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Creep cavitation in CSEF steels

Conference Paper · January 2013

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PARKER, EPRI Advanced materials Conference, 2013

CREEP CAVITATION IN CSEF STEELS

J. Parker
Electric Power Research Institute, 1300 Harris Boulevard, Charlotte,
North Carolina, 28262, USA

ABSTRACT

As long term laboratory creep data became available the original estimates of the allowable stresses
for creep strength enhanced ferritic steels (CSEF) had to be reduced. Thus, even in properly
processed steel, the long term performance and creep rupture strength is below that originally
predicted from a simple extrapolation of short term data. One of the microstructural degradation
mechanisms responsible for the reduction in strength is the development of creep voids. Nucleation,
growth and inter linkage of voids also result in a significant loss of creep ductility. Indeed,
elongations to rupture of around 5% in 100,000 hours are now considered normal for long term
creep tests on many CSEF steels. This relatively brittle behaviour, and the associated creep void
development, promotes burst rather than leak type fracture in components. Moreover, the existence
of significant densities of voids further complicates in-service assessment of condition and weld
repair of these steels. The present paper examines background on the nucleation and development
of creep voids in 9 to 12%Cr martensitic steels and discusses factors affecting brittle behavior.

INTRODUCTION

Creep strength enhanced ferritic (CSEF) steels contain 9 to 12%Cr; typical compositions of P91,
P92 and E911 are compared with X20 in Table 1. These steels are favored in a range of boiler
applications because of the combination of properties which include; high thermal conductivity,
low thermal expansion coefficient, low susceptibility to thermal fatigue, good corrosion and
oxidation resistance, and relatively good creep resistance [1, 2]. These properties derive from the
microstructure, which, when properly processed, exhibits a tempered martensitic matrix containing
a substructure with a high dislocation density and a fine dispersion of second phase precipitates. It
is interesting to note that the typical alloy compositions for these steels frequently do not include
recommendations for limits on trace or ‘other’ elements even though it is well established that these
elements lead to embrittlement in low alloy steels.

Detailed research examining the microstructure of 9 to 12% Cr tempered martensite ferritic steels
has provided key information concerning the formation of new phases and the coarsening of
carbides during long term creep. However, the microstructures of CSEF steels evolve during
service at elevated temperatures and pressures, and creep strain can enhance the changes which
take place. Indeed, a number of microstructural degradation mechanisms have been identified
which are thought to be responsible for the loss of long term creep strength. These include; the
precipitation of new phases (e.g. Laves and Z phases), the dissolution of fine M2X and MX
carbonitrides, the recovery of the dislocation sub-structure and the development of creep voids in
the microstructure [3-6].

The complex nature of the long term creep behavior is emphasized by consideration of data
compilations considering creep ductility. Published information showing the variation of the
reduction of area at fracture after creep testing at 600oC is shown in Figure 1 for Grade 91, Grade
E911 and Grade 92 steels.

Table 1. Typical compositions and heat treatments used for martensitic boiler steels
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In short term tests the samples fail with high ductility due to local deformation and ‘necking’ of the
samples. While even in long durations some high ductility type failures are reported it is apparent
that as lives increase there is a tendency for some tests to fail in brittle manner. This means that for
all three steels there is a very large variation in fracture behaviour in tests at 600 oC of greater than
10,000 hours. This is clearly significant since 600oC is a typical in-service temperature for these
steels. Indeed, in the development of steel P92 a target was set for the minimum reduction of area
to be at least 40% at 10,000 hours and 600°C. Greater understanding of the reasons for the wide
variation in fracture characteristics of these martensitic steels is clearly important.

Figure 1. Relationships between reduction in area and creep life for steel grades P91, E911 and
P92 tested at 600oC [5].

