Subcritical Crack Growth Behavior of A Perovskite-Type

Oxygen Transport Ceramic Membrane

Nagendra Nagabhushana, Thangamani Nithyanantham, and Sukumar
Bandopadhyay
Department of Mining and Geological Engineering, University of Alaska Fairbanks, Fairbanks, Alaska
99775
Jing Zhang*
Department of Mechanical Engineering, University of Alaska Fairbanks, Fairbanks, Alaska 99775
We herein report subcritical crack growth (SCG) studies of La
0.2
Sr
0.8
Fe
0.8
Cr
0.2
O
3d
(LSFCO) perovskite membranes as
oxygen transport membranes (OTM). Two sample batches of perovskite were tested to investigate the effect of temperature,
specic chemical environments, and loading rate on exure strengths, using four-point bend tests. The rst batch was ex-
amined at room temperature in air. The second batch was soaked in an N
2
/air atmosphere at 10001C. Stress rates varied
approximately from 0.2 to 90 MPa/s. The strengthprobabilitytime diagram is constructed for design proposes. Flexural
strength data indicate that the examined OTM material showed little susceptibility to SCG at room temperature in air.
However, the sample is susceptible to SCG in an N
2
/air environment at 10001C. Also, the experiments demonstrate exural-
strength rate dependency, with strength increasing with the stress rate. The observed phenomena are explained by the de-
composition and microstructural transitions in the perovskite.
Introduction
Perovskites have attracted considerable attention
for use in high temperature solid oxide fuel cells, oxy-
gen separators, and catalytic membrane reactors for con-
version of methane to syngas (CO1H
2
).
110
Mixed
ionic and electronic conducing perovskite materials,
such as La
1x
Sr
x
Fe
x
Cr
1y
O
3d
, are particularly prom-
ising due to their potential applications as oxygen trans-
port membranes (OTM) to generate syngas from
natural gas.
11,12
So far, much of the available literature has focused
on membrane synthesis and characterizations. Investi-
gations on the mechanical strength of these oxides are
relatively few. Chou et al.
13
reported room-temperature
mechanical properties of La
1x
Sr
x
Co
0.2
Fe
0.8
O
3
(x 50.20.8), including elastic properties, biaxial ex-
ure strength, and indentation fracture toughness. Creep
Int. J. Appl. Ceram. Technol., ]] []]] 18 (2009)
DOI:10.1111/j.1744-7402.2009.02440.x
Ceramic Product Development and Commercialization
This work was supported by DOE (DE-FC26-99FT40054 and DE-FG36-05GO15194).
One of the authors, J. Z., also thanks the start-up fund and the INE research initiative
award provided by the University of Alaska Fairbanks.
*jzhang6@alaska.edu
r 2009 The American Ceramic Society
behavior of the perovskite also has been reported. Lein
et al.
14
investigated the creep properties of
La
0.5
Sr
0.5
Fe
0.5
Co
0.5
O
3d
and La
0.5
Sr
0.5
CoO
3d
in the
temperature region 90010501C and stress range
528 MPa. Considerably higher creep rates were ob-
served for both materials in N
2
compared with air.
Stress exponents in the creep equation were close to
unity, suggesting a diffusion-controlled creep mecha-
nism. Majkic et al.
15,16
examined the creep behavior
La
0.2
Sr
0.8
Fe
0.8
Cr
0.2
O
3d
in a controlled atmosphere,
with oxygen partial pressure PO
2
ranging from 0.21
to 10
14
atm. At high PO
2
, the creep rate slowly de-
creased with decrease in PO
2
. While at low PO
2
, the
compound exhibited a drastic increase in strain rate with
decreasing PO
2
.
Creep study provides important information of
mechanical properties at high temperature. In real-ap-
plication conditions, the membranes experience com-
bined effect of stress and a chemical environment.
Under such conditions, a more suitable mechanical
property, subcritical crack growth (SCG) should be ex-
amined. Classical fracture mechanics postulates that the
crack grows dynamically when the stress intensity factor
reaches a critical level, the fracture toughness. Actually
the long-term performance of a ceramic component is
not just determined by the initial strength and the
fracture toughness of the material, but also depends
on SCG resistance of the component. The SCG refers
to environmentally enhanced crack propagation at
subcritical stress levels. Because of SCG, the strength
of a component in service usually decreases with
increasing service time. SCG depends on not only
stress conditions but also environments, such as
temperature, chemical atmosphere, and humidity.
However, to the knowledge of the authors, the data of
perovskite La
1x
Sr
x
Fe
x
Cr
1y
O
3d
are not available in
the literature.
With above-mentioned considerations in mind, the
motivation of this study is twofolds. First, a study of
