Ceramics International 43 (2017) 2829–2835

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Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

The effect of chemical composition on high temperature behaviour of Fe MARK

and Cu doped Mn-Co spinels
⁎
Andrea Masia,b,c, , Mariangela Belluscia, Stephen J. McPhaila, Franco Padellaa, Priscilla Realea,
Jong-Eun Hongb,1, Robert Steinberger-Wilckensb, Maurizio Carlinic
a
ENEA C.R. Casaccia, 00123 Rome, Italy
b
School of Chemical Engineering, University of Birmingham, Edgbaston, Birmingham B15 2TT, UK
c
University of Tuscia – DAFNE, 01100 Viterbo, Italy

A R T I C L E I N F O A BS T RAC T

Keywords: Mixed Mn-Co spinels are currently studied as protective coating materials for Solid Oxide Fuel Cells
A. Milling interconnects. Compositional changes in manganese cobaltites lead to modifications in the materials properties,
B. Spinels such as sintering behaviour, thermal expansion and electrical conductivity, with advantages in the technological
C. Thermal expansion application.
C. Electrical conductivity
In this work, the effect of Fe, Cu and simultaneous Fe+Cu doping of Mn-Co spinels has been studied.
Different oxide powder mixtures were prepared with a High Energy Ball Milling (HEBM) treatment, obtaining
highly reactive oxides that easily form single spinel phase compounds by moderate heating. The effect of the
composition is observed on high temperature stability of the spinel phase and on densification behaviour of the
powders, greatly enhanced by copper addition.
Analyses carried out on sintered pellets allow to observe simple relations among dopant concentration,
thermal expansion and electrical conductivity. The combined effect is obtained in case of the simultaneous
addition of multiple dopants. An appropriate composition can be therefore designed to obtain a material
characterized by enhanced sintering behaviour, high electrical conductivity and tailored thermal expansion to
fulfil the application requirements.

1. Introduction compatibility with ferritic stainless steels, have been suggested as the
best candidates.
Development and commercial breakthrough of Solid Oxide Fuel In view of large-scale application, cheap wet-powder coating
Cells (SOFCs) is necessarily linked to reduction of costs and increase of techniques, such as spray coating, screen printing and ink-jet printing,
long-term reliability. One of the key-factors is represented by the would be preferred. These methods rely on their own ink formulations
substitution of ceramic interconnects with metallic parts. High chro- and sintering thermal treatments, and the effectiveness of the coating is
mium ferritic steels have been identified as the most promising therefore related to efficient sintering steps. Sintering Mn-Co spinel
candidate material because of their low cost and their Coefficient of powders in air requires high temperature (e.g. 1000 °C [5]), raising
Thermal Expansion (CTE) compatibility with the SOFC materials [1]. concerns about the degradation of mechanical properties that could be
In operating conditions, however, long-term performance degradation induced in the substrate. To achieve sufficient densification at lower
arises due to the formation of insulating chromium-rich oxides and the temperature, thermal treatments in reducing atmosphere are widely
evaporation of volatile Cr species, that can migrate and react with the used, followed by oxidation steps to recover the spinel structure [6,7].
cathode material, thereby reducing the active surface area [2]. The Alternatively, reduction of sintering temperature can be achieved with
application of protective coating is therefore mandatory to avoid these the introduction of further elements acting as sintering aids, such as Cu
issues, and several materials are being studied, including reactive and Ni [8,9], representing an attractive approach avoiding a more
element oxides, rare earth perovskite and spinel oxides [3,4]. Among expensive multi-step sintering treatment.
these materials, Mn-Co spinels with Co:Mn in the 1:1÷2:1 range, The addition of dopant elements, such as transition metals or
characterized by high conductivity values and good thermal expansion reactive elements like Fe, Ti, Cu, Ni or Y, has furthermore been proven

⁎
Corresponding author at: ENEA C.R. Casaccia, via Anguillarese 301, 00123 Rome, Italy.
E-mail address: andrea.masi@enea.it (A. Masi).
1
Current address: Fuel Cell Laboratory, Korea Institute of Energy Research, 152 Gajeon-ro, Daejeon 34129, Republic of Korea.