The complexities associated with establishing the factors affecting the creep behavior of CSEF
steels mean that it is very challenging to identify and understand the influence of individual
parameters. As emphasized in a recent publication [7], most results published in the literature
suffer from a number of serious drawbacks, for example:
1. Specific elementary processes (for example subgrain coarsening) are studied in isolation
so that the importance of other microstructural events, which are equally important (for
example creep cavitation), are omitted.
2. Microstructural results are often obtained from specimens subjected to accelerated creep
tests. Yet it is well known that the temperature and stress dependence of thermodynamic
driving forces and kinetics affect microstructural development. Indeed, it is unlikely that
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the deformation and softening processes which govern short term creep also occur under
long term creep conditions.
3. Specimens are frequently not available from long term creep testing. While efforts have
been made to produce rupture data, much less emphasis has been placed on providing
interrupted material states. Study of controlled samples at different damage levels is
clearly important to assessing trends in behaviour.
4. Even when samples from long term tests are available, post test metallography is rarely
performed,
5. There have been significant recent developments in the hardware and the instruments
which are available for microstructural characterization. Thus, there is a need to use the
advanced techniques and equipment to these steels (many of which were initially studied
in the 1980s and 1990s).
The present paper reviews information on long term creep fracture behaviour in 9 to 12%Cr
martensitic steels and discusses approaches for minimizing the susceptibility for nucleation of
voids so that creep brittle fracture can be avoided.

FACTORS AFFECTING THE FORMATION OF CREEP CAVITIES

There has been some apparently conflicting evidence reported regarding when creep voids form
during creep of martensitic steels. Indeed, several studies have reported that voids can only be
indentified late in creep life [e.g. 8]. In contrast, other work has demonstrated that creep voids
nucleate relatively early in the creep life [9]. These apparently conflicting observations are
considered with respect to the creep behavior of selected CSEF steels where the results of long
term creep testing have been published.

Damage in 12%Cr (X20) steel

The martensitic steel 12% Cr-Mo-V steel has been used in power boiler applications for around 50
years. Interestingly, even in this steel there are conflicting observations regarding the formation of
creep voids. Thus, reviews of performance have been published showing that remarkable few
components have been found with creep voids detectable by optical microscopy [10]. In contrast,
some experience has shown that creep cracking in components has occurred and replacement of
components has been required. While these observations have all been made for steels operating
beyond 100,000 hours, it could be that the variation in observations is linked to the temperature of
operation. It is well known that the accumulation of creep damage is very dependent on the
exposure temperature. However, the information considered here shows that variable fracture
behaviour has been identified even in samples exposed at the same creep temperature.

The creep behaviour for a number of different X20 steels tested at 550 oC is compared in Figure 2
[11]. These results show data up to and even beyond 100,000 hours duration. While there is no
major difference in creep strength for the different casts there are significant differences in the
reduction in area measured after testing. It is apparent that some casts show reduction in ductility
for test lives of around 10, 000 hours.

At the high stress levels, all of the specimens rupture in a ductile manner. These failures are
linked to voids which form and grow plastically at large inclusions. The inclusions are hard
particles within the plastically deforming matrix and at some critical value of strain void
formation occurs. In general, it has been reported that relatively large oxide and sulfide inclusions
are more effective in the initiation of voids which grow by plastic deformation than small
particles. The generally smaller, second phase particles do not appear to play a role in the ductile
high temperature rupture of 12% Cr-Mo-V steel.
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Figure 2. Creep strength and ductility for samples at 550 oC [11]