SCG behavior will provide a more comprehensive da-
tabase of mechanical property of the oxides. The infor-
mation is critically needed for future design and
optimization. Second, a study on stress rate effect is
also important to evaluate thermally induced stresses.
Thermally induced stresses, generated by the disparities
of the coefcient of thermal expansion among different
components, may cause structural failure during tem-
perature changes in operations. The magnitude of ther-
mally induced stresses is related to the range of
temperature change and also the rate of temperature
changes. Thus, it is important to understand the me-
chanical strength of the membranes subject to various
stress rates.
In this work, we report the slow crack growth of
La
0.2
Sr
0.8
Fe
0.8
Cr
0.2
O
3d
(LSFCO) membranes as a
function of temperature, environment, and stress rate.
The perovskites are evaluated for strength and reliability
through four-point bend tests in two representative en-
vironments: room temperature in air and 10001C in
N
2
/air. In each condition, loading rates are varied to
investigate strength dependence on stress rate. The re-
sults will be tted into a SCG model. The parameters of
the model will be determined. The strengthprobabil-
itytime (SPT) diagram is also constructed for design
proposes. The fracture surfaces are analyzed by X-ray
diffraction (XRD) and Scanning Electron Microscope
(SEM) to explain the observed changes in mechanical
properties and reliability.
Experimental Procedure
Materials and Processing
The oxide membranes of the general composition
La
0.2
Sr
0.8
Fe
0.8
Cr
0.2
O
3d
were provided by Praxair Inc.,
Tonawanda, NY, by a proprietary process. Briey, the
oxide membranes are processed through cold-isostatic
pressing and sintering of the base powder with the above
composition. The microstructure of the provided mem-
branes is shown in Fig. 1. The microstructure of
LSFCO was approximately 3 mm. The average density
of the LSFCO samples as computed from volume mea-
surements was approximately 6.50 g/cm
3
, similar to
other perovskites of this general composition.
17
Mechanical Testing
To study the slow crack growth phenomena, we
use four-point bend test due to its simplicity. OTM
bars were sectioned from the membranes provided
by Praxair. The dimensions of the bars are 3 mm
4 mm48 mm.The sample surfaces are polished
using various grades of SiC sheets (Buehler, Lake Bluff,
IL) and diamond pastes (Buehler) till 1 mm and
the edges of the OTM bars were chamfered because of
testing.
Two batches of total 17 perovskite bars were tested
to investigate the effect of temperature, specic chemical
2 International Journal of Applied Ceramic TechnologyNagabhushana, et al. Vol. ]], No. ]], 2009
environment, and stress rate on exure strengths. The
rst batch was examined at room temperature in air. A
total of nine samples were loaded at room temperature
in air. The second batch of eight samples was loaded in
the xture and heated in owing N
2
up to 10001C.
Thereafter, the nitrogen ow was shut off with the out-
let fully open. The soaking was for 1 h because of ap-
plication of the load. After fracture of the sample, the
furnace power was totally shut off. A typical test had a
heating up period of 2.5 h, soaking of 1 h and a cool
down period of 10007001C in 45 min and 7002001C
in 1.5 h for a sum total of 6 h.
The in situ ftature tests were carried out in an in-
house designed autoclave mounted on a servo-electric
loading frame. The four-point bend exure has an outer
span of 38.1 mm (3/2 in.) and inner span of 19.05 mm
(3/4 in.). The bearing cylinders have a diameter of
4.76 mm (3/16 in.). The loading cross-head speed was
varied from 0.00005, 0.0001, 0.001, to 0.01 mm/s.
After bending testing, the fractured samples were
cut in a low speed saw (Buehler) near to the fracture.
The fractured surfaces were sputtered with gold because
of examination in an SEM (Leitz ISI SR 50, Akashi,
Japan) to characterize the dominating aws and fracture
mechanisms. The outer surfaces exposed to the envi-
ronment were analyzed to determine phases separation
if any in a Siemens D5000 y/y X-Ray Diffractometer
(XRD, Siemens, Munich, Germany) using Cu radiation
at 40 kV/20 mA. Samples were also powdered and an-
alyzed in XRD for information on phase changes. The
XRD were carried out under two conditionsa fast
scan to provide complete data and a slow scan at the
specic peaks with a step angle of 0.011 and a dwell time
of 2 s.
Results
Fracture Strength in Air at Room Temperature
The fracture strength (or modulus of rupture), s
f
,
of the OTM bars in four-point bend exure were cal-
culated by the beam formula
18
s
f

