Journal of Alloys and Compounds 610 (2014) 214223

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Journal of Alloys and Compounds

journal homepage: www.elsevier.com/locate/jalcom

Exploring Cu2O/Cu cermet as a partially inert anode to produce

aluminum in a sustainable way
Li-Chao Feng a,c, Ning Xie b,c,, Wen-Zhu Shao c,, Liang Zhen c, V.V. Ivanov d
a

School of Mechanical Engineering, Huaihai Institute of Technology and Jiangsu Province R&D Institute of Marine Resources, Lianyungang 222005, China
School of Transportation Science and Engineering, Harbin Institute of Technology, Harbin 150090, China
c
School of Materials Science and Engineering, Harbin Institute of Technology, Harbin 150001, China
d
Physical Chemistry Department, Siberian Federal University, Krasnoyarsk 660041, Russia
b

a r t i c l e

i n f o

Article history:
Received 23 February 2014
Received in revised form 27 April 2014
Accepted 28 April 2014
Available online 9 May 2014
Keywords:
Inert anode
Cermet
Aluminum production
Geometrical structure
Sustainable

a b s t r a c t
As an energy-intensive process, aluminum production by the HallHroult method accounts for
signicant emissions of CO2 and some toxic greenhouse gases. The utilization of an inert anode in place
of a carbon anode was considered as a revolutionary technique to solve most of the current environmental problems resulting from the HallHroult process. However, the critical property requirements of the
inert anode materials signicantly limit the application of this technology. In light of the higher demand
for aluminum alloys than for pure aluminum, a partially inert anode was designed to produce aluminum
alloys in a more sustainable way. Here, Cu2O/Cu cermet was chosen as the material of interest. The thermal corrosion behavior of Cu2O/Cu was investigated in Na3AlF6CaF2Al2O3 electrolyte at 960 C to elucidate the corrosion mechanisms of this type of partially inert anode for the production of aluminum or
aluminum alloys. Furthermore, the effects of the geometrical structure of the Cu phase on the thermal
corrosion behavior of Cu2O/Cu cermet in the electrolyte were investigated as well. The thermal corrosion
rate was evaluated by the weight loss method and the results show that the samples prepared with
branch-like Cu have higher thermal corrosion rate than those prepared with spherical Cu, and the corrosion rate increases with decreasing size and increasing lling content of Cu phase. The calculated corrosion rate was about 1.57.2 mg/cm2 h (1.89 cm/y) in the current testing procedure. The Cu contents in
the produced aluminum is less than 6.2 wt.%.
2014 Elsevier B.V. All rights reserved.

1. Introduction
Sustainability has become an increasingly important characteristic in most of the industrial engineering elds. Aluminum production by the HallHroult method is an energy-intensive
process that accounts for a globally signicant amount of CO2
and other greenhouse gas emissions [13]. Currently, the anode
material for this electrolysis process is made of carbon. By using
the carbon anode, the cell reaction is:

1
3
3
Al2 O3 C Al CO2
2
4
4

This means that over tens of millions tons of coke will be consumed
annually and this number keeps increasing with the rising demand
for aluminum on a global scale [4,5]. In addition, because carbon
Corresponding authors. Address: School of Materials Science and Engineering,
Harbin Institute of Technology, Harbin 150001, China (N. Xie). Tel.: +86 451
86412133; fax: +86 451 86414392.
E-mail addresses: xiening@hit.edu.cn (N. Xie), wzshao@hit.edu.cn (W.Z. Shao).
http://dx.doi.org/10.1016/j.jallcom.2014.04.198
0925-8388/ 2014 Elsevier B.V. All rights reserved.

anodes are degraded and replaced frequently, the electrolyte cells

are not able to be covered tightly. This requires a large increase in
energy consumption to maintain the temperature of the electrolytic
cells.
With the increasing energy costs and heightened concerns
about the environmental footprint of the HallHroult process,
there is signicant interest in the utilization of inert anodes, which
are non-consumable during electrolysis, to replace carbon anodes
in the electrolytic cells. If the cells are equipped with inert anodes,
the cell reaction becomes:

2Al2 O3 4Al 3O2

By comparing with Eqs. (1) and (2), theoretically, the product at the
anode will be O2 in place of CO2, which will largely eliminate carbon
emissions during this production process. Likewise, the emissions of
other greenhouse gases, such as most of the CF4 and C2F6 [6], PAH
(from the combustion of the coal tar pitch content in the carbon
anode) [7,8], and SO2 will be eliminated as well. Moreover, the uorides emitted along with the dust and heat will be considerably

