Microstructure influence on creep properties of

heat-resistant austenitic alloys with high aluminum

content
A. Facco, M. Couvrat, D. Magne, M. Roussel, A. Guillet, C. Pareige

To cite this version:

A. Facco, M. Couvrat, D. Magne, M. Roussel, A. Guillet, et al.. Microstructure influence on creep
properties of heat-resistant austenitic alloys with high aluminum content. Materials Science and
Engineering: A, Elsevier, 2020, 783, pp.139276. �10.1016/j.msea.2020.139276�. �hal-02525356�

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Microstructure influence on creep properties of heat-resistant austenitic alloys with high aluminum
content
A. Faccoa,b, M. Couvratb, D. Magnéa, M. Rousselb, A. Guilleta, C. Pareigea,

a
: Normandie Univ, UNIROUEN, INSA Rouen, CNRS, Groupe de Physique des Matériaux, 76000 Rouen,
France.
b
: Manoir Industries, 12 rue des Ardennes, 27108 Val de Reuil.

Abstract:

This work focusses on the link between microstructure and creep properties for heat-resistant austenitic alloys with high
aluminum content (3-5 wt. %). An emphasis was put on the coupling of thermodynamic simulations, microstructural
characterizations by scanning electron microscopy and transmission electron microscopy, and creep testing. The phase
predictions performed by the calculation of phase diagrams method are in good agreement with the observed
microstructure after creep at 1000°C and 1050°C. Correlation between creep properties and microstructure
characterizations at 1000°C and 1050°C revealed that NiAl and α’ (chromium-rich base centered cubic phase) phases
are deleterious for the creep properties at service temperature. Several high Al-content alloys are selected in order to
replace the chromia-forming alloys standardly used in cracking furnaces.

Keywords: heat-resistant; alumina-forming austenitic alloy (AFA); precipitation; creep behavior; alloy
design; phases diagram.