3PS
o
4BW
2
1
where P is the fracture load (N), B is the thickness
(mm), W is the width of the beam (mm), S
o
(38.1 mm)
is the outer span.
The highest strength of 115 MPa was found at the
highest cross-head speed of 0.01 mm/s. Thereafter the
strength continuously decreased with decreasing cross-
head speeds and a low of 86 MPa was recorded at a
cross-head speed of 0.00005 mm/s.
Fracture Strength in N
2
/Air at 10001C
The OTM bars were loaded at the same cross-head
speeds as at room temperature. The exural strengths
were calculated from the fracture load discussed in pre-
vious section. At high cross-head speed 0.01 mm/s, the
strength (110 and 118 MPa for two samples) recorded
was comparable to that of at room temperature (so
called inert strength). Thereafter the strength decreased
much steeper as indicated by a recorded strength of
69 MPa at 0.00005 mm/s.
Slow Crack Growth Analyses
With the load and displacement curves of the spec-
imen tested at various rates, data can be tted into a
slow crack growth model. The basic underlying
assumption of the model is that slow crack growth
rate, v (m/s), is governed by an empirical power-law
crack velocity
18
:
v A
K
I
K
IC

n
2
5 m
Fig. 1. Thermally etched microstructure of LSFCO. The pores are
noted by white arrows.
www.ceramics.org/ACT Subcritical Crack Growth Behavior 3
where A (m/s) is a constant, n is the SCG parameter, K
I
(N m
1/2
) is mode I stress intensity factor, and K
IC
(N m
1/2
) is fracture toughness under Mode I condi-
tion.
Under such assumptions, it can be shown that for
constant stress rate testing, fracture strength is correlated
with stress rate, s

, following the equation

19
:
log s
f

1
n 1
log s

log D 3
where n and D (Pa/s) are the SCG parameters.
In Eq. (3), the stress rate is calculated from the
loadtime curve of the specimen tested
18
s

3 P

S
o
4BW
2
4
where P

is the load rate (N/s), B, W, and S

o
have the
same meaning as in Eq. (1).
The SCG parameters n and D are then determined
by a linear regression analysis using log strength values
over the complete range of individual log stress rates.
The slope of the linear regression line, a, can be calcu-
lated as
19
:
a
K

K
j1
log s

j
log s
j

K
j1
log s

K
j1
log s
j

K

K
j1
log s

j

2

K
j1
log s

j

2
5
where K is the total number of specimens tested ( 58
and 9 in two above mentioned batches, respectively),
s
j

and s
j
is the stress rate and fracture strength of the
individual test specimen, respectively. The SCG param-
eter n is calculated as n 5(1/a)1.
The intercept of the linear regression line is calcu-
lated as
19
:
b