L.C. Feng et al. / Journal of Alloys and Compounds 610 (2014) 214223

reduced, which will greatly reduce the operators exposure to harmful environments during the anode changing procedure [9].
Although replacing the carbon anode with an inert anode is
always ideal for aluminum production, their application is still limited due to some major challenges regarding the general property
requirements for inert anode materials. First of all, the inert anode
must have electrical and thermal conductivities as high as a conductors level; second, the exural and compressive strengths have
to be on the order of 102 MPa; and third, the corrosion rate of the
materials needs to be lower than 1.0 cm/year [10,11]. Unfortunately, it is still a great challenge to materials scientists to develop
a new material that can satisfy all these requirements.
So far, research on inert anode development is focused on three
types of materials: ceramics, metal or metal alloys and ceramic
metal (cermet) composites. Typical ceramic inert anode materials
are Sb2O3, SnO2, CuO, NiFe2O4, NiO, CeO2 and their compounds
[1214]. The main advantage of the ceramic inert anode is its chemical stability in the highly corrosive environment at high temperatures; the metal or alloy inert anodes, on the other hand, have
lower chemical stability but higher thermal and electrical conductivities. Typical metal or alloy inert anode materials are FexCr1x,
Ni, NiAl, CuNiFe, CuAlNiFe, NiFe, etc. [1518]. Cermet
materials, which inherit advantages from both metals and ceramics,
have been considered as another possible inert anode material for
aluminum production [19]. Although the NiFe2O4NiOCu cermets
have been studied for decades, it is still not able to be widely applied
due to some unsolved critical bottle neck problems.

215

In cermet materials, the addition of the metal phase in the

ceramics matrix aims to increase the electrical and thermal conductivities without sacricing chemical stability during the electrolysis process. Due to the chemical instability of the metal
phase, its dosage should be minimized in order to minimize the
corrosion rate. The corrosion behavior of cermet materials as inert
anodes for aluminum production has been investigated extensively. Three main corrosion mechanisms were introduced by former studies: the chemical dissolution of oxides [20], the thermal
reductive reaction with aluminum [21] and the metal phase dissolution [22].
The studies on the chemical dissolution of oxides were focused
on the compounds of Ni and Fe. DeYoung [20] and Diep [23] investigated the relationships between the solubility of Fe2O3, NiO and
NiFe2O4 in NaFAlF3CaF2Al2O3 electrolyte. It was demonstrated
that the following reaction occurred:

3Fe2 O3 2AlF3 6xNaF 6Nax FeOF1x Al2 O3

Although the solubility of aluminum in the electrolyte is limited, it

was also demonstrated that [22] the reaction between the aluminum and the oxides is inevitable, and the reaction could be written
as:

3MOn 2nAl 3M nAl2 O3

Dewing [21] gave an empirical relationship between the temperature and the aluminum concentration in the electrolyte:

Fig. 1. SEM morphologies of the (a) Cu2O, (b) branch-like Cu, (c) spherical Cu with size of 38 lm, and (d) 75 lm.

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L.C. Feng et al. / Journal of Alloys and Compounds 610 (2014) 214223

CAl 0:31759 0:01849CR 0:000344T

 0:00407CaF2  0:000096CaF2 2

0:02285
3 Al2 O3 

where CAl is the mass concentration of the dissolved aluminum in

the electrolyte, [x] is the mass concentration of the compounds,
CR is the molar ratio of NaF and total AlF3, and T is the temperature
in Celsius of the electrolyte. The metal phase dissolution phenomenon was investigated by Tarcy [22]. It was found that the metal
phase, nickel, was removed from the surface of the anode during
the electrolysis procedure, which led to a remarkable decrease of
the electrical conductivity of the anode. Meanwhile, Windisch
[24] found that the dissolution process of copper was different from
that of nickel. The copper, instead of being dissolved directly, was
oxidized rst and subsequently dissolved by the electrolyte as copper oxides.
Due to the fact that the metal phase is the key component of the
cermet to maintain a high electrical conductivity for the inert
anode, the introduction of the corresponding metal impurities into
the nal aluminum is inevitable. However, thanks to the large market demands for aluminum alloys [4], the electrolytic cell equipped
with partially inert anode could be considered as a potential way to
produce aluminum alloys, which have much wider applications
than the pure aluminum. The International Aluminum Institute
(IAI) reported that the ratio of secondary aluminum to primary aluminum was only 17% in 1960, while it had increased to 33% in
2006. IAI claimed that this value will be as high as 40% after
2040 [25]. In light of the tough challenge to develop a fully inert
anode material, the investigation of a partially inert anode material
has become a reasonable approach to mitigate the current environmental problems created during the production of aluminum and
its alloys.
FeNi based cermets have been investigated as fully inert anode
materials for decades and showed a great potential to achieve the