essential to find a middle ground between good

1. Introduction oxidation properties and good creep resistance.
The influence of Al on the microstructure and the creep
Heat resistant austenitic stainless alloys are used in
properties of austenitic alloys was widely studied in the
centrifugally cast tubes for cracking furnaces because of
temperature range of 550-900°C. Fe-Ni-Cr-Al alloys
their excellent creep and oxidation resistances. A
(FCNA) with high Al level, between 4 and 5 wt. %, are
minimum temperature of 850°C is needed for the
used as structural materials combining good mechanical
cracking reaction to take place. This temperature is
properties and good oxidation resistance thanks to the
reached by heating the tubes between 950°C and
precipitation of NiAl phase at 550-650°C [11,12].
1100°C (metal temperature). An unwanted side-
Alumina forming austenitic stainless steels (AFA) with
reaction of coking happens at the inner surface of the
Al-content between 2.5 and 4 wt. % are used for
tube during service, it leads to a decrease in heat transfer
structural purpose in fossil energy conversion and
(as well as an increase in the tube pressure). The tubes
combustion system applications which require good
then have to be heated at even higher temperatures,
creep and oxidation properties between 650 and 900°C.
typically up to 1100°C-1150°C which corresponds to a
Main hardening precipitates in these alloys are MC (M
temperature limit for the material. Moreover, when
stands for metal like Nb and Ti) carbides and
coking becomes critical, decoking process must be
intermetallic compounds such as NiAl, Fe2(Mo, Nb)-
performed. Increase in temperature and decoking
Laves and Ni3Al phases [13–19]. Addition of high Al
process both reduce the tube service life and are very
level can destabilize the single-phase austenitic matrix
costly.
by promoting the formation of the weak body-centered
Nowadays, industrials seek to develop new alloys with cubic α-Fe phase resulting in a drop of creep properties
high Al content to improve environmental resistance, [6,20].
especially the coking resistance, by formation of a
For higher temperature applications (>950°C), nickel
continuous alumina scale at the inner surface of the
base superalloys and austenitic alloys with high Al level
furnace tubes. This oxide is more stable than the Cr-
were developed. Asteman et al. [8] investigated Ni-base
oxide at high temperature [1–8]. Nevertheless, Al is
alloys with 4 wt. % Al (commercial Centralloy® HT-R
known to decrease the creep strength [6,9,10]. The
(Ni25Cr4Al)) and 10 wt. % Al (Ni25Cr10Al) for high
understanding of the influence of Al addition on the
temperatures applications (600-1200°C). In Ni25Cr4Al
microstructure and therefore on the creep properties is
alloy, secondary carbides and γ’ (Ni3Al) precipitation
1
allow to obtain sufficient creep properties at high to make the link between the observed microstructures
temperature. However, the γ’ particles are not stable at and the creep resistance. This work relies on the
temperature above 1000°C which is too low for the coupling of the CALPHAD (CALculation of PHAse
applications of our interest [8,21]. The authors [8] Diagrams) method to forecast the aged microstructure
showed that the increase in Al content from 4 wt. % to especially the phase stability domains appearing at high
10 wt. % decreased the oxidation resistance because of temperature (intermetallic phases, hardening
the formation of a multiphase cast microstructure. precipitates), creep tests and experimental
Nevertheless, they did not investigate the influence of characterization of as cast and ageing microstructures
this multiphase structure on the creep properties. The using SEM (Scanning Electron Microscopy) (imaging,
heat resistant austenitic alloy Manaurite® XTM without EBSD (Electron Backscattered Diffraction) and EDS
Al allows to reach high temperature while keeping (Electron Dispersive Spectroscopy)), TEM
sufficient creep properties [22]. The aim is to design an (Transmission Electron Microscopy) (conventional
alloy with Al, equivalent or more resistant in creep, i.e. TEM, STEM (Scanning Transmission Electron
with lower creep rate, no excessive elongation during Microscopy) and STEM-EDS) and XRD (X-Ray
service and longer creep service life than the Diffraction).
Manaurite® XTM widely used in cracking furnaces.
The challenge is to propose alloys with Al-content 2. Materials and methods
higher than 3.5 wt. % in order to increase the
environmental resistance while keeping good creep 2.1. Materials
properties. At cracking service temperature (950-
1100°C), the creep resistance of these austenitic alloys The tubes were produced by centrifugal casting. The
is mainly guaranteed by the control of secondary average chemical compositions in weight percent of
precipitation of MC (M stands for metal which is mainly the FeNiCrAl alloys are provided in Table 1. The C
Nb and Ti), and M23C6 (M is mainly Cr) carbides. content is measured by a combustion infrared detection
M23C6 carbides are precipitated owing to transformation technique (LECO) and the others element by SEM-
of the primary carbides M7C3 (M is mainly Cr) formed EDS. Mn-content was not measured (NM) because of
during solidification [23–28]. However, the influence of its low concentration (<0.1 wt. %). Al-content decreases
high Al level (>3.5 wt. %) on the microstructure and the from alloy 4 to alloy 1: alloy 4 (4.8 wt. %) – alloy 3 (4.5
creep properties of such alloys is not investigated yet. wt. %) – alloy 2 (4.1 wt. %) – alloy 1 (3.5 wt. %). Except
Al content, the chemical compositions of alloys 1 and 2
This paper focusses on advanced Manaurite® XAl4
are close. These two alloys present the lowest Cr
alloys [29], i.e. on Fe-Ni-Cr-Al alloys of high Ni content
concentration (~ 26 wt. %). Cr content is higher in alloy
(45-55 wt. %) with alloying addition levels of 25-32 wt.
3 and alloy 4 (30-32 wt. %). These two alloys have
% Cr, 3-5 wt. % Al and 0.45 wt. % C. The aim is to
similar composition except in Al. Alloy 5 contains high
study the influence of Al additions on the microstructure
levels of Al (4.7 wt. %) and Ni (55 wt. %) and 26 wt. %
and creep properties. Creep tests were performed, and
of Cr. The commercial Manaurite® XTM which is
microstructures were characterized after creep in order
without Al represents the reference alloy.

Table 1: Average chemical composition of the FeNiCrAl alloys (wt. %).

Element (wt. %) C- Mn Si Ni Cr Nb Al Ti Fe
LECO
Alloy 1 0.43 NM 0.3 47.1 25.6 0.9 3.5 0.1 Bal.
Alloy 2 0.44 NM 0.3 46.8 26.0 0.8 4.1 0.1
Alloy 3 0.43 NM 0.4 44.7 30.8 0.9 4.5 0.1
Alloy 4 0.46 NM 0.3 44.8 31.8 0.7 4.8 0.1
Alloy 5 0.43 NM 0.3 55.0 25.9 0.8 4.7 0.3
XTM 0.45 1.4 1.4 44.3 37.0 0.6 0 0.1

