3.1. Phase Composition and Crystal Structure
XRD analysis confirmed that (ZrO
2)
0.95(Y
2O
3)
0.05, either as-delivered powder used for synthesis or ceramic samples sintered in air at 1600 °C for 10 h, is partially-stabilized zirconia with tetragonal structure and a minor fraction of monoclinic phase. Additions of manganese oxide resulted in the stabilization of the fluorite cubic structure (space group
Fmm). All prepared [(ZrO
2)
0.95(Y
2O
3)
0.05]
1−x[MnO
y]
x (
x = 0.05, 0.10 and 0.15) ceramics were single-phase, with no evidence of impurity phases detectable by XRD. An example of XRD pattern of as-prepared ceramics is given in
Figure 1A.
Polished as-prepared ceramic samples were further inspected by SEM/EDS. Microscopic studies revealed the presence of occasional isolated inclusions of MnO
y with sizes ≤ 2 µm, mainly in the
x = 0.15 samples (
Figure 2). The concentration of inclusions was low (<0.2 vol.% for
x = 0.15, as roughly estimated from the SEM images), so that its influence on the properties studied in this manuscript is considered negligible.
The analysis of available literature data suggests that the solubility of manganese oxide in (Zr,Y)O
2−δ is limited, but varies with yttrium content and temperature. In particular, the equilibrium solubility limits of MnO
y at 1400 °C in air were reported to be 7.6, 10.3 and 11–12 mol.% in 3, 6 and 8 mol.% yttria-substituted zirconia, respectively [
14,
17,
18,
19]. Increasing temperature extends the solubility of MnO
y in (ZrO
2)
0.92(Y
2O
3)
0.08 from ~5 mol.% at 1000 °C to 15–18 mol.% at 1500 °C [
19,
21]. Thus, it can be assumed that the manganese contents in fluorite-type ceramics prepared in the present work, particularly in samples with
x = 0.15, are not equilibrium, but quenched from sintering temperature. This is also supported by the previous results on the processing of the
x = 0.15 ceramics at 1400–1600 °C [
35], showing that the concentration and size of MnO
y precipitates increase with a reduction in time and the temperature of firing.
The lattice parameter of as-prepared fluorite-type solid solutions decreases linearly with increasing manganese content (
Table 1 and
Figure 3). The ionic radius of zirconium cations in an 8-fold coordination in the cubic fluorite lattice is 0.84 Å [
36]. Thus, a decrease in the lattice parameter with
x can reasonably be attributed to the incorporation of manganese cations in a lower coordination (
rVI(
= 0.58 Å,
rVI(
= 0.65 Å or
rVI(
= 0.67 Å [
36]) into the zirconia lattice combined with a simultaneous moderate decrease in the concentration of large yttrium cations (
rVIII(Y
3+) = 1.02 Å [
36]).
The density of prepared ceramics was 90–94% of theoretical (
Table 1). The grain size was in the range of 2–20 µm for
x = 0.05 and 3–80 µm for
x = 0.10–0.15. Additions of manganese resulted in some improvement in sinterability and grain growth, in agreement with literature reports [
28,
37,
38], probably due to the relatively high diffusivity of Mn species in cubic zirconia [
39].
