Author's Accepted Manuscript: J. Malzbender

VLHENMA HKI 18-19 BBKH 1.
Author’s Accepted Manuscript
Mechanical aspects of ceramic membrane materials
J. Malzbender
www.elsevier.com/locate/ceri
PII: S0272-8842(16)30074-8
DOI: http://dx.doi.org/10.1016/j.ceramint.2016.02.136
Reference: CERI12327
To appear in: Ceramics International
Received date: 29 January 2016

Accepted date: 23 February 2016
Cite this article as: J. Malzbender, Mechanical aspects of ceramic membran
m a t e r i a l s , Ceramics Internationa
http://dx.doi.org/10.1016/j.ceramint.2016.02.136
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NGUYỄN ANH PHƯƠNG – 16146449 1

VLHENMA HKI 18-19 BBKH 1.5
Mechanical aspects of ceramic membrane materials
J. Malzbender
Forschungszentrum Jülich, IEK-2, 52425 Jülich, Germany
Abstract
Interest in ceramic transport membrane materials has increased significantly leading also
questions with respect to mechanical reliability and robustness, requiring knowledge of the
mechanical properties. The current review focuses on the mechanical properties of such
ceramics, emphasizing in particular relationships between mechanical properties, non-elastic
effects, phase changes and materials’ stability. Room and elevated temperature application is
considered with a main emphasis on elastic and creep deformation as well as fracture.
Consideration is given to dense membranes as well as porous substrate materials for advanced
asymmetric concepts. Properties are summarized for selected oxygen and proton conductors.
Furthermore, mechanical properties of some selected porous ceramic and metallic substrate
materials are given. In addition to the failure probability associated with the Weibull
distribution of fracture stresses, creep rupture of dense materials and enhanced creep
deformation of porous materials are aspects that need special consideration in the application
of these materials in gas separation systems.
Keywords: Ceramics, membranes, mechanical properties, stability, fracture
1. Introduction
Mixed ionic–electronic conducting (MIEC) materials operating at high temperatures have,
since they provide high counteractive mobility of ions and electrons, high potential for the use
in advanced electrochemical systems, in particular, as oxygen transport membranes for
oxygen separation from ambient air and potential use combustion in pure oxygen in Oxy-fuel
1 2 3 4 5
power plants [ ] and [ ] in catalytic membrane reactors [ ], [ ] and [ ], and as a cathode in

6
solid oxide fuel cells (SOFCs) [ ]. Oxygen production using ceramic mixed ionic–electronic
conducting membranes can be a cost-effective alternative to cryogenic methods. Since H 2-
related technologies gain growing attention due to the increasing importance of H 2 as the
environmentally friendly energy source of the future with great social impact and economical
7
relevance [ ], selected proton conductors are also considered in the current work.
Among many available MIEC compounds mainly two groups of materials, the perovskite ABO 3-
type and the fluorite AO2-type structure [3], appear to have the most promising oxygen
permeation properties. In fact, cubic SrCo 0.8Fe0.2O3−δ was found to exhibit the highest oxygen
8
permeation flux values among the perovskite-structured materials [ ]. Since phase stability of this
compound appears to be an issue, Sr was partially replaced in later works. Currently, the most
9
promising membrane material due to its high oxygen permeation rates [ ] is
Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCF). However, it appears not to be chemically stable under high
oxygen chemical gradients (e.g. air/methane) and against CO 2, hence, it can only be used in Oxy-
fuel process without flue gas recirculation, i.e. a three-end concept where no contact between flue
10
gas and membrane occurs without presence of CO 2 [ ]. La0.6Sr0.4Co0.2Fe0.8O3-δ and the variation
11
La0.58Sr0.4Co0.2Fe0.8O3−δ (LSCF) have lower permeation rates than BSCF [ ], but are expected
12
to be stable under CO2 containing atmospheres [ ]. Recent the potential of oxygen separation by
monolithic doped/multidoped ceria membranes has been shown, where in particular, gadolinium
doped ceria (Ce0.9Gd0.1O1.95−δ, CGO) was suggested as oxygen transport material for syngas
13 14
applications [ , ]. Among the fluorite-structured materials, 20% Pr-doped CeO 2−δ is reported to
possess one of the highest permeation fluxes
[9]. However, this material has a very large chemical expansion at elevated temperatures,
which might result in mechanical reliability issues under application conditions. Such
unfavorable chemical-expansion effects can be reduced by partial replacement of Pr-doping
15
with Gd [ ]. However, this modification decreases ionic and electronic conductivities.

Lanthanum tungstate LaxWO3+1.5x ( , LaWO) is a promising membrane candidate for a
16
temperature range 600-800 °C [7, ]. LWO has an appreciable chemical and (hydro-)thermal
stability, as well as high values of mixed proton-electronic conductivity [7], which are
advantageous for its application, especially under highly reducing and sulfur-containing gas
17
environments. Nd5.5WO11.25−δ has been suggested as alternative material [ ].
Within the bulk-diffusion limited permeation range, the oxygen flux is inversely proportional
to the membrane thickness. Hence, advanced membrane designs are based on thin, defect-free
18
membrane layers mechanically supported by porous substrates [9, ]. The porous substrate
should provide mechanical stability of the membrane structure, since application-related
loads, related to thermal or chemical strains, pressure gradients between feed and permeate
side, cannot be sustained by a thin membrane layer. In order to reduce the materials’ costs for
such a solution, especially with respect to the amount of very expensive oxides, MgO or
19 20
Al2O3 are alternative substrate materials or ferritic steels [ , ]. Where obviously in addition
to the chemical strain of the dense membrane also the thermal expansion mismatch of layer
and substrate needs consideration. In order to limit the review chemical and thermal
expansion is not reviewed in the current work, data can be found for example in [9].
Micromechanical properties are usually assessed via indentation testing, yielding elastic moduli
21 22 23 24 25
[ , , , , ], an important parameter for analysis and simulation of stress states and from length
of indentation induced cracks, as measure of crack growth behavior, the fracture toughness of the
26 27
material [ , ]. Long-term reliability of the component is obviously an important aspect, which
depends on the mechanical properties of membrane materials and in the case of supported
28 29 30 31
structures, also on the properties of substrate materials [ , , , ]. With respect to failure, the
fracture strength of materials is typically characterized, requiring an

assessment of fracture stresses using different methods (where mostly experimentally simpler
bending methods are preferred) and a subsequent statistical analysis via a Weibull approach
32 33 34
[ , , ]. Such data are representative for the material in a particular geometry and loading
state, hence to assess the reliability in application rescaling of the strength to the different
loading situation and geometry via effective volumes or areas is necessary (depending if
35 36
volume or area defects) [ , ]. Reliability does not only depend on the initial strength, but
37
also on subcritical crack growth (SCG) [ ]. The associated correlation between loading rate
and strength is important to assess effects associated with thermally induced stresses of start-
up and shut-down process of units and can be used as a basis for a strength–probability–time
(SPT) lifetime prediction, incorporate the time dependence of strength into failure statistics,
and as basis to assess failure relevance of transient and service stages. Another important
thermo-mechanical aspect with respect to structural stability at elevated temperatures is creep
38 39
resistance [ , ]. A strain of 1 % per year in a compressive mode has been suggested [15] as
a tolerable creep rate to warrant long-term structural stability in membrane application.
The aim of the current review is summarize elastic and fracture properties, with emphasis on
origins of anomalies, sensitivity to subcritical crack growth and creep behavior of fluorite-and
perovskite-based dense ceramic MIEC membranes and possible substrate materials. Porosity
is known to have a large effect on the mechanical properties and is therefore discussed where
data on dense and porous state are available.
2.1. BSCF and BSCFZ
The perovskite-structured barium strontium cobalt iron oxide (Ba–Sr–Co–Fe–O) has attracted a
lot of attention as a promising candidate material for oxygen separation membrane applications
and also as novel cathode material for intermediate-temperature solid oxide fuel cells [9], where
among various compositions, Ba0.5Sr0.5Co0.8Fe0.2O3−δ (BSCF) has emerged to

