International Journal of Minerals, Metallurgy and Materials

Volume 24, Number 1, January 2017, Page 25

DOI: 10.1007/s12613-017-1375-8

Activity coefficients of NiO and CoO in CaOAl2O3SiO2 slag and their

application to the recycling of NiCoFe-based end-of-life
superalloys via remelting

Xin Lu, Takahiro Miki, and Tetsuya Nagasaka

Graduate School of Engineering, Tohoku University, Sendai, Miyagi 980-8579, Japan
(Received: 8 June 2016; revised: 28 September 2016; accepted: 29 September 2016)

Abstract: To design optimal pyrometallurgical processes for nickel and cobalt recycling, and more particularly for the end-of-life process of
NiCoFe-based end-of-life (EoL) superalloys, knowledge of their activity coefficients in slags is essential. In this study, the activity coeffi-
cients of NiO and CoO in CaOAl2O3SiO2 slag, a candidate slag used for the EoL superalloy remelting process, were measured using
gas/slag/metal equilibrium experiments. These activity coefficients were then used to consider the recycling efficiency of nickel and cobalt
by remelting EoL superalloys using CaOAl2O3SiO2 slag. The activity coefficients of NiO and CoO in CaOAl2O3SiO2 slag both show a
positive deviation from Raoults law, with values that vary from 1 to 5 depending on the change in basicity. The activity coefficients of NiO
and CoO peak in the slag with a composition near B = (%CaO)/(%SiO2) = 1, where B is the basicity. We observed that controlling the slag
composition at approximately B = 1 effectively reduces the cobalt and nickel oxidation losses and promotes the oxidation removal of iron
during the remelting process of EoL superalloys.

Keywords: recycling; nickel; cobalt; end-of-life; superalloys; activity coefficients; remelting; slag