3.2. Mn Oxidation State and Oxygen Nonstoichiometry in Air
The XPS spectra were collected on as-sintered crashed ceramic samples. The binding energy (BE) values of the Zr 3
d3/2 and Y 3
d3/2 signals were found at 158.4–158.6 and 183.8–184.0 eV, respectively, in agreement with the literature data on cubic and tetragonal YSZ [
40] and Mn-doped YSZ systems [
41,
42]. The Mn 2
p core-level spectra for all compositions are shown in
Figure 4A; the corresponding BE values are listed in
Table 2. The BEs of the Mn 2
p1/2 and Mn 2
p3/2 signals are given by the positions of the maxima of the main peaks. The asymmetric Mn 2
p3/2 main peak is located at 641.0–641.4 eV with a 2
p3/2–2
p1/2 splitting of 11.7–12.0 eV. These values are closer to the BE of Mn 2
p3/2 peaks reported for MnO (640.6 eV), Mn
3O
4 (641.4 eV) and Mn
2O
3 (641.9 eV) binary oxides rather than for MnO
2 (642.2 eV) [
43]. Therefore, Mn cations in 2+ and 3+ oxidation states are expected to prevail for all compositions, although a minor presence of Mn
4+ ions cannot be discarded based on the obtained XPS data. In addition, a satellite peak at a BE of ~647 eV (full width at half maximum (FWHM) = 3.5 eV) was evidenced in all the Mn 2
p spectra (
Figure 4A). This feature is characteristic of MnO [
44] and has not been reported for neither Mn
2O
3 nor MnO
2, thus further suggesting the presence of Mn
2+ species in the samples. A slightly higher intensity of this satellite feature for
x = 0.05 seems to imply a lower average oxidation state of Mn in this sample. A minor decrease in FWHM of the Mn2
p3/2 peak from 3.3 eV (
x = 0.05) to 3.0–3.1 eV (
x = 0.10 and 0.15) is also likely to be related to a lower concentration of Mn
2+ in the samples with a higher Mn content.
Analysis of the Mn 3
s core level spectrum is more useful to assess the oxidation state of Mn. A representative fitting of the Mn 3
s multiplet for the sample with
x = 0.10 is included in
Figure 4B. The spectra exhibited two components with the splitting magnitude being related to the oxidation state of the Mn ions: typically 6.5–5.7 eV for Mn
2+ in MnO, 5.5–5.2 eV for Mn
3+ in Mn
2O
3, and 4.7–4.5 eV for Mn
4+ in MnO
2 [
45,
46]. The measured Δ(3
s(2)−3
s(1)) values (
Table 2) ranged from 6.4 eV (
x = 0.05) to 5.9 eV (
x = 0.10), thereby supporting a mean Mn oxidation state lower than 3+ in all the samples, as well as a higher concentration of Mn
2+ species in the
x = 0.05 sample.
TGA was employed to determine the absolute values of oxygen nonstoichiometry and average manganese oxidation state in Mn-substituted 5YSZ in air (
Figure 5). The TGA data were obtained on temperature cycling in air followed by the isothermal reduction of the samples in 10% H
2-N
2 flow at 900 °C until constant weight (see discussion below). The calculations were done assuming that all manganese in reduced samples is in a 2+ oxidation state. This assumption is consistent with redox changes in the Mn-O system [
47], and also with the evidence by electron paramagnetic resonance (EPR) studies of manganese-doped zirconia [
48] and YSZ [
49,
50], and the results of thermodynamic modeling of the Zr-Y-Mn-O system [
51].
The TGA results demonstrated that Mn-substituted 5YSZ ceramics exhibit variable oxygen content on temperature cycling in air above 300–500 °C (depending on composition) associated with reversible reduction/oxidation of manganese cations
or, using Kroger-Vink notation:
The calculated average oxidation state of Mn cations in the studied materials in air is below 3+ (
Figure 5B), in accordance with the XPS results. The mean Mn valence is nearly independent of the total manganese content varying in a narrow range 2.61–2.66 at 900 °C and 2.90–2.93 after cooling down to room temperature, although the
x = 0.05 ceramics showed a tendency to a slightly higher relative fraction of Mn
2+ compared to other compositions. These results are in excellent agreement with available literature reports, showing a mixed 2+/3+ oxidation state of manganese cation in Mn-doped YSZ. In particular, the results of EPR and optical absorption spectroscopy studies of 9.5YSZ single crystals containing impurity levels of Mn (≤0.1 wt.%) revealed that the fraction of bivalent manganese, [Mn
2+]/[Mn]
total, in the samples equilibrated with air at 800 °C is close to 45–50% [
49,
50,
52,
53]. Mixed Mn
2+/3+ oxidation state in manganese-doped 8YSZ ceramics was demonstrated by EPR [
48] and XANES (X-ray Absorption Spectroscopy in the Near Edge region) [
16] studies and supported by the thermodynamic modeling of this system [
51]. Appel et al. [
54] performed EELS (Electron Energy Loss Spectroscopy) studies of Mn-doped 7.5YSZ ceramics, and also concluded that Mn cations are in a mixed 2+/3+ state, and that the average Mn oxidation state does not change with manganese content in the studied compositional range (2–10 mol.% of MnO
y). The presence of Mn
4+ in Mn-doped YSZ was ruled out by EPR measurements, even under oxidizing conditions [
48,
50].