be one of the best candidates for both applications [8], indicating the importance of oxygen
non-stoichiometry and B-site cation valence.
The observed high permeation rates are mainly attributed to oxygen vacancies in the cubic
40
perovskite structure [ ], whose amount significantly increases with temperature. However, in
order to be economically justified, oxygen transporting membranes (OTMs) and SOFCs

should operate at temperatures between 773 and 1123 K. Permeation rates in this temperature
range show a degradation which is attributed to a partial phase decomposition of the cubic
41
structure into a hexagonal phase [ ], where the change of radius and spin state of Co is the
main driving force for this phase decomposition. Many scientific studies were performed in
42
order to find a way to eliminate this effect. One promising solution [ ] seems to be the partial
substitution of B-site cations by fixed-valent cations which counteract the radius decrease
3+
during the oxidation to low-spin Co , where the optimal partial substitution to preserve long-
term stability of the cubic structure can be achieved by doping with 3 mol% of zirconium,
which results in chemical composition Ba0.5Sr0.5(Co0.8Fe0.2)0.97Zr0.03O3−δ (BSCFZ).
Several studies concentrated onto mechanical properties of BSCF, in particular fracture and high-
temperature creep [15,24,29,37,38,39]. For real components the mechanical integrity of this brittle
perovskite will be challenged by the boundary conditions of transient and stationary temperature
exposure. In particular, long-term failure mechanisms such as static room temperature fatigue and
creep rupture at operation temperature may occur. Anomalous mechanical behavior observed at
43 44 45 46
rather low temperatures [ , , , ] was attributed to a spin-state transition of B-site ions.
Detailed results and implications are discussed in the following.
2.1.1. Elastic and fracture behavior

Different mechanical testing methods have been used to assess the elastic behavior of the
47
mixed ion electron conducting perovskite BSCF in [ ]. Different experimental methods were
applied for disc shape and tubular geometries from RT to 900 °C on materials provided by
different suppliers. The preparation method, i.e. extrusion as compared to hot pressing did not
influence the materials properties. Although the stress field in terms of the combination of
compressive and tensile stresses as compared to pure compressive stress differed in the used
tests, there was overall agreement with respect to the determined elastic properties as well as
its temperature dependence, implying that the material does not experience a stress dependent
stiffness changes under the testing conditions.
Elastic modulus and internal friction of (BSCF) were determined from resonance frequencies
and damping behavior, respectively, using an impulse excitation method in [46]. An elastic
anomaly around 476 K, with a corresponding peak in the internal friction, was attributed to an
3+
experimentally confirmed spin transition of Co in agreement with finding reported in [44]
based on ring-on-ring tests and depth-sensitive micro-indentation. Measurements of the
thermo-mechanical properties with ring-on-ring test and depth-sensitive micro-indentation
testing revealed an anomaly between 200 °C and 400 °C also in fracture stress and toughness
(Fig. 1) [44,45,46]. At higher temperatures the properties increased.
The effect of subcritical (slow) crack growth at room temperature has been investigated using
fracture stresses obtained in biaxial bending under different loading rates in [37,29]. The
provided data permitted to assess the fracture stresses for different loading rates. Furthermore,
a strength–probability–time plot (SPT in Fig. 2) was derived that permits a prediction of the
lifetime under static loading conditions and hence the long-term reliability at room
temperature. The provided fracture data permit an assessment of the fracture stress in a fast
loading situation. For example in a rather fast loading situation (3 MPa/s) the fracture stress

for a failure probability of 1 % will be ∼46 MPa implying that the material will sustain this
stress if loaded within 15 s. Slower loading decreases this stress, faster loading increases it. In
a loading situation under constant load the failure probability has been assessed using the
strength–probability–time analysis, for example for a failure probability of 1 % this yields a
tolerable stress limit of 25 MPa if a lifetime of 40 years is envisaged. The results imply a
rather low risk of failure for BSCF due to subcritical crack growth.
2.1.2. Porous BSCF
The mechanical stability of porous BSCF material was studied using depth-sensitive micro-
48 49
indentation and ring-on-ring biaxial bending in [ , ]. The porous BSCF was characterized as
potential substrate for the deposition of a dense membrane layer. Indentation tests yielded
values for hardness and fracture toughness up to a temperature of 400 °C, while bending tests
permitted an assessment of elastic modulus and fracture stress up to 800 °C. In addition, the
fracture toughness was evaluated up to 800 °C via bending tests of pre-indented specimens.
Compared to dense BSCF, fracture stress and elastic modulus of porous BSCF (porosity ∼38
%) are ∼50–60% lower for the entire temperature range. At 800 °C fracture toughness values
of porous and dense material are similar. The temperature dependencies of elastic modulus,
fracture strength and toughness were similar to those of dense BSCF (see Fig. 3).
Porous and dense BSCF ceramics were also characterized with respect to their mechanical
behavior and failure limits at room temperature in [29]. Porous materials seemed to be less
sensitive to subcritical crack growth, which might be associated with pores blunting the crack
tip. SPT analysis yielded for porous BSCF a tolerable static stress of 9 MPa (lower than dense
BSCF due to porosity) for a failure probability of 1 % if a lifetime of 40 years is envisaged.
2.1.3. Intermediate temperature anomalies

Up to 200 °C all characteristic mechanical parameters decreased; at high temperatures they
3+
increased. This anomaly agreed with an experimentally confirmed Co spin transition
[43,46]. Detailed thermal expansion measurements along with magnetic as well as
50
conductivity behavior characterizations in [ ] indicated that the temperature dependence of
BSCF properties can be divided into six phases, i.e. five transitions: (I) ~200 K, (II) 200~350
K, (III) 350~500 K, (IV) 500~800 K (V) 800~1050 K, and (VI) 1050~1273 K. The latter three
phases (IV, V, and VI) have been the focus of the earlier studies and attributed to a spin-state
3+
transition of Co , whereas the former three phases (I, II, and III), especially I and II,
appeared to be related to valence and spin-state, since being represented in the susceptibility.
2.1.4. Creep
Although the material clearly exhibits an apparent creep deformation at room temperature
51
[ ], this low temperature creep rate is rather small and will most probably not cause serious
problems for the high-temperature use of BSCF. The influence of the partial cubic-to-
hexagonal phase transformation of BSCF on the elevated temperature creep behavior was
investigated in [38,39] in air in the temperature range 750–950 °C. Arrhenius plots of the
creep rate revealed a significant hysteresis effect. During heating, the creep rate changed
slightly up to ~850 °C and increased substantially above this temperature. Upon cooling from
950 °C it decreased in a nearly linear manner to temperature (see Fig. 4). Microstructural
investigations supported that the hysteresis is linked with the growth and transformation
kinetics of a hexagonal polymorph at the boundaries of cubic BSCF grains. Creep rates under
reduced oxygen partial pressures were significantly higher due to the absence of these
secondary phases. The temperature dependent creep rates demonstrated strong influence of
the hexagonal phase on the creep. It was suggested that, with appropriate thermal treatment,
the presence of the hexagonal phase, which deteriorates the permeation, might be avoided.