2
 2.2. Creep testing EBSD measurements were done with a Hikari EBSD
camera.
Short creep tests at constant load were performed.
TEM samples were prepared from 3 mm disk. They
Cylindrical creep specimens were machined in the
were mechanically polished by SiC grinding papers up
center of the tube, perpendicular to the direction of
to 5 µm and a thickness of 100 µm then an electrolytical
dendrites and to the columnar grains as shown Figure 1
etching by 10 % perchloric acid and 90 % acetic acid
which presents schematic of the creep specimen
solution at 14°C and 20 V was realized with a twin jet
sampling in the columnar zone of the centrifugal cast
electropolisher (Tenupol 5 from Struers). Afterwards, a
tube.
final polishing was performed by ion milling (PIPS II
from Gatan operating at 3 keV +-3° during 5 min). TEM
characterizations were carried out with a probe
corrected JEOL ARM-200F at 200 kV.

2.4. Thermodynamic simulations

Computational thermodynamic calculations were

done with the commercial Thermo-Calc ©
software. Because of the high level of Ni in the
studied alloys, between 44 and 55 wt. %, the more
relevant database is the Nickel base (TCNI8 [30]).
The Nickel database allows prediction of the
Figure 1: schematic of the creep specimen sampling in phases observed in these alumina-forming
the columnar zone. austenitic alloys, particularly, Ni3Al and NiAl
phases which are not predicted by the Iron database
Creep specimens with a diameter of 4 mm and a gauge
length of 32 mm were used for creep tests. The strain (TCFE8 [31]).
was measured on the line with a laser device. The creep
tests were performed at 1000°C and 1050°C under 3. Experimental results
constant loads with initial stresses between 17 MPa and
31 MPa. The creep duration ranged between 33 h and
3.1. Microstructural characterization
1214 h depending on the creep resistance and the creep
conditions (temperature and creep load). The different
3.1.1 As-cast microstructure
alloys were tested in the as-cast state, i.e. without any
additional thermal treatments before creep testing. After
fracture, the creep specimens were water-quenched The centrifugation process and the fast cooling rate
from the creep test temperature. promote the formation of a large columnar zone as
shown in the crystallographic orientation maps of alloy
2.3. Characterizations techniques 2 (Figure 2). Such large grains are beneficial for creep
properties at high temperature for this kind of alloy. The
XRD measurements were performed on as cast samples average grain size in the transversal cross-section is
with a Brüker D8 diffractometer with Co-Kα radiation higher than 400 µm for the five alloys.
(λ=1.789 Å) at 35 kV from 25° to 100°. Samples were
The dendritic structure of these heat-resistant alloys is
polished up to 5 µm.
composed of an austenitic matrix with M7C3 Cr-rich
Standard sample preparation has been performed for the carbides and (Nb;Ti)-rich carbides (hereafter named
SEM characterization. Longitudinal cross sections were MC) observed at the grain boundaries and interdendritic
cut into the crept specimens in order to observe the spaces as shown in Figure 3a). The presence of both Ti
microstructure along the creep direction. The SEM and Nb in MC carbides was confirmed by SEM-EDS
samples were mechanically polished with SiC grinding measurements (Figure 3b)).
papers up to 5 µm and with diamond suspensions up to
Figure 4 presents XRD spectra obtained in alloys 1 to 5.
1 µm. For EBSD samples, finer polishing with diamond
M7C3 and MC are observed after solidification in the
suspension of 0.25 µm and colloidal silica suspension
(0.04 µm) was performed. SEM characterizations were five alloys. In these different alloys, Ni3Al phase also
carried out with a JEOL 7900F operating at 15 kV. appears during the solidification. M7C3 and MC surface
3
fractions in the as cast state for these five alloys are very were obtained by image analysis from several SEM
similar as reported in Table 2. These surface fractions electron back-scattered images.

Figure 2: SEM-EBSD crystallographic orientation maps of a) the transversal cross-section and b) the longitudinal
cross-section of alloy 2. (color should be used)

Figure 3: a) SEM back-scattered electron image of the as-cast alloy 2, MC carbides are in white, M7C3
in dark, and b) EDS spectrum performed in MC carbide.