Table 1
Porosities of the Cu2O/Cu cermets prepared with various contents and structures of
Cu phase.
Cu content, wt.%

Branch like Cu

38 lm spherical Cu

75 lm spherical Cu

10
15
20
25
30
35

2.45
2.47
2.60
2.68
2.22
2.14

2.40
2.58
2.68
2.55
2.58
2.26

2.61
2.39
2.07
2.51
2.57
2.64

goal; however, the demands for AlNi or AlFe alloys are much
smaller than for AlCu, AlSi, or AlZn alloys, which signicantly
limited the possibility of their widespread application. Copper,
one of the major metals in cermet materials, has been proven to
maintain the high electrical and thermal conductivities. Unlike iron
or nickel, copper acts as the main alloying element in most aluminum alloys (from series of 1xxx to 7xxx). As a result, Cu2O/Cu cermet could be considered as a candidate partially inert anode
material to produce aluminum alloys due to Cu being the only element introduced into the product metal. Although the mechanical
and physical properties have been extensively investigated [26
30], the thermal corrosion behavior of Cu2O/Cu cermet in Na3AlF6
CaF2Al2O3 electrolyte at high temperatures (960 C) has never
been reported, and the high temperature corrosive mechanism is
still not clear.
In addition, although some light metal alloys have been successfully prepared in molten salt system [31,32], and the corrosion
behaviors of the alloys in molten salt environment under oxidizing
atmospheres have been studied [33,34], little work has been
reported on the preparation of aluminum alloys in a molten salt
system. Therefore, it is necessary to develop a method for the aluminum alloys preparation in Na3AlF6CaF2Al2O3 molten salt electrolyte at high temperatures (800960 C) and elucidate their
thermal corrosion behavior. Here, the thermal corrosion behavior
of Cu2O/Cu cermet was studied to elucidate the corrosion mechanisms of this type of inert anode for the production of aluminum
or aluminum/copper alloys. Meanwhile, the effects of the geometrical structure of the copper phase on the thermal corrosion behavior of the Cu2O/Cu cermet in the electrolyte have been investigated
as well to help optimize the overall performance of this inert anode
material.
2. Experimental
The Cu2O/Cu cermets were prepared via hot-pressing technology. The Cu2O
powder and Cu powders with different geometrical structures were directly mixed
and then hot pressed. The Cu contents of the samples were 10 wt.%, 15 wt.%,
20 wt.%, 25 wt.%, 30 wt.%, and 35 wt.%, respectively. The average particle size of
Cu2O was about 10 lm. The Cu powders were branch-like or spherical with diameters of 38 lm and 75 lm. Fig. 1 shows the morphology of the raw materials. Part
(a) shows the morphology of the Cu2O powder, which was irregular. The morphology of the branch like Cu particles is shown in Fig. 1(b), while the spherical particles
with diameters of 38 lm and 75 lm are shown in Fig. 1(c and d) respectively. As
can be seen in this gure, the morphology of the Cu powder was either branch-like
or spherical, while the shape of the Cu2O powder was irregular. To diminish the
oxygen from the Cu surfaces, the Cu powders were heated in H2 at 450 C for 2 h
before preparing the composites.
In the hot pressing process, the Cu powders and Cu2O powder were ball-milled
in dehydrated ethyl alcohol for 12 h, and subsequently dried in a vacuum furnace at
80 C. After drying, the temperature was raised to 1050 C with a heating rate of

Fig. 2. Schematic illustration of the thermal corrosion testing device.

L.C. Feng et al. / Journal of Alloys and Compounds 610 (2014) 214223

217

external dimensions were used to test whether the corrosion performances will
be affected by the size of the samples. The testing temperature was 960 C. The corrosion rate was evaluated by the weight loss method and was calculated from the
following equation:

Vs

Fig. 3. Macroscopic appearance of the Cu2O/Cu cermets with different Cu content

after corrosion tests.