1. Introduction Superalloys are one of the most important end uses of

The recycling of end-of-life (EoL) superalloys via the
remelting process is essential to ensure a sustainable supply
of nickel and cobalt [1]. Both nickel and cobalt are critical
metals used in the aviation and aerospace industries, in mil-
itary applications, and in clean energy storage and conver-
sion, and demand for these metals has been rapidly increas-
ing over the past several decades [23]. However, the rela-
tively complicated primary extraction and production
processes of nickel and cobalt from natural ores are accom-
panied by considerable environmental impact, including
large energy consumption and substantial emissions of
greenhouse gases, acid-rain gases, and solid waste [46].
Notably, the declining quality of ores over the past few
decades has resulted in the exacerbation of the environmen-
tal impact of the primary process and further environmental
challenges in ensuring a sustainable supply of nickel and
cobalt [7].
Corresponding author: Xin Lu E-mail: xin.lu.a5@tohoku.ac.jp
University of Science and Technology Beijing and Springer-Verlag Berlin Heidelberg 2017
both nickel and cobalt. Generally, superalloys are classified
as nickel-, cobalt-, or nickeliron-based alloys [89]. They
are commonly used to fabricate turbine blades for use in the
aerospace and power generation industries [10]. After their
service lifetime, NiCoFe-based EoL superalloys can be
recycled as a secondary resource of nickel and cobalt. Al-
though EoL superalloys are typically recycled via the re-
melting process, the high burn-out or oxidation losses of the
alloying elements make the efficient recycling of these su-
peralloys a difficult task [1113].
In the remelting of EoL superalloys, the slag composition
must be carefully selected to reduce the oxidation losses of
nickel and cobalt. As such, knowledge of the activity coeffi-
cients of NiO and CoO in slag is important for both the slag
selection process and the remelting operation. To date, re-
searchers have extensively studied the activity coefficients
of NiO and CoO in various primary production process
slags to improve the production efficiency of nickel and co-
26
balt from natural ore, as will be briefly reviewed later in this
paper. Particular attention has been devoted to the
SiO2FeOx-based slag (fayalite slag) because iron and silicate
are the major components of the typical slags of the primary
production process of nickel and cobalt (produced as a
by-product of the copper or nickel smelting process) [1416].
CaOAl2O3SiO2-based slag is a candidate slag for use in
the remelting process of EoL superalloys. However, the ac-
tivity coefficients of NiO and CoO in such slag have not yet
been systematically reported in the literature. In this study,
as a follow up to our previous study on the thermodynamic
evaluation of the refinability of EoL superalloys by remelt-
ing [17], we measured the activity coefficients of NiO and
CoO in CaOAl2O3SiO2 slag and investigated the influ-
ence of slag composition on the simulated EoL superalloys
remelting process with CaOAl2O3SiO2 slag. The activity
coefficients were obtained from gas/slag/metal equilibrium
experiments under a controlled oxygen partial pressure with
COCO2 gas mixtures. Pure nickel and cobalt crucibles
were used as the metal phase to equilibrate with slag with
different basicities. Finally, the influence of the slag compo-
sition on the oxidation losses of nickel and cobalt and the
controllability of the composition of the NiCoFe alloy
during the simulated EoL superalloy remelting process is
discussed.
2. Literature review
2.1. Activity coefficient of NiO in slag
A brief summary of the activity coefficient of NiO in slag
is shown in Table 1. The activity coefficient of NiO with
respect to the pure solid standard state (NiO(s)) is given, as
will be the case throughout this work. Note that the method
used to recalculate the activity coefficient with respect to the
pure liquid standard state (NiO(l)) in some of the literature
works is explained in detail in the appendix.
Henao et al. [18] measured the NiO(s) in SiO2FeOx slag
by equilibrating the slag with a NiS melt in a magnesia
crucible at 1773 K; they found that NiO(s) presents values
ranging from 3.1 to 8.8 depending on the slag composition.
In another series of experiments using CaOFeOx slag in a
magnesia crucible at 1773 K, NiO(s) was found to present a
smaller value (2.75.4) than that in SiO2FeOx slag, and
they ascribed this to the relative neutrality of NiO in the
predominant slag composition of basic CaO and MgO and
acidic SiO2 [18]. Takeda et al. [19] ascribed NiO(s) in
CaOFeOx slag with values ranging from 3 to 12 by equili-
brating the slag with liquid copper; their results agree well
with those reported by Henao et al. [18].
Int. J. Miner. Metall. Mater., Vol. 24, No. 1, Jan. 2017
Reddy and Acholonu [20] measured NiO(l) in alumi-
na-saturated iron silicate slag by equilibrating the slag with
the CuNi alloys in an alumina crucible. Recalculation of
their results revealed a NiO(s) value of 1.27, which shows
that NiO(s) slightly decreases in iron silicate slag containing
added alumina. In various studies, NiO(s) in magne-
sia-saturated iron silicate slag was investigated by equili-
brating slag with a NiFe alloy or a NiFeCo alloy in a
magnesia crucible [2123]. The reported NiO(s) values in
the range from 2 to 6 in the case of SiO2FeOxMgO (satu-
rated) slag agree well with each other. Pagador et al. [21]
and Henao et al. [22] further investigated the influence of
CaO addition to SiO2FeOxMgO(saturated) slag on NiO(s)
and attributed the observed substantial increase in NiO(s)
upon the addition of CaO to the stronger affinity between
CaO and SiO2 compared to that between NiO and CaO, or
SiO2. Meanwhile, Henao et al. [22] also observed that NiO(s)
for alumina-added SiO2FeOxMgO (saturated) slag is con-
siderably larger than that in alumina-free slag because of the
relatively strong affinity between alumina and magnesia.
Interest in iron-free slag and flux has increased substan-
tially in recent years. Because CaOAl2O3-based slag can be
utilized as an iron-free slag for the deoxidation and denitro-
genization of nickel [24], researchers have investigated the
NiO(s) in CaOAl2O3 slag by equilibrating the slag with the
NiS alloy at 1773 K [25] and 1873 K [26], respectively.
The results of these studies agree well and suggest that the
larger value of NiO(s) in CaOAl2O3 slag than that in
CaOFeOx slag is due to the greater chemical affinity be-
tween CaO and Al2O3 than between CaO and FeOx. How-
ever, no systematic data has been reported for the value of
NiO(s) in CaOAl2O3SiO2 slag.
2.2. Activity coefficient of CoO in slag
Table 2 briefly summaries the activity coefficient of CoO
in various slags. Here as was the case with NiO, the activity
coefficient of CoO is presented with respect to the pure solid
standard state (CoO(s)); the method used to convert the ac-
tivity coefficient with respect to the pure liquid standard
state (CoO(l)) reported in some of the literature is explained
in the appendix.
Wang et al. [2728] measured CoO(s) in SiO2FeOx slag
by equilibrating slag with CuCo and AuCo. Grimsey and
Toguri [29] evaluated the results of Wang et al. and ex-
pressed CoO(s) in relation to the cobalt content in the sili-
ca-saturated slag. The value of CoO(l) in a SiO2FeOx slag
with a composition approaching the silica saturation point,
as reported by Katyal and Jeffes [30], was 1.00, which we
recalculated for CoO(s) to obtain 2.75 by converting the
X. Lu et al., Activity coefficients of NiO and CoO in CaOAl2O3SiO2 slag and their application to the recycling ... 27