The substitution of Zr
4+ by lower-valence Mn
3+/2+ generates oxygen vacancies in the fluorite lattice. The electroneutrality condition for Mn-substituted YSZ is given by
The increase in manganese content results in a gradual increase in the concentration of oxygen vacancies and also in the extent of oxygen nonstoichiometry variations with temperature (
Figure 5A). A specific feature observed in the thermogravimetric curves, and therefore in temperature dependencies of calculated parameters, is a change in slope at 820–880 °C, probably corresponding to a limiting range for partial relaxation of quenched-in conditions. The exact reason for this is under question; possible factors may include a change of limiting stage of redox re-equilibration process (surface exchange ↔ bulk diffusion) or order-disorder processes in the fluorite lattice.
3.3. Electrical Transport Properties under Oxidizing Conditions
All prepared Mn-substituted 5YSZ ceramics exhibit semiconducting behavior: electrical conductivity increases on heating. As-prepared ceramic materials show a comparable level of conductivity in the high-temperature range in air (
Figure 6). Increasing the Mn content from
x = 0.05 to
x = 0.10 results in a moderate reduction in σ, while further substitution results in an enhancement in electrical transport. At the same time, substitution by manganese is accompanied by a gradual decrease in the activation energy of electrical conductivity (
Table 3). As a result, the electrical conductivity of the studied materials increases with the Mn concentration in the fluorite lattice at temperatures below ~650 °C.
Isothermal electrical measurements at 900 °C revealed, however, that all the Mn-substituted 5YSZ exhibited a quite slow relaxation of electrical conductivity with time under oxidizing conditions. This was observed even for as-prepared samples in atmospheric air: the conductivity of
x = 0.10 and
x = 0.15 samples tended to increase with time, while the sample with
x = 0.05 showed the opposite behavior (
Figure 7A). Thermogravimetric studies showed that this is accompanied by a slow weight gain (i.e., oxygen uptake) for all compositions.
Since the Mn content in prepared materials at temperatures ≤ 1000 °C is expected to be non-equilibrium (quenched from sintering conditions), a possible explanation for the slow transient processes occurring even in air at 900 °C could be very sluggish exsolution of the excess of Mn from the fluorite lattice; however, one could not find microstructural changes supporting this. No evidence of Mn segregation on the surface of polished samples was observed by SEM/EDS, even after prolonged annealing at 900 °C for 360 h (
Figure 8). On the contrary, even a short treatment at the higher temperature, 1400 °C, resulted in manganese exsolution from the bulk of ceramics and accumulation of MnO
y grains on the surface (
Figure 8). This suggests that cation diffusivity and the phase re-equilibration at ≤900 °C are very slow, in agreement with some indications in literature [
19], and are unlikely to be responsible for the observed relaxation processes.
The structural studies also do not support the possible exsolution of Mn. A significant decrease in manganese concentration in the fluorite lattice would result in a lattice expansion and the onset of a Mn-rich phase. On the contrary, it was found that while all materials remain single-phase solid solutions (
Figure 1B), annealing in air at 900 °C results in a contraction of the fluorite unit cell (
Figure 3). This implies that slow oxygen uptake at 900 °C is associated with Mn
2+ → Mn
3+ oxidation, and lattice shrinkage is caused by a corresponding decrease in the average size of manganese cations (e.g.,
rVI(
= 0.65 Å and
rVI(
= 0.83 Å [
36]).
A slow relaxation process at 900 °C was also observed in the course of ionic transference numbers determination by the EMF method.