http://dx.doi.org/10.1016/j.ceramint.2016.11.135
Received 18 October 2016; Received in revised form 18 November 2016; Accepted 19 November 2016
Available online 20 November 2016
0272-8842/ © 2016 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
A. Masi et al. Ceramics International 43 (2017) 2829–2835

effective in enhancing application related to properties such as evaluating chromium presence by means of energy-dispersive X-ray
chromium retention capability or electrical conductivity [8,10,11]. microanalysis (Hitachi TM3030Plus).
However, changes in composition affect the thermal expansion beha- X-Ray diffraction analyses (XRD) were carried out on a 120°
viour: Mn-Co spinels possess CTE values in the 9.7÷13.5·10−6 K−1 angular dispersion X-ray diffractometer (Italstructure, curved position
[12–15] and 10.6÷14.1·10−6 K−1 [5,8,10,16] ranges, respectively at sensitive detector from INEL), equipped with Fe Kα1 radiation source.
800 °C and at 1000 °C. Cu and Ni doping produces an increase in CTE Phase identification was performed on collected patterns using the
[8,9,14,15,17], while Fe and Ti lower this property [10]. No clear PDF-2 database [20] as reference data. Lorentzian fitting of selected
relation between CTE and dopant concentration can be however reflections allowed to evaluate cell parameters and to calculate
deduced from the literature, mostly due to the high dispersion of accordingly theoretical densities, considering nominal compositions
results. Furthermore, to the best of our knowledge, no results have of the samples.
been reported related to the effect of simultaneous doping. Morphology of the samples was evaluated using N2 adsorption at
HEBM is a consolidated, cost effective and environmentally friendly 77 K technique (Quantachrome Autosorb-iQ). Specific surface area
powder processing technique widely applied in material science. The (SSA) values were obtained by applying the BET method [21]. BET
6
technique consists in the exposure of defined quantities of powder particle size l was calculated as l= SSA ∙ ρ , where ρ is the material
reactants to repeated energy transfer phenomena obtained by colliding density.
balls. The kinetic energy released from the balls to the powder can Thermogravimetric analysis was carried out in air using a Perkin
induce several physico-chemical phenomena, the first being repre- Elmer thermobalance (Pyris Diamond TG/DTA, Perkin Elmer) with the
sented by fine grinding of particles, and therefore formation of new following procedure: heating scan up to 1200 °C at 5 °C/min, 60 min of
active surfaces. Nanostructuration of the powder can occur at this isothermal step and cooling to room temperature at 5 °C/min.
stage, enhancing significantly powder reactivity, followed by interdiffu- Dilatometric measurements were performed in a push-rod dilat-
sion, atomic rearrangements, nucleation of stable or metastable phases, ometer (DIL 402C, NETZSCH). To evaluate sintering behaviour,
amorphization, re-crystallization phenomena and so on [18]. consolidated pellets of about 6 mm diameter length were obtained by
In our previous works, High Energy Ball Milling (HEBM) was uniaxial cold pressing (3.5 T/cm2) and heated in air with a heating rate
evaluated as a synthesis route to obtain mixed spinels starting from of 5 °C/min up to 1200 °C. Thermal expansion measurements were
oxide powders [15,19]. A HEBM treatment carried out on Mn-Co carried out with a heating rate of 10 °C/min on pellets of about 6 mm
oxides promotes the room temperature solid state mechano-chemical diameter and 2.5 mm height sintered as described later in the text.
reaction between Mn and Co oxide mixtures, with a unitary reaction Average CTE was calculated between room temperature and 800 °C as:
1 ∆L
yield after 65 h of milling. Powders obtained after relatively short CTE = L ∆ T , where L0 is the initial length and ΔL represents the length
0
mechano-chemical treatments (e.g. 10 h), despite not containing a change occurring in the ΔT temperature range.
single phase compound, are characterized by significantly enhanced To assess electrical conductivity, pellets of about 10 mm diameter
reactivity with respect to pristine oxides, and easily evolve to form the were obtained by uniaxial cold pressing (3.5 T/cm2) and sintered
equilibrium products when subjected to moderate heating (i.e. T & similarly to thermal expansion samples. The conductivity was mea-
<800 °C). sured by applying the Van der Pauw method [22] (PAR273A potentio-
In this work, to study the effect of Fe, Cu and simultaneous Fe+Cu stat coupled to a HP 3457A multimeter) in the 500–800 °C tempera-
doping on the chemico-physical properties of Mn-Co spinels, different ture range. Activation energy Ea was calculated from the Arrhenius plot
powder mixtures of Mn, Co, Fe and Cu oxides are prepared and σ Ea
obtained using the formula: σ = T0 e− kT , where σ is the conductivity, T
subjected to a HEBM treatment. The obtained highly reactive powder
the temperature, σ0 the pre-exponential factor, Ea the activation
samples are characterized in their thermal evolution and sintering
energy and k the Boltzmann's constant.
properties, and differences on powder densification behaviour and high
temperature spinel stability induced by the dopant contents are
observed and reported. Finally, the effect of different metal composi- 3. Results and discussion
tions on thermal expansion and electrical conductivity of sintered
samples is evaluated and discussed. 3.1. Powder characterization