K
j1
log s
j

K
j1
log s

j

2

K
j1
log s

j
log s
j


K
j1
log s

j

K

K
j1
log s

j

2

K
j1
log s

j

2
6
The SCG parameter D is calculated as D510
b
.
The plot of Eq. (3), the log of exural strength as a
function of log stress rate, is shown in Fig. 2. The SCG
parameters n and D were calculated as 23.57, 94.71 and
11.28, 80.2 in air at room temperature and in N
2
/air at
10001C, respectively.
SPT Diagram
From the design point of view, it is important to
predict the long-term performance of the ceramic mem-
branes. The SPT diagram is a useful tool, which repre-
sents the failure probability as a function of stress and
time. To construct SPTs, the stresses are transformed to
an equivalent stress. s
1s
, the stress that converts the
failure stress s
f
measured at a stress rate of s

into an
equivalent stress that would have caused the sample to
fail in 1 s
20
s
1s
s
f
s
f
s

n 1

1=n
7
where n is the SCG parameter.
The construction of SPT diagram requires Weibull
parameters. Because we only have the Weibull param-
eters of this material in a C-ring shape,
21
we need to use
effective volume
22
to derive the equivalent character-
istic stress for the four-point bending specimens.
Effective volume, kV, in the ceramic literature is
the size of a hypothetical tension test specimen that,
when stresses to the same level as the test specimen in
question, has the same probability of fracture. For two
different geometries of test specimens fabricated from
the same material, the following relationship holds
22
:
s
0;1

V
s
0;2

k
2
V
2
k
1
V
1

1=m
v
8
Fig. 2. Flexure strength as a function of stress rate (log/log plot)
under two conditions (see text). The dotted lines are the linear
regress results based on Eq. (3).
4 International Journal of Applied Ceramic TechnologyNagabhushana, et al. Vol. ]], No. ]], 2009
where s
0
is Weibull characteristic strength, m
v
is Wei-
bull modulus, subscripts 1 and 2 denote two different
specimens, subscript V refers to volume distribution, k is
a dimensionless load factor. V is gage volume of test
specimen.
The effective volume for a C-ring specimen is
22
kV
CRing
r
o

m
v
f yf r 9
where
f y

p
p G
m
v
1
2

G
m
v
2
1


; f r
2

r
o
r
a
r r
a
r
o
r
a

r
1m
v

dr
and r
a
5(r
o
1r
i
)/2 5(5.7514.65)/2 55.2 mm, where
r
o
and r
i
is the outer and inner radius of the C-ring,
respectively. The gamma function G may be found in
any handbook on mathematical functions. Because
there is no closed form solution for Eq. (9), we use nu-
merical integration to calculate the effective volume of
the C-ring specimen to be 1.2521 mm
3
.
For the four-point bending specimen, the effective
volume is
22
kV
B4

L
i4
L
o4

m
v
1

1
2m
v
1
2

V
B4
10
where V
B4
5bdL
o4
, L
i4
( 519.05 mm) and L
o4
( 538.1 mm) is the length of inner or outer span, re-
spectively, b ( 54 mm) and d ( 53 mm) is the width
and height of the cross section of the specimen. The
calculated effective volume of the four-point bending
specimen is 23.1 mm
3
.
With the effective volumes of the four-point bend-
ing and C-ring specimens and characteristic strength of
C-ring (178 MPa), the equivalent characteristic strength
of the four-point bending specimen is calculated using
Eq. (8) as to be 97.0 MPa. This value will be used below
to construct the SPT diagram.
At 10001C and N
2
/air, the characteristic strength of
the four-point bending samples, s
0
, is 97.0 MPa, as
discussed above. The Weibull modulus m is 4.8.
21
The
tests were carried out by monotonically loading in
diametral compression to fracture at a constant cross-
head speed of 0.5 mm/min.
21
The basic steps of con-
struction of the SPT diagrams for the samples at high
temperature and reactive environment are as follows: (i)
The strain rate is estimated as 0.5 mm/5.75 mm/
min 51.5 10
3
s
1
where 5.75 mm is outer diame-
ter of the C-ring.
21
(ii) The corresponding stress rate, s