Figure 7B illustrates the drift of E
exp/E
th ratio with time for air/Pt/(Mn-substituted YSZ)/Pt/O
2 concentration cells. E
exp and E
th designate experimentally measured open-circuit voltage of the cell and theoretical voltage defined by the Nernst equation, respectively. In the classic EMF method, the E
exp/E
th ratio gives an average ionic transference number in a given p(O
2) range. Gorelov’s modification of the EMF method [
32,
55,
56] was employed in the present work to account for the non-negligible polarization of cell electrodes resulting in underestimation of ionic transference numbers. As shown in
Figure 7B, E
exp/E
th values decreased slowly with time and required over 70 h at 900 °C to stabilize. The measured E
exp/E
th ratio and the average oxygen-ion transference numbers at the beginning of the experiment (immediately after sealing the sample at 950 °C and cooling down to 900 °C) and after ≥70 h of sample equilibration are summarized in
Table 4. For all Mn-substituted 5YSZ ceramics, E
exp/E
th and
values decreased after the relaxation process implying a decline in ionic contribution and/or an enhancement of electronic contribution to total electrical transport. The extent of these changes is correlated with the nominal Mn concentration. In agreement with electrical conductivity measurements (
Figure 7A), the ohmic resistance of the
x = 0.05 sample increased during the relaxation process, while
x = 0.10 and 0.15 samples exhibited a decrease in resistance with time (
Table 4).
Figure 9A shows the temperature dependence of the average oxygen-ion transference numbers of Mn-substituted 5YSZ under air/oxygen gradient after equilibration at 900 °C. All compositions demonstrated negligible dependence of
on temperature at 700–900 °C. Substitution by manganese leads to a gradual transformation from a predominantly ionic conductor (
x = 0.05) to a mixed conductor with similar contributions of ionic and electronic transport (
x = 0.10), and then to a material with prevailing electronic conduction (
x = 0.15) under oxidizing conditions close to air.
Calculations of partial contributions to total conductivity demonstrated that increasing Mn concentration in the fluorite lattice results in the gradual enhancement of electronic transport but simultaneously suppresses ionic conduction (
Figure 9B). Yttria-doped zirconia is known to exhibit very low
p-type electronic conductivity under oxidizing conditions. For instance, the electronic conductivity of 8YSZ in air at 900 °C was reported to be as low as ~10
−5 S × cm
−1 [
57]. Additions of manganese lead to an increase in electronic conductivity by orders of magnitude (
Figure 9B). Similar observations were previously reported for Mn-doped 3YSZ [
22] and 8YSZ [
19,
21,
22,
23,
24] within the manganese solubility ranges.
Oxygen-ionic conductivity of Mn-substituted 5YSZ at 900 °C decreases twice with increasing Mn content (from 1.2 mS × cm
−1 for
x = 0.05 to 0.56 mS × cm
−1 for
x = 0.15), despite an increase in the concentration of oxygen vacancies (
Figure 9B), and is lower compared to 8YSZ (δ = 0.074, σ
O = 10 mS × cm
−1 at 900 °C [
58]). It is known that zirconia-based solid electrolytes exhibit the highest oxygen-ionic conductivity when the concentration of acceptor-type dopant (alkaline-earth or rare-earth cation) is close to the minimum required for the stabilization of cubic fluorite structure [
59,
60]. For the (ZrO
2)
1−x(Y
2O
3)
x system, this corresponds to
x = 0.08–0.10 [
60,
61]. Further substitution results in a decline in the ionic conductivity, mainly due to defect association that causes a decrease in the mobility of ionic charge carriers. As for other zirconia-based systems, a decrease in σ
O with manganese content in the studied range of solid solution can be assigned, most likely, to coulombic interaction between the point defects, manganese cations
and
and oxygen vacancies
, and formation of complex defect associates. Previously, Appel et al. [
54,
62] suggested the association of manganese ions and oxygen vacancies and the formation of ordered microdomains in Mn-doped 7.5YSZ (5–10 mol.% of MnO
y), based on EELS and electron diffraction studies. Kawada et al. [
19] found that the ionic conductivity in Mn-substituted 8YSZ in air increases with manganese substitution of up to 4 mol.% of MnO
y, and declines on further substitution; they also attributed it to the defect association at high Mn substitution levels. An additional factor possibly contributing to the decrease in ionic transport with Mn substitution is the strain caused by lattice shrinkage, which may result in an increase in the migration barrier for oxygen ion diffusion [
24].