2.1.4.1. Creep rupture
Creep rupture at typical operating temperatures was analyzed in [37] using three-point
bending tests at 850 °C and 900 °C, permitting a determination of the failure stress in this
combined tensile–compressive mode. The creep rupture data were described by a modified
Monkman–Grant relationship. The creep rupture duration and hence creep survival time
decreases considerably with temperature and applied stress (Fig. 5). A temperature increase of
50 K reduces the rupture time by a factor of ∼5–10. Under this combined tensile–compressive
creep mode, an apparent failure strain of ∼40 % was estimated. However to operate the
component for 40 years the applied stress at 850 °C should be less than 0.4 MPa. For a
temperature of 800 °C the respective stress limit was estimated to be approximately 4 MPa.
C-ring creep tests in [38] revealed the formation of cavities along the grain boundaries normal
to the tensile stresses that ultimately might lead to creep rupture. Note that, whereas under
compressive loading creep strains of ∼1 % per year might be sustained, a strain of ∼0.2 % can
already lead to damage under tensile loading. A tensile creep rupture test has been developed
52
in [ ], based on the application of tensile stresses at elevated temperatures, where only a
limited central length of the tubes was heated and cold ends clamped. Figure 3.c presents
creep rupture times for two tests on BSCF tubes. Based on the BSCF bending test failure,
significantly longer rupture times would be expected, i.e. failure at ~ 375 h should occur in
four-point bending for a bending stress of almost 25 MPa. The time to rupture will be affected
by the stress gradient in the case of four-point bending, hence leading in this case to a less
critical situation or in other words, in the case of a tensile test to a more critical situation and
rupture occurs for similar times under almost 50 % reduced stresses.
2.1.5. Zr doped BSCF

BSCF suffers from partial decomposition of cubic to hexagonal polymorphs at ∼825 °C,
associated with a significant oxygen permeation drop [40,41]. Partial B-site substitution with 3
mol% zirconium has been suggested as one solution for transformation suppression [42].
Thermo-mechanical characteristics of Ba0.5Sr0.5(Co0.8Fe0.2)0.97Zr0.03O3−δ (BSCFZ) were
53
assessed and compared to BSCF data in [ ]. Elastic moduli and fracture strengths of BSCFZ
showed similar temperature dependencies with lower absolute values. The creep deformation
was found to be similar for both materials. Slight differences in mechanical properties of
BSCF and BSCFZ were most likely a result of different production procedures also being
reflected in the microstructures and not necessarily induced by the Zr doping.
54
In another study the dopant level was varied [ 54], i.e. BSCF-Z100·x (x = 0, 0.01, 0.03, 0.05
and 0.1). Diffusional creep was confirmed as the predominant creep mechanism for T ≥ 850
°C. This was supported by the high activation energies and low stress exponents observed for
steady-state creep, and by the fact that the grain-size-normalized creep rates of the different
compositions coincided within the limits of experimental uncertainty (see Fig. 6).
Creep characteristics of dense BSCFZ and its dependence on the secondary phase have been
55
extensively analyzed in [ ] indicating that creep behavior of both BSCF and BSCFZ at
temperatures below 850 °C depends on the thermal history of the tested specimen (see also
Fig. 4). The analyses indicated possible existence of secondary phase even at 950 °C and
proved a nonlinear creep rate – temperature dependence in both heating and cooling
sequences, which are associated with a change of the secondary phase amount.
The creep deformation of porous BSCFZ was found to be larger than for the dense material,
where the difference between the results for porous and dense material increased with

increasing temperature (see Fig. 5 [55]), indicating that an operation of dense membrane layer
on a porous substrate might be difficult above the dissolution limit of the hexagonal phase.
2.1.6. Post-operational inspection

56
On the contrary to the annealing studies [ ], that revealed the formation of hexagonal phase
only in air, the studies of operated tubes confirmed hexagonal phase also on the vacuum side,
which appears to be related to oxygen transport. Fractographic investigations suggest that the
thermal exposure of BSCF under application relevant conditions can lead to crack initiation
(see Fig. 8) and eventually failure (i.e. proofing the importance of mechanical
characterization), which could be avoided by a modification of the operation procedure.
2.2. LSCF
La0.6Sr0.4Co0.2Fe0.8O3−δ and La0.58Sr0.4Co0.2Fe0.8O3–δ (due to its similar properties abbreviated
LSCF) perovskite-type oxide are well known for their high elevated temperature electronic and
57
good oxygen ionic conductivity [ ], which qualifies the material for application as cathode in
58 59
solid oxide fuel cells [ ] and oxygen transport membrane (OTM) [ ]. Especially in the case of
SOFCs the material lead to large success in the reduction of degradation effects and long term
60
operation [ ]. Although yielding lower permeation than BSCF [11], for membrane application it
is expected to be more thermo-chemically stable with respect to CO 2 exposure and does not show
formation of secondary phases at elevated temperatures [59].
A number of reports exist on its mechanical properties, in particular fracture and elevated-
61 62 63 64 65 66
temperature creep [29,45,46,50, , , , , , ]. Again mechanical integrity will be challenged by
transient and stationary temperature exposure and long-term failure mechanisms such as static
room temperature fatigue and creep rupture. Due to its rhombohedral room temperature

67
structure, ferroelastic deformation and domain switching occurs at low temperatures [ ] and a
phase change to a cubic structure at operation relevant temperatures [61,62,50,46].
2.2.1. Elastic and fracture behavior
Polycrystalline LSCF revealed in bending tests a non-linear deformation behavior at room
temperature and a linear one at elevated temperatures (≥ 800 °C) [61,62]. The non-linearity
originates from ferroelastic domain switching in grains with rhombohedral symmetry (see Fig.
9). Such domains cannot form in the cubic structure that exists at elevated temperatures.
The stiffness as measured via bending tests showed an increase of about 50 % above 600 °C
and 700 °C in vacuum and air [61,62], respectively. Elastic moduli determined from
resonance frequencies exhibited an anomaly between 473 and 1113 K [46], which was
68
attributed to the transition from rhombohedral to cubic symmetry, see also [ ]. The
mechanical deformation of lanthanum strontium cobalt ferrite under uniaxial compression was
investigated at various temperatures in [64]. The material revealed a rather complex
mechanical behavior related to its ferroelasticity and stress–strain curves obtained in the 1st
and 2nd loading cycles were completely different. Susceptibility measurements indicated that
69
LSCF is in a ferromagnetic state below ∼220 K and paramagnetic above ∼250 K [ ]. The
fracture stress decreases about 10 % from RT to 200 °C, and increases again from 200 °C to
700 °C to values slightly higher than at RT [61,62]. Temperature dependency of elastic
modulus, fracture strength and fracture toughness were in good agreement [46]. With respect
to subcritical crack growth, SPT predictions indicated that dense LSCF might tolerate a static
stress of 35 MPa for 40 years, with a failure probability of 1 %, being similar to BSCF [29].
Whereas it was explicitly shown in [65] that data and temperature dependence of LSCF60
agrees with reported results for LSCF58, LSCF38 behaves differently, especially in terms of