Table 1. Summary of the values of the activity coefficient of NiO in different slags from the literature
Slag NiO(s) pO2 / Pa T/K Alloy phase Note Ref.
2
CaOAl2O3 512 10 1 1773 NiS MgO crucible [18]
CaOAl2O3 530 0.110 1873 NiS MgO crucible [26]
CaOFeOx 312 1060.1 1523 CuNi [19]
2
CaOFeOx 2.75.4 10 1 1773 NiS MgO crucible
[18]
SiO2FeOx 3.18.8 1021 1773 NiS MgO crucible
(%Fe)/(%SiO2) = 1.34,
Al2O3(saturated)SiO2FeOx 1.27 105102 1573 CuNi [20]
NiO(l) = 0.375
SiO2FeOxMgO (saturated) 25 104100 1773 FeNiCo MgO crucible [23]
SiO2FeOxMgO (saturated) 3 105102 1773 NiFe MgO crucible [21]
4 2
SiO2FeOxMgO (saturated) 26 10 10 1773 NiFe MgO crucible [22]
MgO crucible,
CaOSiO2FeOxMgO (saturated) 4 105102 1773 NiFe [21]
(%CaO)/(%SiO2) 0.9
4 2
CaOSiO2FeOxMgO (saturated) 314 10 10 1773 NiFe MgO crucible [22]
4 2
Al2O3SiO2FeOxMgO (saturated) 423 10 10 1773 NiFe MgO crucible [22]

Table 2. Summary of the values of the activity coefficient of CoO in different slags, as reported in the literature
Slag CoO(s) pO2 / Pa T/K Alloy phase Note Ref.
1.94 + 0.123 CuCo, or
SiO2(saturated)FeOx 1050.1 15231623 [2729]
(% Co) AuCo
5 4
SiO2(saturated)FeOx 0.91 0.09 10 10 1573 CoFeAu [31]
Silica close to saturation
SiO2FeOx 2.75 1.9 1056.8 103 15231623 CoCu [30]
(35wt%).
CaOFeOx 1.4 1060.1 1523 CuCo [19]
5 3
CaOFeOx 3.19 1.9 10 6.8 10 15231623 CoCu CoO(l) = 1.16 [30]
CaOFeOx 2.1 1 1023 102 1573 PtFeCo [32]
5 3
CaOSiO2FeOx 5.72 1.9 10 6.8 10 15231623 CoCu CoO(l) = 2.08, B = 0.9 [30]
CaOSiO2FeOx 3 1 1023 102 1573 PtFeCo (%SiO2) = 4% [32]
3
1.1 10 = 0.2379(%CoO) + 0.2731
0.55 CoCu
2.4 104 in pure liquid
Al2O3SiO2FeOx 1673 [34]
5 = 0.0395(%CoO) + 0.1782
0.89 4.5 10 CoCu
in pure liquid
Al2O3SiO2FeOx 3.13 1.9 1056.8 103 15231623 CoCu CoO(l) = 1.14 [30]
SiO2FeOxMgO (saturated) 2 1050.1 16731873 NiFeCo [35]
4
SiO2FeOxMgO (saturated) 14.5 10 100 17731873 FeNiCo [23]
Al2O3SiO2FeOxMgO 10.415 104102 1773 FeNiCo MgO crucible [22]
CaOSiO2FeOxMgO
1.737.0 2.9 1079.9 105 15731873 FeCuCo 1.2313.45, in pure liquid [36]
(saturated)
CaOSiO2FeOxMgO
3 1050.1 16731873 NiFeCo B = 0.9 [35]
(saturated)
pS2 was also controlled,
CaO Al2O3MgO 5.6 0.110 1873 NiCo [26]
MgO crucible

