Field of the invention
[0001] The present invention relates to a nickel-based superalloy which can be applied,
for example, for making both tools for the iron and steel industry, used for the hot
deformation of steels and alloys, and aerospace components, i.e. for applications
in which high mechanical properties and/or resistance to wear/erosion at high temperature,
up to 1300°C, are required.
State of the art
[0002] Nickel-based superalloys are today the most used for making components working at
high temperature, up to 1000°C, and subjected to severe stresses. They are currently
the best compromise in terms of high and low temperature mechanical properties, mechanical
and thermal fatigue strength, creep resistance, and resistance to oxidation and to
corrosion.
[0003] Various nickel-based superalloys are known, with the corresponding manufacturing
and thermal treatment process.
[0004] The components with single crystal structure exhibit the best performance in terms
of creep resistance, followed by the directional structures (formed by columnar grains)
and equiaxic structures, in which the weakest part is represented by the grain boundaries.
Indeed, elements such as B, Zr and Hf, strengthening the grain boundaries, are added
to the equiaxic and directional components. The directional components are better
than the equiaxic components because they exhibit columnar grains along the direction
of application of stress and the transverse grain boundaries are virtually absent;
single crystal structures, in which the grain boundaries do not exist, exhibit a strength
which depends only on the composition of the matrix.
[0005] A typical nickel-based superalloy consists of a nickel alloy matrix (γ austenitic
phase with face-centered cubic lattice, fcc), solid-solution strengthened by adding
refractory elements and a series of precipitated phases of intermetallic compounds
and carbides, which contribute to further strengthening and thermal stabilization
of the metal.
[0006] The various chemical elements must be properly balanced to confer stability to the
material, in addition to creep resistance and to hot oxidation/corrosion resistance.
The superalloy composition may be described in general terms by splitting the various
elements into groups:
- a first group of elements, such as Co, Fe, Cr, W, Mo (more recently also Re and Ru),
which act as solid-solution strengtheners of the austenitic matrix;
- a second group of elements, such as Al, Ti, Ta and Nb, which form precipitates coherent
with the matrix of the Ni3X type (γ' phase), causing precipitation hardening of the matrix; the γ' phase is
generally present in fractions from 15% to 65% by volume;
- a third group of elements, consisting of C, B, Zr and Hf; carbon forms carbides, such
as MC, M23C6 and M6C reacting with Cr, Mo, W, Ta, Ti and Nb, while B, Zr and Hf segregate at the grain
boundaries, thus improving ductility and strength of the material (in the case of
equiaxic and directional components);
- yttrium (Y) and other elements belonging to the rare earth metals (REM) group are
often added to increase high-temperature oxidation resistance; also aluminium, when
present in contents higher than 5%, contributes to considerably increasing the resistance
to high-temperature oxidation by forming a protective α-Al2O3 based film.
[0007] Today, the maximum working temperature of a superalloy is approximately 1100°C and
related to the third-generation SX alloy CMSX-1 0 with a high content of Re (up to
6%). Second-generation alloys, such as, for example, the CMSX-4 alloy described in
document
US4643782, contain 3% of Re, while rhenium was absent from the first-generation alloys. Such
alloys are used for the construction of gas turbine blades subject to high mechanical
and thermal working stresses (typical application in the first stages of turbines).
[0008] The introduction of rhenium (Re), in addition to other refractory elements, allows
a further strengthening of the matrix and contributes to maintaining high corrosion
resistance, even though the content of Cr is lowered, with respect to first-generation
alloys.
[0009] The CMSX-4 alloy was designed so as to have a high creep resistance and can work
for a short time at up to 1093°C.
[0010] The CMSX-10 alloy exhibits excellent castability, high creep resistance, high fatigue
strength for both Low Cycle Fatigue (LCF) and High Cycle Fatigue (HCF) and good resistance
to corrosion and to oxidation of the component as such.
[0011] The thermal treatment of the as-cast alloy is a key step in improving the features
of these materials and stability at high temperatures. Strength is optimized by means
of microstructural homogenization, solution heat treatment, and reprecipitation of
the γ' phase into very fine particles. Therefore, the alloy composition is always
designed to provide an adequate metallurgical window (i.e. a considerable difference
between the solvus temperature of the γ' phase and the solidus temperature of the
alloy, with T
solidus>T
solvus) so as to allow to obtain a complete dissolution and reprecipitation of the γ' phase
by means of appropriate treatments, before working at high temperature.
[0012] The aforesaid considerable temperature difference varies from 40 to 150°C, being
T
solidus of the alloy higher than T
solvus of the γ' phase.
[0013] The complex third-generation alloys usually contemplate a thermal ageing treatment,
often in two steps, to induce the fine precipitation of the γ' phase after solution
heat treatment and controlled cooling treatment.