2. Experimental procedure The XRD patterns of the 10 h milled powders are reported in Fig. 1.
All the examined samples are characterized by similar patterns, with
Mn3O4 (Sigma Aldrich, 97%), Co3O4 (Sigma Aldrich, 99%), CuO significant peak broadening ascribable to nanostructuration of crystal-
(Carlo Erba, 99%) and Fe2O3 (Carlo Erba, 99%) were mixed in lites and strain. Starting with the MnCo1.8Fe0.2 pattern, main peaks
stoichiometric quantities to obtain the compositions reported and are ascribable to the presence of a cubic spinel compound, compatible
labelled in Table 1. The HEBM process was performed in a with Co3O4 phase (JCPDS card n. 42-1467). Peaks related to the
SPEX8000M mixer mill, using cylindrical steel vials (60 cm3 volume) Mn3O4 compound are not evident, confirming that the cobalt rich
and steel balls (10 mm diameter) with powder to balls weight ratio of phase exhibits a high stability during the mechano-chemical treatment,
1:10. Vials were loaded with 8 g of powder, sealed in argon atmosphere as already observed in the case of similar oxides mixtures [15,19]. The
and subjected to 10 h of milling. After the milling treatment, the asymmetry of Co3O4 peaks towards lower angles could be ascribed to
absence of contamination from the milling media was assessed the nucleation of a cubic spinel phase characterized by higher lattice
parameter, most likely a mixed spinel similar to MnCo2O4 (JCPDS card
Table 1 n. 23-1237). The small broadened peaks at 2θ≅48° is due to the
Sample nomenclature and nominal composition. presence of highly destructured Fe2O3 phase (JCPDS card n. 33-0664),
and are more evident in the MnCo1.6Fe0.4 pattern, as expected due to
Sample name Atomic ratio Nominal composition
the higher iron content. In the case of copper containing samples,
Mn Co Fe Cu instead, clear evidences of CuO phase (JCPDS card n. 48-1548) are not
observed, suggesting low stability of CuO structure during the HEBM
MnCo1.8Fe0.2 0.33 0.60 0.07 MnCo1.8Fe0.2O4 treatment, most likely due to facile diffusion of small copper ions into
MnCo1.6Fe0.4 0.33 0.53 0.14 MnCo1.6Fe0.4O4
the spinel lattice during the mechano-chemical treatment. In the
MnCo1.8Cu0.2 0.33 0.60 0.07 MnCo1.8Cu0.2O4
MnCo1.6Fe0.2Cu0.2 0.33 0.53 0.07 0.07 MnCo1.6Fe0.2Cu0.2O4 MnCo1.6Fe0.2Cu0.2 pattern, similar to what is observed for
MnCo1.8Fe0.2 sample, features of a hematite phase are visible.

