Materials Science & Engineering A 614 (2014) 171179

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Materials Science & Engineering A

journal homepage: www.elsevier.com/locate/msea

Inuence of ber orientation and matrix processing on the tensile

and creep performance of Nextel 610 reinforced polymer
derived ceramic matrix composites
E. Volkmann a, K. Tushtev a,n, D. Koch b, C. Wilhelmi c, G. Grathwohl a, K. Rezwan a
a

Advanced Ceramics, University of Bremen, Am Biologischen Garten 2, 28359 Bremen, Germany

Ceramic Composite Structures, Institute of Structures and Design, German Aerospace Center, Stuttgart, Germany
c
EADS Deutschland GmbH, Airbus Group Innovations, Munich, Germany
b

art ic l e i nf o

a b s t r a c t

Article history:
Received 6 May 2014
Received in revised form
9 July 2014
Accepted 10 July 2014
Available online 18 July 2014

The tensile and creep performance of two Nextels 610 (N610) reinforced polymer derived ceramic
composites (UMOX, OXIPOL) is studied up to 1200 1C. Independent of the ber orientation ( 7451 or
01/901) all samples exhibit a segment where the strain rate was constant. The creep performance in
7451 is matrix dominated and shows a more pronounced primary creep regime, due to changes within
the matrix. The following creep regime with a constant strain rate might be attributed to viscous ow of
the SiOC within the matrix based on activation energy (283 kJ/mol) and stress exponent (0.6). In 01/901
orientation the creep and tensile performance is independent of oxidation, but directly inuenced by
grain structure of the ber. The coarser and non-uniform microstructure of the bers in UMOX
decreases the stationary creep rates and changes the diffusional creep mechanism. The possibility to
modify the microstructure of the ber during the manufacturing process might be used to adjust e.g. the
strength and creep stability of these materials related to the desired applications.
& 2014 Elsevier B.V. All rights reserved.

Keywords:
Ceramic-matrix composites (CMCs)
Oxides
Creep
High-temperature properties

1. Introduction
Ceramic matrix composites (CMCs) resulting of polymer inltration and pyrolysis (PIP) have been proven to be promising
candidates for application in oxidizing atmospheres, like in hot
structures of re-entry vehicles [1], thermal protection systems [2]
or gas turbines [35]. The PIP process is one of the most versatile
and cost-effective manufacturing routes [6,7], due to the possible
application of knowledge gained from the polymer composite
eld [8]. However, the commonly used polysiloxane precursors
result in a SiOC matrix containing residual amounts of carbon.
Therefore, compared to all-oxide composites these materials are
not inherently oxidation resistant, and application of these composites in oxidative atmospheres will lead to the formation of
silica [9]. In combination with often used fugitive coatings [10] this
can cause an increase of the interfacial adhesion accompanied by a
decrease of toughness, due to a bridging of the interfacial gap [11
13]. Besides the effects on the matrix, also the often used
polycrystalline Nextel 610 ber (N610) is inuenced by an exposure to high temperatures. Schmcker et al. showed that in the
case of WHIPOX based on pure alumina matrices an outwards

Corresponding author. Tel.: 49 421 218 64947; fax: 49 421 218 64932.
E-mail address: tushtev@uni-bremen.de (K. Tushtev).

http://dx.doi.org/10.1016/j.msea.2014.07.027
0921-5093/& 2014 Elsevier B.V. All rights reserved.

diffusion of the grain growth inhibiting silica in the bers leads to

a pronounced grain growth in the peripheral regions of the N610
bers [14,15]. This effect could be reduced by the addition of an
appropriate amount of silica to the matrix system [16]. An inverse
behavior was found for CMCs based on SiOC, mullite or zirconia/
alumina matrices. Here, a tendency to smaller grains in the
peripheral zone can be observed [17].
The different grain structures might inuence the ber dominated
CMC properties, as the performance of the ber is based on its
microstructure. Investigations on single laments after thermal
exposure showed a decrease of strength due to grain coarsening
[15,1820]. In contrast, an increasing grain size improves the creep
resistance of the bers [21]. While numerous studies were conducted
on the creep performance of all-oxide CMCs [2231], only few works
were published regarding polymer derived composites. An elaborate
overview regarding CMCs for gas turbine applications including a PIP
manufactured SiC/SiCNO composite with a BN interface was published
by Lara-Curzio [5]. It was shown, that in comparison to metallic alloys
superior high temperature stabilities could be achieved. Regarding
composites with oxide reinforcements, Gonczy and Sikonia [32]
investigated the creep performance of a 01/901 Nextels 312 reinforced
Blackglas (SiOC) composite using a BN interface at 566 1C in air
atmosphere. The loads in the study ranged from 55 to 96 MPa leading
to creep rates between 5.5
10  10 and 1.1
10  8 s  1. In 2004, Casas
and Martinez-Esnaola [33] tested a N610 reinforced polymer derived

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E. Volkmann et al. / Materials Science & Engineering A 614 (2014) 171179

composite with a fugitive coating between 1000 and 1200 1C and

between 50 and 80 MPa. They determined a stress exponent of
9.2 and activation energy of 5.9
105 J/mol.
However, the creep performance of polymer derived composites will be inuenced by the occurring changes in the matrix and
interface. Furthermore, possible manufacturing process related
changes of the initial N610 microstructure might also alter the
composite performance. Nevertheless, to the authors knowledge
no studies exist that investigate these inuences. Therefore, in the
present study two 01/901N610 reinforced polymer derived composites with different ber microstructures were tested under
static load conditions between 900 1C and 1200 1C in air atmosphere. While both materials were tested in ber direction (onaxis) to analyze the inuence of the ber structure, one material
was also tested in 451 (off-axis). The off-axis orientation was used
to analyze the inuence of the matrix changes.