[0014] Also in third-generation alloys, Cr, although in lower content, is always present
in percentages by weight higher than 1 %, e.g. in ranges from 1-4% to 3-12%. Disadvantageously,
nickel-based superalloys offering a higher strength at very high temperature, specifically
up to 1300°C, are not currently available, which would allow, for example:
- in the iron and steel field, to avoid the limits presented by the currently used materials
by increasing thermo-mechanical stress at high temperature;
- and in the aerospace field, to facilitate an increase of the system speeds (e.g. missiles),
closely connected to the raising of temperatures to which some specific components,
such as propulsion system parts and control surfaces directly concerned by the aero-thermodynamic
stress, are subjected.
[0015] The need for a nickel-based superalloy which allows to fulfill the aforesaid needs
is therefore felt.
Summary of the invention
[0016] It is the main object of the present invention to make a nickel-based superalloy
which offers a strength at very high temperature, up to 1300°C, higher than that of
the known superalloys by raising the T
solidus of the alloy and developing an intermetallic phase γ' (gamma prime) in high percentages
by volume, higher than 70%, which maintains its features practically unchanged until
the incipient melting of the alloy, having a T
solvus, i.e. a dissolution temperature of the γ' phase, higher than the T
solidus of the alloy, i.e. the temperature at which the liquid phase starts being present.
[0017] It is a further object of the present invention to provide a more cost-effective
manufacturing process of the aforesaid nickel-based superalloy.
[0018] The present invention thus proposes to reach the aforesaid objects by making a nickel-based
superalloy which, in accordance with claim 1, has a composition by weight percentage
comprising cobalt from 1 to 8%; tungsten from 7 to 15%; molybdenum from 1 to 8%; tantalum
from 7 to 15%; aluminium from 4 to 9%; chromium lower than 0.5%; carbon lower than
or equal to 0.1%; the remaining being nickel and inevitable impurities; said superalloy
comprising an intermetallic phase (γ') of the Ni
3X type where X is aluminium and/or tantalum, and having a solvus temperature (T
solvus) of the intermetallic phase (γ') higher than the solidus temperature (T
solidus) of the alloy.
[0019] A second aspect of the present invention relates to a manufacturing process of the
aforesaid nickel-based superalloy in which, in accordance with claim 12, said superalloy
is cast by means of either an equiaxic solidification method, or a directional solidification
method, or a single crystal solidification method.
[0020] Further aspects of the invention relate to a component for iron and steel tooling
according to claim 13, such as for example an industrial plug for piercing steel billets,
and an aerospace component according to claim 15, such as the nozzle flap of an aeronautic
engine.
[0021] The objective of obtaining a high-temperature strength, until 1300°C, higher than
that of the known superalloys is reached by means of a chemical composition of the
superalloy so to:
- have a high content of elements strengthening the matrix by solid-solution hardening;
- have an intermetallic γ' phase, as further matrix strengthening phase, stable to high
temperatures.
[0022] The superalloy has a very low chromium content (< 0.5% by weight): such an element
was not introduced in the composition, or however was introduced in a very low percentage
with respect to the known superalloys, so as to increase the matrix solubility of
other elements, such as W, Ta and Mo, which have a higher solid solution hardening
effect on the matrix.
[0023] According to a preferred embodiment, the alloy is of the dual-phase type, formed
by intermetallic γ' phase of the Ni
3X type, where X is aluminium and/or tantalum, i.e. of the Ni
3(Al, Ta) type, distributed in a nickel solid solution (matrix). The intermetallic
phase is formed during solidification, thus its T
solvus is higher than the T
solidus of the alloy.
[0024] The high mechanical strength is thus promoted by the fact that the intermetallic
γ' phase, which contributes to matrix hardening, having a T
solvus higher than the T
solidus of the matrix, is not dissolved during high-temperature operation, thus maintaining
its properties until the incipient melting of the alloy.
[0025] The (T
solvus - T
solidus) difference is higher than 5°C. In an example below, it is equal to 9 °C, but may
also reach 15-20 °C or more.
[0026] The superalloy according to the present invention, named NiTaWAI, has a nickel rich
composition, with predetermined additions of tungsten and tantalum, refractory elements
and aluminium.
[0027] The alloy also contains a predetermined amount of molybdenum, while it is essentially
free from chromium.
[0028] The chemical composition was designed and optimized to improve strength at high temperatures,
specifically up to 1300°C.
[0029] The alloy may be mainly used for the production by investment casting of components
with equiaxic, directional or single crystal structure.
[0030] It may also be used as powder, after specific gas-atomization process, for making
coatings, by using thermal spraying techniques, such as HVOF (High Velocity Oxy Fuel),
APS (Air Plasma Spray), VPS (Vacuum Plasma Spray) and PTA (Plasma Transferred Arc).
[0031] The applications of the superalloy, object of the present invention, relate to various
industries.
[0032] In the iron and steel field, the tooling for forming metallic semi-finished products
at high-temperature are generally made of steels for hot applications and of Cobalt
and Nickel based superalloys.