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Fig. 1. X-ray powder diffraction patterns of the different samples after 10 h of milling; Fig. 2. Thermogravimetric curves as a function of temperature for the different samples;
(1) Co3O4 (2) MnCo2O4 (3) Fe2O3 reflections. solid lines represent weight% change, dotted lines the derivative of wright% versus
temperature.
Therefore, as shown in the XRD analysis, the 10 h HEBM treatment
does not produce a single equilibrium spinel phase but some meta- metastable non-stoichiometric mixed valence spinels has been ob-
stable mixture of metal oxides. served for similar systems and ascribed to high reactivity due to high
Nitrogen adsorption measurements at 77 K were carried out to nanostructuration of the compounds [23], and it is supposed that
calculate BET specific surface area and thus evaluate the degree of similar mechanisms occur here, due to the defectivity induced by the
particle aggregation. The obtained values are reported in Table 2. Mn- HEBM treatment.
Co-Fe samples exhibit comparable surface areas, while Cu addition Regarding the influence of the composition on this weight gain step,
seems to favour higher degrees of aggregation resulting in lower it can be observed that the magnitude of the weight gain increases
surface areas. The size of particles calculated with BET ranges between following the order: MnCo1.6Fe0.4 & <MnCo1.8Fe0.2 &
160 and 330 nm. <MnCo1.6Fe0.2Cu0.2 & <MnCo1.8Cu0.2. This can be related to the
In order to evaluate the differences in the high temperature initial powder composition: Co3O4 precursor is substituted with species
behaviour of the powders, which is induced by the cobalt substitution, characterized by different oxygen content (i.e. Fe2O3 and CuO), and it is
thermogravimetric analyses up to 1200 °C were carried out and are likely to suppose that, with Fe and Cu ions presence in the spinel lattice
reported in Fig. 2. The samples exhibit an initial weight loss, ascribable due to the mechano-chemical treatment, the oxygen uptake of the
to adsorbed humidity departure. In the 200e500 °C temperature range metastable spinels will be inversely related to the initial oxygen
a weight gain step is instead observed. This phenomenon can be related content.
to the powder comminution and activation induced by the HEBM, Following this weight gain step, in the 500e700 °C temperature
carried out in Ar atmosphere. Highly reactive new surfaces are range a gradual weight loss can be observed, related to the rearrange-
produced during the mechano-chemical treatment that interacts with ment and homogenization of the oxidized compound to form the
oxygen already at low temperature giving rise to the oxidation expected high temperature single spinel phase. At about 800 °C, in fact,
phenomena observed during the thermal treatment. Moreover, the the curves reach a plateau, suggesting that no further oxygen release
HEBM treatment induces a high degree of interdiffusion of the occurs. Also in this weight change step a relationship between the
precursor oxides with solid state reactions at the new interfaces, most weight loss and the material composition can be observed: in parti-
likely with the formation of highly anion defective lattices, due to the cular, the weight loss increases following the order: MnCo1.8Cu0.2 &
milling atmosphere. Subsequent filling of the oxygen vacancies may <MnCo1.6Fe0.2Cu0.2 & <MnCo1.8Fe0.2 & <MnCo1.6Fe0.4. The sam-
therefore occur when exposed to air at moderate temperatures. The ples characterized by the higher initial oxygen content show therefore
occurrence of similar weight gain phenomena and the existence of the higher mass loss. The substitution of the Co2+/Co3+ precursor with
higher or lower oxidation state species, respectively Fe3+ from Fe2O3
Table 2
and Cu2+ from CuO, affects the oxidation behaviour of the milled
BET surface area and BET particle size for the 10 h HEBM powders. powder both during the formation of the metastable spinels and during
the homogenization reaction that produce equilibrium compounds. In
Sample BET (m2/g) la (nm) our previous work [19], we observed that during mechano-chemical
treatment of Mn and Co oxides the reaction proceeds through nuclea-
MnCo1.8Fe0.2 6.0 ± 0.3 182 ± 9
MnCo1.6Fe0.4 6.8 ± 0.3 163 ± 8 tion and growth of mixed phases rather than through interdiffusion
MnCo1.8Cu0.2 3.3 ± 0.2 323 ± 20 phenomena of the starting oxides. Observing how the thermal beha-
MnCo1.6Fe0.2Cu0.2 3.8 ± 0.2 287 ± 16 viour of the doped powders is influenced by the initial composition, it is
a 6 likely to suppose that the formation of Fe and Cu doped phases occurs
l= SSA ⋅ ρ
.

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already during the milling step, suggesting that a similar reaction