2. Materials and methods

Comprehensive information about the used composite materials UMOX and OXIPOL is given as follows.
2.1. Materials
2.1.1. UMOX
UMOX is the standard oxide based CMC used at EADS Deutschland GmbH/Airbus Group Innovations (Munich, Germany). The matrix
is based on a commercial micron-sized mullite powder and polysiloxane precursor. Coated continuous N610 alumina bers (3M, St. Paul,
US) are used as reinforcing material. A fugitive coating is used to
assure crack deection and the oxide CMC is manufactured by the PIP
process [22]. Therefore, the bers are coated with a phenolic resin
which is converted to a thin carbon layer during pyrolysis. Before this,
the coated, oxide ber rovings are inltrated with liquid pre-ceramic
matrix slurry (Liquid Polymer Inltration, LPI) and wound onto a
constantly rotating drum or mandrel (up to 1.5 m in diameter).
Subsequently, unidirectional prepregs are cut and stacked in a
symmetrical, bidirectional lay-up consisting of 16 layers. After drying
this stack is vacuum packed and consolidated in an autoclave
(p410 bar, T4423 K). Conversion of the precursor to a ceramic
matrix is achieved by pyrolysis in an argon atmosphere at 1570 K.
Two re-inltration cycles of the composite with a polymeric precursor,
followed by further high temperature treatment, reduce the open
porosity to 13 vol%. The nal composite exhibits a raw density of
2.46 g/cm3, a carbon content of approximately 1 mass% and a ber
volume content of E50 vol%. Finally, the carbon layer on the bers is
removed by an oxidative heat treatment leaving a 4080 nm wide gap
between the ber and matrix.
2.1.2. OXIPOL
OXIPOL, a recently developed oxide composite, is manufactured
at the DLR Institute of Structures and Design (Stuttgart, Germany)
via PIP process. It is built up by N610 bers and a SiOC matrix
derived from polysiloxane precursors [26]. Comparable with
UMOX, damage tolerance is guaranteed via a fugitive coating
with a nal thickness o100 nm achieved by pyrolsis and oxidation of a polyphenolic resin coating.
Instead of the wet inltration of ber tows, here coated fabric
sheets (8 harness satin, DF-19, 3M, St. Paul, US) and layers of resin
powder (MK, Wacker Chemie, Germany) are stacked up to a
laminate and warm pressed. Thereby, the fabrics are inltrated
with the polymer, which is cured under axial load and at low
pressure (50 mbar). After pyrolysis at 1370 K four additional PIP
with plunging the composite in a liquid polysiloxane precursor
assisted by near-vacuum are performed to reduce the CMCs'

porosity. The resulting CMC contains a total porosity of 15 vol%, a

raw density of 2.36 g/cm3 and a carbon content of 5 mass%. A ber
orientation and content of 701/901 (112 tows in load direction)
and 43 vol% are used for the investigated materials.

2.2. Methods
2.2.1. Quasi-static and creep test under tension
Tensile tests at ambient temperature were accomplished according
to DIN EN 658-1 on a Zwick 1465 (Zwick, Ulm, Germany) universal
testing machine. Tensile tests at elevated temperatures and tensile
creep tests were performed on a Kappa 050 creep test machine
(Zwick, Germany) according to DIN EN 13235 and DIN EN 1893:2005,
respectively. The tensile modulus is calculated based on a linear
regression tted to the stressstrain curve in the region before the
onset of quasi-plastic effects. Creep tests at 1000 1C were performed at
several loads. Besides normal creep tests with a single constant load
also creep rupture tests with a stepwise load increase were used. The
applied stresses varied between 40% and 90% of the corresponding
tensile strength at 1000 1C. Additionally, creep tests at various temperatures between 900 1C and 1200 1C under the constant stress of
50 MPa were performed to obtain information about the activation
energies. All samples were heated by an induction heating system
using a constant heating rate of 30 K/min up to test temperature,
where the samples were hold for 10 min before the actual test to
assure a constant temperature distribution. During the test the
pyrometer was used as feedback control for the heating system, while
a thermocouple type K was used to verify the temperature in the
beginning and at the end of the test. To prevent ageing effects a new
thermocouple was used for each sample. Before the study a correction
curve for the pyrometer was evaluated in a heating experiment with a
thermocouple up to 1200 1C. Furthermore, the temperature prole
along the sample surface was veried by a type R thermocouple. The
test equipment and the resulting temperature distribution in the
susceptor area are depicted in Fig. 1.
The load application in all tests was realized using a constant
displacement rate of 1 mm/min, The strain rates varied at ambient
temperature from E0.01%/s for the on-axis composites to E0.015%/s
for the off-axis samples. The rates increased with increasing temperature up to nearly twice of the values for the tests at 1200 1C. The strain
measurement was realized with a laser based strain measurement
system (Fiedler, Germany) for ambient and high temperature. For this
purpose markings of the samples were accomplished by airbrushing a
suspension of ethanol and partly stabilized zirconia powder (TZ-3YS,
Tosoh Corporation, Japan). This powder was chosen, because of the
negligible sintering activity at the test temperatures. Additionally, the
stable white color of the marks allows a reasonable resolution of the
measuring signal, although the surface color of the samples changed
during creep tests (cf. Fig. 1). At room temperature a clip on the
extensometer (MTS, US) was also used. Dog bone shaped samples
(length: 180 mm width at gage section: 15 mm) were used for all
tests. The gage length for strain measurement was 25 mm (cf. Fig. 1).
Tensile tests were conducted in on-axis (01) and off-axis (451)
directions for both materials, while creep tests were performed in both
directions for UMOX and only in the on-axis direction for OXIPOL.
2.2.2. Grain size analysis
Sections of the composite samples were ground and polished,
followed by thermal etching between 1100 and 1200 1C for 30 min
to reveal the grain structure. Subsequently, images of ve bers
were taken with a Zeiss Supra 40 (Zeiss, Germany) scanning
electron microscope at 100k magnication (2 mm
3 mm, 2
images/ber). Afterwards, the images were used to determine
the grain sizes by the line-intercept method with the help of the
image analysis software Lince (TU Darmstadt, Germany).

E. Volkmann et al. / Materials Science & Engineering A 614 (2014) 171179

173

Fig. 1. High temperature test setup (left) showing also the temperature distribution along the susceptor. The temperature prole was measured with a thermocouple at the
sample surface. Visual change of the as received (AR) sample surface after a 150 h creep test (right). All pictures were taken with equal camera settings. The change of the
surface color is related to the formation of silica due to the oxidation of residual carbon in the material.