[0033] Such materials exhibit their limits as the high-temperature thermo-mechanical stresses
increase, caused by the need to process high-alloy steel materials which present a
high hot deformation strength and which cause problems of wear and degradation of
the forming tools.
[0034] In the aerospace industry, the generalized increase of system speeds (e.g. missiles)
is closely linked to the temperature increase to which some specific components are
subjected.
[0035] We can mention some control surfaces directly concerned by the aerothermodynamics
stress (which increases with speed and contributes to increasing surface temperatures)
and parts of the propulsion systems, the development trend of which is generally based
on the increase of combustion temperatures.
[0036] The main advantage of the invention with respect to the alloys currently in use can
be identified in high strength, high wear resistance and high thermal fatigue strength
up to 1300°C.
[0037] The high mechanical properties of the alloy are due to its chemical composition,
to contents of Cr lower than 0.5% and thus to the presence of a higher content of
solid-solution matrix strengthening elements and to the presence of the intermetallic
phase up to the incipient melting temperature of the alloy. Furthermore, the as-cast
alloy in virtue of its features can be used without thermal treatment after casting,
contrary to the last-generation alloys which, instead, require complex, extremely
expensive cycles of solution heat treatment and ageing in furnace.
[0038] The dependent claims describe preferred embodiments of the invention.
Brief description of the figures
[0039] Further features and advantages of the present invention will be more apparent in
the light of the detailed description of preferred, but not exclusive, embodiments
of a nickel-based superalloy and of a manufacturing process thereof, illustrated by
way of non-limitative example, with the aid of the accompanying drawings, in which:
Figure 1 depicts the microstructure of the superalloy according to the invention,
observed under an optical microscope at different magnifications;
Figure 2 depicts the microstructure of the superalloy according to the invention,
observed under a SEM at different magnifications;
Figure 3 depicts the microstructure of the intermetallic γ' phase observed under a
SEM;
Figure 4 depicts the yield strength pattern according to the test temperature of the
superalloy of the invention (NiTaWAI) and of the nickel-based reference alloy (Ni-Ref);
Figure 5 depicts the ultimate tensile strength pattern according to the test temperature
of the superalloy of the invention (NiTaWAI) and of the nickel-based reference alloy
(Ni-Ref);
Figure 6 depicts the wear resistance of the superalloy according to the invention
(NiTaWAI), compared with the Ni- and Co-based reference alloys shown in Table 9, following
a hot sliding wear test;
Figure 7 depicts the thermal fatigue strength of the superalloy according to the invention,
compared with the Ni- and Co-based reference alloys;
Figure 8 depicts, from left to right, a resin prototype of an industrial plug, ceramic
shells for casting the molten bath and some pilot industrial bits made in said shells;
Figure 9 depicts the comparison between two industrial plugs, formed by NiTaWAI superalloy
and nickel-based reference superalloy, respectively, after laboratory piercing tests;
Figure 10 depicts some steps of the plug manufacturing process, such as shell sintering
and shell breakage, and some finished components;
Figure 11 depicts nozzle flaps of an aeronautic afterburner;
Figure 12 depicts a thermodynamic cycle with an afterburner turbojet in flight; the
ideal cycle is shown by a dashed line;
Figure 13 depicts the thrust increase of a turbojet in step of afterburning;
Figure 14 depicts the temperature variation (single cycle) measured on the surface
and at a depth of 1 mm of superalloy specimens subjected to thermal cycles;
Figure 15 depicts a superalloy specimen invested by a high-temperature, highspeed
gas flow.
Detailed description of preferred embodiments of the invention
Chemical composition of the superalloy
[0040] Tables from 1 to 3 and Tables from 4 to 6 respectively show the composition of the
nickel-based superalloy, according to the invention, named NiTaWAI, in Equiaxic (EQ)
or Directionally Solidified version (DS) and Single Crystal version (SX).
[0041] The tables show the ranges of percentage by weight of the chemical composition; specifically,
the broadest ranges (Tab. 1 and Tab. 4), the preferred ranges (Tab. 2 and Tab. 5)
and the narrowest ranges (Tab. 3 and Tab. 6) of the superalloy chemical composition
of the invention are shown for each version, EQ/DS and SX. The alloy was designed
so as to obtain a material with high mechanical performance at high temperatures,
up to 1300°C. Its composition was optimized on the basis of the following criteria:
- a high predetermined content of W, Ta and Mo, matrix strengthening elements by solid-solution
and by means of the formation of carbides. Ta improves hot oxidation resistance, while
W and Mo tend to reduce it. Ta increases the fraction by volume of the γ' phase, Ni3(Al, Ta), and strengthens it; furthermore, it allows the formation of primary carbides
which are very stable also at very high temperatures. High concentrations of Ta, however,
contribute (strongly depending on the content of elements with a high atomic number)
to formation of the γ' eutectic phase with a reduction of the high-temperature mechanical
strength; excessively high Mo and W contents also lead to the formation of embrittling
phases;
- a high predetermined content of aluminium which strengthens the matrix by forming
the γ' phase, Ni3(Al, Ta), persistent up to the alloy melting temperature. Indeed, the γ' phase exhibits
a solvus temperature higher than the solidus temperature of the alloy; however, Al
values higher than 10% promote the formation of the γ' eutectic phase, with the decrease
of the high-temperature mechanical strength;
- presence of C, Zr, Hf and B in the case of equiaxic or directional castings, for improving
grain boundary strength and thus material ductility.
