

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microstructure is clearly visible on the optical micrographs of the as-cast samples (Fig.

1d-f). The chemical composition of the Cu-rich and Ni-Fe-rich phases determined by
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EDX are Cu86Ni9Fe5 and Cu37Ni32Fe31 (wt.%) respectively, and do not vary significantly
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with the solidification rate. However, this latter impacts the dendrite size, which increases

from less than 100 µm in length (10 µm in diam.) for the faster solidification (Fig. 1d)

to +500 µm in length (30 µm in diam.) for the slower one (Fig. 1f).

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3.2. Homogenization of the alloy

Homogenization treatments were carried out at 1070°C on Cu-Ni-Fe samples cast in the

graphite mold for different durations. As shown in Fig. 2, the dendrites becomes less and

less discernible as time increases. After 50 h of heating (Fig. 2e), no dendrite can be

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observed, suggesting that the alloy homogenization is complete. According to the

calculated equilibrium phase diagram of the Cu-Ni-Fe system established by Gallino et

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al. 15 (see Fig. S1 in Supporting Information), the Cu65Ni20Fe15 alloy should be bi-

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phased as this composition falls within the miscibility gap at 1100C. However, Gallino

et al. have demonstrated experimentally that this miscibility gap is smaller than expected

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from thermodynamic considerations and it exists a window of temperature situated
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around 1070C in which Cu-Ni-Fe alloys can be homogenized into a single -phase (see
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Fig. S2 in Supporting Information). Although these conclusions were reached for Cu-Ni-
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Fe alloys with a mass fraction of Cu ranging from 0.1 to 0.7 and a Ni/Fe mass ratio fixed
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at 1/1, our results on the Cu65Ni20Fe15 composition suggest that such a homogenization
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process is also possible for a Ni/Fe mass ratio of 1.33.

The grain size is typically around 250 µm. Micrometric pores (black zones) are also
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discernible and their amount is estimated at 1 vol%. When the homogenization is

performed under HIP, the porosity is decreased to 0.1% (Fig. 2f). Note that for samples
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cast in the ceramic mold (i.e. at a lower cooling rate resulting in larger dendrites), a heat-
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treatment time longer than 50 h was required for a complete homogenization of the alloy

(data no shown).

EDX analyses confirm the good chemical homogeneity of the Cu-Ni-Fe alloy after

50 h of heat treatment at 1070°C with no evidence of chemical segregation (Fig. 3b) in

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contrast to the as-cast alloy where Ni-Fe-rich and Cu-rich zones are clearly visible (Fig.

3a). Note that no significant change in the microstructure of the homogenized alloy was

observed after subsequent annealing for 100 h at 700C (data not shown), suggesting that

its chemical homogeneity can be preserved at the Al electrolysis temperature (to be

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confirmed after weeks/months of heating). This differs from Gallino’s works showing

discontinuous coarsening along the grains boundaries of homogenized Cu-Ni-Fe alloys

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after annealing for 400 h at 750C [15,16].

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Fig. 4 shows the XRD patterns of the as-cast (in graphite mold) and homogenized

(50 h) Cu-Ni-Fe alloy. In both cases, one can observe only one series of peaks indexed to

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a face centered cubic (fcc) phase with a lattice parameter of 3.606 Å. The presence of the
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Cu-rich and Fe-Ni-rich fcc phases in the as-cast alloy is not detectable by the present
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XRD analysis as their lattice parameter value is nearly the same, inducing an overlapping
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of their respective diffraction peaks 10,17. Although the peak positions of both XRD
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patterns are almost identical, there is a noticeable variation of the peak intensity between
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them. In the case of as-cast Cu-Ni-Fe alloy, the relative intensity of the various peaks is

close to what is expected for an fcc structure, decreasing regularly as (h2 + k2 +l2)
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increases, where h, k and l are the Miller indices of the peak. In the case of homogenized

Cu-Ni-Fe alloy, the intensity of peaks (200) and (220) is less than (311). However, upon
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a 90° rotation of the sample on the sample holder, the intensity of peaks (200) and (220)

becomes larger than (311) (data not shown). This texturing effect must occur due the
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large grain size (ca  200 µm, see Fig. 2e).