The behavior of total electrical conductivity vs oxygen partial pressure under oxidizing conditions, in the p(O
2) range between 10
−5 and 1.0 atm (
Figure 10), is an interplay between ionic and electronic contributions to electrical transport, and is defined by dominating charge carriers. For all compositions, the defect equilibrium is governed by
or
where
is the electron-hole, in combination with the electroneutrality condition given by Equation (3). The contribution of electronic transport to the total conductivity in the
x = 0.05 ceramics is only a few percent in air. As a result, the total conductivity of this material shows a moderate increase with reducing p(O
2) due to an increase in the oxygen vacancy concentration, and therefore, ionic conductivity. Similar behavior was reported for 3YSZ with 3.0–7.6 mol.% MnO
y under oxidizing conditions at 1000–1100 °C [
29]. On the contrary, electronic conductivity prevails in the
x = 0.15 sample in air, when electron holes should become the dominant charge carriers. Note that the contribution of polarons by transfer between Mn
3+ and Mn
2+ is less likely, due to the diluted state of manganese cations in the fluorite lattice. Reducing p(O
2) is accompanied by a decrease in
,
p-type electronic transport and the total conductivity. This coincides with the dependencies observed for 8YSZ doped by 6–10 mol.% MnO
y under oxidizing conditions [
20,
24]. The
x = 0.10 solid solution with the electronic transference number close to 0.5 in air exhibits smother variations of σ
total with oxygen partial pressure compared to the
x = 0.15 ceramics. For all compositions, the dependencies of defect concentration and electrical conductivity become weaker at lower temperatures.
Note also that the obtained σ-p(O
2) dependencies under oxidizing conditions agree well with the trends in variation of conductivity and transference numbers during the initial relaxation of as-prepared samples at 900 °C (
Figure 7). Slow oxygen uptake with time is associated with the oxidation of manganese cations, generation of electron-holes and elimination of oxygen vacancies, leading to a decrease in ionic conductivity and an increase in hole transport. Considering the non-negligible and nearly reversible changes of the oxygen content on temperature cycling (
Figure 5), a slow oxygen exchange with the gas phase cannot be a reason for a prolonged equilibration of the samples at 900 °C. The slow processes of defect association and clustering seem to be a more likely explanation, although more detailed studies are required to find the exact reasons.
3.4. Cycling between Oxidizing and Reducing Conditions
Thermogravimetric studies showed that all Mn-substituted 5YSZ powdered samples demonstrate an apparently reversible behavior on cycling between air and 10% H
2-N
2 atmospheres at 900 °C (
Figure 11A). The samples show a slow oxygen uptake with time in air, but nearly instantly lose oxygen upon switching to a reducing atmosphere, and then exhibit a constant weight suggesting a full reduction of manganese cations to a 2+ oxidation state. Switching back to oxidizing atmosphere results in a rapid oxidation to a state corresponding to the mean manganese valence of 2.55–2.60. This is followed, again, by a slow further oxidation.
XRD analysis confirmed that all samples remain single-phase solid solutions with cubic fluorite structure after annealing in 10% H
2-N
2 flow for 24 h at 900 °C (
Figure 1C). The reduction leads to an expansion of the fluorite lattice (
Figure 3) caused by an increase in the average ionic radius of manganese cation on Mn
3+/2+→Mn
2+ transformation. Thermogravimetric studies also confirmed that manganese oxidation state, and therefore the oxygen nonstoichiometry remains constant on thermal cycling in 10% H
2-N
2 atmosphere (
Figure 12A), and that the reduced samples exhibit a reversible behavior on isothermal cycling between reducing and oxidizing atmospheres (
Figure 11B).
Electrical studies demonstrated that reduced Mn-substituted 5YSZ ceramics exhibit essentially p(O
2)-independent electrical conductivity under reducing conditions (
Figure 10). Reduction at 900 °C resulted in an enhancement of total conductivity of
x = 0.05–0.10 ceramics compared to oxidizing conditions; the degree of this enhancement diminishes with decreasing temperature. On the contrary, the
x = 0.15 samples showed a drop in electrical conductivity after reduction at 900 °C, and the extent of this drop became larger with decreasing temperature.