At low stress levels, creep cavitation appears to be the dominant damage mechanism. This change
in the rate controlling mechanism results in much lower strains to rupture, Figure 2. Indeed, as
shown in Figure 3, post test metallographic examination of samples which failed with low reduction
of area (R of A) revealed significant numbers of individual voids. Indeed, not only were creep voids
and micro cracks found at the fracture location but also along the specimen gauge length even well
away from the fracture surface. These observations demonstrate that, under the testing conditions
employed, void nucleation had taken place generally throughout the whole gauge length. Final link
up of damage as expected focused at a specific location but even here the deformation observed is
mostly associated with developing the strain needed to grow cracks across the section.
Damage development in long term creep tests of tempered martensite ferritic steel (German grade:
X20) at a stress of 120MPa and a temperature of 550oC has been reported [7, 12]. These test
conditions resulted in a creep life of 139,971 hours. Tests were also performed under the same
loading conditions but interruptions after 12,456, 51,072 and 81,984 hours, that is at life fractions
of about 9%, 37% and 59%. It was reported that nucleation of cavities was found in each of the
samples examined. Thus, it appeared that void nucleation occurs continuously during creep.
Detailed study showed that it appeared that the number of creep voids present, i.e. the cavity
density, was proportional to the creep strain. Indeed, this observation has been reported previously
for creep tests on X20 steel samples [13]. Comparison of the results of the test programmes suggests
that, even though the specifics of the steels and the tests performed were different, a similar
relationship reasonably described all the results, Figure 4.

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Figure 3. Creep damage detected at different locations along the gauge length of a sample tested
at 550oC [11]

Figure 4. Relationship between the cavity density and creep strain for creep tests performed on
X20 steel samples.
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As illustrated in Figure 3, a characteristic feature of creep cavitation in high chromium ferritic

steels, is that cavities are not only found on prior austenite grain boundaries (PAGBs) but also in
the interior of former austenite grains. There are additional internal surfaces such as sub- grain
boundaries and high angle ferrite boundaries, which have formed during tempering, where
segregation can occur preferentially and which will facilitate diffusion. However, a quantitative
metallographic evaluation of the cavity population showed that cavities on PAGBs which were
oriented at 90o to the maximum stress direction play the dominant role in the rupture process.

Damage in Grade 91 steel

There has been a very wide range in the reported reduction in area of creep tests performed on
Grade 91 base metal. This wide range is illustrated with reference to Figure 1. As shown, the
measured R of A begins to fall even for test lives of the order of 5,000 hours at 600oC. In contrast,
some tests of close to 100, 000 hours are shown with a reported R of A above 70%. While this
range may be in part explained by differences in test temperatures and specimen dimensions,
further evaluation of specific test results is of value to review potential trends in behaviour. It is
however, apparent that under condition of low R of A fracture occurs as a result of the nucleation
and growth of creep voids. A typical micrograph with cavities in Grade 91 base metal is shown in
Figure 5.

Figure 5. Typical micrograph showing creep voids developed in Grade 91 base metal.

Previous work has shown that there is a relationship between N:Al ratio and creep strength in
tempered martensitic Grade 91 base metal [14]. This trend has been explained on the basis that in
Grade 91 steel the levels of nitrogen are set so that strengthening will involve the formation of MX
type carbides, nitrides and carbonitrides. When excess aluminium is present in the steel, this
combines with nitrogen to form aluminium nitrides [14]. These aluminium nitrides are relatively
large and so do not contribute to creep strength. Thus, since the level of free nitrogen is reduced by
the formation of aluminium nitrides, the volume fraction of MX precipitates is decreased and the
creep strength is decreased. Previous work has shown that there can be a link to the formation of
aluminium nitrides and increased susceptibility for the nucleation of creep voids. This observation
is consistent with the behavior reported for other boiler steels where steels with higher inclusion
levels exhibited lower creep ductilities than ‘clean’ steels of the same composition [15].

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Examination of Grade 91 steel after creep testing has been performed to measure the number
density of creep voids and to evaluate factors involved in void nucleation. It is apparent that the
creep behaviour of tempered martensitic steels is influenced by nonmetallic inclusions. In cases
where these inclusions exceed a critical size there is established evidence that voids are nucleated
on the ‘hard’ particles. Photomicrographs in Figure 6 illustrate this behaviour. A back scattered
electron micrograph of the creep voids present is shown in Figure 6a, with Figures 6b and c showing
elemental maps for oxygen and silicon. It is apparent at least some of the creep voids are associated
with particles which have relatively high concentrations of silicon and oxygen.

a b c

Figure 6. Micrograph showing creep voids developed in Grade 91 steel (a), an elemental map of
the same area showing local concentrations of oxygen (b) and an elemental map of the same area
showing local concentrations of silicon (c).