mechanism is involved.
Further increase of temperature above 1000 °C leads to a third
weight loss phenomenon, that can be related to metal reduction from
the spinel phases with related oxygen release, due to the formation of
Me(II) oxide phases. The existence of a high temperature spinel-MeIIO
multi-phase boundary is known for Co-Mn oxide mixtures [24], and
the data reported here suggest that a similar behaviour is retained with
Fe and Cu addition to the spinel composition, with some differences in
the onset temperature. Co substitution with Fe appears to extend the
spinel stability region. Copper substitution promotes instead the spinel
de-mixing at lower temperature.
During the successive cooling stage, the weight loss associated to
the high temperature phase transition is recovered for all the stoichio-
metries, compatibly with spinel stability at intermediate temperature.
In the case of the MnCo1.8Cu0.2 sample, weight gain occurs in two
steps, suggesting a multiple oxidation process that could be due to
multiple high temperature dual-phase regions, as observable in the Cu-
Co oxides phase diagram [25].
To evaluate sintering behaviour, consolidated pellets were formed
with the 10 h HEBM powders. The pre-sintering densities are reported
in Table 3: similar values of density are obtained for all the different
samples, as expected from the processing of morphologically similar
powders. Shrinkage and shrinkage rate curves are reported in Fig. 3.
Mn-Co-Fe samples show behaviour comparable to similar Mn-Co
Fig. 3. Dilatometric curves as a function of temperature of the different samples; solid
spinels [15], with sintering temperatures of about 1040e1060 °C and
lines represent the length change, dashed lines the derivative of the length change versus
maximum densification rates at 1150 °C approximately. The addition temperature.
of Cu significantly improves sintering: in the case of MnCo1.8Cu0.2
and MnCo1.6Fe0.2Cu0.2 samples, shrinkage starts at approximately
925e950 °C, with maximum densification rate occurring at T≅1000 °C.
XRD analysis carried out on the pellets after dilatometric measure-
ments indicated however the presence of secondary phases: differently
with respect to thermogravimetric measurements, thermal treatment of
the pellets at 1200 °C could result in the lack of recovery of the single
spinel structure upon cooling. This is most likely due to high packing
and higher crystals growth, limiting oxygen diffusion. Being crucial to
obtain single phase pellets to evaluate precisely thermal expansion and
electrical conductivity properties, different sintering procedures were
studied to obtain dense single phase pellets. In the case of the
MnCo1.8Fe0.2 and MnCo1.6Fe0.4 sample, requiring sintering tem-
perature of 1200 °C to achieve high density values, a lower temperature
(800 °C) dwell step was introduced to facilitate spinel recovery. The
significantly lower sintering temperature of Cu containing compounds,
as evidenced by dilatometric analysis, allowed to reduce the maximum
treatment temperature to 1000 °C still obtaining dense pellets.
The sintered densities obtained for the different samples, reported
in Table 3, show how Cu inclusion leads to a significant enhancement
of densification: Cu substituted samples are in fact characterized by
higher density with respect to Mn-Co-Fe samples even with a reduction
in sintering temperature of 200 K.
X-Ray diffraction patterns of the sintered samples are reported in
Fig. 4. All compositions exhibit a single cubic spinel phase. The

Table 3 Fig. 4. X-ray powder diffraction patterns of the samples after sintering treatment;
Sintering thermal treatments. specified reflections are ascribable to a cubic spinel phase.

Sample Green Sintering Sintered

density (%) treatment density (%) Table 4
Lattice parameter (a) of the cubic spinel cell calculated from XRD patterns of the sintered
MnCo1.8Fe0.2 66 ± 1 4 h@1200 °C 92 ± 1 samples.
+4 h@800 °C
MnCo1.6Fe0.4 66 ± 1 4 h@1200 °C 90 ± 1 Sample a (Å)
+4 h@800 °C
MnCo1.8Cu0.2 65 ± 1 4 h@1000 °C 97 ± 1 MnCo1.8Fe0.2 8.319(7)
+4 h@800 °C MnCo1.6Fe0.4 8.351(8)
MnCo1.6Fe0.2Cu0.2 65 ± 1 4 h@1000 °C 95 ± 1 MnCo1.8Cu0.2 8.277(8)
+4 h@800 °C MnCo1.6Fe0.2Cu0.2 8.312(8)

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Fig. 6. Coefficient of thermal expansion calculated at 800 °C as a function of the cobalt

substitution in comparison with the undoped material (as reported in [15]).
Fig. 5. Thermal expansion curves of the sintered samples.