Table 1 - Broadest nominal composition (% by weight) of the NiTaWAI alloy, EQ and
DS versions
Ni (%) |
Co |
W |
Mo |
Ta |
Al |
C |
Hf |
Zr |
B |
Cr |
Ti |
Si |
S |
P |
(%) |
(%) |
(%) |
(%) |
(%) |
(%) |
(%) |
(%) |
(%) |
(%) |
(%) |
(%) |
(%) |
(%) |
base |
1-8 |
7-15 |
1-8 |
7-15 |
4-9 |
0.01-0.1 |
<0.5 |
<0.05 |
<0.05 |
<0.5 |
<0.1 |
<0.05 |
<0.002 |
<0.003 |
Table 2 - Preferred nominal composition (% by weight) of the NiTaWAI alloy, EQ and
DS versions
Ni |
Co |
W |
Mo |
Ta |
Al |
C |
Hf |
Zr |
B |
Cr |
Ti |
Si |
S |
P |
(%) |
(%) |
(%) |
(%) |
(%) |
(%) |
(%) |
(%) |
(%) |
(%) |
(%) |
(%) |
(%) |
(%) |
(%) |
base |
3-7 |
9-12 |
3-6 |
9-12 |
5-8 |
0.01-0.1 |
<0.5 |
<0.05 |
<0.05 |
<0.5 |
<0.1 |
<0.05 |
<0.002 |
<0.003 |
Table 3 - Narrowest nominal composition (% by weight) of the NiTaWAI alloy, EQ and
DS versions
Ni |
Co |
W |
Mo |
Ta |
Al |
C |
Hf |
Zr |
B |
Cr |
Ti |
Si |
S |
P |
(%) |
(%) |
(%) |
(%) |
(%) |
(%) |
(%) |
(%) |
(%) |
(%) |
(%) |
(%) |
(%) |
(%) |
(%) |
base |
4-5.5 |
9.5-11 |
4.5-6 |
9.5-11 |
5.5-7 |
0.01-0.1 |
<0.5 |
<0.05 |
<0.05 |
<0.5 |
<0.1 |
<0.05 |
<0.002 |
<0.003 |
Table 4 - Broadest nominal composition (% by weight) of the NiTaWAI alloy, SX version
Ni |
Co |
W |
Mo |
Ta |
Al |
C |
Cr |
Ti |
Si |
S |
P |
(%) |
(%) |
(%) |
(%) |
(%) |
(%) |
(%) |
(%) |
(%) |
(%) |
(%) |
(%) |
base |
1-8 |
7-15 |
1-8 |
7-15 |
4-9 |
<0.01 |
<0.5 |
<0.1 |
<0.05 |
<0.002 |
<0.003 |
Table 5 - Preferred nominal composition (% by weight) of the NiTaWAI alloy, SX version
Ni |
Co |
W |
Mo |
Ta |
Al |
C |
Cr |
Ti |
Si |
S |
P |
(%) |
(%) |
(%) |
(%) |
(%) |
(%) |
(%) |
(%) |
(%) |
(%) |
(%) |
(%) |
base |
3-7 |
9-12 |
3-6 |
9-12 |
5-8 |
<0.01 |
<0.5 |
<0.1 |
<0.05 |
<0.002 |
<0.003 |
Table 6 - Narrowest nominal composition (% by weight) of the NiTaWAI alloy, SX version
Ni |
Co |
W |
Mo |
Ta |
Al |
C |
Cr |
Ti |
Si |
S |
P |
(%) |
(%) |
(%) |
(%) |
(%) |
(%) |
(%) |
(%) |
(%) |
(%) |
(%) |
(%) |
base |
4-5.5 |
9.5-11 |
4.5-6 |
9.5-11 |
5.5-7 |
<0.01 |
<0.5 |
<0.1 |
<0.05 |
<0.002 |
<0.003 |
[0042] Minor elements, considered impurities, may be present, such as:
Nb < 500 ppm,
Y < 20 ppm,
Mn < 1000 ppm,
N < 50 ppm.
[0043] Rare earth metals (REM) and yttrium are not deliberately added, although they improve
hot oxidation resistance, because they lower the solidus temperature of the alloy.