Fig. 2. Left: grain size distributions of UMOX and OXIPOL in the as received state. The squares in the boxes indicate the average, the lines correspond to 1st, 2nd (median)
and 3rd quartile of the distributions and the whiskers end at the maximum and minimum, respectively. The dashed line corresponds to the grain size in virgin N610 bers
[16]. Right: SEM images of the microstructure in the center of a thermally etched Nextel 610 in UMOX composite.

3. Results
3.1. Grain size analysis
The grain size distributions of the N610 bers in UMOX and
OXIPOL are depicted in Fig. 2 (left). The grain sizes are best described
by a log-normal distribution comparable to earlier works by Armani
[34]. In the as received state the grain size within UMOX
(4.9570.64 log nm, approx. 141 nm) was nearly twice as big as
for OXIPOL (4.3870.39 log nm, approx. 80 nm). While the data for
OXIPOL is comparable with results reported in the literature [18] for
untreated N610 bers, the effect of pyrolysis temperature is manifested by the data of UMOX. Besides a wider distribution (box
width) also higher maximum grain sizes were found for UMOX. The
broad distributions are based on normal and abnormal grain growth
[35] within the ber, which is depicted in Fig. 2 on the right side.
3.2. Tensile tests
The tensile performance of UMOX and OXIPOL in on-and offaxis directions is shown in Fig. 3. Linear stressstrain responses at
room temperature and 1000 1C were observed for both materials
in the on-axis direction. An increase of the test temperature to
1200 1C lead to a clearly non-linear behavior for OXIPOL, while the
curve shape of UMOX remained nearly linear. Tensile loading in
off-axis orientation (451) also leads to a non-linear stressstrain
relationship, which was more pronounced for OXIPOL and higher
temperatures. The average tensile strengths and the corresponding
standard deviations of the composites, which are shown in Fig. 3C,

were higher for UMOX. While UMOX tested in on-axis direction exhibited a strength of 1957 1 MPa, 12378 MPa, and
114 74 MPa, in the case of OXIPOL only strengths values of
1357 11 MPa, 59 72 MPa, and 66 72 MPa were determined at
ambient temperature, 1000 1C and 1200 1C, respectively. The same
trend was found regarding the off-axis loading. Here, the strengths
of OXIPOL were 58 75 MPa, 56 72 MPa, and 23 70 MPa and of
UMOX 13475 MPa, 104 77 MPa, and 927 1 MPa, tested at
ambient temperature, 1000 1C and 1200 1C, respectively.
Fig. 3D shows the average Young's moduli and the standard
deviations of the composites tested at room and high temperature
and in both directions. Both materials exhibited higher moduli in
the on-axis direction with maximum values of 112 74 GPa and
897 1 GPa for UMOX and OXIPOL, respectively. An increase of
the test temperature to 1000 1C decreased the on-axis moduli by
approximately 510%, while testing at 1200 1C lead to a reduction
up to 50%. In contrast, regarding the matrix dominated 451
orientation only tests at 1200 1C reduced the moduli, while for
1000 1C no decrease was observed compared to the ambient
temperature values. Actually, in the case of OXIPOL the test
temperature 1000 1C increased the modulus by 40%.
3.3. Creep tests
Creep tests at several loads were performed at 1000 1C to
investigate the stress sensitivity. Representative creep curves and
curves of the strain rate vs. time are shown in Fig. 4. The applied
stresses in Fig. 4 (left) correspond to 40%, 55%, 70% and 80% of the
tensile strength at 1000 1C for the on-axis direction and to 65%,

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E. Volkmann et al. / Materials Science & Engineering A 614 (2014) 171179

Fig. 3. Inuence of the test temperature and loading direction on representative tensile curves of UMOX (A) and OXIPOL (B). Comparison of average tensile strength
(C) and tensile modulus (D) of the tested composites. Bars on top indicate the standard deviation based on three tests.

Fig. 4. Inuence of applied stress and loading direction on representative strain time and strain rate vs. time curves of the creep and creep rupture tests (left). Inuence of
material type and loading orientation on the onset of secondary creep (right). The dashed line in B corresponds to the linear extrapolation of the regression used for the
strain rate determination.

75% and 85% in case of the off-axis direction. The displayed off-axis
sample survived 75 h at 65% and 50 h at 75% before it failed after
8 more hours at 85% and E1.5% creep strain (133 h). In on-axis

direction UMOX survived more than 250 h at 40% and 120 h at

55%. An increase of the load from 55% to 75% leads to creep failure
after additional 50 h and in total 0.4% strain. Immediate loading at

E. Volkmann et al. / Materials Science & Engineering A 614 (2014) 171179

80% of the tensile strength caused failure after more than 100 h
and 0.4% strain. The maximum creep strains ranged from
0.3 70.1% for UMOX 01/901, and 0.6 70.1% (OXIPOL 01/901) up
to 1.6 70.2% for the matrix dominated UMOX 451 samples. The
reduction of the cross-sectional area after the creep tests at
1000 1C was o 0.5% for UMOX 7451, o 1.4% for UMOX 01/
901 and E 1% for OXIPOL 01/901. Regarding the 01/901 tests at
1200 1C, these values increased to 1.7% for UMOX and E 5% for
OXIPOL. Interestingly, this reduction of the area was caused by a
decrease of the width in case of UMOX while for OXIPOL mainly
the thicknesses of the samples were reduced.
All samples of UMOX and OXIPOL showed primary and secondary creep regimes, while no tertiary creep was observed. In comparison to the on-axis direction the secondary creep regime seems to be
less stable for the off-axis direction. Therefore, the determined creep
rates in this orientation can be considered as minimum strain rates.
Typical creep curves at 50 MPa for all tested composites are shown in
Fig. 4 (right). The primary creep region was more extended (E50 h)
and pronounced for the 451 samples, which were only tested in the
case of UMOX. Comparing the on-axis composites, OXIPOL showed a
later onset of the secondary creep regime (E5 h vs. E1 h).
The secondary creep rates of the samples tested at 1000 1C are
listed in Table 2. The stationary creep rates of virgin samples and
samples of creep rupture tests, subjected to equal stresses were
found to be comparable. Therefore, the average values and
standard deviations shown in Table 2 were calculated without
respect to the test history of the samples. The observed creep rates
varied between 1.5
10  9 s  1 and 5.5
10  9 s  1 (UMOX) and
were signicantly lower as for OXIPOL. Here, creep rates in the
range of 4.9
10  9 s  1 and 5
10  8 s  1 were found. In off-axis
orientation of UMOX secondary creep rates between
4.5
10  9 s  1 and 1.3
10  8 s  1 were observed.
Creep tests at different temperatures were accomplished to determine the apparent activation energies. The determined creep rates for
tests under an applied stress of 50 MPa are listed in Table 3. The onaxis creep rates for tests at 50 MPa at 1000 1C varied between
2.3
10  9 s  1 and 3.4
10  8 s  1 for UMOX and OXIPOL, respectively. Tests at 1200 1C lead to a rate increase by several orders of
magnitude up to 7
10  6 s  1 and 1.9
10  4 s  1 for UMOX and
OXIPOL, respectively. In the off-axis direction the rates at 50 MPa
varied between 6.6
10  10 s  1 and 4.4
10  8 s  1 for temperatures
between 900 1C and 1100 1C.