the temperature dependence of the elastic modulus (see Table 1). Lower strength and Weibull
moduli determined for LSCF38 suggest that improvement of production and processing are
necessary. Weibull moduli appeared to decrease at elevated temperatures for dense materials.
2.2.2. Porous LSCF
The porosity effect on elastic modulus and strength appears to be similar for LSCF as reported
for BSCF [65], very low characteristic strengths (see Table 1) led to low tolerable stresses for
long term exposure to static loads for porous LSCF [37], where the overall elevated
temperature behavior agreed with that observed for the respective dense variant [65]. A rather
low Weibull modulus for the porous material was associated with the used tape casting [65].
2.2.3. Ferroelastic domains and ferromagnetic–paramagnetic transition
Reports indicated LSCF comprises at RT of rhombohedral and cubic phase, with a cooling
rate and atmosphere dependent ratio [62]. Purely rhombohedral material was obtained with
low cooling rates; purely cubic by fast cooling in air or slow cooling under vacuum. SEM and
TEM verified a domain structure in rhombohedral grains [62,67]. Direct SEM observations
verified the influence of the stress on domain switching (see Fig. 9). In-situ TEM observations
on a heating stage verified the limited thermal stability of domains. Mechanical stresses cause
domain switching being reflected macroscopically in non-linear deformation behavior [64].
Associated with the ferromagnetic–paramagnetic transition around 250 K, the thermal
expansion coefficient possesses its minimum and increases by almost a factor of two from 250
K to 350 K (below to above RT). Thermal expansion, susceptibility and conductivity display
monotonic changes with increasing temperature from 350 K to 800 K, whilst the conductivity
started to decrease and α demonstrates a drastic increase around 800 K due to the oxygen loss
accompanied by the reduction of the transition metals [19].

2.2.4. Creep
A distinctive ferroelastic creep that due to its low magnitude should not endanger the
application of the material was observed at 293 K in [64], whilst typical ferroelastic stress–
strain curves were obtained in the temperature range from 473 K to 873 K.
The creep behavior of dense La0.58Sr0.4Co0.2Fe0.8O3−δ (LSCF) perovskite was studied in the
temperature range 750–950 °C in air and vacuum (PO2 ≈ 4 mbar) in [63]. A transition in the
apparent activation energy was found between 800 and 850 °C for both oxygen partial
−1
pressures. The apparent activation energy is ∼250 kJ mol for the temperature range 700–
−1
800 °C under vacuum (PO2 ≈ 4 mbar) and ∼480 kJ mol for 850–950 °C in both
atmospheres. Above 850 °C, the creep rate of LSCF is higher in vacuum than in air although
the same cubic structure exists. The stress exponent of the creep law is in the range 1.9–2.5
for all temperatures, which excludes a transition of creep mechanism. It is suggested that,
below 800 °C, cation vacancies originate from the necessary balance with the substituted
cations in LSCF, and the determined activation energy reflects the energy barrier for cation
migration via these vacancies. Above 850 °C, additional vacancies appear to be formed
intrinsically, and the activation energy represents the sum of the thermally activated formation
energy of cation vacancies and migration energy of cations. A single creep rupture test on
dense LSCF in [37] indicated that this material is less prone to creep rupture than BSCF.
2.2.4.1. Creep of porous LSCF
Porous LSCF creep was studied in [66] in the temperature range 750 to 950 °C. The creep
exponent was between 3.0 and 3.9 in the stress range 15–30 MPa, which is higher than that
reported for dense LSCF (1.9–2.5 [63]). The activation energy from 800 to 950 °C was ~530
kJ/mol (dense LSCF ~480 kJ/mol [63]). The ratio of creep of porous to dense material

increased progressively with increasing temperature (see Fig. 7) that might be related to
surface diffusional effects. Additional tests at room temperature revealed non-linear stress-
strain curves and a ferroelastic creep similar as for dense LSCF due to domain switching.
Since the creep deformation appeared to exceed an acceptable level [15], a strategy for
reduction of creep deformation could be a decrease of operation temperature or pressure ratio.
Both will reduce the oxygen flux through the membrane. In order to compensate the creep, a
smart design of the support might be an option as reported for a new generation supports with
70
straight pore channels perpendicular to load direction, freeze drying manufactured [ ].
2.2.5. Post-operational inspection
Interesting with respect to mechanical behavior is also a study on strontium surface
71
segregation for LSCF annealed with and without uniaxial compressive loads [ ]. In both
cases, surface segregation of Sr-rich phase was clearly observed on grain boundaries. The size
of segregated particles increased with increasing annealing time. The number of particle was
fewer, whereas the particle size was larger for a compressed sample, which was attributed to
grain-boundary sliding as well as Sr diffusion aiding high-temperature creep deformation.
The effect of the partial pressure difference on the mechanical behavior of LSCF is reported
72
in [ ] for samples annealed under an oxygen gradient. The mechanical properties of cross-
sections were characterized using indentation testing. Chemical strains for BSCF and LSCF
were too small to detect them after cooling to RT by XRD; however, the results suggest that
the indentation crack length is affected by chemical strains for LSCF, but not for BSCF. An
anisotropy of the indentation crack length and corresponding apparent fracture toughness was
related to interaction of domain switching and residual strain that was also associated with the
−5
observation that vacuum (10 mbar) annealed LSCF showed surface cracking on heating in

air (see Fig. 10), whereas for BSCF such fracture features were not observed. In this light,
components made form LSCF may fail during start-up or shut due to internal stresses.
2.3. STF
Recently, the cubic perovskite SrTi 1-xFexO3-δ (STF) has been identified as a promising stable
73
membrane material [ ], compositions, especially with high iron content, exhibit high ambipolar
conductivities and oxygen surface exchange kinetics comparable to LSCF. Compressive creep
74
tests on STF (x = 0.3, 0.5 and 0.7) in [ ] yielded activation energies (341– 477 kJ mol−1) and
stress exponents in the temperature range 800–1000 °C and stress range 10–100 MPa. Results
indicated that steady-state creep rate is mainly limited by cation lattice diffusion. For STF50 and
STF70, the stress exponents are ~1.1–1.5. For STF30, however, they are in the range 2.0–2.4,
suggesting a contribution of dislocation creep. Creep rates (Fig. 11) were similar to LSCF and
LSC; but significantly lower than for BSCF and BSCFZ.
2.4. CGO
With respect to chemical stability, cerium oxide and doped cerium oxides are promising
materials for membrane applications. Ce0.8Gd0.2−yPryO2−δ membrane materials and the
75
influence of an addition 2 mol% of CoO was assessed in [ ]. CGO material showed
significantly higher elastic modulus and fracture strength compared to LSCF and BSCF as
reported in [29]. Materials preparation and compositional variations were compared with
respect to elastic modulus, hardness and fracture toughness [75]. Overall, the elastic modulus
of ceria-based ceramics was only slightly affected by the Gd- and/or Pr-doping and the
differences in elastic properties resulted mainly from the variations in material porosity.
Fracture toughness of the Gd- and Pr-doped materials, measured locally with the aid of
indentation, appeared to reduce with increasing temperature. This temperature-dependent