[0044] The chromium content is maintained very low, lower than 0.5% by weight, both to increase
solubility in matrix of elements, such as W, Ta and Mo, which are much more effective
in solid solution matrix hardening, and to prevent the formation of embrittling phases.
[0045] The amount of the individual elements to be introduced in the alloy, which may vary
according to the previously indicated ranges (Tables from 1 to 6), is selected according
to the fundamental requirements that embrittling phases are not formed and that the
solvus temperature of the intermetallic phase γ' is higher than the solidus temperature
of the alloy, so as to reach the required final properties, primarily high tensile/compression
strength, resistance to erosion, high-temperature wear, and to thermal fatigue, as
well as a good hot oxidation behaviour.
[0046] The as-cast alloy can be used without any thermal treatment, because as there is
no metallurgical window (T
solvus > T
solidus) the intermetallic phase cannot be dissolved during high-temperature operation.
[0047] An example of the microstructure of the alloy, object of the invention, is shown
in Figure 1, showing the micrographies acquired under the optical microscope at different
magnifications. The white phase is the γ' intermetallic phase. Figure 2 shows the
images taken by a Scanning Electronic Microscope (SEM) with different magnifications
and the following Table 7 shows the SEM microanalysis with EDS system (Energy Dispersion
Spectrometry) of the present phases: the matrix B, the intermetallic phase A and the
carbides C rich in W, Ta and Mo.
Table 7- EDS analysis (ref. Figure 2 a-b)
Area |
Al |
Co |
Ni |
Mo |
Ta |
W |
(%) |
(%) |
(%) |
(%) |
(%) |
(%) |
A (intermetallic phase) |
6 |
6 |
65 |
1 |
12 |
10 |
B (matrix) |
5 |
7 |
66 |
4 |
6 |
12 |
C (carbides) |
1 |
4 |
18 |
18 |
21 |
38 |
[0048] The γ' fine phase has dimensions of about 1 µm. The coarse intermetallic phase presents
dimensions of about 100 µm. The γ' fine phase is shown in Figure 3. The fraction by
volume of the alloy γ' phase varies within the composition range mainly according
to the contents of Ta and Al.
[0049] The percentage by volume of the γ' phase is advantageously comprised in the 70-90%
range.
[0050] Table 8 shows the relation between Al and Ta content and the percentage by volume
of γ' phase present in the alloy of the invention.
Table 8 - Percentage by volume of the γ' phase according to the Ta and Al contents
(% by weight)
Ta |
Al |
Percentage of γ' phase |
(%) |
(%) |
(%) |
11 |
5 |
74 |
12 |
5 |
76 |
9 |
6 |
83 |
9 |
7 |
91 |
9 |
8 |
90 |
Properties of the NiTaWAI superalloy
[0051] The mechanical properties, wear resistance, thermal shock resistance and oxidation
resistance of the alloy, object of the present invention, are shown below. The features
of the alloy are compared with the features of some Ni- and Co-based reference alloys,
the composition of which is shown in Table 9, used at high-temperatures in the iron
and steel field.
Tab. 9 - Composition (% by weight) of the comparison alloys
|
Ni |
C |
Si |
Mn |
Co |
Cr |
Mo |
W |
Fe |
Al |
|
(%) |
(%) |
(%) |
(%) |
(%) |
(%) |
(%) |
(%) |
(%) |
(%) |
Ni-Ref |
base |
0.03 |
0.17 |
0.34 |
--- |
15.90 |
17.40 |
4.7 |
1.20 |
--- |
Co-Ref |
--- |
0.32 |
0.30 |
1.4 |
base |
29.90 |
3.40 |
--- |
--- |
--- |
NiMoWAI |
base |
0.04 |
--- |
--- |
--- |
--- |
9.90 |
10.10 |
--- |
6 |
■ Hot mechanical resistance
[0052] Table 10 shows the yield strength Rp
0.2 and the ultimate tensile strength Rm of the NiTaWAI alloy measured at various temperatures,
from 300°C to 1300°C. These values are compared with those of the Ni-based reference
alloy, indicated by Ni-Ref, commonly used for iron and steel industry applications,
the composition of which is shown in Table 9. The corresponding graphs are shown in
Figures 4 and 5.
[0053] The NiTaWAI alloy up to 1200°C shows an increase of yield strength of over 80 MPa
and an increase of the ultimate tensile strength of over 130 MPa with respect to the
reference alloy Ni-Ref.