20 C/min and was followed by hot pressing with 25 MPa and a 40 min soak in a
graphite mold. The furnace chamber was purged with 1.0 atm of argon gas from
the start of the hot pressing procedure. The relative densities of the prepared samples were tested according to the Archimedes method, and the porosities of the prepared samples are listed in Table 1. As can be seen in this table, the porosities of the
prepared samples are all about 2.5%.
The schematic illustration of the thermal oxidation testing device is shown as
Fig. 2. The samples were immersed in the electrolyte (5 wt.%CaF2 + 5 wt.%Al2O3 +
Na2AlF6) which was isolated in a covered graphite crucible. Samples with various

2m1  m2
S1 S2 t

where Vs is the corrosion rate (g/cm2 h), m1, m2 and S1, S2 are the mass (g) and surface areas (cm2) before and after the corrosion test, respectively, and t is the corrosion time (h). As samples will lose mass through both dissolution and mechanical
wear, and gain mass through formation, remnant electrolyte was removed from
the samples before weighing to minimize error. Samples were immersed in molten
NaCl for 60 min, cooled and then ultrasonically cleaned in pure water to minimize
error.
The phase structures were determined by X-ray diffraction pattern (XRD) on a
Rigaku D/max-rA X-ray diffractometer with Cu Ka radiation (k = 1.5406 ). The surface morphologies of the samples were observed by scanning electron microscopy
with energy dispersive spectroscopy (SEM/EDS), performed on Hitachi S-4700 scanning electron microscopy. After that, the cross sectional optical microscopy was
observed on Zeiss-MC80-DX.
The electrolysis experiment was performed in an electrolysis cell with a volume
of nearly 100 cm3 which was placed in a stainless steel container. Cu2O/Cu cermet
anodes with a rectangular shape were used for testing. Alumina was added periodically (manually) into the cell to maintain approximately the saturation level. Shortterm (25 h) and long-term (100 h) electrolysis tests were used to measure the
electrochemical properties of the Cu2O/Cu cermets. An Al electrode was used as
the reference anode. The current density was 0.8 A/cm2, and the distance between
the anode and the cathode was about 4 cm. The electrolyte was Na3AlF6CaF2
Al2O3, and electrolysis temperature was 960 C.

3. Results and discussion

The samples immersed in the electrolyte for 16 h have been
demonstrated their thermal stability in light of the minimal

Fig. 4. Cross sectional optical microstructures of Cu2O20 wt.% Cu cermet prepared with branch-like Cu after corrosion for (a) 2 h; (b) 4 h; (c) 8 h; and (d) 16 h.

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L.C. Feng et al. / Journal of Alloys and Compounds 610 (2014) 214223

variation of the external dimensions of all samples with various

sizes, shown in Fig. 3. The cross sectional optical microstructure
(OM) of the samples immersed in the electrolyte for different durations is shown in Fig. 4. As exhibited in part (a), (b), (c) and (d) of
this gure, the reaction layers are able to be evidently observed in
all samples. The thicknesses of the reaction layers are 12 lm,
18 lm, 30 lm and 35 lm corresponding to the immersion time
of 2 h, 4 h, 8 h and 16 h, respectively. It increased 30 lm during
the rst 8 h but only 5 lm during the next 8 h, suggesting that
the growth rate of the layer is quicker in the initial stage during
the whole corrosion process. Furthermore, due to the sintering
effect and the increasing quantity of the CuAlO2, the density of
the layer increases with increasing immersion time. The quantity
of the micropores in the reaction layer reduced signicantly after
being immersed for 8 h. In addition, the Cu concentration at the
interface between the reaction layer and the cermet matrix varies
with increasing corrosion time. As demonstrated in part (a), after
2 h of corrosion, the distribution of the Cu particles at the interface
exhibited little difference from the center of the sample; while
being corroded for 4 h, remarkable Cu accumulation at the interface area can be observed, shown as part (b). With an even longer
corrosion time, shown as part (c) and (d), the content of the Cu particles was sharply decreased and hardly be observed at the interface area. The high magnication cross section OM morphology
of the samples further demonstrated the remarkable difference of
the samples with corrosion time of 4 h and 8 h, shown as Fig. 5.
Fig. 6 gives the corrosion rate as a function of Cu content of the
sample prepared with branch-like Cu after being immersed for 8 h.
As illustrated in this gure, the corrosion rate increases remarkably
with increasing Cu content. It was about 0.68  103g/cm2 h with
Cu content of 10 wt.% while it increased to 2.63  103g/cm2 h
with Cu content of 35 wt.%. This is not a surprising result because
the Cu phase is much less stable than the Cu2O phase during the
corrosion process. The OM cross sectional morphology of the samples with Cu content of 10 wt.% and 35 wt.% immersed in the electrolyte for 4 h are shown as part (a) and part (b) in Fig. 7. It can be
seen from this gure that the thickness of the reaction layers are
similar for these two samples, while the porosity of the sample
with 10 wt.% Cu is lower than the one with 35 wt.% Cu, which
resulted in a relatively lower corrosion rate.
Fig. 8 demonstrated the effects of the geometrical structure of
the Cu phase on the corrosion rate of the cermet materials. It can
be seen from this gure that the sample prepared with branch-like
Cu and spherical Cu with size of 75 lm have the highest and the
lowest corrosion rate with values of 2.63 and 1.18 mg/cm2 h,