4
 Figure 4: Diffraction spectra of the alloys 1, 2, 3, 4 and 5.

Table 2: Measured carbides surface fractions

𝐬𝐬 𝐬𝐬
𝐟𝐟𝐌𝐌 𝟕𝟕 𝐂𝐂𝟑𝟑
𝐟𝐟MC

Alloy 1 4.4±0.2 0.6±0.1

Alloy 2 4.8±0.4 0.7±0.1
Alloy 3 5.0±0.5 0.6±0.1
Alloy 4 4.9±0.2 0.7±0.1
Alloy 5 4.7±0.5 0.6±0.1

3.1.2 Microstructure after creep at temperature. However, due to the addition of high
service temperature contents of Al and Cr, and low content of Ni in alloys 3
and 4, NiAl and α’ phases appear and become stable at
Figure 5 presents the molar fractions of phases as a
service temperature in these alloys (Figure 5). The
function of temperature for alloys 1 to 5. The phase
Ni3Al phase is not stable at service temperature even for
diagrams have been calculated using the CALPHAD
the alloy 5 containing high levels of Al and Ni.
method. At service temperature (950-1100°C), the
classical phases expected in refractory steels without Al Backscattered electron images of alloys after annealing
addition, are the austenitic matrix, M23C6 Cr-rich at 1050°C during 100 h are shown in Figure 6. In good
carbides and the MC type carbides rich in carbide agreement with the phase diagrams of Figure 5, only
former elements such as Nb and Ti. According to the MC (bright contrast) and M23C6 carbides (darkest
thermodynamic simulations, because of the high levels phase) are observed in alloys 1, 2 and 5 (Figure 6a,
of Al and Cr, B2 NiAl and Cr-rich BCC (chromium-rich Figure 6b and Figure 6e respectively). Two types of
base centered cubic) α’ (base centered cubic chromium- M23C6 carbides are present: coarse M23C6 carbides
rich) phases can precipitate. NiAl and α' phases are not originating from the transformation of the primary M7C3
expected at service temperature in alloys 1, 2 and 5. carbides and finely dispersed secondary carbides M23C6
Indeed, NiAl and α’ are predicted, up to 950°C and resulting from the release of C in the matrix during the
896°C respectively for alloy 2 and up to 954°C and transformation of M7C3 into M23C6 [26,28]. In alloys 3
921°C respectively for alloy 5. In alloy 1, α’ is stable up and 4 (Figure 6c and Figure 6d respectively), an
to 887°C and no NiAl phase is expected whatever the additional phase in light grey contrast is observed. This

5
phase appears under two different types: under the form Figure 8. These nanoscale precipitates are invisible on
of plate shape precipitates dispersed in the γ matrix SEM images. According to the SAED patterns
(further called type I) and type II which forms at the performed in α’ and NiAl phases, the crystallographic
interface between Cr carbides and the austenitic matrix. relationship is cube-cube. The lattice parameter of the
The phase has been identified thanks to TEM NiAl phase was determined considering the lattice
investigations as NiAl phase. Figure 7 presents type I substructure diffraction spots of the SAED pattern
NiAl precipitate and the Figure 8 a TEM image and the Figure 8b) and is 𝑎𝑎𝑁𝑁𝑁𝑁𝑁𝑁𝑁𝑁 = 2.83 ± 0.07 Å and the lattice
corresponding selected area electron diffraction pattern parameter of the α’ phase was determined using the
(SAED) of the NiAl phase in [012] zone axis in alloy 4 SAED pattern Figure 8c) and is 𝑎𝑎α’ = 2.89 ± 0.09 Å.
crept at 1050°C. The obtained value are similar to those observed in the
The α’ phase was also identified by TEM in alloys 3 and literature : 𝑎𝑎𝑁𝑁𝑁𝑁𝑁𝑁𝑁𝑁 ≅ 2.88 − 2.89 Å [10,11,18,19] and
4 at 1050°C. The phase forms nanoscale precipitates 𝑎𝑎α’ ≅ 2.88 Å [18]. The cube-cube orientation
mainly observed at matrix/NiAl interfaces and in the relationship and the close lattice parameters indicate
NiAl phase as shown on the TEM image of Figure 7 and that these phases are coherent.

Figure 5: Mole fraction of phase as a function of temperature according to TCNI8 [32]. Red dashed lines define the
service temperature range (950°C- 1100°C).

6
 Figure 6: Backscattered electron images of alloys 1, 2, 3, 4 and 5 after annealing at 1050°C during 100 h.

Figure 7: Dark field STEM image of NiAl plate and the corresponding TEM-EDS element maps performed in the
alloy 4 after creep at 1050°C. (color should be used)

7
 Figure 8: a) TEM image, b) the corresponding SAED performed in the NiAl phase and c) the corresponding SAED
performed in the α’ phase in the alloy 4 after creep at 1050°C.