3.3 Oxidation behavior

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 Oxidation kinetics of the as-cast and homogenized Cu-Ni-Fe alloy was investigated

by means of thermogravimetric measurement for 20 h at 700°C under air (Fig. 5). As

seen in Fig. 5b where the square of the weight gain is plotted versus time, the oxidation

of both alloys follows a parabolic evolution, which is characteristic of a diffusion-

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controlled process. Due to the high oxygen concentration at the surface of the electrode,

all of the surface metals will oxidize. Oxygen will diffuse into the alloy and metal will

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diffuse out to the surface. The higher oxidation rate observed during the first 2 h for

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both alloys can be attributed to the rapid outward diffusion of copper in copper oxides, as

Cu has the higher inter-diffusivity coefficient compared to Fe and Ni in Cu-Ni-Fe alloys

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[18]. From 2 h, a decrease of the oxidation rate is observed, which can be associated to
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the internal oxidation of Ni and Fe, limiting the outward diffusion of Cu in CuOx. This
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limitation appears more marked for the homogenized alloy. As a result, the total weight
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gain of the homogeneous alloy after 20 h of oxidation is reduced by 34% compared to the

as-cast alloy, indicating a better resistance to oxidation induced by the homogenization

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process. This is also evidenced by comparing the parabolic rate constant kp of the as-cast
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and homogenized alloys determined between 2 and 20 h of oxidation, which are 14 x10-11
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and 5.5 x10-11 g2 cm-4 s-1, respectively (i.e. a decrease by a factor of 2.5). For comparison,

Gallino et al. [16] observed a 29% decrease of the weight gain (after 24 h of oxidation at
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800C under 1 atm O2) and a decrease by a factor of 1.6 of the kp constant (from 3.4 to

2.1 x 10-9 g2 cm-4 s-1) for homogenized versus as-cast Cu70Ni15Fe15. The higher kp values
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from Gallino’s work can be related to the higher temperature and O2 pressure for

oxidation than in the present study. The positive impact of the homogenization treatment

on the alloy oxidation resistance is, however, more marked in the present study. It must

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also be noted that the kp rate constant of the present homogenized Cu65Ni20Fe15 alloy is

20 times smaller than the one measured under similar oxidation conditions for a

homogeneous Cu65Ni20Fe15 alloy synthesized by high-energy ball milling [12]. This

could be attributed to the much finer microstructure of the ball-milled Cu-Ni-Fe alloy

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constituted of nanosized grains compared to 250 µm grains in the present case (Fig. 2e).

The large amount of grain boundaries in ball-milled Cu-Ni-Fe alloy, where oxygen atoms

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can easily diffuse, is likely to accelerate its oxidation. Its larger porosity (5% compared

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to 1% in the present case) may also be detrimental for its oxidation resistance.

The oxide scales formed on the as-cast and homogenized Cu-Ni-Fe after different

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oxidation times (1, 10 and 20 h) at 700°C under Ar-20% O2 have been characterized by
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cross-section SEM-EDX analyses as shown in Fig. 6a-f. The different oxides formed on
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both alloys are indicated on the cross-section SEM images superimposed with EDX
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elemental maps of Ni, Cu, Fe, and O (Fig. 7a-f).

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A major difference in the structure of the oxide scale is already visible after 1 h of
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oxidation. The oxide scale formed on the homogeneous alloy (Fig. 6b and 7b) presents a

uniform bi-layered structure constituted of an outermost CuO layer (5 µm thick) and an
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inner layer (5 µm thick) mainly composed NiO and FeOx with a few inclusions of

Cu2O. The oxide scale is rather dense without significant pores and cracks. In contrast,
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the oxide scale formed on the as-cast alloy appears non-uniform and cracked with large
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delaminated and porous zones (Fig. 6a and 7a). The outermost part of the oxide scale (5-

15 µm thick) is composed of CuO with large inclusions of Cu2O situated above depleted

Cu-rich zones of the alloy. Beneath the CuO/Cu2O layer, the Ni-Fe-rich dendrites are

covered with a thin layer of Ni and Fe oxides, whereas the preferential outward diffusion

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of Cu from the Cu-rich matrix results in the formation of large holes in the bulk of the

alloy. This highlights the major deleterious impact of the chemical inhomogeneity of the

as-cast Cu-Ni-Fe alloy on its ability to form a dense and homogenous surface oxide in the

early stage of the oxidation process.