Table 5 summarizes the results of measurements of average oxygen-ion transference numbers using air/(10% H
2-N
2) concentration cells. The results suggest that all Mn-substituted 5YSZ ceramics are ionic conductors under reducing conditions with negligible contribution of electronic transport. Thus, the reduction-induced changes in conductivity are in agreement with the expected changes in the concentration of defects as described by Equations (4) and (5): a decrease in electron-hole concentration and
p-type electronic transport and an increase in oxygen-vacancy concentration and ionic conductivity. Apparently, manganese cations remain in a 2+ oxidation state in the studied p(O
2) range under reducing conditions resulting in p(O
2)-independent total (ionic) conductivity. This is in agreement with the data on manganese oxidation state in doped 9.5YSZ single crystals (Mn content ≤ 0.1 wt.%) determined by combined EPR and optical absorption measurements [
49,
50,
52,
53], and also with the results of thermodynamic modeling of the Zr-Y-Mn-O system [
51].
Figure 12B shows the composition dependence of ionic conductivity in Mn-substituted 5YSZ at 900 °C under reducing conditions. While oxygen vacancy concentration increases linearly with Mn content, σ
O goes through a maximum (2 mS × cm
−1) at
x ~0.10, although still being lower compared to 8YSZ (10 mS × cm
−1 [
58]). This differs from the results obtained under oxidizing conditions where ionic conductivity decreases with increasing Mn content, presumably due to the increasing impact of the defect association. All manganese is in a 2+ oxidation state under reducing conditions, and Mn
2+ cations have a stronger tendency to form dopant-vacancy pair clusters (a lower dopant-vacancy binding energy) compared to Mn
3+ [
63]. The observed maximum of ionic conductivity for
x = 0.10 under reducing conditions may imply the relevance of steric effects, namely lattice expansion on reduction with an impact on the oxygen-ion mobility.
The electrical studies also showed that the reducibility or reduction kinetics of at least bulk samples decreases with reducing temperature down to 700–800 °C. As an example,
Figure 13A compares the σ-p(O
2) data at 700–800 °C for the
x = 0.10 samples reduced under different conditions. The sample preliminary reduced at 900 °C was found to exhibit higher conductivity than the sample reduced at 700 or 800 °C.
Another observation is that treatments under reducing conditions promote certain microstructural changes of the ceramics surface. SEM/EDS inspection of polished
x = 0.10 and
x = 0.15 samples after annealing in 10% H
2-N
2 flow at 900 °C for 240 h revealed the irregular accumulation of MnO
y both at the grain boundaries and at the surface of grains, particularly around and inside the pores (
Figure 14). Segregation of MnO
y was also detected on the surface of ceramics samples after prolonged electrical measurements under reducing conditions at 700–900 °C. It should be noted that the manganese oxide exsolution under reducing conditions was rather surprising given that it was not observed under oxidizing conditions even after longer annealing (
Figure 8B) and that the thermodynamic calculations predict an increase in Mn solubility on reduction [
51]. Nonetheless, the experimental results imply that reducing conditions promote the exsolution of excess manganese from the fluorite lattice, even though the process is sluggish and is likely to be limited to the exposed grain boundaries and surface.
Reduction-induced microstructural changes at the surface seem to be responsible for not entirely reversible changes in electrical conductivity on cycling between oxidizing and reducing conditions. An example is shown in
Figure 13B for the
x = 0.15 ceramics at 800 °C. The sample showed an apparently reproducible variation of conductivity, with a faster decrease on reduction and slower recovery during oxidation. However, the level of conductivity dropped compared to the initial value obtained during initial measurements under oxidizing conditions. Post-mortem XRD analysis of that sample (crushed into powder) still showed the cubic fluorite structure with no evidence of phase impurities.