Figure 7. Relationships between Reduction of Area and creep rupture life for Grade 91 steel
samples with different levels of ‘trace elements’ [16, 17]. Some of the trace elements are not
controlled in applicable component specifications even though elements such as Tin (Sn), Antimony
(Sb) and Copper (Cu) can significantly reduce the creep ductility.

When considering nucleation of creep cavities the local microstructure and composition are clearly
of particular interest. Elements which have been shown to decrease the resistance to creep fracture
in engineering steels include phosphorus (P), sulfur (S), Copper (Cu), Tin (Sn), Antimony (Sb),
Arsenic (As). A systematic study evaluating the influence of these elements on the strength and
fracture behavior has been published [16, 17]. The reduction in the rupture life resulting from the
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higher amount of tramp elements at 650oC does not appear to be caused by the increase in the creep
rate, but rather by the decline in creep ductility. This is consistent with the Sb and Sn-doped samples
exhibiting minimal R of A. Consequently, the rupture life associated with the Sb- and Sn-doped
samples is shorter than that of the P- and S-doped samples, Figure 7. The rupture life associated
with the Cu-doped sample was seen to be independent of the content of Cu. This is because the Cu-
doped samples exhibited poor ductility irrespective of Cu content, Figure 7b. Poor ductility linked
to elevated copper levels has also been found in other work (18).

The results from Grade 91 provide insight into why the observed distribution of cavities in
tempered martensitic base metal is very variable for different casts. It is apparent that the size and
distribution of non-metallic inclusions and the concentration of trace elements both significantly
influence the nucleation of creep voids. Since these factors will not simply influence the behaviour
at grain boundaries, voids nucleate in different positions. In the steels with lowest creep ductility,
void nucleation starts early in life and continues with increasing strain.

Damage in Grade 92 steel

It is apparent from consideration of Figure 1, that variability has also been noted in the fracture
behaviour of Grade 92 base metal samples. An alternative approach to assessment of creep fracture
behaviour to the typical variation of R of A with rupture life is shown in Figure 8. Here, the rupture
life reported for different test temperatures is shown, with selected ranges in R of A designated by
different symbols. The general key to this Figure is that samples with an R of A greater than 50%
are shown as an open circle, with tests with an R of A below 50% are shown as a solid square. The
difference between open and solid symbols facilitates comparison of the results.

Figure 8. Variation in Reduction of Area for different test temperatures and creep rupture lives for
Grade 92 steel base metal samples.

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Greater definition of the specific ductility ranges are provided through the use of different colors.
The tests included in Figure 8 cover data from many different sources, yet a general trend in the
rupture behaviour is apparent. Thus, for tests at 650oC and durations near to, or above 10,000 hours
the ductility is below 50%. In contrast, for tests at 550oC even with durations approaching 100, 000
hours the reported ductilities are above 50%. Interestingly, the results reported for tests at 600oC,
i.e. near to the design temperature for many Grade 92 steel components, tests with durations above
10,000 hours show a mixed behaviour. Thus, some steel casts show relatively low ductility at lives
around 10,000 hours yet others show R of A above 50% even at creep rupture lives very close to
100,000 hours. Review of background information provided with the creep test data [19] suggests
that different fracture behaviour was related to the level of silicon in the steels. The reduction in
ductility could be linked to the presence of silicates.

Clearly, the fact that very low creep ductilities have been reported in Grade 92 base metal samples
using test conditions near typical operation of advanced boilers requires further study. The fact that
differences in fracture characteristics have been found for tests in different temperature regimes
and for different compositions, suggests that both fabrication and creep testing factors are important
in establishing details of damage. In view of the metallurgical complexities of advanced tempered
martensitic steels, careful planning, selection of samples for examination followed by the
application of advanced microscopy are required to establish trends in behaviour. Details from
these characterization activities have been presented [20]. However, selected information is
provided here to compliment the present review of fracture behaviour in 9 to 12% Cr steels.