behavior was not reflected, however, in fracture toughness measurements carried out using an
indentation-strength method, which are more representative for the global properties.
Critical strains of CGO estimated fracture strength and elastic modulus in [19] increases
slightly with increasing porosity (see Fig. 12), which might be a result of crack tip blunting by
pores. Although both dense and porous CGO indicated a higher sensitivity to subcritical crack
growth [29], the allowable stress for a 40 years static load at room temperature conditions was
comparable to the data obtained for porous BSCF and LSCF.
The creep behavior of doped and undoped cerium oxides was assessed in [75]. Values of the
activation energies ranged between 50 and 160 kJ/mol, being very close to the activation
energy of oxygen self-diffusion in Ce1−xGdxO2−0.5x. The stress exponents suggested diffusion-
or a combination of diffusion- and dislocation-related mechanisms. Creep properties of the
cerium oxides without Co-doping appeared to be superior to Co-doped material.
2.5. CTF
Creep of Ca0.5Sr0.5Ti0.6Fe0.15Mn0.25O3-δ and CaTi0.6Fe0.15Mn0.25O3-δ have been characterized in
[14]. Fig. 13 shows the creep rate along with literature data on other relevant membrane
materials. CTFMn25 exhibits a high creep resistance. LSCF and BSCF/BSCFZ exhibit higher
creep rates with similar activation energies [63,55]. Evaluation of the creep data on CTFMn25
revealed a stress exponent of 1.5, implying that creep was dominated by a diffusional
mechanism. The determined activation energy of 5.1 ± 0.4 eV excluded oxide ions as the rate
controlling species [16] and implied that cation diffusion is rate controlling for creep in these
materials. The creep data on CTF10 exhibited a stress exponent of 1.6 and activation energy
of 4.4 ± 1.1 eV, which implies a similar creep mechanism as for CTFMn25. Considering the

significant porosity of the CTF10 specimen and rather similar grain sizes, the lower creep rate
of CTF10 indicated a decrease in creep resistance with Mn-doping for CTFMn25.
A three-dimensional defect study was carried out on porous CaTi 0.9Fe0.1O3−d ceramic
membrane material as a model study for the use of computed tomography in microstructural
76
analysis and mechanical characterization in [ ]. Exemplified for CaTi0.9Fe0.1O3−δ ceramics,
the study showed that three-dimensional visualization, data extraction and statistical analysis
make the computed tomography clearly advantageous in defect analysis over the commonly
used fractography. Although strength data implied that materials production and processing
required further improvement, it was verified that CT data can be used for numerical
simulation and hence for a direct assessment of the material behavior under realistic loading
configurations. The study also showed that information on microstructures and defects can
lead to misleading conclusions if the loading via FEM is not considered, since geometrical
imperfections can become more important than the defects. It was concluded that, in general,
if a material’s requirement is to possess pores and if they are the failure-relevant defects, finer
pores, compensated by their higher amount to reach the same porosity, are more desirable.
2.6. LNO
77
La2NiO4+δ (LNO) has been suggested as a rather chemical stable membrane material in [ ].
A strong change of elastic modulus and internal friction observed for dense LNO between RT
and 100 °C was attributed to an orthorhombic-tetragonal transition. No further indication of
phase transition could be observed up to 950 °C. An increase of fracture stress of porous
La2NiO4+δ from 700 to 900 °C was attributed to the primary creep. Oxygen was continuously
released from ~400 °C up to 1000 °C with a stable thermal expansion coefficient.
2.7. LWO

La5.4WO12-δ (LWO) was studied in [78]. The room temperature Young’s modulus was ~ 130
GPa, independent of grain size, with a decrease by ~ 20 % up to 1000 °C. Ring-on-ring
bending test yielded a characteristic strength of 59 ± 3 MPa. It was shown that a factor ~ two
higher strength value could be obtained for more homogeneous microstructure. Large
agglomerates, irregular pores and pore zone areas were identified as strength limiting flaws by
fractography analysis. The strength was found to decrease by ~ 30 % up to 1000 °C. An
unexpected strength increase by ~ 4 % at 400 °C was observed. Complementary annealing
studies indicated a relationship to the onset of chemical / thermal expansion, where longer
annealing led to lower strength values. The strength was independent of the loading rate;
hence, LWO does not seem to be prone to subcritical crack growth effects. Creep appeared to
be governed by cation diffusion as the predominant mechanism. Creep parameters were n =
1.2 ± 0.3, p = 1.3 ± 0.4 and Qa = 370 ± 120 kJ / mol in the temperature and stress range 1050
– 1450 °C and 20 – 63 MPa, respectively. Creep experiments did not reveal any significant
change in the creep rates under different atmospheres.
2.7.1. Porous LWO
The mechanical properties were determined for La 5.4WO12-δ for an application relevant porosity
range 30 – 40 % [78]. It was shown that elastic modulus, hardness and strength decrease with
increasing porosity. Strength values decreased almost linear with increasing porosity. The
Weibull modulus was in the range 8-16 indicating a homogeneous flaw distribution. For
specimens with low fracture stresses rather large pores were identified as failure origin. The
secondary phase La6W2O15 in the surface resulted in lower strength values.
2.8. NWO
Creep results of single phase cubic Nd 5.5WO11.25−δ (NWO) with ~ 8% porosity and fine grains
(grain size 1 ± 0.5 μm, elastic modulus 125 ± 5 GPa) are reported in [78]. Deformation rates

were obtained at T ≥ 1050 °C. An average stress exponent of n = 1.3 ± 0.2 and an activation
energy = 540 ± 30 kJ/mol suggested a diffusional creep mechanism. The stress exponent
increases above 1150 °C. Overall, NWO55 shows higher creep rates and higher activation
energy than LWO, former being associated with a smaller grain size.
2.9. Alternative substrate materials
Although it is often preferred to use identical materials for membrane and porous substrate to
reduce thermal expansion mismatch, due to materials cost alternative materials might be used.
2.9.1. MgO
Advanced design concepts for the application of oxygen transport ceramic membranes are
based on thin layers supported by porous substrates, where porous MgO has been suggest.
The effect of sintering conditions on porosity and mechanical properties, i.e. elastic modulus
and fracture stress as function of temperature are summarized in [19] for planar and tubular
geometry. O-ring and ring-on-ring bending test yielded similar characteristic fracture
strengths (~ 40 ± 7 MPa), whereas the elastic modulus decreases slightly with increasing
testing temperature. Data were in agreement with literature values for porous ceramics. The
addition of boehmite appeared to enhance the materials strength. An estimate of the fracture
toughness was also given. A linear increase of the elastic modulus with increasing sintering
temperature was observed, associated with a porosity reduction.
2.9.2. Al2O3
Aiming at the use in pre-combustion systems, alumina substrate with different pore sizes were
characterized with respect to their mechanical properties in [20]. Although porosity of the
micro- and nano-porous materials (see Fig. 14) were equal, bending test assessed elastic
moduli and fracture stress values revealed significant differences, indicating that based on

mechanical considerations a nano-porous material is far superior. Microstructural
investigations supported that the higher strength of the nano-porous material is a result of a
larger contact area between grains. The nano-porous material appears also to be superior to
other membrane substrate suggested in literature (see Table 2), indicating the potential of
nano-porous materials for the use as porous substrates. However, initial permeation tests
indicated that the nano-porous substrates lead to an approximately one decade lower flow rate
that the micro-porous substrate material [20]. This will lead to a higher flow resistance and a
higher risk for concentration polarization. Hence for the application as membrane substrate an
optimization that considers both mechanical aspects and flow rate is required.
2.9.3. Metallic substrates
In an application as porous substrates for oxygen transport membranes, the alloy will be
exposed to temperatures of 700 to 900 °C for long durations, raising high demands in
particular with respect to corrosion resistance and creep. The necessary porosity will leads to
a reduction in elastic modulus and enhanced creep. A higher elastic modulus of the substrate
compared to the ceramic layers can be favorable as crack propagation in the ceramic layer
79 80
becomes less likely (see also [ , ]). The typically rather large creep deformation of steels at
elevated temperature might be problematic for the structural stability of the component,
although creep can relax stresses that might result from differences in thermal expansion.
From creep rates measured for dense FeCrAl alloy, the highest applied stress to stay below
this limit suggested in [79] of 1% strain per year is 11 MPa at 700 °C, 5 MPa at 800 °C, and 3
MPa at 900 °C. A membrane during operation can be exposed to an applied stress of 30 MPa
81
[ ] leading to very challenging conditions for long-term operation of a metal-supported
component at high temperature.