Fig. 6. Corrosion rate of Cu2OCu cermets prepared using branched Cu powders

with different Cu contents.

respectively, and the sample prepared with spherical Cu with size

of 38 lm has a medium value of 1.86 mg/cm2 h (the cross sectional
optical microstructures of these samples are shown in Fig. 9). Comparing with our former studies, it was found that the effects of the
geometrical structure of the Cu on the electrical or thermal conductivities are opposite to that of the corrosion rate. It was demonstrated that for the same Cu content, the samples prepared with
branch-like Cu have higher electrical and thermal conductivities
than the ones prepared with spherical Cu, and for those prepared
with spherical Cu, the increasing of the Cu size will lead to decreasing electrical and thermal conductivities [2628]. Consequently,
another challenging problem yet to be solved is to optimize the
geometrical structure of the Cu phase to achieve the lowest corrosion rate without sacricing the high electrical and thermal
conductivities.
The crystallographic structures of the reaction layer, which was
removed from the sample prepared with 20 wt.% of branch-like Cu
immersed in the electrolyte for 8 h, have been conrmed by XRD
analysis (Fig. 10). It clearly shows a pure CuAlO2 peak and little
impurity peaks were observed. The corresponding SEM/EDS analysis further demonstrated the chemical compositions of the reaction
layer contain Al, Cu and O (shown in Fig. 11). The element mapping
image is exhibited in Fig. 12. In this gure, part (a) gives the SEM
image of the interface between the reaction layer and the cermet
matrix of the sample prepared with 20 wt.% of branch-like Cu

Fig. 5. High magnication of the cross sectional optical microstructures of Cu2O/20 wt.% Cu cermet prepared with branch like Cu after corrosion for (a) 4 h and (b) 8 h.

L.C. Feng et al. / Journal of Alloys and Compounds 610 (2014) 214223

219

Fig. 7. Optical microstructure of Cu2OCu cermets prepared using branched Cu powders after corrosion for 8 h with Cu content of (a) 10 wt.% and (b) 35 wt.%.

Fig. 8. The effects of the geometrical structure of the Cu phase on the corrosion rate
of the Cu2O/Cu cermet.

immersed in the electrolyte for 8 h. Parts (b) to (g) are the element
mapping image corresponding to Cu, Al, F, Na, O and Ca, respectively. As was found in this gure, the concentration of Cu is homogeneous in the cermet matrix and slightly lower in the reaction
layer; however, the uorine and aluminum were segregated out
of the reaction layer and hardly observed in the matrix. Similar
to the Cu concentration, the Na, O and Ca were also distributed
in the matrix homogeneously and slightly higher at the reaction
layer area.
The corrosion of the Cu2O/Cu cermet in the Na3AlF6CaF2Al2O3
electrolyte could be described by twofold mechanisms: the dissolution of the cermet to form CuAlO2 passive layer and the physical
migration of the Cu phase into the electrolyte. First, from the thermodynamic perspective, the reaction between the Cu2O/Cu and the
Al2O3 are described as follows:

1
1
Cu2 O Al2 O3 CuAlO2
2
2

DG 1200 K 9:26 kJ=mol

1
1
Cu Al2 O3 O2 CuAlO2
2
4

DG 1200 K 50:47 kJ=mol

Apart from the reactions above, assuming the existence of O2, the
following reactions will also occur:

1
1
Cu2 O O2 CuO DG 1200 K 9:10 kJ=mol
2
4
CuO Al2 O3 CuAl2 O4

DG 1200 K 9:59 kJ=mol

9
10

Fig. 9. Cross sectional optical microstructures of Cu2O35 wt.%Cu cermet with

different geometrical structure of Cu after corrosion for 4 h (a) branch like Cu, (b)
spherical Cu with size of 38 lm, (c) spherical Cu with size of 75 lm.