A typical micrograph showing the development of cavities after creep testing of Grade 92 base
metal is shown in Figure 9a. Samples were selected for examination after testing at 550oC, 600oC
and 650oC. As indicated in Figure 8, all the tests at 650oC with duration of above about 10,000
hours showed an R of A below 50%. Detailed characterization of samples tested to failure at 9,037,
10,682 and 19,124 hours at 650oC showed that a uniformly high number of creep voids were present
along the gauge length, Figure 9b. This evidence on Grade 92 steel supports the earlier results
showing a high degree of uniformity in void density for long term tests on X20 steel, Figure 3. For
the Grade 92 tests, the size of cavities at fracture was generally in the range from 2.1 to 3 µm [20].
However, detailed sizing was difficult because the void s were not spherical.

Figure 9. Typical micrograph showing creep voids in a Grade 92 steel base metal sample (a) and
the number density of voids present along the gauge length for samples tested to failure at 9,037,
10,682 and 19,124 hours at 650oC (b)[20].

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Because of the complex shapes of the creep cavities even careful metallographic preparation and
evaluation has difficulties to unambiguously characterize voids and their relationship to
microstructural details. A sophisticated approach involving serial ion beam sectioning followed by
documentation was therefore applied [21]. This approach allowed both the void shape and the
associated particles to be reconstructed in three dimensions. An example of a reconstruction is
shown in Figure 10. In the reconstruction shown, the cavity has a diameter of around 2 µm. This
void was clearly associated with a boron nitride particle of around 1-1.5 µm. Much smaller second
phase particles including Laves phase were found to decorate the inside of many of the cavities. In
some cases, fine manganese sulphide (MnS) or alumina (Al2O3 ) particles were found within the
cavities. It is potentially the case that the fine MnS or Al 2O3 formed in the steel at very high
temperatures act as sites which promote the nucleation of boron nitride during subsequent cooling.

Details of the characterization process and selected results are presented in another paper at this
conference [20]. Further research examining additional Grade 92 base metal samples is in progress.
It is anticipated that a broader pattern of results for steels with different composition and after a
variation of heat treatments will become available in the future.

Figure 10: An example of a single SEM cross-section slice taken in sample 600-A 6 mm away from
fracture surface (a). A reconstruction of the data showing the pore (shown in blue, purple and
green) and associated particle (shown in red) in 3D (b)[20]

DISCUSSION

For typically processed tempered martensitic steel base metal, it has been observed that the long
term performance and creep rupture strength is below that originally expected from simple
extrapolation of short term creep data. This effect has resulted in reductions in some of the values
quoted as representing long term creep life. The reasons for the loss of long term creep rupture
strength have been investigated extensively [for example 3, 4, 5, 6] for a number of 9 to 12 Cr
steels. The following microstructure degradation effects appear to be primarily responsible for the
loss of creep strength:
 The formation of new phases which lead to dissolution of fine M2X and MX
carbonitrides,

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 Recovery of the dislocation substructure (increase in subgrain size) and reduction in the
overall dislocation density. This is believed to initiate as the result of preferential
recovery of microstructure in the vicinity of PAGBs, and
 The development of creep voids resulting in a significant loss of creep ductility

The precipitation of Z phase, M6X carbonitrides and Laves phase during creep can cause a loss of
creep strength at long times. The loss of strength occurs if the formation of these phases is sufficient
to result in a significant reduction in the fine M2X and MX and or M23C6 precipitates. The size
(which determines the climb distance required to overcome the particle and the number density
(which determines the mean particle spacing and thus the particle back stress are critical to
stabilizing the dislocation substructure and hence, play a major role in determination of the creep
strength. It has been the primary focus of the present paper to consider the factors affecting the
nucleation and growth of creep voids. This focus was established in part because high densities of
small voids can have a particularly significant influence on approaches to manage the safe life of
boiler components and in part because while the creep dependent microstructural changes have
been widely studied, there is less work reported on creep void development. This is particularly
true for the tempered martensitic microstructures present in base metal.