4. Discussion
The grain size analysis of UMOX and OXIPOL revealed a clear
inuence of the processing conditions on the ber microstructure.
OXIPOL exhibited a grain size distribution comparable to the
untreated ber [18], due to a pyrolysis temperature below
1470 K. In contrast, the average grain sizes of the N610 in UMOX

175

were approximately two times bigger, related to the processing

temperature above 1470 K. Comparable results were found in a
previous study investigating the inuences of processing conditions and matrix compositions on the evolution of the grain
structure of N610 bers within ceramic matrix composites [17].
The larger grain sizes found after pyrolysis or exposure to
temperatures 41470 K can be explained by the onset of grain
growth within the N610 at these temperatures. Schmcker et al.
[15,18] observed that while an exposure to 1470 K for 1 h only
leads to a small increase of the grain size (E30%), an increase of
the exposure temperature to 1570 K resulted in a signicant

Table 2
Stress dependency: overview of the determined secondary creep rates at 1273 K.
For samples with standard deviations at least two samples were tested. Samples
tested as virgin samples are written in italics.
Material Abs. applied
stress (MPa)

On axis
UMOX 50
68
80
86
92
97
OXIPOL 30
42
53
Off-axis
UMOX 50
62
68
78
88
93

Rel. applied
stress % of
strength

Average sec.
creep rate (s  1)

Standard
deviation
(s  1)

40
55
65
70
75
80
50
70
90

2.25E-09
3.28E-09
4.25E-09
4.83E-09
4.55E-09
5.09E-09
4.88E-09
1.65E-08
4.23E-08

9.35E-10

50
60
65
75
85
90

5.20E-09
5.90E-09
6.43E-09
6.56E-09
1.08E-08
1.31E-08

1.22E-08
9.90E-10
1.60E-09
2.60E-10

Table 3
Temperature dependency: overview of the determined secondary creep rates at
50 MPa.
Test
temperature (1C)

(Average) sec.
creep rate (s  1)
UMOX

(Average) sec.
creep rate (s  1)
OXIPOL

On-axis
1000
1100
1200

2.25E-09
1.25E-08
7.01E-06

3.37E-08
Not tested
1.87E-04

Off-axis
900
1000
1200

6.40E-10
5.20E-09
4.45E-08

Not tested
Not tested
Not tested

Table 1
Properties of the tested composites.
UMOX
Reinforcement ber
Reinforcement type
Reinforcement lay-up
Coating
Matrix polymer
Filler particles
Pyrolysis temperature (K)
Re-Inltration cycles
Residual carbon content (mass%)
Total porosity (%)
Fiber volume content (%)

9.19E-10

Nextel 610, 3M, US

UD tape
[01/901]S or [ 7 451]Symmetrical
Phenolic resin/fugitive
Polysiloxane
Mullite
1570
2
E1
E13
4951

OXIPOL

2/2 twill fabric

[01/901]S or [ 7 451]Symmetrical

None
1370
4
E5
E 15
43

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E. Volkmann et al. / Materials Science & Engineering A 614 (2014) 171179

coarsening of the microstructure (E80% bigger average). Besides

the increase of the average grain size, also abnormal grain growth
could be observed for the N610 within UMOX (cf. Fig. 2 right
side). However, recent studies showed that the exaggerated grain
growth in N610 bers seems independent of the matrix composition [14,17]. Currently, it is believed that the abnormal grain
growth in alumina is an extrinsic effect controlled by impurities.
However, despite several studies over last years [3537], the
mechanisms are still not fully understood.
The tensile and creep behavior of CMCs in the ber direction
are dominated by the properties of the reinforcement. In the case
of the polycrystalline N610 these are related to their grain
structure. However, besides the microstructure of the ber, also
the ber matrix adhesion, the matrix composition and the reinforcement type (woven/not woven/) and orientation contribute
to the nal composite performance. Therefore, the analysis of the
underlying effects is very complex, especially if the properties of
the composites' constituents change during the tests. To investigate the basic properties and to dene a rational loading for the
creep tests tensile tests were performed. The tests showed a nearly
linear behavior for both composites in on-axis direction at room
temperature and 1000 1C. However, at 1200 1C OXIPOL exhibited a
marked non-linear curve with approximately six times higher
fracture strains. This can be explained by overlaying creep strains,
due to the constant test rate of 1 mm/min used for all tests in
combination with the higher creep rates at 1200 1C [4]. In off-axis
direction, the mullite ller and the higher pyrolysis temperature of
UMOX increased the strength and stiffness of the composites. In
ber direction, the higher tensile strengths and stiffness can be
mainly related to the smaller ber volume fraction of OXIPOL and
the different reinforcement types. The modulus of UMOX at
ambient temperature is E24 GPa higher compared to OXIPOL.
This corresponds quite well to the stiffness increase based on the
higher ber volume fraction. This can be explained by the
presumably low contribution of the matrix to the stiffness in onaxis direction. Regarding a comparable SiOCmullite matrix composite Peters et al. [38] found that the matrix only contributes 6%
to the on-axis stiffness. Therefore, in the case of the even more
porous and pure SiOC matrix of OXIPOL it might be assumed that
the matrix possesses a comparably low or even lower stiffness
contribution. Hence an increase of the ber volume fraction by 7%
(cf. Table 1) would lead to an approximate stiffness increase of
26 GPa (0.07
373 GPa (EN610)). Besides that, UMOX is reinforced by stacked, straight orientated UD-prepregs, while the
woven bers in the fabrics of OXIPOL are not perfectly orientated
and might have suffered some damage during weaving [31]. The
decreasing performance of the composites at high temperatures is
mainly related to the decrease of the ber properties [39]. The
strength of the N610 decreases to about 65% and 40% of its original
strength from ambient temperature to 1000 1C and 1200 1C,
respectively. The strengths' of UMOX and OXIPOL decreased to
E63% and 45% at 1000 1C to 58% and 49% at 1200 1C. Here, the
increase of the relative strength values of OXIPOL at 1200 1C might
be explained by the overlaying creep effects.
The duration of the primary creep regime was evaluated based
on the regression for the determination of the secondary creep
rates. The time corresponding to the point, where the linear
extrapolation deviated from the creep curve was considered as
end of the primary creep regime. Regarding UMOX in off-axis
(7451) direction the primary creep regime lasts approximately 50
times longer compared with the on-axis (01) direction (cf. Fig. 4B
and D). The creep response of the composite under off-axis loading
is dominated by the matrix. The matrix of UMOX is composed of
inert relatively creep stable mullite particles and mainly glassy
SiOC containing approximately 1% free carbon. The low creep
resistance of the SiOC facilitates the re-arrangement of the bers