Table 10 - High-temperature traction test results
T (°C) |
Rp 0.2% (MPa) |
Rm (MPa) |
Ni-Ref |
NiTaWAI |
Ni-Ref |
NiTaWAI |
300 |
204 |
742 |
383 |
749 |
600 |
269 |
644 |
335 |
684 |
900 |
163 |
465 |
234 |
509 |
1100 |
--- |
213 |
--- |
236 |
1150 |
60 |
--- |
63 |
--- |
1200 |
36 |
126 |
39 |
183 |
1250 |
--- |
17 |
--- |
19 |
1300 |
--- |
10 |
--- |
13 |
[0054] Furthermore, the hardness at ambient temperature of the NiTaWAI alloy is equal to
445 HV; that of the Ni-Ref alloy is equal to 220 HV.
■ Wear resistance
[0055] Figure 6 shows the wear resistance of the NiTaWAI alloy compared with the Ni- and
Co-based alloys shown in Table 9, determined by a hot sliding test.
[0056] The test conditions are:
- Test time: 8 hours
- Test temperature: 1200°C on the NiTaWAI alloy
- Load: 400N
- Relative speed between specimens in contact: 0.5 m/s.
[0057] The wear properties are shown in terms of weight variations of the specimen. It is
worth noting that the alloy according to the present invention exhibits a wear resistance
approximately double with respect to that of the nickel-based reference alloy.
■ Thermal fatigue strength
[0058] Figure 7 shows the thermal fatigue strength of the NiTaWAI alloy compared with the
Ni-Ref and Co-Ref reference alloys. Such a property is shown in terms of crack density
(number of cracks per surface unit found on specimen, on the sample section, at determined
magnifications). The crack density of the NiTaWAI superalloy is approximately 1/4
with respect to the Ni-based reference alloy (Ni-Ref).
[0059] The tests were carried out on cylindrical specimens with a thermal cycle from 100°C
to 1200°C for 500 cycles.
■ Oxidation resistance
[0060] The alloy of the invention (NiTaWAI) subjected to static oxidation tests is more
resistant than the Ni-Ref and Co-Ref reference alloys (described in Table 9). Indeed,
oxidation tests carried out on approximately 20 mm in diameter, 50 mm long cylindrical
samples show that at the end of the test:
- the cylindrical sample formed by NiTaWAI appears shiny, metallic grey in color, with
approximately 0,5 mm thick scale, compact and strongly adherent to the matrix;
- the cylindrical sample formed by Ni-Ref appears crumbly and consumed from the surface
inwards;
- the cylindrical sample formed by Co-Ref tends to descale, exhibits the formation of
a thin scale, extremely weak and poorly adhering to the matrix.
Melting process for manufacturing the superalloy of the invention
[0061] The melting process for manufacturing the nickel-based superalloy according to the
present invention contemplates the following steps:
- heating the charge material comprising Ni, Co, W, Mo, Ta, C with the respective percentages
by weight shown in Table 1 or Table 4;
- melting the charge elements Ni, Co, W, Mo, Ta, C to obtain a liquid bath;
- first degassing of the liquid bath by means of rotary vacuum pumps, with pressure
lower than 0.2 mbar in the melting chamber;
- adding Al to reach the percentage by weight shown in Table 1 or 4;
- second degassing of the liquid bath by means of rotary vacuum pumps;
- possible addition of Zr and B, so as to reach the percentages by weight shown in Table
1, if an equiaxic or directional structure is required.
[0062] The idea of the suggested solution is tested in the various examples which are related
to the above-described embodiment.
EXAMPLE 1
Example of manufacturing of components for tooling of iron and steel industry by means
of a casting process
[0063] The NiTaWAI alloy may be mainly used for the production by investment casting of
equiaxic, directional or single crystal components.
[0064] Specifically, said alloy was cast for making industrial plugs used during the billet
piercing stage for the production of seamless pipes made of medium-high alloy steels.
A series of pilot scale plugs, tested by a pilot piercer, was carried out before making
the industrial plugs.
[0065] The components are made by means of VIM (Vacuum Induction Melting) technology which
is the most versatile melting technology for nearly all special Fe-, Ni- and Co-based
alloys, for the production of both ingots and castings.
[0066] The composition used for the component above is such to advantageously confer the
solvus, solidus and
liquidus temperatures to the alloy shown in Table 11. Such temperatures were measured by means
of DTA (Differential Thermal Analysis).
Table 11 - T
solvus, T
solidus and T
liquidus of the NiTaWAI alloy
Tsolidus (°C) |
Tliquidus (°C) |
Tsolvus (°C) |
of the alloy |
of the alloy |
of the γ' phase |
1357 |
1379 |
1366 |
[0067] In this case, the difference between T
solvus and T
solidus is 9°C.
Description of the process
[0068] A water cooled copper coil is used in the melting process of the charge, said coil
being crossed by an alternating current which encompasses the refractory crucible
thus generating eddy currents in the charge material which is heated by joule effect.
[0069] The magnetic stirring that the process generates in the bath guarantees both homogenization
and a more accurate control of the chemistry and temperature of the molten mass, and
transportation of material needed for performing the required chemical-physical reactions,
such as, for example, degassing. It also allows exact composition and reproducibility
of the product.