It is now clearly established that for creep conditions at or close to those of components in power
boilers, creep voids can be nucleated early in life [9]. There have been different opinions published
regarding void nucleation. In particular, several papers have suggested that creep voids are only
formed late in life [e.g. 8]. This diversity of findings is due to a number of factors, including the
following:
 Selection of laboratory test conditions which result in damage which is not relevant to
long term behaviour,
 Testing steels with a composition and microstructure which are not susceptible to
formation of voids,
 Post test examination which is limited to the surface of the samples (when creep
damage in CSEF steels is greatest below the surface), and
 Using methods of sample preparation and evaluation which do not properly reveal the
creep voids present

In long term creep tests on CSEF steels, the voids grow throughout the creep life and will be around
1 to 2μm in size at, or very close to, fracture. This size of void is important because it is only
relatively close to fracture that individual voids can be relatively easily identified using optical
microscopy at the magnifications around 400 times magnification. Due to the non symmetrical
shape of the creep voids, sample preparation is critical to identification of voids. It appears that
long term creep exposure of X20 steel can results in the development of higher densities of voids
than in other tempered martensitic steels. In X20 steel it is generally agreed that the number density
of voids increases with creep strain, with the number of voids at or very close to fracture in the
range 2000 to 10,000 mm-2.[11,13].

To provide an evaluation of creep void development in CSEF steels several key publications have
been reviewed [22, 23]. A summary of information reported for the change in void density with
life fraction in the creep strength enhanced martensitic steels is presented in Figure 11. The
development of creep damage is frequently modeled using an equation of the form:

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In this equation, t is the exposure time in hours, tr is the time to rupture in hours, Є is the
instantaneous strain and Єr is the strain at rupture and λ is a material parameter rel ated to the
creep ductility under the conditions of interest. In most situations encountered in long term creep,
and certainly for in service components, the mechanism of cavity growth is linked to local creep
strain. Thus, the growth or dilation rate is considered to be constrained, thus the volume change
due to void formation and growth must be accommodated by strain.

Figure 11. Summary of information regarding the increase in the number density of creep voids
with life fraction for long term creep tests on different creep strength enhanced ferritic steels.

Under these conditions then the strain fraction in the above equation can be replaced by a number
fraction of voids as:

where N is the number of voids per mm2 and Nf is the number of voids per mm2 at fracture.

The values of the parameters in this equation have a significant influence on the form of this
relationship. The way the value of key parameters relates to damage rate is illustrated in Figure 11.
Both of the lines drawn in this Figure have been based on the same number of voids at fracture,
namely Nf of 1200 voids mm-2. However, the calculations of the relationship between number of
creep voids and life fraction have been made for different values of λ. As λ increases from 2 to 3,
the curve defining the rate of change in void density becomes steeper; this is particularly true at
high life fractions. It is interesting to note in Figure 11 that for a number fraction of voids of 600
voids mm-2 the calculated life fraction range is 70 to 90%, a range which approximately bound the
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experimental data. Clearly having the understanding to define, at least semi quantitatively, how
microstructural factors change Nf and λ is key to applying observations of creep voids to component
performance. It should be emphasized that details of the most appropriate value of N f to use in
practice seem to be of lower significance than understanding of the ductility parameter λ. The key
issue in both cases is how rapidly the creep voids link to form cracks, i.e. what is the life fraction
associated with the transition from a density of say a thousand voids mm-2 until micro crack
formation and crack development occur in a component?