standard state to the pure solid state. The value that Grim-
sey and Liu reported for CoO(s) in silica-saturated slag was
0.91 0.09 [31], which is lower than other previously re-
ported values [2930].
Experimental studies on the activity coefficient of CoO in
calcium ferrite slag, a relatively recent type of slag used in
the copper process, have also been reported by various re-
searchers. As part of a study on the equilibrium distribution
of minor elements between slag and copper alloy at 1523 K,
Takeda et al. [19] reported CoO(s) to be approximately 1.4
28
in calcium ferrite slag. On the basis of results for the pure
liquid standard state (CoO(l) = 1.16) reported by Katyal and
Jeffes [30], we recalculated CoO(s) to be 3.19 in calcium
ferrite slag. Teague et al. [32] reported the value of CoO(s)
to be 2.1 in calcium ferrite slag at 1573 K. Notably, no sig-
nificant difference was observed between the values of
CoO(s) in calcium ferrite slag and in iron silicate slag [19].
The effects of the addition of CaO to SiO2FeOx slag or
of the partial substitution of CaO by SiO2 in calcium ferrite
slag on the activity coefficient of CoO in slag have also been
investigated. Katyal and Jeffes [30] found that the addition
of CaO to iron silicate slag resulted in an increase in CoO(s)
in the slag. Teague et al. [32] reported that CoO(s) increased
as the SiO2 content was increased to 4% in calcium ferrite
slag and found that any further increase in the SiO2 content
resulted in a decrease in CoO(s) According to a review by
Chen et al., the strong interaction between CaO and the
added SiO2 reduces the interaction between CoO and CaO
and therefore results in an increase in the activity coefficient
of CoO, whereas the addition of excess SiO2 results in a de-
crease in CoO(s) because of the precipitation of spinel crys-
tals and the interactions between CoO and SiO2 [33].
The effects of the addition of alumina and magnesia on
the activity coefficient of CoO in SiO2FeOx slag have been
investigated quite intensively [22,23,30,3436]. These pre-
vious studies indicate that the addition of alumina to slag
slightly influences the activity coefficient of CoO [30, 34],
whereas the addition of magnesia always results in an in-
crease in the activity coefficient [22,23,3536]. As was the
case with the addition of CaO, this effect can be largely at-
tributed to the strong interaction between magnesia and sili-
cates, which results in a reduced interaction between CoO
and silicates.
In recent years, attention has been devoted to iron-free
slag because of its potential application in the nickel process.
Henao and Itagak [26] measured the activity coefficient of
CoO by equilibrating NiCo alloy with CaOAl2O3 in a
magnesia crucible at 1873 K, where the partial pressures of
both O2 and S2 were controlled by a COCO2SO2 gas
mixture. They reported a value of 5.6 for CoO(s) and found
that CoO(s) remained almost constant irrespective of the
oxygen partial pressure. However, no systematic data has
been reported in the literature for the value of CoO(s) in
CaOAl2O3SiO2 slag.
3. Material and experiment method
The activity coefficients for NiO and CoO in
CaOAl2O3SiO2 slag were determined by equilibrating
Int. J. Miner. Metall. Mater., Vol. 24, No. 1, Jan. 2017
CaOAl2O3SiO2 slag with a pure cobalt or pure nickel
crucible under a COCO2 atmosphere at 1673 K. As was
mentioned in the literature review, the activity coefficients
of NiO and CoO in various slags tend to be determined by
equilibrating the slag phase with different nickel or cobalt
alloys: CuNi, FeNi, FeCoNi, and NiS alloys are used
to determine the activity coefficients of NiO, and AuCo,
FeAuCo, NiFeCo, FeCuCo, and NiCo alloys are
used to determine the activity coefficients of CoO. With this
approach, a lower experimental temperature can be achieved
and the required holding time before reaching the equili-
brium state can be reduced. However, when an alloy is used
as the metal phase in the equilibrium experiments, the accu-
racy of the obtained activity coefficient of NiO or CoO in
the slag will be highly dependent on the accuracy of the
thermodynamic properties of Ni or Co in the corresponding
alloys. From this perspective, using a pure nickel or pure
cobalt crucible as the metal phase can eliminate the influ-
ence of the uncertainty of the thermodynamic data used for
Ni or Co in alloys and thus greatly increase the reliability of
the results. CaCO3 (>99.99%) and Al2O3 (>99.0%) from
Kanto Chemical Co., Inc. (Japan) and SiO2 (>99.9% purity)
from Kojundo Chemical Laboratory Co., Ltd. (Japan) were
used as the starting materials for the slag. CaO was prepared
by the calcination of CaCO3 powder at 1373 K for 4 h and
was confirmed by XRD. Nickel powder (>99.9% purity)
from Kojundo Chemical Laboratory Co., Ltd. (Japan) or
cobalt powder (>99.5%) from Wako Pure Chemical Indus-
tries, Ltd. (Japan) was melted in a high-frequency induction
furnace (MU-1700D, Sekisui Chemical Co., Ltd.) under an
argon atmosphere. After the sample had cooled, a crucible
was formed from the obtained nickel or cobalt ingot using a
mechanical method. The prepared nickel crucible or cobalt
crucible containing the designed slag was placed into anoth-
er alumina protecting crucible for the equilibrium experi-
ments at 1673 K.
To investigate the influence of the Al2O3 content in slag,
another series of experiments was carried out by equilibrat-
ing the slag containing 37% of the Al2O3 with molten CuNi
or CuCo alloy in an alumina crucible. Copper powder
(>99.9% purity) from Kojundo Chemical Laboratory Co.,
Ltd. (Japan) was used as the solvent and was melted with
nickel or cobalt powder in a high-frequency induction fur-
nace under an argon atmosphere. Approximately 3 g of al-
loy was placed into an alumina crucible and then covered
with 3 g of slag for the equilibrium experiments.
A schematic of the experimental apparatus is provided in
Fig. 1. A vertical MoSi2 resistance furnace connected to a
proportionalintegraldifferential (PID) controller with a
X. Lu et al., Activity coefficients of NiO and CoO in CaOAl2O3SiO2 slag and their application to the recycling ... 29