ITM has verified its excellent performance as interconnector material for SOFCs in the so far
longest ever operated SOFC stack (> 70,000 hours) that is still under operation [60]. Hence it
is obviously also a promising materials as porous mechanical support for membrane materials
82
[ ]. The temperature dependence of mechanical properties, i.e. Young´s modulus, ultimate
tensile strength (UTS), Poisson´s ratio, coefficient of thermal expansion and creep behavior
have been compared for dense and porous ITM in [82]. Elastic modulus increases by a factor
of 4 for the porous material due to the smaller effective area. The UTS is reduced by a factor
of ~ 8 for the porous material. The Poisson’s ratio is approximately reduced by a factor of 1.5.
The coefficient of thermal expansion is independent of porosity. The creep mechanism
appears to depend on the temperature and on the applied stress.
2.10. Sealant materials
Tubes or plates have to be joined to larger components to enhance the flux. Depending on the
design joining technologies might be used. Options are also glass-ceramic and metallic
83 84 85 86
sealants that find already frequent use in solid oxide fuel cells [ , , , ]. Although a number
of studies concentrated on the properties of such materials for the SOFC application
[84,85,86], revealing in particular limitations due to atmospheric conditions for metallic
87
sealants [ ] and creep and reduced elevated temperature strength values for glass-ceramic
88 89 90
sealants [ , , ], studies on sealants for membrane application focused more on the materials
91 92 93 94 95
interactions [ , ] and reports on the mechanical properties are limited [ , , ]. In particular
in [95] it was stated that for BSCF, reactive brazing in air atmosphere (RAB) is the only
technical applicable solution for a heat resistant and gas tight sealing to metals, however,
brazing BSCF to heat resistant austenitic steel AISI 314 led to a change in BSCF
microstructure at the interface due to reactions with copper oxide (CuO) from the used AgCu
braze alloy. After aging for 500 h at 850 °C in air atmosphere, a further change in the
microstructure appeared, which leading to an additional interfacial porosity increase and

needle shaped phase at ceramic grain boundaries that might be characteristic of the hexagonal
phase formation discussed in 2.1.1. Mechanical tests with the BSCF/AISI 314-joints showed a
decrease of the room temperature strength after aging by a factor of around two.
3. Conclusions
Mechanical properties were summarized for selected oxygen conductors un-doped and Zr doped
Ba0.5Sr0.5Co0.8Fe0.2O3−δ, La0.6/0.58Sr0.4Co0.2Fe0.8O3−δ, SrTi1-xFexO3-δ, Ce0.8Gd0.2−yPryO2−δ,
Ca0.5Sr0.5Ti0.6Fe0.15Mn0.25O3-δ, CaTi0.6Fe0.15Mn0.25O3-δ, La2NiO4+δ, and for the proton
conductors La5.4WO12-δ and Nd5.5WO11.25−δ. Furthermore, properties of some selected porous
ceramic and metallic substrate materials were given. The importance of failure probability
associated with the fracture stress Weibull distribution; creep rupture of dense and enhanced creep
deformation of porous materials have been emphasized. In particular, a study on micro-porous and
nano-porous alumina substrates indicated that the strength can be enhanced by the use of a nano-
porous material, although being on the expense of a reduction of the flow rate. Particular
advantage of the STF compositions is their elevated temperature chemical and single phase
stability under different atmospheres. Fractographic investigations suggest that the thermal
exposure of BSCF under application relevant conditions can lead to crack initiation and eventually
failure, which could be avoided by a modification of the operation procedure. On the other side a
study of the fracture toughness of LSCF after exposure to an oxygen gradient indicated, similar as
fracture features during air exposure after a vacuum annealing study, that gradient conditions
exposure can also be dangerous for this perovskite.
Advanced oxygen separation units are based on thin membrane layers that are mechanically
supported by a porous substrate. One of the most important aspects for the long-term stability
at elevated temperatures is the creep behavior, which was assessed in the current study for
various potential membrane and substrate materials. Fluorite-structured ceria membranes and

magnesia substrates showed the lowest creep rates of the investigated materials and satisfy the
“1% creep strain per year” criterion up to 900 °C. For example LSCF38, MgO and all
investigated cerium oxides (CeO2−δ and its three Gd-/Pr-doped variations:
Ce0.8Gd0.2−xPrxO2−0.5(0.2−x)−δ, with x = 0, 0.1 and 0.2) satisfied at around 800 °C the creep
limit criterion, suggested to be necessary to warrant reliable long-term stability for membrane
systems, but only ceria materials and MgO fulfilled this requirement also at higher
temperatures. As might be expected, the metalls revealed stronger creep than the ceramics,
with creep rates significantly higher than 1 % per year. The creep deformation of porous
LSCF and BSCFZ was found to be larger than for the dense material, where the difference
between the results for porous and dense material increased with increasing temperature,
indicating that an operation of dense membrane layer on a porous substrate might be difficult.
The comparison with respect to a tolerable creep rate aims to avoid failure of the oxygen
generation system that might occur due to deformation of its functional elements. Such high
creep rates can result in large deformations and structural instability and in the case of tensile
strains even in creep rupture. Since the creep deformation appeared to exceed an acceptable
level for some materials, a strategy for reduction of creep deformation could be a decrease of
operation temperature or pressure ratio. Both will reduce the oxygen flux through the
membrane. In order to compensate the creep, a smart design of the support might be an option
as reported for a new generation supports with straight pore channels perpendicular to load
direction, freeze drying manufactured. However, the creep can also aid the relaxation of
stresses that might result from differences in thermal expansion and a detailed consideration
of the effects in an actual design requires detailed finite element simulations.
Acknowledgement
The author would like to thank the coworkers, financially supported by national and European
projects that supported the study of membrane materials and substrates in the last decade.

Captions
Fig. 1: Normalized fracture toughness, strength and elastic modulus of BSCF after [45].
Fig. 2: Strength – probability – time plot of BSCF, LSCF and CGO after [52,37].
Fig. 3: Elastic modulus (a) and average fracture stress (b) of dense and porous BSCF after
[65].
Fig. 4: Creep rated of BSCF and BSCFZ after [55].
Fig. 5: a) Creep rupture times for BSCF in three-point bending along with a typical image of
creep rupture cracks in b) [38,37]. In c) tensile creep test of dense BSCF tubes at 850 °C (D =
10 mm, d = 8 mm), applied stresses 12.5 MPa (blue curve) and 16 MPa (red curve),
respectively.
Fig. 6: Normalized creep rates for BSCF-Z100·x (x = 0, 0.01, 0.03, 0.05 and 0.1) [54].
Fig. 7: Ratio of creep rate of porous to dense BSCF and LSCF after [66].
Fig. 8: Crack extending from elongated pores after the operation in a demonstrator unit [56].
Fig. 9: Change of ferroelastic domain direction due to the application of an in-plane load [67].
−5
Fig. 10: Vacuum (10 mbar) annealed LSCF showed surface cracking on heating in air [72].
Fig. 11: Comparison of creep rates of STF with data for BSCF, BSCFZ, LSCF and LSC [74].
Fig. 12: Critical strain of CGO (diamond) and SYT (round symbol) as function of porosity
[65].
Figure 13: Creep rate of dense CTFMn25 and porous CTF10 under a compressive load of 30
MPa along with literature data for dense LSCF, BSCF and GGO [14].
Fig. 14: a) Micro- and b) nano-porous Al2O3 [20].
Fig. 15. Comparison of the creep rates of different membrane and substrate materials [15].