in load direction until the laments are blocked by the mullite

particles or themselves. In the present case, the observed 1%
primary creep strain would be already explained by a decrease
of the reinforcement angle by E0.51
cos 451

adjacent leg a
hypotenuse h

Assuming no ber strain (h1) and 1% strain, the corresponding

angle can be calculated as follows:
cos  1 X a1:01 cos  1 cos 451:01 44:41

In the present case, the oxidation of the SiOC results in the

formation of silica, which possesses an up to three orders of
magnitude lower viscosity at 1000 1C [40]. Therefore, besides the
inherently low creep resistance of the SiOC, especially the formation of amorphous silica during oxidation might increase the
mobility of the bers with the tendency to homogenize the stress
distribution in the composite. As the oxidation is nishing and the
bers are approaching their stationary position, primary creep
effects are fading away and transition to secondary creep would be
observable.
In the case of UMOX approximately 90% of the nal oxidation
(mass gain) is completed [12] after 50 h, which is in good
agreement with the observed onset of the constant creep deformation. Hence, it might be concluded that the primary creep
regime in off-axis direction is mainly attributed to the rearrangement of the reinforcement, which is facilitated by the
amorphous silica formed during oxidation.
In on-axis orientation a longer primary creep region was
observed for fabric reinforced OXIPOL, which might be explained
by a straightening of the bers in load direction. However,
compared with the off-axis reinforced material the primary creep
region is negligible in on-axis direction. For matrix dominated
creep behavior (7 451) changes within matrix result in a pronounced primary creep regime, while with bers in load direction
the creep performance is nearly independent of the matrix
changes. Additionally, grain growth within the N610 ber can be
neglected, due to the used test temperatures below or equal
1470 K. Hence, especially for the ber dominated 01/901 composites the evaluation of the secondary creep regime is very
important. The stationary creep rates of oxide ceramic matrix
composites in on-axis direction are directly related to the properties of the reinforcing bers [25,26,41,42]. In the present case, the
stress dependence could be described by the following Norton
Bailey equation [41,43]:

_ s A n

where _ s is the secondary/minimum creep rate, A is a temperature

depending constant encompassing the activation energy and
structural parameters, is the applied stress in MPa and n is the
stress exponent. It is important to note, that the theoretical
assumptions for the equation, i.e. a homogenous, isotropic material with a microstructure staying unchanged during deformation
are not valid for the composite material. In the case, however,
when secondary creep is reached and creep is governed by the
creep rate of a highly creep resistant constituent, i.e. reinforcing
bers, these assumptions may be approached. The stress dependence of numerous ceramic composites could be described reasonably well by this power-law [27,33,41,4346], which is often
attributed to the domination of the secondary creep regime by one
of the constituents.
Fig. 5 shows the secondary creep rates vs. the applied stress for
the two composites. The stress exponent of 01/901 OXIPOL is E3.8,
which is comparable to values measured for N610 bers, tows or
other N610 reinforced composites [25,41,4749]. Regarding N610
bers the dominating creep deformation mechanism was

E. Volkmann et al. / Materials Science & Engineering A 614 (2014) 171179

Fig. 5. Stress dependence of secondary creep rates of the tested composites at

1000 1C. Bars are related to the standard deviation. Values without bars are based
on one sample only.

attributed to interface reaction controlled diffusion (ICD) [21,50].

However, UMOX showed a signicantly lower stress exponent of
about 1.2 for the on-axis direction. Values around 1 are often
found for ne grained alumina [51] and normally attributed to a
diffusional creep mechanism like the NabarroHerring or Coble
creep [52]. In the present case, the grain structures of the N610
bers used in OXIPOL and UMOX differ as can be seen in Fig. 2.
The stationary creep rate varies with the grain size according to
_ s  d  m , where m is the grain size exponent which is 1 for
interface reaction controlled creep of N610 bers [50], 2 for the
NabarroHerring creep and 3 for the Coble creep, respectively
[52]. The average grain size of UMOX is approximately twice of
the grain size of OXIPOL. Assuming ICD and the average grain size
of UMOX would lead to a E50% lower creep rate. However, the
obtained creep rates of OXIPOL were about 18 times higher for a
comparable applied stress (50 MPa). Besides the grain size the
inuence of the lower ber volume fraction (FVF) also might be
considered. For this purpose the initial ber stresses parallel to the
applied loads 01
f iber were calculated based on the global strain
CMC , the ber modulus Ef and the composite modulus ECMC ,
which is related to the FVF [25]