The different spatial scales involved, the heterogeneous thermodynamic simulations via TCNI8 for these alloys.
distribution of the phases and the low contrast between It is thus possible to use the thermodynamic data base
phases make difficult phase fraction measurements. For to estimate mole fractions of the phases in the alloys.
these reasons only phase compositions have been Mole fractions of NiAl, α’, MC and M23C6 for the five
measured and compared to compositions predicted by alloys are given in Table 4 at 1000°C and 1050°C. To
the Nickel database (TCNI8) of the CALPHAD method summarize: alloys 1, 2 and 5 do not contain any NiAl
at 1050°C. Comparison is performed in Table 3 for NiAl and α' phases, only secondary MC and M23C6 develop.
and α’ phases after creep at 1050°C and show a very NiAl and α' phases are observed in alloys 3 and 4 with
good agreement. All these results validate the use of the the highest molar fractions in alloy 4 for both phases.

Table 3: Chemical compositions of NiAl and α’ phases after creep at 1050°C in alloy 4 as measured
by TEM-EDS. Also provided TCNI8 predicted compositions.

NiAl α’
TEM-EDS (wt. %) TCNI8 (wt. %) TEM-EDS (wt. %) TCNI8 (wt. %)
Ni 63.7 63.7 9.4 7.0
Al 19.8 18.3 1.4 0.6
Fe 8.7 10.3 12.0 15.7
Cr 7.5 7.2 77.2 76.6
Nb 0.3 0.3
Ti - 0.1

Table 4: TCNI8 predicted NiAl, α’, M23C6 and MC molar fractions at 1000°C and 1050°C.

𝐓𝐓𝐓𝐓
𝐟𝐟𝐍𝐍𝐍𝐍𝐍𝐍𝐍𝐍 𝐟𝐟𝛂𝛂𝐓𝐓𝐓𝐓′ 𝐓𝐓𝐓𝐓
𝐟𝐟𝐌𝐌 𝟐𝟐𝟐𝟐 𝐂𝐂𝟔𝟔
𝐓𝐓𝐓𝐓
𝐟𝐟𝐌𝐌𝐌𝐌
Molar fractions
1000°C 1050°C 1000°C 1050°C 1000°C 1050°C 1000°C 1050°C
Alloy 1 0 0 0 0 7.0 6.8 0.9 0.9
Alloy 2 0 0 0 0 7.5 7.3 0.7 0.7
Alloy 3 4.9 3 5.9 3 7.2 7.2 0.7 0.7
Alloy 4 7.2 5.4 6.8 4.2 8.4 8.4 0.5 0.5
Alloy 5 0 0 0 0 6.6 6.9 0.8 0.8

At 1000°C, higher mole fractions of NiAl and α' are temperature in these alloys as shown in Figure 9. Creep
present in alloys 3 and 4. Other features consisting in cavities are observed at NiAl/carbides interface. It is
duplex structures of NiAl and α’ appear at this worth noting that no cavities or micro-cavities are
8
observed in as-cast materials. Centrifugation process diagrams. This phase which is not present after
ensures to obtain materials without any porosity. solidification and after annealing treatment at 1000°C
during 176 h, appears during short creep test (89.8-99.2
Although NiAl phase is not predicted by the CALPHAD
h) at 1000°C or during short thermal ageing (16 h).
method for alloy 2 (Figure 5), SEM characterization of
Appearance and dissolution of this phase during ageing
alloy 2 crept at 1000°C for 89.8-99.2 h reveals that this
or creep can be explained as follows. As shown by
phase is present (Figure 10). As for alloys 3 and 4, creep
Roussel et al. [28], depletion in Cr and enrichment in Ni
cavities seem to appear preferentially at the
at the primary Cr-carbide/matrix interface after
NiAl/carbides interfaces. In order to check the stability
solidification (Figure 12). The presence of these
of the NiAl phase in alloy 2 at 1000°C, annealing
chemical gradients at the matrix/carbide interface after
treatments at 1000°C during 16 h and 176 h followed by
solidification can act as an additional driving force for
a water-quench were performed. After 16 h the NiAl
the heterogeneous nucleation of the NiAl phase. This
phase is present at the carbides/matrix interfaces (Figure
agrees with the fact that only type I NiAl particles are
11a)) but disappears after 176 h (Figure 11b)).
observed. Similarly, some type II NiAl particles not
Consequently, as predicted by the thermodynamic
predicted by the thermodynamic simulations appear in
simulations, the NiAl phase is not stable at 1000 °C.
alloy 5 during creep at 1000°C.
This confirms the validity of the CALPHAD phase