Pt6%Rh/Pt30%Rh thermocouple was used. The tempera- In the preliminary experiments, the gas/slag/metal equili-
ture was controlled within 1 K in the heating area of the brium state was achieved by two methods: (1) repeating ex-
furnace. The samples were heated under an argon atmos- periments with extended heating times; (2) carrying out the
phere until the required temperature of 1673 K, and then the experiment such that the equilibrium composition was ap-
gas was switched to COCO2 gas mixtures with a total vo- proached from two opposite directions, i.e., the reduction of
lumetric gas flow rate of 200 mL/min. The oxygen partial NiO from slag to the metal phase and the oxidation of nickel
pressure was calculated on the basis of the following equa- to the slag phase. The results confirmed that a heating time
tions: of 48 h was sufficient for the equilibrium experiments, and
1 this heating time was used in all of the experiments. When
CO(g) + O 2 (g) = CO 2 (g) (1)
2 the heating procedure was completed, the samples were
G1 = 280480 + 85.3T , J/mol [37] (2) quickly withdrawn from the heating area and quenched un-
2
der helium gas.
pCO2 G Following quenching, the slag and metal samples were
pO2 = exp 1 p (3)
pCO RT subjected to chemical analysis. The slag was first treated by
where G1 is the standard Gibbs free energy change alkali fusion with a flux composed of a mixture of Na2CO3
(J/mol) of the reaction represented in Eq. (1); pO2, pCO, and and Na2B4O7 in a platinum crucible and was then dissolved
pCO2 are the oxygen partial pressure (Pa) and the controlled with diluted hydrochloric acid. The content of cobalt and
partial pressure of CO (Pa) and CO2 (Pa) with atmospheric nickel in slag or copper alloy was determined by inductively
pressure (101325 Pa) used as the total pressure, respectively; coupled plasma atomic emission spectrometry (ICP-AES).
p is the conversion factor (101325 Pa/atm); R and T are Under these experimental conditions, NiO and CoO were
the gas constant (JK1mol1) and temperature (K), respec- considered the only nickel and cobalt oxide products in the
tively. respective slags.

Fig. 1. Schematic of the apparatus used for the equilibrium
experiments.
4. Results
4.1. Equilibrium distribution ratio and pO 2
Fig. 2 shows the effect of the oxygen partial pressure on
the equilibrium distribution ratio of nickel at 1673 K when a
pure nickel crucible was used. It is found that the logarithm
of the equilibrium distribution ratio of nickel increases in
proportion to 1/2 the order of the logarithm of oxygen par-
tial pressure in all of the samples when the basicity (B) of
the slag is between 0.9 and 1.1. The B of slag is defined as
the mass percentage ratio between CaO and SiO2 in the slag
(B = (%CaO)/(%SiO2)).

Fig. 2. Relationship between pO2 and the equilibrium distribution ratio of nickel in slag with B = 0.9 (a), B = 1.0 (b), and B = 1.1
(c) and metal.
30 Int. J. Miner. Metall. Mater., Vol. 24, No. 1, Jan. 2017

The equilibrium reaction between nickel and NiO in slag G4

1
is expressed by the following equations: NiO = Ni xNi ( pO2 / p)1/2 xNiO exp
(8)
RT
1
Ni(s) + O 2 (g) = NiO(s) (4) where xNi and Ni are unity because a pure nickel crucible
2
was used as the metal phase and where xNiO in the slag was
G4 = 233102 + 84.2T , J/mol [37] (5) analyzed by ICP-AES. The pO2 was controlled by the
NiO xNiO COCO2 gas mixture and calculated by Eq. (3). Similarly,
G4 = RT ln (6)
Ni xNi ( pO2 / p)1/2 the activity coefficient of CoO in slag can be obtained from
where NiO, Ni, xNiO, and xNi are the activity coefficients of the Gibbs free energy change shown in Eq. (10).
NiO and nickel (both with respect to the pure solid standard 1
Co(s) + O 2 (g) = CoO(s) (9)
state) and the mole fractions of NiO and nickel in slag, re- 2
spectively.
G10 = 233944 + 70.4T , J/mol [37] (10)
Thus, the relationship between the equilibrium distribution
1 G9