01
f iber E f f E f CMC E f

CMC
ECMC

According to this relationship, the 25% lower tensile modulus of

OXIPOL results in E30% higher initial ber stresses. This would
decrease the creep rates of OXIPOL at comparable ber stresses
from 18 times to 13 times of the measured values.
Finally, the differences of the grain size distributions have to be
taken into account. While the N610 in OXIPOL exhibited a uniform,
ne grained structure, a non-uniform grain structure was observed
in UMOX. A ne-grained microstructure containing also large,
elongated grains like in UMOX will result in an increased creep
resistance due to interlocking effects [34,53]. Therefore, the
normalization procedure of the creep rates on the basis of average
grain sizes and initial stress is not sufcient. The reduced creep
rates of UMOX can then be explained by the additional effect of
these large interlocking grains.
However, in contrast to the stress exponents the apparent
activation energies of UMOX and OXIPOL in on-axis direction
are comparable. The apparent activation energy of the creep
process can be calculated by the slope of the log _ vs. 1/T plot
[54] (cf. Table 3). Regarding the on-axis tested composites 616 kJ/
mol and 644 kJ/mol were calculated for UMOX and OXIPOL,
respectively. Both values are in good agreement with values
for pure alumina (625 kJ/mol [51]), single N610 bers

177

(660 kJ/mol [49]) or earlier studies for N610 reinforced SiOC/

mullite composites (590 kJ/mol [33]). These apparent activation
energies are then attributable to cation diffusion processes and can
be compared with the related true activation energy (635 kJ/mol)
as determined for pure alumina [51]. Therefore, a ber dominated
creep process, as suggested, is likely. In 7451 direction the
apparent activation energy is signicantly lower (283 kJ/mol). As
mentioned before, the off-axis orientation of the bers will lead to
a matrix dominated creep process, explaining for example the
longer primary creep regime. This assumption is supported by the
determined apparent activation energy of 283 kJ/mol, which is in
good agreement with values determined for pure SiOC by Rouxel
et al. (296 kJ/mol, [55]) and Papendorf et al. (283 kJ/mol, [56]) for
the activation energy for viscous ow of SiOC. The lower creep
resistance of the matrix material leads to higher secondary creep
rates for the off-axis composite. However, the maximum difference of the secondary creep rates between on- and off-axis of a
factor three is rather small compared to differences up to three
orders of magnitude reported for an all-oxide N720/AS weak
matrix composite [57]. This might be attributed to the relatively
dense and strong matrix, which also explains the good tensile
strength and stiffness in off-axis direction. Similar to studies
regarding the off-axis creep performance of N720/alumina [29]
and N720/aluminamullite [23] two regimes could be distinguished relating the secondary creep rates to the applied stresses
(cf. Fig. 5). Depending on the applied stress, exponents of 0.6 and
4 for stresses below and beyond 80 MPa were found, respectively.
The exponent of E0.6 for applied stresses below 80 MPa is
comparable to values found for the compressive creep of SiOC.
Here in a temperature range between 1100 1C and 1200 1C values
between 0.697 0.08 and 1.02 70.01 were found [56]. The calculated stress exponent close to one is related to viscous ow as the
main creep mechanism of the matrix, which was also found for
silicon oxynitride [58], SiOC [55,56] and SiCN glasses [59]. Therefore, based on the apparent activation energy and the stress
exponent it can be concluded that the creep behavior in off-axis
direction below 80 MPa is dominated by viscous ow of the SiOC
in the matrix.
However, after exceeding a certain stress (E80 MPa) the creep
rates in the off-axis direction increase, leading to an eight times
higher stress sensitivity. This behavior was also found for weak
matrix composites investigated by Ruggles-Wrenn [23,29] for
stresses higher than 3040 MPa, which in that case corresponded
to loads were a signicant non-linear stressstrain response was
observed in the tensile curves. This leads to the assumption, that
beyond a certain stress (here E 80 MPa) a ber re-orientation
might be facilitated, due to additional damage occurring within
the matrix.
In Fig. 6 the fracture surface of an off-axis reinforced UMOX
sample crept above 80 MPa is shown. Besides ber pull-outs and
short pull-out length, inter- and intra-laminar cracks can be seen.
The rst shear based inter-laminar cracks will lead to a higher
mobility, facilitating a kind of layer-re-orientation that might be
followed by intra-laminar damage. The enhanced ber mobility,
the resulting higher stresses within the bers, and the additional
matrix loading, due to crack formation might increase the strain
rates and lead to a higher stress exponent. Hence, it might be
concluded, that in contrast to the stress exponents and creep rates
below the limit stress, the rates beyond this stress cannot be
used to identify a certain creep mechanism, due to the enhanced
crack formation within the composites.
The maximum creep strains in off-axis direction are approximately ve times higher than in on-axis direction. The nal failure
of all materials under creep conditions was rather brittle, as
illustrated in Fig. 6 exemplary for the 451 UMOX composite.
The nal failure of oxide based N610 reinforced composites can be

178

E. Volkmann et al. / Materials Science & Engineering A 614 (2014) 171179

Fig. 6. Fracture surface of UMOX sample after off-axis ( 7 451) creep test at
89 MPa.

related to the creeping bers, that fail due to the coalescence of

cavities [49], like it was shown by Hackeman et al. for an N610/
alumina CMC. In off-axis direction, bers might also fail due to a
local stress concentrations caused by the cracking of the matrix. In
the case of OXIPOL the 100% higher maximum creep strain
compared to UMOX is a combination of the higher creep rates
based on the ne-grained microstructure, the owing pure SiOC
matrix [40,55] and the possible straightening of the woven bers.
This hypothesis is supported by comparing the dimensional
changes. In on-axis direction, the cross-sectional reduction of
OXIPOL is nearly twice of the values for UMOX. Additionally, in
contrast to the cross-ply reinforced UMOX, in the case of OXIPOL
the reduction of ber undulations caused a more pronounced
thickness decrease. However, for the creep tests below 1200 1C all
materials show a good dimensional stability with a reduction of
the cross-sectional area of about 1%.