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After 10 h of oxidation, the homogeneous alloy still presents a uniform bi-layered

oxide scale with a total thickness of 20 µm (Fig. 6d and 7d). However, the formation of

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pores can be observed, especially at the oxide/alloy interface. On the inhomogeneous

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alloy (Fig. 6c and 7c), the CuO layer has grown due to the Cu outward diffusion and still

presents large pores. The inward diffusion of oxygen has nearly fully converted the Cu2O

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inclusions in CuO in addition to increase the thickness of the inner NiO+FeOx rich layer.

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After 20 h of oxidation, a 15-20 µm thick and cracked/delaminated outermost CuO
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layer is observed on the as-cast alloy (Fig. 6e and 7e). The growing of the inner
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NiO+FeOx rich layer (10-40 µm thick) results in the disappearance of the inner porous

Cu-depleted zones. A few Cu2O inclusions are also observed near the oxide/alloy
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interface. For the homogenized alloy (Fig. 6f and 7f), the oxide scale is thinner but
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cracks are also observed in the outermost CuO layer. This cracking may originate from
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the thermal shock during the sample extraction from the furnace. However, the fact that

such cracking is not observed after 1 and 10 h of oxidation suggests that the oxide layer
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becomes more fragile as the oxidation time increases. Regarding the inner NiO+FeOx

rich layer, its growing between 10 and 20 h of oxidation is very limited compared to the
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as-cast alloy. Note that a nearly continuous Cu2O-rich layer is formed in this inner layer.

This layered structure can be explained by the fact that oxygen dissolution in the alloy

and Cu enrichment underneath the NiO+FeOx rich layer may continue slowly after 10 h

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of oxidation. After a certain time, the oxygen activity at the oxide/alloy interface

becomes sufficient to oxide Cu. Thereby a new sequence of layered CuO/(NiO+FeOx)

structure is initiated. This was also observed by Haugsrud et al. during prolonged high-

temperature oxidation of a biphased Cu55Ni30Fe15 (wt.%) alloy [19].

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On both alloys, there is no clear evidence of the formation of NiFe2O4. Indeed, on

the basis of the EDX analyses performed in different regions of the oxide scales shown in

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Fig. 6a-f, the Fe:Ni atomic ratio is never equal to 2, as expected for NiFe2O4.

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Additionally, XRD analyses of the oxide scales have been performed on as-cast and

homogenized alloys after 20 h of oxidation (Fig. 8). On the as-cast alloy, the CuO outer

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scale is clearly identifiable. A small portion of Cu2O and NiO is also detected. No peak

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attributable to Fe2O3, Fe3O4 or NiFe2O4 phase is observed. On the homogenized alloy, the
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thinner CuO outer layer allows the detection of NiO as well as Fe3O4 or NiFe2O4 formed
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in the inner layer. The Fe3O4 and NiFe2O4 phases cannot be differentiated by the present

XRD analysis as their characteristic peaks tend to overlap due to very small difference in
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their respective lattice parameter (8.378 Å for Fe3O4 versus 8.337 Å for NiFe2O4
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according to JCPDS file 01-071-6336 and 00-054-0964, respectively). If any, the

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formation of NiFe2O4 seems to be limited, which is unexpected considering that the

formation of (NiO + FeOx) rich zones in both alloys should favor the reaction between
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NiO and Fe2O3 to form NiFe2O4 (ΔG°f (1000 K) = -727 kJ mol-1) [20]. However, it is

known that the solid-solid interaction between NiO and Fe2O3 takes place at a slow rate
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and requires prolonged heating at temperatures above 1100C for the complete

transformation of the reacted oxides into the nickel ferrite phase [21]. The addition of a

small amount of Li2O, likely to increase the mobility of the reacting cations thanks the