[0070] The superalloy melting cycle in VIM furnace consists of various steps: charging,
melting, refining, chemical analysis and composition correction, casting.
[0071] The charge material includes alloying elements, except for reactive constituents
which are introduced later by means of a charging system arranged on the top of the
furnace. Reactions, such as degassing and deoxidizing, occur during the steps of melting
and refining.
[0072] At the end of the refining period, the reactive elements, such as, for example, Al,
Ti, Si, Zr, Hf, are introduced.
[0073] After a time required for the optimal mixing of the bath, the chemical analysis is
carried out with possible additions of alloying elements if lacking in the composition.
At the end, the molten mass is cast into a ceramic shell or, in the case of semi-finished
products which are later machined by means of a machine tool to make the final item,
into an ingot mould.
[0074] Raw materials only with purity of at least 99.9% were used as charge materials in
order to prepare the NiTaWAI alloy.
[0075] The following operative practice was used for making equiaxic ingots and castings:
- heating the charge material;
- melting the charge elements Ni, Co, W, Mo, Ta, C;
- first degassing of the liquid bath by means of rotary vacuum pumps, with pressure
lower than 0.2 mbar in the casting chamber;
- adding Al;
- second degassing of the liquid bath by means of rotary vacuum pumps;
- adding Zr and B, the most reactive elements;
- casting into ceramic shell, preheated to 1130-1170°C, or into ingot mould.
[0076] Zr and B are added a few instants before the casting itself, respecting only the
times needed for solubilisation and homogenization in the liquid bath due to their
tendency to form oxides.
Making of prototype/industrial components
[0077] A series of prototype plugs, to be tested on a pilot system, was made before proceeding
with the manufacturing of industrial plugs for piercing steel billets.
[0078] The various manufacturing steps of the components contemplate making a series of
resin prototypes which are assembled for making appropriate ceramic shells within
which the molten bath is cast, with consequent manufacturing of the plugs. Figure
8 shows, from left to right, a resin prototype of an industrial plug, ceramic shells
for casting the molten bath and some pilot industrial plugs made in said shells.
[0079] The alloy according to the invention was compared to the Ni-based reference alloy
(Ni-Ref). The standard plug formed by Ni-based reference alloy, mounted on the pilot
piercer, could not pierce more than three billets: a considerable deformation of the
plug nose and a considerable amount of material stuck thereto was observed after the
first three piercings. The NiTaWAI alloy plugs pierced 14 billets (a factor approximately
5 times higher) without presenting any deformation and only a slight layer of material
stuck thereto was observed. Figure 9 shows the comparison between the two plugs during
piercing.
[0080] For the NiTaWAI alloy plugs various test parameters were used, among which extremely
different thermal conditions, in order to verify the effect of thermal shock:
- a plug was preheated and its temperature was maintained over 800°C: after 14 perforations,
the bit was as new;
- a plug was not preheated, the test was carried out starting from cold and cooling
in still air to 500°C and then, for the last five parts, it was rapidly cooled from
1100°C to approximately 200°C by means of compressed air, for a total of 14 parts.
The plug remained sound also in this case.
[0081] The industrial components were made after making the pilot scale plugs: they were
cast according to the previously described melting process. Figure 10 shows some steps
of the process, such as shell sintering and shell breakage, and some finished components.
EXAMPLE 2
Example of manufacturing of an aerospace component
[0082] A further application of the invention is in the aeronautic field for components
subject to high-temperature erosive wear. In the specific case, it relates to aeronautic
engine nozzle flaps, shown in Figure 11. Such components are subjected to high thermo-mechanical
stress in particular steps of the aircraft motion, in which a considerable addition
propulsion thrust is required. The need to correctly adapt the section of the exhaust
pipe to jet speed variations, which may be very large, normally implies that turbojets
with afterburner have variable geometry nozzles: the latter need is generally fulfilled
by nozzle flaps in which a crown of hydraulic jacks acts on fans which can be either
closed or opened according to the operating conditions of the turbo reactor. Furthermore,
the adoption of an adjustable nozzle facilitates starting of the turbojet, while the
possibility of varying the exhaust gas ejection conditions allows a certain reduction
of specific consumptions. Thus, the above-described operating needs require the use
of nozzle flaps also during standard operation and not only during the steps of afterburning.
Such a condition induces a higher thermo-mechanical stress on such components and
therefore the need to adopt better performing materials, both from the point of view
of mechanical resistance and from the point of view of wear and erosion resistance,
is stringent. The operating temperatures at which they work can be inferred from the
graph shown in Figure 12, exemplifying the thermodynamic cycle of a turbojet with
afterburner. The materials usually used, such as commercial Ni- and/or Co-based superalloys,
disadvantageously limit the time of use of such propulsion systems. The graph in Figure
13 shows the increase of thrust, and therefore of load, to which the nozzle flaps
are subjected in particular operating conditions.