ratio of nickel in slag and the metal phase and the oxygen par- CoO = Co xCo ( pO2 / p)1/2 xCoO exp (11)
tial pressure can be expressed by the following equation: RT
x 1 1 The obtained results are shown in Table 3. The activity
lg NiO = lg pO2 lg p +
xNi 2 2 coefficient of NiO and CoO, both in the pure solid standard
(7) state, in CaO15%Al2O3SiO2 slag obtained in the present
G4
lg exp + lg Ni lg NiO study are shown in Fig. 3. We observed that NiO and CoO
RT vary within the ranges from 1.2 to 5.1 and from 1.1 to 4.5,
where G4 is constant at the specific temperature and respectively, according to the B of the slag. Meanwhile, both
Ni is unity because a pure nickel crucible is used. Therefore, NiO and CoO in the slag reach peak values when B ap-
if NiO in the slag remains constant, the logarithm of the proaches unity, as indicated by the dotted curve, and the
equilibrium distribution ratio of nickel should increase in values in acid slag are slightly smaller than those in basic
proportion to 1/2 order of the logarithm of the oxygen par- slag. In Fig. 3, the NiO and CoO values taken from the lite-
tial pressure. Fig. 2 confirms that NiO in slag remains con- rature are also shown as functions of the slag basicity for
stant under these experimental conditions. comparison purposes [3839]. The results obtained in this
study agree well with the values of NiO and CoO from lite-
4.2. Activity coefficient of NiO and CoO in CaOAl2O3 rature, and the influence of B on the NiO and the CoO is sim-
SiO2 slag ilar.
According to Eq. (6), the activity coefficient of NiO in To investigate the effect of the alumina content, the activ-
slag can be calculated by the following equation: ity coefficients of NiO and CoO in CaO37%Al2O3SiO2

Table 3. Activity coefficients of NiO and CoO in CaOAl2O3 SiO2 slag at 1673 K
Slag: CaO15%Al2O3SiO2; Metal: pure nickel or pure cobalt; lg( pO2 / Pa) = 4.8

No. B xNiO NiO(s) No. B xCoO CoO(s)

NiB0.55 0.55 0.0082 1.15 CoB0.55 0.55 0.050 1.06
NiB0.8 0.8 0.0034 2.76 CoB0.8 0.8 0.023 2.35
NiB0.9 0.9 0.0024 3.90 CoB0.9 0.9 0.019 2.77
NiB1.0 1.0 0.0019 5.06 CoB1.0 1.0 0.012 4.48
NiB1.1 1.1 0.0021 4.45 CoB1.1 1.1 0.016 3.39
NiB1.2 1.2 0.0021 4.45
Slag: CaO37%Al2O3SiO2; Metal: CuNi or CuCo; lg( pO2 / Pa) = 1.7

No. B xM in CuM M(s) in CuM xMO in slag MO(s)

Ni37%A 1.0 0.0035 2.65 0.0054 5.84
Co37%A 1.0 0.013 7.43 0.029 6.53
X. Lu et al., Activity coefficients of NiO and CoO in CaOAl2O3SiO2 slag and their application to the recycling ... 31

Fig. 3. Comparison of the activity coefficients of NiO and CoO in CaOAl2O3SiO2 slag obtained in the present study and those
reported in the literature [3839].

slag with B = 1 were investigated by equilibrating slag with are obtained by the CALPHAD method and are shown in
a CuNi and a CuCo alloy, respectively. In this case, xNi Table 4 [4243]. Then, the values of Ni and Co in the pure
and xCo in the copper alloy after equilibrium were analyzed solid standard state, as calculated by the method outlined
by ICP-AES. In the case of molten copper alloy, in a pure in the appendix, were used to calculate the activity coeffi-
liquid standard state, we calculated Ni and Co according to cients of NiO and CoO in the slag using Eqs. (8) and (11),
the following equation by assuming the molten copper alloy respectively. These results are also shown in Table 3. The
to be a substitutional sub-regular solution; the free energy of effect of the alumina content in the slag on the activity
the solution can be expressed with RedlichKister polyno- coefficients of NiO and CoO are shown in Fig. 4. The re-
mials [4041]: sults show that both the activity coefficients of NiO and
RT ln M (l) = 0CuM xCu
2
+ 1CuM xCu
2
(4 xCu 3) + CoO in CaOAl2O3SiO2 slag increase slightly in slag
2 2 with a higher alumina content, and the effect of the alu-
CuM xCu (2 xCu 1)(6 xCu 5) +
mina content on CoO is observed to be larger than that on
3 2
CuM xCu (2 xCu 1)2 (8xCu 7) (12) NiO. However, the effect of the alumina content on the ac-
where M denotes nickel or cobalt, pCuM (p = 0, 1, 2, 3) tivity coefficients is much smaller than that of the slag ba-
are the interaction parameters of copper and nickel, which sicity.
Table 4. Interaction parameters used to calculate Ni and Co
M 0
CuM 1
CuM 2
CuM Ref.
Nickel 12048.61 + 1.29093T 1861.61 + 0.94201T 0 [42]
Cobalt 35200 4.945T 1000 0.083T 0 [43]