TABLES
Table 1. Characteristic strengths and Weibull moduli of LSCF material [65].
Material LSCF58-dense LSCF60_6% LSCF60_46% LSCF38_6%
σ0(RT) [MPa] 73 ± 2 75 ± 3 18 ± 2 77 ± 3
m (RT) 10.6 ± 0.4 (15) 11.4 ± 1.2 (7) 3.4 ± 0.4 (5) 6.2 ± 0.4 (14)
σ
0(800 °C) - 170 ± 30 21 ± 3 125 ± 33
[MPa]
m (800 °C) - 3 ± 1 (3) 4 ± 1 (4) 1.7 ± 0.3 (5)
Table 2. Comparison of mechanical properties of different substrate materials [20].
Consignment Al2O3 Al2O3 MgO [19] CGO [29] BSCF [29] LSCF [29]
Atech IEK-1
Porosity 42 43.5 36 43 34 46
E [GPa ] 48 ± 10 102 ± 13 55 ± 3 57 ± 14 35 ± 3 12 ± 4
σ0 [MPa ] 42 ± 1 157 ± 11 41 ± 2 55 ± 3 31 ± 1 18 ± 2
Fracture strain 0.088 0.15 0.075 0.096 0.089 0.15
m 7±1 3±1 4±2 5±2 4±2

FIGURES
Fig. 1.
Fig. 2.

Fig. 3.
Fig. 4.
Fig. 5.

Fig. 6.
Fig. 7.
Fig. 8.
Fig. 9.

150 µm
Fig. 10.
Fig. 11.
Fig. 12.

Fig. 13.
Fig. 14.
Fig. 15.

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48 M. Lipińska-Chwałek, F. Schulze-Küppers, J. Malzbender, Stability aspects of porous
49 M. Lipińska-Chwałek, J. Malzbender, A. Chanda, S. Baumann, R.W. Steinbrech,

Mechanical characterization of porous Ba0.5Sr0.5Co0.8Fe0.2O3−δ, J. Eur. Ceram. Soc., 31
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50 W. Araki, Y. Arai, J. Malzbender, Transitions of Ba0.5Sr0.5Co0.8Fe0.2O3−δ and
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51 W. Araki, J. Malzbender, Mechanical behaviour of Ba0.5Sr0.5Co0.8Fe0.2O3−δ under
uniaxial compression, Scripta Mater., 69 (2013), pp. 278–281
52 G. Pećanac, J. Malzbender, Strength and creep behaviour of ceramic materials,

HETMOC project report, 2015.
53 G. Pećanac, L. Kiesel, R. Kriegel, J. Malzbender Comparison of thermo-
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54
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55
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analysis on the creep of dense BSCFZ perovskite, J. Membr. Sci., 456 (2014), pp. 134–138

56 B. Rutkowski, R. Kriegel, J. Malzbender, Ex-service analysis of membrane tubes after

the operation in a demonstrator unit, J. Membr. Sci., 462 (2014) pp. 69–74

57 Y. Teraoka, H.M. Zhang, K. Okamoto, N. Yamazoe, Mixed ionic-electronic

conductivity of
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58J. Malzbender, P. Batfalsky, R. Vaßen, V. Shemet, F. Tietz, Component interactions after

long-term operation of an SOFC stack with LSM cathode, J.PowerSources,201(2012)196–203
59 F. Schulze-Küppers, S. Baumann, F. Tietz, H.J.M. Bouwmeester, W.A.
Meulenberg,
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membranes, J. Eur. Ceram. Soc., 34 (2014), pp. 3741–3748
60 L Blum, P Batfalsky, Q Fang, LGJ de Haart, J Malzbender, N Margaritis, SOFC Stack
and System Development at Forschungszentrum Jülich, J. Electrochem. Soc., 162 (2015)
F1199– F1205
61 B.X. Huang, J. Malzbender, R.W. Steinbrech, L. Singheiser, Mechanical properties of
La0.58Sr0.4Co0.2Fe0.8O3−δ membranes, Solid State Ionics, 180 (2009), pp. 241–245
62
B.X. Huang, J. Malzbender, R.W. Steinbrech, E. Wessel, H.J. Penkalla, L. Singheiser,
Mechanical aspects of ferro-elastic behavior and phase composition of
La0.58Sr0.4Co0.2Fe0.8O3−δ, J. Membr. Sci., 349 (2010), pp. 183–188
63
B.X. Huang, R.W. Steinbrech, S. Baumann, J. Malzbender, Creep behavior and its
correlation with defect chemistry of La0.58Sr0.4Co0.2Fe0.8O3−δ, Acta Mater., 60 (2012), pp.
2479–2484
64 W. Araki, J. Malzbender, Ferroelastic deformation of La0.58Sr0.4Co0.2Fe0.8O3−δ under
uniaxial compressive loading, J. Eur. Ceram. Soc., 33 (2013), pp. 805–812
65 M. Lipińska-Chwałek, F. Schulze-Küppers, J. Malzbender, Strength and elastic modulus
of lanthanum strontium cobalt ferrite membrane materials, Ceram. Int., 41 (2015), pp.1355–1360
66 Y. Zou, F. Schulze-Küppers, J. Malzbender, Creep behavior of porous

La0.6Sr0.4Co0.2Fe0.8O3−δ oxygen transport membrane supports, Ceram. Int., 41 (2015), pp.
4064–4069
67 B.X. Huang, R.W. Steinbrech, J. Malzbender, Direct observation of ferroelastic

domain effects in LSCF perovskites, Solid State Ionics, 228 (2012) pp. 32–36
68 Y. Kimura, T. Kushi, S. Hashimoto, K. Amezawa, T. Kawada, Influences of
temperature
and oxygen partial pressure on mechanical properties of La0.6Sr0.4Co1-yFeyO3-δ, J. Am.
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69 W Araki, T Abe, Y Arai, Anomalous variation of the mechanical behaviour of

ferroelastic La0.6Sr0.4Co0.2Fe0.8O3−δ during the ferro-to-paramagnetic transition, Scripta
Mater., 99 (2015), pp. 9–12

70
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through robust freeze-cast bilayered dual-phase membranes, Chem. Sus. Chem., 7 (2014), pp.
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71
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6 B.X. Huang, J. Malzbender, The effect of an oxygen partial pressure gradient on the
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73 C.-Y. Yoo, H.J.M. Bouwmeester, Oxygen surface exchange kinetics of SrTi1-xFexO3-δ
mixed conducting oxides, Phys. Chem. Chem. Phys., 11 (2012), pp. 11759–11765
74 S.F.P. ten Donkelaar, V. Stournari, J. Malzbender, A. Nijmeijer, H.J.M. Bouwmeester,