,
is calculated as 123 GPa 1.5 10
3
5184.5 MPa/s,
where 123 GPa refers to the assumed Youngs modu-
lus.
23
Using the SCG parameter n ( 511.28) and s
f
( 597.0 MPa) in Eq. (7), the equivalent stress that
would fail at 1 s is 150.8 MPa. (iii) Combination of
this stress and 1F 51/e (corresponding to the charac-
teristic strength s
0
), where F is failure probability, gives
the rst data point on the 1 s line on the SPT diagram.
(iv) Draw the 1 s line with a slope of Weibull parameter
4.8.
21
(v) A series of lines parallel to this line, with a
spacing between the lines equal to (Ln10)/n or 2.3/n.
Each line represents a decade increase in life time. The
constructed SPT diagram is shown in Fig. 3. Note that
only selected lines are given for clarity. Using this SPT
diagram, the design stress, under a suitable failure prob-
ability, can be estimated. For example, at a failure prob-
ability of 1/e, or 37%, the design stress of a lifetime of
30 years should be o10 MPa.
Fracture Microstructural Analyses
The susceptibility to slow crack growth of the
OTM samples exposed to the environment was further
examined with fracture analysis. The fractured samples
were sputter coated with gold and examined using SEM.
Microscopic analysis indicated that the origins of frac-
ture in both the sets of samples were consistently from
the surface. The cracks typically were initiated at the
surface and had propagated toward the center of the
4
3
2
1
0
1
2
3
1.5 2 2.5 3 3.5 4 4.5
Ln(Stress), MPa
L
n
(
L
n
(
1
/
(
1