[0083] Some NiTaWAI alloy specimens were subjected to a high-temperature erosion test designed
and made for the purpose, and compared with the Ni-based alloy named Ni-Ref above.
A thermal depositing apparatus, commonly known as HVOF (High Velocity Oxy Fuel), capable
of generating high-temperature supersonic flows, was used. Generally, such systems
are used for surface coating processes by means of wear and corrosion resistance materials;
in such a case, the HVOF was instead used as liquid fuel rocket engine for producing
a controlled gaseous flow, because this is more similar to that actually occurring
during the steps of emission. The temperature profile on the surface of the specimens
was obtained by controlling the kinematics of the torch mounted on a 6-axis robot.
[0084] Figure 14 shows the temperature variation in a single cycle, measured at the surface
(curve 1) and at 1 mm of depth (curve 2) in superalloy specimens subjected to thermal
cycles repeated 100 times.
[0085] The flow speed at torch outlet (kerosene-oxygen combustion products) was equal to
approximately mach 2,5. In order to make the test more severe, alumina powder with
a grain size of 80-100 µm and a flow rate of 10 g/min was injected in the highspeed
gaseous flow. Figure 15 shows an image of the HVOF system during the test.
[0086] The test results in Table 12, while indicating a progressive erosive wear damage
for both alloys (NiTaWAI and Ni-Ref), have shown a better behaviour of the NiTaWAI
alloy of the invention.
Table 12 - High-temperature erosion test results
Number of test cycles |
Alloy |
Percentage loss by weight with respect to the initial value (%) |
20 |
Ni-Ref |
2 |
NiTaWAI |
2 |
40 |
Ni-Ref |
4 |
NiTaWAI |
3 |
60 |
Ni-Ref |
8 |
NiTaWAI |
7 |
80 |
Ni-Ref |
13 |
NiTaWAI |
10 |
100 |
Ni-Ref |
16 |
NiTaWAI |
12 |
1. A nickel-based superalloy having a composition by weight percentage comprising cobalt
from 1 to 8%; tungsten from 7 to 15%; molybdenum from 1 to 8%; tantalum from 7 to
15%; aluminium from 4 to 9%; chromium lower than 0.5%; carbon lower than or equal
to 0.1%; the remaining being nickel and inevitable impurities; said superalloy comprising
an intermetallic phase (γ') of the Ni3X type, where X is aluminium and/or tantalum,
and having a solvus temperature (Tsolvus) of the intermetallic phase (γ') higher than the solidus temperature (Tsolidus) of the alloy.
2. A superalloy according to claim 1, wherein the difference between said solvus temperature
(Tsolvus) and said solidus temperature (Tsolidus) of the alloy is at least 5°C.
3. A superalloy according to claim 1 or 2, wherein the percentage by volume of the intermetallic
phase (γ') is at least 70%.
4. A superalloy according to claim 3, wherein the percentage by volume of the intermetallic
phase γ' is comprised in the 70-90% range.
5. A superalloy according to claim 1, wherein titanium lower than 0.1%; silicon lower
than 0.05%; sulfur lower than 0.002% and phosphorus lower than 0.003% are present
in percentage by weight.
6. A superalloy according to any of the preceding claims, wherein carbon is present in
the range from 0.01 to 0.1 %, in case of an equiaxic (EQ) or directional (DS) structure.
7. A superalloy according to any claim from 1 to 5, wherein carbon is lower than 0.01
%, in case of a single crystal (SX) structure.
8. A superalloy according to claim 6, wherein hafnium lower than 0.5%; zirconium lower
than 0.05% and boron lower than 0.05% are present in percentage by weight.
9. A superalloy according to any of the preceding claims, wherein there are present impurities,
such as Nb < 500ppm, Y < 20ppm, Mn < 1000ppm and N < 50ppm.
10. A superalloy according to any of the preceding claims, wherein cobalt from 3 to 7%;
tungsten from 9 to 12%; molybdenum from 3 to 6%; tantalum from 9 to 12%; aluminium
from 5 to 8% are present in percentage by weight.
11. A superalloy according to claim 10, wherein cobalt from 4 to 5.5%; tungsten from 9.5
to 11%; molybdenum from 4.5 to 6%; tantalum from 9.5 to 11%; aluminium from 5.5 to
7% are present in percentage by weight.
12. A manufacturing process of a nickel-based superalloy according to claim 1, wherein
said superalloy is cast by means of an equiaxic solidification method, a directional
solidification method or a single crystal solidification method.
13. A component for tooling of the iron and steel industry for making tubular elements,
wherein a nickel-based superalloy according to claim 1 is at least part of its structure.
14. A component for tooling of the iron and steel industry according to claim 13, wherein
said component is a plug for piercing steel billets.
15. An aerospace component, wherein a nickel-based superalloy according to claim 1 is
at least part of its structure.
16. An aerospace component according to claim 15, wherein said component is an aeronautic
engine nozzle flap.