Figure 9: Backscattered electron image of alloy 4 after creep at 1000°C 31 MPa and the corresponding EDS-Ni and
EDS-Al maps. M23C6 and α’ are in dark grey and NiAl in bright grey. Are also pointed out creep cavities (green dash
lines) and duplex structures (red bold lines). (color should be used)

9
Figure 10: Backscattered electron image of alloy 2 after creep at 1000°C 31 MPa and the corresponding EDS-Ni and
EDS-Al maps. MC carbides are in white, M23C6 in dark grey and NiAl in bright grey. Are also pointed out the creep
cavities (green dash lines). (color should be used)

Figure 11: Backscattered electron images of alloy 2 annealed at 1000°C a) during 16 h and b) during 176 h then water-
quenched. MC carbides are in white, M23C6 in dark grey and NiAl in bright grey.

Figure 12: STEM-EDS profile at the M7C3/matrix interface. (color should be used)

10
 3.2. Creep behavior Phases observed in the crept specimen are the same as
those observed in the alloys annealed at 1050°C during
Creep tests were conducted at 1000°C and 1050°C 100 h. In Table 5, rupture time t r (h), elongation at break
under stresses from 17 MPa to 31 MPa. Figure 13 Ar (%) and minimum creep rate in secondary stage ε̇
presents the creep curves of alloys 1 to 5 and the (%/h) are provided. The NiAl presence in the crept
Manaurite XTM® obtained at 1050°C under 17 MPa. specimen are also indicated by a cross mark in Table 5.

Figure 13: Creep curves at 1050°C under 17 MPa. Are also reported the predicted mole fractions α’ and NiAl and the
Al-contents.

Table 5: Elongation at break, creep rupture time and minimum creep rate at 1050°C under 17 MPa and 22.2 MPa.
Also given the NiAl presence (cross mark) in the crept specimen.

𝐀𝐀𝐫𝐫 (%) 𝐭𝐭 𝐫𝐫 (h) 𝛆𝛆̇ (∙ 𝟏𝟏𝟏𝟏−𝟑𝟑 %/h) NiAl presence

σ (MPa) 17 22.2 17 22.2 17 22.2 17 22.2
XTM 15.0 11.7 442.6 125.1 1.2 2.7
Alloy 1 0.7 0.8-1.3 891.6 236.4-331.9 0.1 0.9-2.0
Alloy 2 1.4 1.5-3.2 1065.7 211.8 -330.5 0.1 1.1-1.5
Alloy 3 1.5 3.6-5.5 292.3 53.0-59.3 1.6 5.2-8.5 X X
Alloy 4 6.1 3.9-4.3 133.7 33.7-35.7 6.0 11.7-37.7 X X
Alloy 5 4.9 4.5-5.9 1213.5 165.6-161.3 0.1 3.8-4.8

Whatever the creep conditions, alloys 1 and 2 have than those of alloys 3 and 4 whereas Al content of alloy
similar rupture time and similar creep rate in the 5 is higher than the one of alloy 3 and equivalent to the
secondary stage. These alloys present better creep one of alloy 4. Creep properties of Alloy 5 are roughly
properties than XTM, i.e. lower creep rate in the similar to those of alloys 1 and 2 but with a less abrupt
secondary stage, higher creep rupture time and lower ternary stage which ensure a more ductile fracture. The
elongation at break. Creep rates in the secondary stage creep properties are much better than the reference
for alloys 3 and 4 are more than ten times higher than Manaurite® XTM. These results show that Al rich
for alloys 1 and 2 and their rupture times are much alloys (up to 4.7 wt. %) can exhibit better creep
shorter at 1050°C 17 MPa. Alloy 4 presents the worse properties than the XTM which is without Al. Alloys 1,
creep behavior at 1050°C. The creep properties of alloy 2 and 5 are good candidates to replace the XTM used in
5 at 1050°C 22.2 MPa and at 1050°C 17 MPa are better cracking furnaces.

11
Figure 14 presents the creep curves of alloys 1 to 5 at secondary stage were deduced (Table 6). As a reminder,
1000°C under 31 MPa from which rupture time, NiAl phase is observed in alloys 2, 3, 4 and 5 after creep
elongation at break and minimum creep rate in at 1000°C.