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formation of cationic vacancies, could also be an effective way to promote the formation

of the nickel ferrite phase [21,22]. The solid-solid interaction that gives to NiFe2O4 is also

affected by the NiO/Fe2O3 ratio, which may be non-optimal in the present case. It must

also be noted that the formation of NiFe2O4 may be more favourable under Al electrolysis

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conditions because of the dissolution of the CuO outer layer that impacts on the NiFe2O4

formation, as recently shown on ball-milled Cu-Ni-Fe anodes with different Cu contents

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[12]. Comparative Al electrolysis tests with as-cast and homogenized Cu-Ni-Fe alloys are

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planned to confirm this issue.

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4. Conclusion

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It was shown that monophased Cu65Ni20Fe15 alloy can be prepared by casting from pure
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elements as long as an appropriate post-casting heat-treatment is performed to
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homogenize the composition of the material. Homogenisation of Cu65Ni20Fe15 improves

its high-temperature oxidation resistance thanks to the formation of a denser and more
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uniform oxide scale. It consists of a CuO outer layer and a (NiO+Fe3O4)-rich inner layer.
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There is no evidence of the formation of NiFe2O4 under the present oxidation conditions,
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which may result from kinetic limitations. This work opens the way to the mass-

production of low-cost inert anodes for CO2-free aluminum electrolysis.

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Acknowledgements
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The authors thank the Natural Sciences and Engineering Research Council of Canada

(NSERC) (grant STPGP 494283-16), Prima Québec (grant R13-13-001), Metal7 and

Kingston Process Metallurgy for supporting this work.

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Data availability

All experimental data are available from the corresponding author on reasonable request.

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14 G. Goupil, S. Jucken, D. Poirier, J.G. Legoux, E. Irissou, B. Davis, D. Guay, L.

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[16] I. Gallino, M.E. Kassner, R.Busch, Oxidation and corrosion of highly alloyed Cu–
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Figure captions

Figure 1 Cross-section photographs (a-c) and optical micrographs (d-f) of the

Cu65Ni20Fe15 alloy cast in iron (a, d), graphite (b, e) and ceramic (c, f) molds.

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Figure 2 Optical micrographs of the Cu65Ni20Fe15 alloy before (a) and after a post-

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casting heat-treatment at 1070˚C under 1 atm Ar for 10 h (b), 20 h (c), 30 h

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(d), 50 h (e) and for 2 h under 100 MPa Ar followed by 38 h under 1 atm Ar

(f).

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Figure 3 N
BSE-EDX mapping images of the as-cast (a) and homogenized (b)
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Cu65Ni20Fe15 alloys.
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Figure 4 XRD patterns of the as-cast and homogenized Cu65Ni20Fe15 alloys

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Figure 5 Weight gain (a) and square of weight gain (b) as a function of the oxidation
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time at 700C under air for the as-cast and homogenized Cu65Ni20Fe15 alloys.
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Figure 6 Cross-section SEM images and corresponding EDX mapping images and

concentration profiles of Cu, Ni, Fe and O elements for the as-cast (a, c, e)
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and homogenized (b, d, f) Cu65Ni20Fe15 alloys after 1 h (a, b) , 10 h (c, d) and

20 h (e, f) of oxidation at 700C under 1 atm of Ar:O2 (80:20). The elemental

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 concentrations for various zones of the samples are given in at.% in the

tables.

Figure 7 Cross-section SEM images superimposed with EDX elemental maps of Ni

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(yellow), Cu (red), Fe (blue) and O (green) for the as-cast and homogenized

Cu65Ni20Fe15 alloys after 1, 10 and 20 h of oxidation at 700C under 1 atm of

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Ar:O2 (80:20). The composition of the oxide layers determined from the EDX

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analyses shown in Fig. 6 are indicated on the figure.

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Figure 8 XRD patterns of the as-cast and homogenized Cu65Ni20Fe15 alloys oxidized
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for 20 h at 700C under 1 atm of Ar:O2 (80:20).
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