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75 M. Lipińska-Chwałek, F. Schulze-Küppers, J. Malzbender, Mechanical properties of

pure and doped cerium oxide, J. Eur. Ceram. Soc., 35 (2015) pp. 1539–1547
76 G. Pećanac, J. Malzbender, F. Pauly, M.L. Fontaine, P. Niehoff, S. Baumann, T. Beck,
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Singheiser, Mechanical characterization of ceramics by means of a 3D defect analysis,
Ceram. Int., 41 (2015), pp. 2411–2417
77 B.X. Huang, J. Malzbender, R.W. Steinbrech, Thermo-mechanical properties of
La2NiO4+δ, J. Mater. Sci., 46 (2011), pp. 4937–4941
78 V.K. Stournari, Thermo-mechanical properties of mixed ionic-electronic conducting

membranes for energy application, Ph.D. Thesis, RWTH Aachen, Germany, 2015.
79 J.A. Glasscock, L. Mikkelsen, Å.H. Persson, G. Pećanac, J. Malzbender, P. Blennow,
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80 J. Malzbender, G. de With, Cracking and residual stress in hybrid coatings on float

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81 M. Schulz, R. Kriegel, W. Burckhardt, Modeling of oxygen flux and stress distribution
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82 V. Vasechko, G. Pećanac, B. Kuhn, J. Malzbender, Mechanical properties of porous
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83 J. Malzbender, R. W. Steinbrech, L. Singheiser, A review of advanced techniques for

characterising SOFC behavior, Fuel Cells, 9 (2009), pp. 785–793

84 J. Malzbender , J. Mönch, R.W. Steinbrech, T. Koppitz, S.M. Gross, J. Remmel,

Symmetric shear test of glass-ceramic sealants at SOFC operation temperature, J. Mater. Sci.,
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85 B. Kuhn, F.J. Wetzel, J. Malzbender, R.W. Steinbrech, L. Singheiser, Mechanical

performance of reactive-air-brazed (RAB) ceramic/metal joints for solid oxide fuel cells at
ambient temperature, J. Power Sources, 193 (2009), pp. 199–202.
86 B. Kuhn, E. Wessel, J. Malzbender, R.W. Steinbrech, L. Singheiser, Effect of

isothermal aging on the mechanical performance of brazed ceramic/metal joints for planar
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87 T. Bause, J. Malzbender, M. Pausch, T. Beck, L. Singheiser, Damage and Failure of

Silver Based Ceramic/Metal Joints for SOFC Stacks, Fuel Cells, 13 (2013), pp. 578–583.
88 J. Malzbender, Y. Zhao, T. Beck, Fracture and creep of glass-ceramic solid oxide fuel
cell sealant materials, J. Power Sources, 246 (2014), pp. 574–580
89 Y. Zhao, J. Malzbender, Elevated temperature effects on the mechanical properties of

solid oxide fuel cell sealing materials, J. Power Sources, 239 (2013), pp. 500–504
90 J. Malzbender, Y. Zhao, Flexural Strength and Viscosity of Glass Ceramic Sealants for
Solid Oxide Fuel Cell Stacks, Fuel Cells, 12 (2012), pp. 47–53
91 K. Bobzin, N. Kopp, S. Wiesner, Influence of Filler and Base Material on the Pore
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92 S. Dabbarh, E. Pfaff, A. Ziombra, A. Bezold, Brazing of MIEC ceramics to high

temperature metals, Ceram. Trans., 215 (2010), pp.213–223
93 A. Kaletsch, A. Bezold, E.M. Pfaff, C. Broeckmann, Effects of Copper Oxide Content
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94
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95 K. Bobzin, M. Ote, S. Wiesner, A. Kaletsch, C. Broeckmann, Characterization of Reactive
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VLHENMA HKI 18-19 BBKH 1.

Author’s Accepted Manuscript

Mechanical aspects of ceramic membrane materials

Received date: 29 January 2016

NGUYỄN ANH PHƯƠNG – 16146449 1

Mechanical aspects of ceramic membrane materials

Forschungszentrum Jülich, IEK-2, 52425 Jülich, Germany

ceramics, emphasizing in particular relationships between mechanical properties, non-elastic

of these materials in gas separation systems.

Keywords: Ceramics, membranes, mechanical properties, stability, fracture

Mixed ionic–electronic conducting (MIEC) materials operating at high temperatures have,

in advanced electrochemical systems, in particular, as oxygen transport membranes for

NGUYỄN ANH PHƯƠNG – 16146449 2

conducting membranes can be a cost-effective alternative to cryogenic methods. Since H 2-

Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCF). However, it appears not to be chemically stable under high

unfavorable chemical-expansion effects can be reduced by partial replacement of Pr-doping

NGUYỄN ANH PHƯƠNG – 16146449 3

Lanthanum tungstate LaxWO3+1.5x ( , LaWO) is a promising membrane candidate for a

should provide mechanical stability of the membrane structure, since application-related

fracture strength of materials is typically characterized, requiring an

NGUYỄN ANH PHƯƠNG – 16146449 4

thermo-mechanical aspect with respect to structural stability at elevated temperatures is creep

a tolerable creep rate to warrant long-term structural stability in membrane application.

data on dense and porous state are available.

2.1. BSCF and BSCFZ

among various compositions, Ba0.5Sr0.5Co0.8Fe0.2O3−δ (BSCF) has emerged to

NGUYỄN ANH PHƯƠNG – 16146449 5

non-stoichiometry and B-site cation valence.

order to be economically justified, oxygen transporting membranes (OTMs) and SOFCs

which results in chemical composition Ba0.5Sr0.5(Co0.8Fe0.2)0.97Zr0.03O3−δ (BSCFZ).

Detailed results and implications are discussed in the following.

2.1.1. Elastic and fracture behavior

NGUYỄN ANH PHƯƠNG – 16146449 6

stiffness changes under the testing conditions.

based on ring-on-ring tests and depth-sensitive micro-indentation. Measurements of the

thermo-mechanical properties with ring-on-ring test and depth-sensitive micro-indentation

(Fig. 1) [44,45,46]. At higher temperatures the properties increased.

NGUYỄN ANH PHƯƠNG – 16146449 7

2.1.2. Porous BSCF

BSCF due to porosity) for a failure probability of 1 % if a lifetime of 40 years is envisaged.

2.1.3. Intermediate temperature anomalies

NGUYỄN ANH PHƯƠNG – 16146449 8

Up to 200 °C all characteristic mechanical parameters decreased; at high temperatures they

[43,46]. Detailed thermal expansion measurements along with magnetic as well as

NGUYỄN ANH PHƯƠNG – 16146449 9

2.1.4.1. Creep rupture

2.1.5. Zr doped BSCF

NGUYỄN ANH PHƯƠNG – 16146449 10

Thermo-mechanical characteristics of Ba0.5Sr0.5(Co0.8Fe0.2)0.97Zr0.03O3−δ (BSCFZ) were

reflected in the microstructures and not necessarily induced by the Zr doping.

NGUYỄN ANH PHƯƠNG – 16146449 11

2.1.6. Post-operational inspection

characterization), which could be avoided by a modification of the operation procedure.

La0.6Sr0.4Co0.2Fe0.8O3−δ and La0.58Sr0.4Co0.2Fe0.8O3–δ (due to its similar properties abbreviated

formation of secondary phases at elevated temperatures [59].

NGUYỄN ANH PHƯƠNG – 16146449 12

phase change to a cubic structure at operation relevant temperatures [61,62,50,46].

2.2.1. Elastic and fracture behavior

Polycrystalline LSCF revealed in bending tests a non-linear deformation behavior at room

NGUYỄN ANH PHƯƠNG – 16146449 13

2.2.2. Porous LSCF

2.2.3. Ferroelastic domains and ferromagnetic–paramagnetic transition