Fig. 4. Effect of Al2O3 content on the activity coefficients of
NiO and CoO.
5. Discussion
5.1. Effect of basicity on the activity coefficients of NiO
and CoO
The experimental results show that the activity coeffi-
cients of NiO and CoO in CaOAl2O3SiO2 slag peak when
the basicity of the slag is unity. The relationship between
slag basicity and the activity coefficient of FeO in
CaOAl2O3SiO2 slag and in CaOSiO2FeO slag with
constant iron content is shown in Fig. 5 [4445]. Similar to
the activity coefficients of NiO and CoO, the activity coeffi-
cient of FeO in these slags also tends to decrease in both
acidic slag and basic slag and reaches a peak value in slag
32
with a basicity near unity. The FeO iso-activity curves re-
ported by Banya and Hino [46] in their review of the activity
of FeO in CaOSiO2FeO slag also suggest that the activity
coefficient of FeO reaches a maximum in CaOSiO2FeO
slag with basicity near unity.
Fig. 5. Effect of slag basicity on the activity coefficient of FeO
in different slag systems.
The relationship between the slag composition and the
activity coefficient of components in slag are considered to
be complex and highly influenced by factors such as the slag
structure. However, from a thermodynamic perspective, the
effect of slag basicity on the activity coefficients of NiO and
CoO in CaOAl2O3SiO2 slag can be largely attributed to
the chemical properties of NiO and CoO. Notably, in
CaOAl2O3SiO2 slag, NiO and CoO behave more like
amphoteric oxides compared to the major components in the
slag. In acid slag with a lower basicity (SiO2 rich), both NiO
and CoO can form 2NiOSiO2 and 2CoOSiO2 with negative
standard Gibbs free energy changes of 1.76 kJmol1 [47]
and 26.25 kJmol1 [37], respectively, at 1673 K. As the
basicity increases, the additional CaO reacts with SiO2 to
form CaOSiO2 and 2CaOSiO4 much more easily, with
more negative standard Gibbs free energy changes of
94.3 kJmol1 and 145.6 kJmol1 at 1673 K [37], respec-
tively. The substantial decrease in the activity of SiO2 in
CaOAl2O3SiO2 slag has been attributed to this formation
of CaOSiO2 and 2CaOSiO2 [48]. The formation of
CaOSiO2 and 2CaOSiO2 also explains the higher the activ-
ity coefficients obtained for NiO and CoO upon the addition
of CaO. Meanwhile, because the chemical affinity of NiO
and CoO toward CaO is even weaker than that toward SiO2,
the activity coefficients of NiO and CoO are greater in acid
slag than in basic slag. The observed trend for the activity
coefficients of NiO and CoO is in good agreement with the
results of previous studies on the activity coefficients for
NiO [18,2122] and CoO [30,32,35] in other slag systems.
Int. J. Miner. Metall. Mater., Vol. 24, No. 1, Jan. 2017
In each of these previous reports, the authors consistently
found that the activity coefficient of the component is highly
influenced by the affinity of major components in the slag
when then the affinity of such components toward the major
components is relatively lower.
5.2. Effect of slag composition on the resource efficiency
of the remelting process of EoL superalloys using
CaOAl2O3SiO2 slag
Because the remelting process using CaOAl2O3SiO2
slag has potential for use in the recycling of
NiCoFe-based EoL superalloys, determining the effect of
slag composition on the resource efficiency is important.
Because nickel and cobalt both have substantially higher
economic value than iron in EoL superalloys (LME price on
July 3, 2015: US$12060/t for nickel, US$32755/t for cobalt,
US$150/t for steel billet), the industry is more focused on
finding cost effective, efficient methods for the recycling of
nickel and cobalt. In the case where the activity coefficients
for NiO and CoO are higher than that for FeO, the oxidation
losses of Ni and Co can be controlled during the recycling
process.
In the results obtained from the equilibration experiments
in this study, both NiO and CoO present much higher values
than FeO in CaOAl2O3SiO2 slag with a basicity close to
unity, as shown in Fig. 6. In this figure, the values of NiO
and CoO obtained in this study are compared with the litera-
ture results for FeO in CaOAl2O3SiO2 slag at 1673 K [44].
These results suggest that controlling the basicity of
CaOAl2O3SiO2 at approximately unity would benefit the
recycling of nickel and cobalt during the remelting of EoL
superalloys because the iron is preferentially oxidized into
the slag and nickel and cobalt losses are reduced.
Fig. 6. Comparison of the activity coefficients of FeO, NiO,
and CoO in CaO15%Al2O3SiO2 slag. The standard-state li-
terature results for FeO [44] were converted to pure solid for
comparison.
X. Lu et al., Activity coefficients of NiO and CoO in CaOAl2O3SiO2 slag and their application to the recycling ... 33