One key microstructural factor related to the number of creep voids nucleated appears to be the
distribution of non-metallic inclusions above a critical size. Inclusions may be directly linked to
void nucleation or the presence of one type of inclusions may promote formation of other, even
larger particles. It appears that this seeding of inclusions can be illustrated with reference to the
formation of BN in P92 and P122 steels. Detailed study indicates that the BN inclusions in P122
are different from those of the P92 steel. In P122 steel it appears that the BN agglomerate in large
colonies, which grow up to about 20μm in size [24]. These colonies consist of many individual
inclusions of about 2 or 3μm in size. In P92 steel [17], coarse size BN type inclusions grown up to
4μm are observed. In both of these commercial heat resistant steels, it appears that alumina type
inclusions, which may be sourced to the furnace refractory in melting process, are key to the
formation of large BN type inclusions.

Figure 12. The influence of temperature on dissolution of BN inclusions [24].

Under slow cooling following solidification, it appears that the BN inclusions develop on the
alumina or magnesia particles which are formed during deoxidation or originate from the refractory
of the steel making furnace. Once formed these BN inclusions grow rapidly to over 1μm in size.
Microstructural assessment indicates that subsequent heat treatment at temperature up to about
1150oC, does not dissolve the coarse size BN type inclusions [22], Figure 12. However, raising the

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heat treatment temperature to 1200 oC, results in the coarse size BN inclusions dissolving with time.
It has been reported that all coarse size BN inclusions completely disappeared after a short holding
time at 1250 oC, Figure 12.

The relationship between boron and nitrogen concentration associated with the formation of BN
inclusions in high Cr ferritic heat resistant steels is shown in Figure 13. Chemical analyses of
twenty-three steels, including P122 and P92, with different concentrations of boron and nitrogen
were reported. In each steel, SEM examination was performed to establish, or otherwise, the
existence of BN inclusions. Except for the commercial P92 and P122 steels, manufacture of each
cast involved melting of 50 to 150 kg of steel, hot working at 1200 to 1000 oC, normalizing at
1100oC and holding 0.5 to 1h, tempering at 770 to 800 oC and holding 1 to 4h. In Figure 13, solid
circles represent casts where coarse size BN inclusions, i.e. over the size of 1μm, were observed.
The triangular symbols show small BN inclusions, i.e. under 0.5μm, and open circles represent no
BN. In this experimental concentration range, BN type inclusions could not be found by SEM
observation in the concentration range less than 0.001%B or 0.015%N.

Figure 13. Presence of BN inclusions in 9 to 12%Cr steels as a function of the concentration of

boron and nitrogen. [24].

The fact that in the majority of steels with boron and nitrogen large sized BN inclusions are present,
means that in each case about 80% of added boron forms BN inclusions. After normalizing at
1100oC and tempering at 800oC only 20% of added boron remains dissolved in the metal matrix,
Figure 14. It is the available (i.e. not in BN inclusions) boron which is thought to have the beneficial
effects on creep strength. These benefits are achieved through improvements in the stability of
precipitates and positive influences at grain boundaries.

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Figure 14. Relationship established between total Boron and Boron available for improving
creep performance (as indicated by the amount of soluble Boron) for 9% Cr steels [24].

ASSESSMENT OF COMPONENT PERFRORMANCE BASED ON CREEP VOIDS

Observations of creep voids for assessment of condition of in-service components have been used
for many years. The most widely used approaches for this form of evaluation is through the
application of metallurgical replicas. In the majority of cases, the use of replicas for these
assessments was carried out on low alloy steels, often by examination of welds and the associated
heat affected zone (HAZ).

In CSEF steels, service experience suggests that in many cases creep damage has been detected in
the HAZ, and this is frequently referred to as Type IV damage. It is apparent that in many cases,
the greatest extent of Type IV damage occurs below the surface of the component. Thus, the benefit
from carrying out inspections using replication on the outside surface of the component is limited.
However, 12%Cr (X20) steel has been used in boiler and piping applications for a long time.
Damage in the tempered martensitic base metal of components has been reported and used to assess
component life. The following observations are based on a summary from numerous inspections,
including the use of metallographic replicas, from one major utility [25, 26].