negative trend between CTE value and iron content, while

evidence of well-defined peaks suggests a significant crystal growth MnCo1.8Cu0.2 sample is characterized by higher CTE value than the
during the sintering process. Peak shifts with respect to the standard undoped sample. Consistently with the single metal doped samples, the
MnCo2O4 phase are observed for the different compositions, high- combined effect is obtained in the MnCo1.6Fe0.2Cu0.2 compound, the
lighted by the calculated cell parameters reported in Table 4. In CTE of which is ranged between those of MnCo1.8Fe0.2 and
particular, due to the different size of dopants ionic radius with respect MnCo1.8Cu0.2. This result suggests that the CTE of Mn-Co spinels
to the substituted cobalt [26], Fe-Co substitution promotes the can be tuned in the examined range by compositional tailoring, as the
enlargement of the lattice (8.27 Å for MnCo2O4 [20]), differently from effect of the cobalt substitution with copper and iron on CTE is retained
Cu-Co substitution that, due to similar ionic radii, does not induce with the simultaneous doping.
significant changes in the cell parameter. Regarding the dependence of the CTE with the composition, the
obtained results are in agreement with previous studies that suggest
3.2. Thermal expansion the occurrence of a relation between CTE and the different occupations
and valence states in the spinel lattice [28]. In particular, mixed
Thermal expansion compatibility between the substrate and the element spinels characterized by higher valence differences among
coating material is a crucial factor to avoid mechanical stress that could the sites possess higher CTE, especially when this difference occurs
arise during thermal cycles or long term operation and could promote between octahedrally coordinated cations [28]. In Mn-Co spinels,
cracking or delamination of the coatings. To evaluate CTE of the tetrahedral sites are occupied preferentially by CoII species, while
examined materials, the sintered pellets were subjected to dilatometric octahedral sites are occupied by CoII, CoIII, MnIII and MnIV. The
analyses. In Fig. 5 the expansion curves are reported, and average CTE amount of CoII and MnIV, strictly connected due to charge neutrality
values calculated between room temperature and 800 °C are listed in restraints, is maximum when Co:Mn~2 [29]. The substitution of Co
Table 5. All the samples exhibit a linear behaviour through all the with Fe occurs with FeIII species occupying preferentially octahedral
measured temperature range. The results here obtained are compar- sites in place of Co atoms [11], reducing the amount of octahedral CoII
able to values found in literature for similar compounds (e.g. [10]). and therefore the amount of species characterized by different valences.
Considering the thermal expansion of ferritic stainless steels, i.e. When copper is added to the compound, instead, Cu atoms tend to
11e13·10−6K−1 [27], MnCo1.8Cu0.2 samples possess lower compat- occupy preferentially tetrahedral sites [30], with the presence of CuI
ibility with respect to the Fe containing samples. and CuII species. Moreover, copper addition is likely to promote
To evaluate how cobalt substitution with Fe and Cu affects this octahedral MnIII oxidation to MnIV to maintain charge neutrality
property, in Fig. 6 are depicted the CTE values at 800 °C versus the [30], increasing further the number of different valence species in the
cobalt content for the different samples, compared with result pre- lattice and therefore CTE.
viously obtained on a MnCo2O4 spinel [15]. It can be observed a clear When Co is substituted by both Fe and Cu, the enhancement of CTE
due to CuI and CuII introduction on tetrahedral sites is counterbalanced
Table 5 by the CTE decrease induced by the FeIII presence in octahedral sites,
Thermal expansion coefficient measured between room temperature and 800 °C for the and, with Fe and Cu ions not being competitors for lattice sites
different samples. occupation in the examined composition range, the overall CTE change
Sample CTE (·10−6 K−1) [30–800°]
can be considered as limited to the sum of the single dopants
contributions.
MnCo1.8Fe0.2 12.7 ± 0.1
MnCo1.6Fe0.4 11.1 ± 0.1
3.3. Electrical conductivity
MnCo1.8Cu0.2 13.7 ± 0.1
MnCo1.6Fe0.2Cu0.2 12.9 ± 0.1
Electrical conductivity was evaluated by means of Van der Pauw

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Fig. 8. Conductivity values measured at 800 °C as a function of the cobalt substitution in

comparison with the undoped material (as reported in [15]).

Fig. 7. Arrhenius plots of electrical conductivity measured (dots) for the different
samples and linear fits of the experimental points (dashed lines). octahedral sites. Furthermore, Cu atoms in tetrahedral sites could
contribute indirectly through mediation of charge transfers between
close Mn atoms in octahedral sites [31]. The electrical conductivity
Table 6
Activation energy calculated from the Arrhenius plot of 10 h milled samples. enhancement observed with copper addition therefore could be attrib-
uted to an indirect enhancement of Mn pairs contribution.
Sample Ea (eV) Similarly to what was observed for CTE, most likely due to the
absence of competition for lattice site occupation among the dopants,
MnCo1.8Fe0.2 0.54 ± 0.03
MnCo1.6Fe0.4 0.53 ± 0.03 our results suggest that the effect of the simultaneous substitution is
MnCo1.8Cu0.2 0.46 ± 0.03 limited to the sum of the single factors.
MnCo1.6Fe0.2Cu0.2 0.50 ± 0.03