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L.C. Feng et al. / Journal of Alloys and Compounds 610 (2014) 214223

It should be noted that both the CuAlO2 reaction layer and the
Cu2O matrix will be dissolved during the electrolysis process. However, the CuAlO2 layer has a lower corrosion rate, and therefore signicantly retards the corrosion process.
According to the results obtained above, the yearly thermal corrosion thickness of the Cu2O/Cu cermet in the Na3AlF6CaF2Al2O3
electrolyte at 960 C was calculated based on the following
equation:

Fig. 10. XRD pattern of the reaction layer from the Cu2O20 wt.% Cu cermet
prepared with branch-like Cu after corrosion for 8 h.

1
Cu Al2 O3 O2 CuAl2 O4
2

DG 1200 K 59:91 kJ=mol

1
1
CuAlO2 Al2 O3 O2 CuAl2 O4
2
4

11

DG 1200 K 9:43 kJ=mol

12

In the above equations, the O2, whose concentration at the interface

between the Cu2O/Cu cermet and the Na3AlF6CaF2Al2O3 electrolyte is governed by the parameters of the electrolysis process, plays
an important role in determining the nal content of the CuAl2O4. In
this thermal corrosion process, the main reaction product is CuAlO2
and little CuAl2O4 was observed; consequently, Eq. (7) represented
the main reaction in this thermal corrosion process. Secondly, dislodgement and dissolution of the Cu in the electrolyte may also
occur. In the initial stage of the corrosion, the growth direction of
the CuAlO2 crystals is normal to the interfaces, and form rod shaped
crystals (Fig. 13). Due to the increased thickness and the decreased
porosity of the CuAlO2 layer with prolongation of the corrosion
duration, the dissolution of the Cu particles into the electrolyte will
be largely prohibited which results in the decreasing corrosion rate.
In this gure, the Cu particles that migrated into the pores of the
CuAlO2 layer were shown in the yellow ellipses. The red ellipses
reveal the necking location which represents the dissolving process.

Vs

 24  365

13

where C is the annual corrosion depth, Vs is the corrosion rate, and q

is the density of the samples. Table 2 lists the results of the calculated annual thermal corrosion depth of the samples with different
geometrical structures of the Cu phase. As a result of the thermal
corrosion rate, the sample prepared with spherical Cu with a diameter of 75 lm and branch-like Cu have the lowest and the highest
annual corrosion rate with values of 1.53 and 3.42 cm/y (1.18 and
2.63 mg/cm2 h), respectively, while the sample prepared with
spherical Cu with a diameter of 38 lm has the medium value of
2.41 cm/y (1.86 mg/cm2 h).
After the thermal corrosion tests, the short term (25 h) and the
long term (100 h) electrolysis tests were used to evaluate the performances of the Cu2O/Cu cermets. The residual current density, Ir,
was measured with the reversible potential (2.25 V) of reaction (2),
and the polarization resistance, dened as the slope of the potential-current curve (dE/di) in the vicinity of stable potential, appears
to satisfy the following conditions:
 Low residual current density: Ir < 50 mA/cm2.
 Relatively low polarization resistance: dE/di.
Moreover, these cermet anodes also satisfy:
 High open circuit potential value: A > 2.0 V;
 Minimal variation of the external dimensions, and
 The electrical resistance of the materials did not increase with
increasing electrolysis time.
The long-term electrolysis tests showed that the relatively stable performances of the cermets. The over voltage, dened as the
difference between the electrode voltage under a specic current
density and the balance voltage, is higher than that of the Pt anode.
The residual current density was <10 mA/cm2, although it was

Fig. 11. EDS spectra of the layer on the surface of the Cu2O20wt.% Cu cermet prepared with branch like Cu after corrosion for 8 h.