Metallographic assessment of voids is typically assessed using the optical microscope at a

magnification of 400 times. Detailed quantification of the number density of voids (expressed as
the number of voids per square millimeter) may also be performed at higher magnification.
Numerous small sub-microscopic creep voids with diameters less than 0.1µm initiate as early as
10 percent of the creep life. These voids grow and become visible under an optical microscope at
a magnification of 400 x when they have achieved a size of 1µm. At high creep life fractions, i.e.
close to crack initiation, the number of voids visible at 400 times does not change significantly but
the size increases. The guidance from evaluation of X20 components is that further engineering
assessment of bends should be performed if the void density exceeds 500 voids mm-2 or if more
than 50 percent of the voids observed exceed a size of 2.5 μm [25, 26].
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Figure 15. Creep voids observed in an X20 steel main steam bend during an inspection after
around 160,000 hours (a) & after a further approximately 12550 hours (b) [25].

The expected behavior is illustrated by consideration of actual field measurements

• on a 12CrMoV
steel steam pipe bend which operated at 532°C. This bend had been incorrectly heat treated during
fabrication and hence exhibited low creep ductility. After operation for approximately 160,000
hours inspection showed that high numbers of creep voids were present, Figure 15a. The average
void density was estimated as 1025mm-2. Using typical values for the number density of voids at
crack initiation, this void density indicates that cracking was imminent. However, no replacement
component was available. Instrumentation was used to directly monitor the component and
operating conditions were reduced to minimize the rate of creep damage development. A final
inspection was performed after an additional operating period of 12,550 hours. Because of the need
to monitor the damage in this bend it was possible to track void size with time. As shown in Figure
16, the percentage of voids greater than 2.5μm increased respectively to 23%, 34% and 43%. Over
this same period, the fraction of voids greater than 3.5μm increased from 3% to 20%. It is thus clear
that significant void growth had taken place.

Figure 16. Change in void diameter for increasing operating time in a 12CrMoV steel piping bend
[25, 26]
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PARKER, EPRI Advanced materials Conference, 2013

CONCLUDING REMARKS

The creep strengthening mechanisms of tempered martensite ferritic steels has been referred to as
carbide stabilized substructure hardening. Thus, the excellent strength of these steels is due to the
fact that high densities of fine carbo-nitrides retain a dislocation substructure during operation at
elevated temperature and stress. Changes in composition and heat treatment clearly have a marked
effect on creep strength. However, it now appears that metallurgical processing factors can also
influence long term ductility through changes in the susceptibility to the nucleation and growth of
creep voids.

Tempered martensitic steels such as X20, Grades 91, 92, E911 and 122 all exhibit a trend to
relatively low ductility as creep rupture times increase. The tendency for brittle behaviour is in all
cases due to the formation of creep voids on prior austenite grain boundaries and at other
microstructural features such as lath boundaries. The detail of the number of voids formed, and the
tendency for reductions in strain to fracture, is different for the different steels. However, it appears
that in all cases, void nucleation is related to the presence of trace elements and hard non-metallic
inclusions. A key factor in determining whether the inclusions nucleate voids is the particle size.
Thus, only inclusions of a sufficient size (the critical inclusion size is directly linked to the creep
stress) will act directly as nucleation sites. However, even fine inclusions formed during steel
making (such as Al2O3) may also play a role in promoting void formation. Analysis of the creep
cavities formed in P92 steel after creep exposure revealed that the majority of them were associated
with hard ceramic particles. Chemical analysis revealed that the vast majority of these particles
were BN which appeared to be associated with MnS or Al2O3 . It appears that the BN inclusions
develop on the alumina or magnesia particles which are formed during de-oxidation or originate
from the refractory of the steel making furnace. Once formed, post fabrication heat treatment above
about 1200oC appears to be sufficient to dissolve the BN. Control of composition in combination
with modified heat treatment practices during fabrication offers the potential to reduce the
susceptibility for brittle creep fracture behavior in CSEF steels.

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