4. Conclusions
method in the temperature range 500e800 °C. In Fig. 7 the Arrhenius
plots are reported. All samples exhibit a linear relation: evaluating the Doped spinels were successfully produced by a mechano-chemically
slope of the linear fits to the Arrhenius curves activation energy was enhanced solid state reaction synthesis. The effect of doping has been
calculated, and results are reported in Table 6. All samples show clearly highlighted with respect to high temperature stability, sintering
similar values of about 0.5 eV, suggesting a similar conduction behaviour, CTE and electrical conductivity.
Through a high energy ball milling treatment, Fe and Cu substi-
mechanism.
In Fig. 8 the conductivity values measured at 800 °C for the tuted Mn-Co highly reactive oxide mixtures were obtained. The
powders easily form the expected single cubic phase when exposed to
different samples are reported as a function of the cobalt content,
and compared with an undoped MnCo2O4 spinel [15]. It can be moderate temperature (T & <800 °C). Influence of the dopant content
was observed on thermal stability of the spinel phase, enhanced by Fe
observed a clear decreasing trend upon the substitution of Co with
Fe, with conductivity of about 51 S/cm and 36 S/cm for MnCo1.8Fe0.2 and decreased by Cu addition.
Regarding the densification behaviour, Cu addition resulted highly
and MnCo1.6Fe0.4 samples respectively. Co substitution with Cu
significantly increases conductivity, and similar enhancements are effective in reducing sintering temperature and achieving higher
density at lower temperature, while iron doping did not lead to
observed when cobalt is substituted in the reference material
(Mn1.8Co1.8Cu0.2 versus MnCo2O4) or in the iron doped sample significant improvement with respect to the undoped Mn-Co sample.
The measurement of thermal expansion of the sintered pellets
(MnCo1.6Fe0.2Cu0.2 versus Mn1Co1.8Fe0.2).
The electrical conductivity in spinels is associated with a small indicated a direct relation between Co substitution and CTE, which
decreased with Fe content and was increased by Cu doping. The sample
polaron hopping mechanism between mixed valence elements on
octahedral sites and in Mn-Co oxides it is related to CoII/CoIII and substituted with both Cu and Fe revealed a combined effect on CTE,
ranged between that of Fe or Cu doped sample. Similar influence of the
MnIII/MnIV pairs [13,28]. The valence state concentration ratio affects
therefore significantly conductivity properties. The observed decrease composition was observed also on electrical conductivity, lowered by Fe
doping and greatly enhanced by Cu addition, with the mixed Cu-Fe-
in conductivity with Fe substitution is related to the preferential
occupation of octahedral sites by FeIII atoms, not involved in polaron Mn-Co sample behaving coherently.
formation, limiting the charge carrier density [11]. Regarding Cu Substitution of Co with Fe and Cu to obtain a Fe-Cu doped Mn-Co
addition, the conductivity enhancement could be due to multiple spinel proved therefore as a versatile approach to enhance sintering
factors: the aforementioned promotion of MnIII oxidation to MnIV to behaviour and electrical conductivity while retaining thermal expan-
maintain charge neutrality [30], occurring with the presence of CuI and sion compatibility with ferritic stainless steels. This suggests that a
CuII species in the lattice, could increase the number of active pairs on multiple doping approach can represent an effective strategy to design
cobaltite materials properly tailored on the application.

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Acknowledgments [15] A. Masi, M. Bellusci, S.J. McPhail, F. Padella, P. Reale, J. Hong, R. Steinberger-
Wilckens, M. Carlini, Cu-Mn-Co oxides as protective materials in SOFC technology:
the effect of chemical composition on mechanochemical synthesis, sintering
This work is supported by the FCH JU within the project SCORED behaviour, thermal expansion and electrical conductivity, J. Eur. Ceram. Soc. 37
2:0 under contract. 325331. The authors wish to thank Dr. Claudia (2017) 661–669. http://dx.doi.org/10.1016/j.jeurceramsoc.2016.09.025.
[16] Y. Liu, J.W. Fergus, C. Dela Cruz, Electrical properties, cation distributions, and
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