structure within UMOX resulted in an exponent of E 1 (1.2),

which is typical for diffusional creep mechanisms found in negrained alumina like e.g. Coble creep.
In off-axis orientation (UMOX) the matrix plays the key role
for creep deformation. The pronounced primary creep regime is
explained by a re-arrangement of the bers, which is facilitated by
the formation of glassy silica, due to the oxidation of the SiOC ( E
up to 50 h). Subsequently a stable secondary creep regime is
observed. Below a limit stress of E 80 MPa a stress exponent
close to 1 (0.6) and an apparent activation energy of 283 kJ/mol
can be calculated corresponding to a creep deformation due to
viscous ow of the SiOC in the matrix. Beyond this stress, the
creep response seems to be inuenced by increasing internal
damage, which was also found for several all-oxide composites
with a porous matrix [23,29].
The possible existence of a limit stress in PIP and all-oxide
composites, at which a drastic increase of the creep rates can be
expected, should be further investigated, due to its importance for
possible applications. Furthermore, the present study clearly
indicates, that the pyrolisis temperature and the resulting matrix
and ber microstructure have a high impact on the mechanical
performance of this materials. Hence, by the adaptation of the
manufacturing process the ber related mechanical properties of
the materials should be adjustable according to the desired
applications. Hence, further studies should be conducted focusing
on the inuence of the pyrolysis conditions on microstructural
changes within the ber and matrix.

Acknowledgment
Parts of this study were included within the HiPOC program.
Therefore, the authors would like to thank the German Federal
Ministry of Education and Research (BMBF).

References
5. Conclusion
The tensile and creep performance of two SiOC containing
composite materials (UMOX and OXIPOL) reinforced with N610
bers were investigated. The inuence of ber microstructure was
evaluated by on-axis tests for OXIPOL and UMOX. Additionally,
UMOX off-axis tests were accomplished to investigate the
inuence of matrix changes.
The tensile tests revealed a higher strength and stiffness of the
UMOX material. In off-axis direction, this can be attributed to
the higher pyrolysed mulliteSiOC matrix. In on-axis direction, the
lower strengths and stiffness of OXIPOL might be explained by the
lower ber volume content, and possible ber damage suffered
during the weaving process of the reinforcement fabric.
The creep tests in the ber dominated orientation (01/901)
showed an approximately 1050 times shorter primary creep
regime compared with the matrix dominated off-axis ( 7451)
direction. This leads to the conclusion that changes or creep of
the matrix are negligible in on-axis orientation. Therefore, the
creep performance is mainly related to the ber properties. The
200 K higher processing temperature of UMOX leads to coarser,
non-uniform grain structure of the N610 bers. In OXIPOL the
native ne-grained N610 microstructure remained unchanged. The
different ber structures lead to lower creep rates for UMOX and
to different creep mechanisms. The unchanged N610 grain structure in OXIPOL resulted in a stress exponent around 3.5 (3.8) at
1000 1C, which is typical for creep of N610 bers and can be
attributed to interface reaction controlled diffusion. The grain

[1] W.P. Fischer, H. Ritter, Proceedings of the 42nd International Conference on

Environmental Systems, American Institute of Aeronautics and Astronautics,
2012.
[2] R. Knoche, E. Werth, M. Weth, J.G. Garca, C. Wilhelmi, M. Gerends, in:
D. Singh, J. Salem, S. Widjaja (Eds.), Proceedings of the Cocoa/Daytona Beach
Conference, ICACC2011, John Wiley & Sons, Inc., Hoboken, NJ, USA, 2011.
[3] M. Gerends, Y. Cadoret, C. Wilhelmi, T. Machry, R. Knoche, T. Behrendt,
T. Aumeier, S. Denis, J. Gring, D. Koch, K. Tushtev, Proceedings of the ASME
Turbo Expo 2011, ASME, Vancouver, Canada, 2011, pp. 45460.
[4] M. Gerends, C. Wilhelmi, T. Machry, R. Knoche, E. Werth, T. Behrendt, D. Koch,
S. Hofmann, J. Gring, K. Tushtev, E. Volkmann, Proceedings of the ASME
Turbo Expo 2013: Power for Land, Sea Air, San Antonio, Texas, USA, 2013.
[5] E. Lara-Curzio, in: M. van Roode, M.K. Ferber, D.W. Richerson (Eds.), Ceramic
Gas Turbine Design and Test Experience: Progress in Ceramic Gas Turbine
Development, ASME Press, Materials Park, Ohio, 2003, pp. 441493.
[6] G. Motz, S. Schmidt, S. Beyer, in: W. Krenkel (Ed.), Ceramic Matrix Composites,
Wiley-VCH, Germany, 2008, pp. 165186.
[7] N. Chawla, Y.K. Tur, J.W. Holmes, J.R. Barber, J. Am. Ceram. Soc. 81 (1998)
12211230.
[8] R. Jones, A. Szweda, D. Petrak, Compos. Part A: Appl. Sci. Manuf. 30 (1999)
569575.
[9] S. Modena, G.D. Sorar, Y. Blum, R. Raj, J. Am. Ceram. Soc. 88 (2005) 339345.
[10] J.H. Weaver, J. Yang, F.W. Zok, J. Am. Ceram. Soc. 91 (2008) 40034008.
[11] E. Volkmann, K. Tushtev, D. Koch, C. Wilhelmi, J. Gring, K. Rezwan, Compos.
Part A: Appl. Sci. Manuf. (2014) (submitted for publication).
[12] E. Volkmann, L. Lima Evangelista, K. Tushtev, D. Koch, C. Wilhelmi, K. Rezwan,
J. Mater. Sci. 49 (2013) 710719.
[13] S. Hoenig, E. Klatt, M. Frie, C. Martin, I. Naji, D. Koch, Ceramic Engineering and
Science Proceedings, vol. 570, 2012, 195.
[14] M. Schmcker, P. Mechnich, J. Am. Ceram. Soc. 91 (2008) 13061308.
[15] M. Schmcker, F. Flucht, P. Mechnich, Mater. Sci. Eng. A Struct. Mater. Prop.
Microstruct. Process. 557 (2012) 1016.
[16] M. Schmcker, P. Mechnich, J. Am. Ceram. Soc. 93 (2010) 18881890.
[17] E. Volkmann, M.D. Barros, K. Tushtev, W.E.C. Pritzkow, D. Koch, J. Gring,
C. Wilhelmi, G. Grathwohl, K. Rezwan, Adv. Eng. Mater. (2014) (accepted for
publicaton).