Figure 14: Creep curves at 1000°C under 31 MPa. Are also reported the Al-contents and pointed out the presence of
NiAl.

Table 6: Creep rupture time and minimum creep rate at

1000°C under 31 MPa. Also given the NiAl presence 4. Discussion: link between microstructure and
(cross mark) in the crept specimen. creep properties
𝐭𝐭 𝐫𝐫 (h) 𝛆𝛆̇ (∙ NiAl
𝟏𝟏𝟏𝟏 %/h)
−𝟑𝟑 presence A clear trend appears: the higher the mole fractions of
NiAl and α' phases the worse are the creep properties:
Alloy 1 169.5 2.7 - creep rate in the secondary stage increases and the creep
Alloy 2 89.8- 13.4-16.1 X rupture time drops. Alloys with no NiAl and α' phases
99.2
exhibit good creep properties even if they contain Al.
Alloy 3 63.7 15.8 X
Alloy 4 38.3 12.1 X
These results show that NiAl and α' phase have a
Alloy 5 66.0 33.5 X deleterious effect on creep resistance of the alloys. This
deleterious effect of NiAl phase is confirmed by the
behavior of alloys 2 and 5. At 1050°C, alloy 2 which
As at 1050°C, alloys 3 and 4 exhibit the worst creep does not contain any NiAl phase presents creep
properties with ε̇ more than four times higher than properties as good as alloy 1. Likewise, alloy 5 exhibits
values for alloy 1 at 1000°C under 31 MPa and their good creep properties at 1050°C, much better than the
rupture times are much shorter. Moreover, contrary to alloys 3 and 4 which contain NiAl phase. At 1000°C
what was observed at higher temperature and lower where some residual NiAl particles are observed, creep
stress, alloys 2 and 5 presents lower creep properties properties of alloys 2 and 5 decrease with respect to
than alloy 1 with a higher creep rate in the secondary those of alloy 1. Alloy 1 shows the best creep resistance
stage and lower creep rupture time. Alloy 1 presents a whatever the temperature. These good creep properties
very abrupt ternary stage. originate from the presence of the secondary carbides
and the absence of NiAl phase.

12
 studied MCrAlY coating composed of γ-matrix, γ’,
NiAl and α', α' also contributes to the increase in
ductility and the decrease in strength at high
temperature. These ductile phases at service
temperature are the limiting factor for creep resistance.

5. Conclusions

Figure 15: TEM image of dislocations in a NiAl plate Several FeNiCrAl alloys with 3.5-4.8 wt. % of Al
in the alloy 4 after creep at 1050°C. were investigated in this paper. Their as cast
microstructure consists in M7C3 and MC carbides
The loss in strength and the increase in ductility of the
after solidification. During ageing, secondary
NiAl and α' phases can be pointed out in order to explain
the deleterious character of these phases. Above 0.45Tm
precipitation of carbides occurs and as a
(melting temperature), NiAl shows a drop in strength consequence improves the creep properties.
[33,37] coincident with a sharp increase in ductility Depending on their chemical composition, these
[33–36]. The drop in strength his even more pronounced alloys can contain NiAl and α’ phases at high
above about 0.6Tm which corresponds to the service temperatures as predicted by the thermodynamic
temperature of the materials presented in this paper simulations performed with the nickel database of
[33]. Consequently, at service temperature, the NiAl Thermo-Calc® (TCNI8) and validated by the
phase does not remain an effective obstacle for microstructural observations at 1000°C and
dislocation motion [12,13,16–19,38] and a loss of creep 1050°C. The results obtained clearly show the
properties is observed. This agrees well with the TEM deleterious character of NiAl and α’ phases for the
image presented in Figure 15 which reveals the presence
creep properties at service temperature (1000°C-
of dislocation lines inside a NiAl precipitate
characteristic of the ductile behavior of the NiAl phase.
1050°C). High aluminum containing FeNiCr alloys
This assumption is consistent with the ductile behavior with high creep properties are good candidates in
of the MCrAlY coatings attributed to the NiAl ductility order to replace the reference Manaurite® XTM
[39–41]. Moreover, according to Texier et al. [39] who alloy.

Funding
This work has been funded by the Agence Nationale de la Recherche (ANR), project IPERS, grant number LAB COM
– 15 LCV4 0003.

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