L.C. Feng et al. / Journal of Alloys and Compounds 610 (2014) 214223

221

Fig. 12. Element mapping of Cu2O/20 wt.%Cu cermet after corrosion for 8 h (a) backscattered electron image; (b) Cu; (c) Al; (d) F; (e) Na; (f) O; and (g) Ca.

relatively high at the early stage of the test. At the beginning of the
test, the Cu2O/Cu anode contacted the electrolyte directly; as a
result, the relatively high corrosion rate will lead to a high residual
current density. With the formation of an external protective layer,
the residual current density decreased with increase of testing
time. The anode potential was stable up to the critical potential
of 2.75 V. The corrosion rate was determined by the residual current density, and it was about 1.57.2 mg/cm2 h (1.89 cm/y) in
the current testing procedure. The Cu contents in the produced aluminum is less than 6.2 wt.%.

The corrosion of the Cu2O/Cu cermet is a dynamic dissolution

process. Both the inert CuAlO2 layer and the Cu2O matrix will be
dissolved with the development of the electrolysis process. In addition, some of the Cu particles will be dislodged or oxidized then
dissolved in the electrolyte; therefore, the 6% of Cu in the nal alloy
is not only from the dissolution of the metal Cu phase but also from
the electrolysis of the dissolved Cu2O and the CuAlO2. Although the
chemical composition of the Cu2O/Cu cermet at the surface will be
signicantly changed, the composition and microstructure at
the inside part of the bulk Cu2O/Cu cermet will not be changed

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2.63, 1.86 and 1.18 mg/cm2 h, respectively. After the electrolysis

tests, by using the sample prepared with 25 wt.% of branch like
Cu as a reference, the calculated corrosion rate was about 1.5
7.2 mg/cm2 h in the current testing procedure. The Cu contents
in the produced aluminum is less than 6.2 wt.%.

Acknowledgements
This work was nancially supported by the National Natural
Science Foundation of China (No. 51371072), the Priority Academic
Program Development of Jiangsu Higher Education Institutions, the
Lianyungang Scientic Plan-Industrial Program (CG1312), the Lianyungang Scientic Plan-Industrial Program (CG1204) and the Six
Talent Peaks Program of Jiangsu Province (2013-ZBZZ-032).

References

Fig. 13. SEM morphology of the CuAlO2 layer on the surface of the Cu2O20 wt.% Cu
cermet prepared with branch like Cu after corrosion for 8 h.

Table 2
Annual thermal corrosion rate of Cu2O/Cu cermet in Na3AlF6CaF2Al2O3 electrolyte
at 960 C.
Geometrical structures of the Cu phase

Corrosion rate, mg/cm2 h

Branch-like Cu
Spherical Cu38 lm
Spherical Cu75 lm

2.63
1.86
1.18

signicantly during the electrolysis process. As a result, the electrical resistance of the bulk Cu2O/Cu cermet will not sharply change
with the development of the electrolysis process.
The oxidation behavior of the Cu2O/Cu cermet in the Na3AlF6
CaF2Al2O3 electrolyte at high temperatures contains complicated
mechanisms that are challenging the high temperature oxidation
theories. Further studies must be performed to investigate the
existing passivation process.
4. Conclusions
In summary, for mitigating the signicantly negative environmental impacts which result from the current aluminum production process, the Cu2O/Cu cermet was prepared as the potential
inert anode material to prepare aluminum or aluminum/copper
alloys. The thermal corrosion behavior of the Cu2O/Cu cermet with
different geometrical structures of the Cu phase was investigated.
After analysis by SEM/EDS and XRD, it was found that only a passive CuAlO2 layer was formed during the corrosion procedure.
The thicknesses and density of the layer increased with increasing
corrosion time, and the rate of thickness and density increase at
the initial stage is higher than the late stage. Furthermore, the thermal corrosion rate was evaluated by the weight loss method and
the results show that the thermal corrosion rate of the samples
prepared with branch-like Cu is higher than for those prepared
with spherical Cu, and the corrosion rate increases with decreasing
sizes and increasing lling contents of the Cu phase. The thermal
corrosion rate was about 0.68 mg/cm2 h with Cu content of
10 wt.% while it increased to 2.63 mg/cm2 h with Cu content of
35 wt.%. The sample prepared with branch-like Cu and spherical
Cu with size 38 lm, 75 lm have thermal corrosion rate values of

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