E. Volkmann et al. / Materials Science & Engineering A 614 (2014) 171179

[18] M. Schmcker, F. Flucht, H. Schneider, in: W. Krenkel, R. Naslain, H. Schneider

(Eds.), High Temperature Ceramic Matrix Composites, Wiley VCH, Weinheim,
2001, pp. 7378.
[19] P.E. Cantonwine, J. Mater. Sci. 38 (2003) 461470.
[20] P.E. Cantonwine, J. Mater. Sci. 38 (2003) 471480.
[21] J.C. Goldsby, H.M. Yun, G.N. Morscher, J.A. DiCarlo, Mater. Sci. Eng. A 242
(1998) 278283.
[22] M.B. Ruggles-Wrenn, B.A. Whiting, Mater. Sci. Eng. A 528 (2011) 18481856.
[23] M.B. Ruggles-Wrenn, M. Ozer, Mater. Sci. Eng. A 527 (2010) 53265334.
[24] M.B. Ruggles-Wrenn, T. Kutsal, Compos. Part A: Appl. Sci. Manuf. 41 (2010)
18071816.
[25] S. Hackemann, F. Flucht, W. Braue, Compos. Part A: Appl. Sci. Manuf. 41 (2010)
17681776.
[26] M.B. Ruggles-Wrenn, C.L. Genelin, Compos. Sci. Technol. 69 (2009) 663669.
[27] M. Ruggles-Wrenn, T. Yeleser, G. Fair, J. Davis, Appl. Compos. Mater. 16 (2009)
379392.
[28] M.B. Ruggles-Wrenn, N.R. Szymczak, Compos. Part A: Appl. Sci. Manuf. 39
(2008) 18291837.
[29] M.B. Ruggles-Wrenn, G.T. Siegert, S.S. Baek, Compos. Sci. Technol. 68 (2008)
15881595.
[30] M. Ruggles-Wrenn, P. Koutsoukos, S. Baek, J. Mater. Sci. 43 (2008) 67346746.
[31] C.G. Levi, J.Y. Yang, B.J. Dalgleish, F.W. Zok, A.G. Evans, J. Am. Ceram. Soc. 81
(1998) 20772086.
[32] S.T. Gonczy, J.G. Sikonia, in: N.P. Bansal (Ed.), Handbook of Ceramic Composites, Springer, US, 2005, pp. 347373.
[33] L. Casas, J.M. Martinez-Esnaola, Mate. Sci. Eng. A Struct. Mater. Prop.
Microstruct. Process. 368 (2004) 139144.
[34] C.J. Armani, Air Force Institute of Technology, Air Force Air University, Ohio,
US, 2011.
[35] I.-J. Bae, S. Baik, J. Am. Ceram. Soc. 80 (1997) 11491156.
[36] H.P. Cahoon, C.J. Christensen, J. Am. Ceram. Soc. 39 (1956) 337344.
[37] S.I. Bae, S. Baik, J. Am. Ceram. Soc. 76 (1993) 10651067.
[38] P.W.M. Peters, B. Daniels, F. Clemens, W.D. Vogel, J. Eur. Ceram. Soc. 20 (2000)
531535.

179

[39] D.M. Wilson, in: Wea Krenkel (Ed.), Proceedings of the 4th International
Conference on High Temperature Ceramic Matrix Composites, Wiley-VCH, 2001.
[40] T. Rouxel, G.D. Soraru, J. Vicens, J. Am. Ceram. Soc. 84 (2001) 10521058.
[41] M.B. Ruggles-Wrenn, S.S. Musil, S. Mall, K.A. Keller, Compos. Sci. Technol. 66
(2006) 20892099.
[42] L.P. Zawada, R.S. Hay, S.S. Lee, J. Staehler, J. Am. Ceram. Soc. 86 (2003)
981990.
[43] S. Mall, M.A. Sullivan, Int. J. Appl. Ceram. Technol. 8 (2011) 251260.
[44] J.J. Brennan, K.M. Prewo, J. Mater. Sci. 17 (1982) 23712383.
[45] S. Mall, B.H. Boyer, Compos. Part A Appl. Sci. Manuf. 43 (2012) 11531159.
[46] M.B. Ruggles-Wrenn, S. Mall, C.A. Eber, L.B. Harlan, Compos. Part A Appl. Sci.
Manuf. 37 (2006) 20292040.
[47] C.J. Armani, M.B. Ruggles-Wrenn, G.E. Fair, R.S. Hay, Int. J. Appl. Ceram.
Technol. 10 (2013) 276284.
[48] V.H. Hammond, D.M. Elzey, Scr. Mater. 46 (2002) 287291.
[49] D.M. Wilson, D.C. Lueneburg, S.L. Lieder, Proceedings of the 17th Annual
Conference on Composites and Advanced Ceramic Materials: Ceramic Engineering and Science Proceedings, John Wiley & Sons, Inc., 1993, pp. 609621.
[50] D.M. Wilson, D.C. Lueneburg, S.L. Lieder, Composites and Advanced Ceramic
Materials, Cocoa Beach, 1993.
[51] A. Chokshi, J. Porter, J. Mater. Sci. 21 (1986) 705710.
[52] W.R. Cannon, T. Langdon, J. Mater. Sci. 23 (1988) 120.
[53] K. Tanoue, Metall. Mater. Trans. A 29 (1998) 519526.
[54] W.R. Cannon, T.G. Langdon, J. Mater. Sci. 18 (1983) 1.
[55] T. Rouxel, G. Massouras, G.D. Soraru, J. SolGel Sci. Technol. 14 (1999) 8794.
[56] B. Papendorf, E. Ionescu, H.-J. Kleebe, C. Linck, O. Guillon, K. Nonnenmacher,
R. Riedel, J. Am. Ceram. Soc. 96 (2013) 272280.
[57] D.J. Buchanan, R. John, L.P. Zawada, Compos. Sci. Technol. 68 (2008)
13131320.
[58] S. Hampshire, M.J. Pomeroy, Key Eng. Mater. 287 (2005) 259264.
[59] L. An, R. Riedel, C. Konetschny, H.J. Kleebe, R. Raj, J. Am. Ceram. Soc. 81 (1998)
13491352.