The influence of slag composition on the remelting
process of EoL superalloys, as determined experimentally, is
shown in Fig. 7. A Ni40%Co10%Fe alloy was assumed as
the initial EoL superalloy for a simulated remelting process
at 1873 K with 10%CaO15%Al2O3SiO2 slag by weight,
and the molten alloy was assumed to be equilibrated with
the slag at all times. We obtained the activity coefficients of
NiO and CoO in the pure solid standard state at 1873 K by
recalculating the experimental results under the assumption
that the molten CaOAl2O3SiO2 slag was a regular solu-
tion. We used the activity coefficient reported by Taniguchi
et al. [44] for FeO in pure liquid. Meanwhile, the interac-
tions between NiO, CoO, and FeO in the slag were ignored
and their activity coefficients were assumed to be constant
because the considered slags had very low NiO, CoO, and
FeO contents. The activity coefficients of nickel, cobalt, and
iron in the molten alloy were calculated using the
CALPHAD method by treating the NiCoFe alloy phase
as an ordinary substitutional sub-regular solution [49] with
the interaction parameters reported previously [5052].

Fig. 7. Influence of slag basicity on the nickel and cobalt losses (a) and the removal of iron and cobalt (b) during the simulated re-
melting process of EoL superalloys with CaOAl2O3SiO2 slag.

As the remelting process proceeds, iron is oxidized and signed by taking thermodynamics into account to maximize
transferred into the slag. The (%NiO) and (%CoO) in the resource efficiency during the recycling of EoL superalloys.
slag will then increase corresponding to the higher oxygen
partial pressure. As shown in Fig. 7(a), the (%NiO) and
(%CoO) in the slag are considerably lower when
CaO15%Al2O3SiO2 slag with B = 1.0 is used under the
same remelting conditions, which indicates that oxidation
losses of nickel and cobalt can be substantially reduced by
maintaining the slag basicity at approximately unity during
the remelting of the EoL superalloy. Meanwhile, as shown
in Fig. 7(b), the iron in the EoL superalloys can be reduced
much faster using CaO15%Al2O3SiO2 slag with B = 1.0
than that with B = 0.8 or using the simulated slag where the
activity coefficients of NiO, CoO, and FeO are assumed to
be unity.
Fig. 8. Controllability of alloy composition during the re-
Fig. 8 shows the controllability of the alloy composition
melting of EoL superalloys with CaOAl2O3SiO2 slag.
during the remelting of the EoL superalloys when the
CaOAl2O3SiO2 slag is used. An alloy with a higher
[%Ni]/[%Co] can be obtained by increasing the ratio of 6. Conclusions
(%NiO) and (%CoO) in the slag: an almost linear correla-
tion is observed. Notably, the influence of the iron content in The activity coefficients of NiO and CoO in
the alloy on the correlation between the (%NiO)/(%CoO) in CaOAl2O3SiO2 slag at 1673 K were investigated via
the slag and the [%Ni]/[%Co] in the alloy was found to be gas/slag/metal equilibrium experiments, and the results
negligible. As such, the remelting conditions can be de- were used to analyze the influence of slag composition on
34 Int. J. Miner. Metall. Mater., Vol. 24, No. 1, Jan. 2017

the recycling efficiency of the NiCoFe-based EoL supe-

GA-10

= 17479.82 10.1139T , J/mol [53] (A-11)
ralloy remelting process with CaOAl2O3SiO2 slag. We
GA-10


drew the following conclusions from the results of this Ni(s) = Ni(l) exp (A-12)
study. RT
(1) The activity coefficients of both NiO and CoO Co(s) = Co(l) (A-13)
showed positive deviations and varied within the range from
GA-13 = 16200.00 9.1629T , J/mol [53]

(A-14)
1 to 5 in CaOAl2O3SiO2 slag as the basicity of the slag
was changed.
GA-13


Co(s) = Co(l) exp (A-15)
(2) The value of the activity coefficients for both NiO
RT
and CoO peaked in the CaOAl2O3SiO2 slag when the slag
composition approached B = (%CaO)/(%SiO2) = 1.
Acknowledgements
(3) The activity coefficients of NiO and CoO are higher
than that of FeO in CaOAl2O3SiO2 slag with B = 1, which
The author (Xin Lu) gratefully acknowledges the support
indicates that controlling the basicity of CaOAl2O3SiO2
of a scholarship provided by the Japan Society for the Pro-
slag at approximately unity for EoL superalloys remelting
motion of Science (No. H26-3293) and the scholarship pro-
improves the nickel and cobalt recycling efficiency by re-
vided by the Ministry of Education, Culture, Sports, Science
ducing the nickel and cobalt oxidation losses and by prefe-
and Technology, Japan (Registered number: 123032) during
rentially removing iron by oxidation.
his doctor course. Helpful comments and discussion pro-
vided by Dr. Elizabeth Webeck, Graduate School of Engi-
Appendix
neering, Tohoku University during the preparation of this
paper are gratefully acknowledged.
A-1 Method for converting the standard state of activity
coefficient of oxides in slag
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