F
)
)
)
10^5 sec
10^7 sec
3 years ~ 10^8 sec
30 years ~10^9 sec
Fig. 3. Strengthprobabilitytime diagram for the LSFCO tested
at 10001C in N
2
/air.
www.ceramics.org/ACT Subcritical Crack Growth Behavior 5
samples. The surface aws were approximately of the
order of 20 mm (Fig. 4).
The interaction of the propagated crack with the
microstructure was better illustrated in the secondary
cracks. As shown in Fig. 5, the secondary cracks have
followed a transgranular mode through the OTM
grains. Additionally, two distinct precipitates, a coarse
(0.50.8 mm) and very ne (0.10.25 mm) were ob-
served. These precipitates were formed at the grain
boundary and grain boundary junctions (marked by
red arrows) as shown in Fig 6. Though the formation of
stress induced secondary cracks and precipitates inu-
enced the slow crack growth and reduced the n value
significantly, they were insensitive to fracture behavior
at the high stress rate (100 MPa/s). This is clearly shown
in the Fig. 2. This kind of behavior is quite possible as
the crack initiating surface aws are significantly larger
then the precipitates and secondary cracks.
XRD Analyses
The microstructural transitions also suggest the
possible formation of precipitates and phase decompo-
sitions at high temperature. XRD was performed to ex-
amine the possible phase transition. The full scale and
the selected peak XRD analyses of the OTM samples
exposed to the environment are shown in Fig. 7.
Slow XRD scan of fractured samples indicated that
the major peaks were no longer single and had decom-
posed to several peaks, as shown in Fig. 8. There was
small but perceptible decomposition peaks in the sam-
ples subject to a high stress rate. Indexing of the X-ray
Fig. 4. Surface aws (noted by arrows) as the fracture origins.
Fig. 5. The secondary cracks have followed a transgranular mode
through the grains. Arrows show the interaction between the cracks
with pores.
Fig. 6. Transgranular fracture and precipitates (marked by the
arrows).
6 International Journal of Applied Ceramic TechnologyNagabhushana, et al. Vol. ]], No. ]], 2009
peaks indicated the existence of Brownmillerite (or
Sr
2
Fe
2
O
5
-type phases) and Aurivilius type of structures.
The nonequilibrium conditions could probably be due
to the nature of the applied stress eld (strain rates) that
leads to transition in crystal structures and increases ki-
netics of decomposition. The formations of Brown-
millerite or Sr
2
Fe
2
O
5
type structures, which are
orthorhombic, are attributed to the ordering of oxygen
vacancies. The transition from cubic to orthorhombic
structure leads to 2.6% increase in strain. Thus residual
stresses generated could inuence the fracture behavior
of the OTM membrane.
Discussions
The SCG parameter n characterizes the resistance
of a material to SCG. A high n value is usually inter-
preted as a low susceptibility to SCG. The high value of
n 523.6 at room temperature in air indicates that the
OTM material is not very susceptible to slow crack
growth. However, the value of n decreases drastically to
11.3 in N
2
/air, which is o50% at room temperature,
indicating that the OTM material is prone to SCG. A
value of nB5 or lesser indicates a brittle ceramic that is
affected by SCG. For LSFCO materials, there was no
slow crack growth study reported in the literature. As a
reference, our n value is substantially lower than those of
reported high-purity dense alumina (nB60).
2426
It is
reasonable to suspect that surface defects and pores of
the LSFCO are responsible for the low n value as cracks
initiated from the surface and propagated preferentially
along the weakest interfaces that are inuenced by the
residual stresses. Moreover, the secondary cracks and
precipitates that were formed when the perovskite mem-
brane was exposed to the N
2
/air atmosphere also inu-
ence the n value.
The secondary cracks were observed very close to
the transition from intergranular to transgranular modes
of fracture and indicated the possible presence of local-
ized residual stresses. It is evident from the XRD anal-
ysis that the nonequilibrium decomposition of the
LSFCO leads to transition in crystal structures. The
formation of orthorhombic Brownmillerite or
Sr
2
Fe
2
O
5
-type structures, from the parent perovskite
cubic structure leads to 2.6% increase in strain, which
causes a localized residual stresses. Residual stresses can
alter the trajectory of the crack paths in the OTM struc-
tures. Regions of transgranularly fractured grains also
indicated increased formation of precipitates.
At room temperature, only a single perovskite phase
is expected. At high temperature, XRD analysis revealed
that samples exposed to an environment of N
2
/air at
10001C indicated that the major XRD peak (2y 5321)
had a perceptible shift toward the higher angle as the
stress rate increases. Similar trend of shifting to higher
angles has also been observed in the strontium-doped
lanthanum manganite as temperature increases.
27
Slow
XRD scans showed there was small but perceptible de-
composition peaks in the samples subject to a high stress
rate, suggesting that second phase is presented.
Fracture analysis in combination with X-ray anal-
ysis indicated the strength degradation is aided by the
Fig. 7. X-ray diffractionscans of the oxygen transport membranes
samples exposed to N
2
/air at 10001C at varying stress rates.
(1) 0.01mm/s; (2) 0.001 mm/s; (3) 0.0001 mm/s; (4) 0.00005mm/s.
Fig. 8. Rened X-ray diffraction scans of the major peaks
(2y 5321) of the oxygen transport membranes samples indicating a
shift and decomposition of the single peaks. (1) 0.01 mm/s;
(2) 0.001 mm/s; (3) 0.0001 mm/s; (4) 0.00005 mm/s.
www.ceramics.org/ACT Subcritical Crack Growth Behavior 7
decomposition of the grains. Line scans analysis across
the fractured grains indicated that the bulk of the grain
exhibited the same elemental composition as at the
room temperature. However, grain boundaries were
rich in strontium and the grains markedly strontium
decient. It has been shown that strontium content has
substantial effect on the mechanical properties.
13
This
also corresponded well with previous observations con-
cluding a build up of strontium at the grain boundaries
and the strontium-decient grains acting as acceptors.
28
The transitions and expansion/decomposition indicate
the possibilities of residual stresses, which inuence
crack growth and fracture in the OTM material. The
expansion mechanism was related to heterogeneous
phase equilibria. The secondary phases involved in these
phase equilibria are determined by the cation stoic-
hiometry of the materials.
11
Conclusions
(1) LSFCO perovskite membranes show little
susceptibility to the slow crack growth at room
temperature in air. However, the membranes are
susceptible to SCG in a N
2
/air environment at
10001C.
(2) The observed susceptibility to SCG is
attributed to the possible phase decomposition and
microstructural transitions in the environment.
(3) LSFCO perovskite membranes show a
dependence of fracture stress on stress rate. The
faster the specimen is loaded, the higher its strength
with a reduced ductility. Specimens loaded at higher
rates may be better able to maintain their strength at
high temperatures for limited periods.
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