3.5. Thermochemical Expansion
The dilatometric curves of Mn-substituted 5YSZ ceramics in air exhibit a non-linear behavior, and can be approximated by three segments in the studied temperature range (
Figure 15A). In the low-temperature range below ~400 °C, when the oxygen exchange with the gas phase is frozen, the observed expansion of oxide materials corresponds to the “true” thermal expansion of the lattice originating from the anharmonicity of atomic vibrations. Increasing temperature gives rise to a “chemical” contribution to the thermochemical expansion [
64,
65] associated with the increase in [Mn
2+]/[Mn
3+] ratio on heating due to oxygen losses from the lattice and the reduction of Mn cations, and consequently an increase in their average ionic radius. The changes in the slope of dilatometric curves reflect the corresponding inflections in temperature dependencies of the oxygen nonstoichiometry and the mean manganese valence (
Figure 15A).
In the low-temperature range, the average linear thermal expansion coefficients (TECs) of the Mn-substituted 5YSZ ceramics decrease slightly with increasing manganese content (
Figure 15B and
Table 6), in correlation with changes in the lattice parameter (
Figure 3). On the contrary, average TEC values increase with Mn content in the high-temperature range, particularly above ~850 °C, due to the increasing contribution of the chemical expansion. Still, the average thermal expansion coefficients of prepared Mn-substituted 5YSZ ceramics at 25–1100 °C (
Table 6) is comparable to that of the 8YSZ solid electrolyte (10.7–10.9 ppm/K [
66,
67]), while somewhat excessive expansion at higher temperatures may be useful for buffer interlayers to bridge the gap between TECs of zirconia-based solid electrolyte and oxygen electrode materials including classical (Ln,A)MnO
3+δ (10–13 ppm/K [
67,
68,
69]), state-of-the-art (La,Sr)Co
0.2Fe
0.8O
3−δ (LSCF) (average 14.8–15.4 ppm/K [
69] but up to 22.0–24.5 ppm/K at 700–1100 °C [
70]) or layered Ruddlesden-Popper Ln
2NiO
4−δ-based nickelates (12–15 ppm/K [
71]).
Heating the Mn-substituted 5YSZ ceramics in a reducing atmosphere results in a noticeable expansion between 400 and 600 °C caused by Mn
2+/3+→Mn
2+ reduction (
Figure 16A). After reduction, the materials show moderate dimensional changes on thermal cycling in a 10% H
2-N
2 atmosphere with average TECs at 25–1100 °C even somewhat lower compared to that in air (
Table 6), due to the constant 2+ oxidation state of manganese cations under reducing conditions. The dimensional changes were reversible or nearly reversible on re-oxidation. Interestingly, the contraction of the reduced ceramics on heating in air occurs in two steps, in correlation with the oxygen nonstoichiometry variations in air (
Figure 5), once again implying different oxygen exchange/diffusion kinetics and/or different defect structure in Mn-substituted zirconia at temperatures ≤ 800 °C and ≥900 °C.
Figure 16B shows the linear chemical expansion of Mn-substituted 5YSZ ceramics on reduction estimated from the dynamic dilatometric data on cooling in the corresponding atmospheres, and defined as (L
red− L
ox)/L
ox where L
ox and L
red are linear dimensions of the sample in oxidized and reduced states at a given temperature, respectively. Chemical expansion naturally increases with manganese additions, thus increasing the risk of stresses at the electrolyte/buffer layer interface in a hypothetical SOC configuration when Mn-substituted 5YSZ is applied as an interlayer onto the 8YSZ electrolyte at the fuel side. At the same time, the dimensional changes on the reduction of
x = 0.10 ceramics are comparable to those of fuel electrode materials such as La(Sr)Cr(Mg,Fe)O
3−δ [
72] or highly reduced Sr
0.85LnTiO
3−δ [
73] under similar conditions. Furthermore, the chemical expansion of even
x = 0.15 ceramics is ~3 times lower compared to gadolinia-doped ceria Ce
1−xGd
xO
2−δ (
x = 0.1–0.2), a conventional buffer layer material which exhibits a linear expansion of up to ~1.2% on reducing p(O
2) from atmospheric to ~10
−20 atm at 900 °C [
74,
75].