[0001]The present invention relates to a cobalt-based
10 alloy powder, a cobalt-based alloy sintered body, and a
method for producing a cobalt-based alloy sintered body.
Background Art
[0002]
15 Cobalt (Co) based alloy materials are, together with
nickel (Ni) based alloy materials, typical heat-resistant
alloy materials, and are called super alloys. These
materials are widely used for high-temperature members of
turbines (for example, gas turbines and steam turbines).
20 Cobalt based alloy materials are higher in material costs
than Ni based alloy materials, but are better in corrosion
resistance and abrasion resistance and are more easily
subjected to solute strengthening than the latter
materials. Thus, the former materials have been used as
25 turbine static blades and combustor members.
3
[0003]
Regarding heat-resistant alloy materials, up to the
present time, various improvements have been made in alloy
composition and in producing process. On the basis of the
5 improvements, regarding Ni based alloy materials, the
strengthening thereof has been developed by the
precipitation of their ’ phase (for example, their Ni3(Al,
Ti) phase), and has been a main current. On the other
hand, regarding cobalt-based alloy materials, there is not
10 easily precipitated an intermetallic compound phase which
contributes largely to an improvement of the materials in
mechanical properties such as the ’ phase in the Ni based
alloy materials. Thus, researches have been made about
precipitation strengthening by a carbide phase.
15 [0004]
For example, Patent Literature 1 (JP Sho 61-243143
A) discloses a Co based superplastic alloy characterized
by precipitating carbide lumps and carbide grains each
having a grain size of 0.5 to 10 μm into a base of a
20 cobalt-based alloy which has a crystal grain size of 10 μm
or less; and discloses that the cobalt-based alloy
includes the following C: 0.15-1%, Cr: 15-40%, W and/or
Mo: 3-15%, B: 1% or less, Ni: 0-20%, Nb: 0-1.0%, Zr: 0-
1.0%, Ta: 0-1.0%, Ti: 0-3% and Al: 0-3%, and the balance
25 of Co, all of the “%”s being each percent by weight.
4
Patent Literature 1 states that a Co based superplastic
alloy can be formed which shows super plasticity even in a
low-temperature range (including, for example, 950 C) to
have an elongation of 70% or more, and can further be
5 formed in complicatedly-shaped products by plastic working
such as forging.
[0005]
Patent Literature 2 (JP Hei 7-179967) discloses a
cobalt-based alloy that is excellent in corrosion
10 resistance, abrasion resistance and high-temperature
strength, and includes Cr: 21-29%, Mo: 15-24%, B: 0.5-2%,
Si: 0.1% or more and less than 0.5%, C: more than 1% and
2% or less, Fe: 2% or less, Ni: 2% or less, and the
balance made substantially of Co, all of the “%”s being
15 each percent by weight. Patent Literature 2 states that
this Co based alloy has a composite microstructure in
which a molybdenum boride and a chromium carbide are
relatively finely dispersed in a quaternary alloy phase of
Co, Cr, Mo and Si, and is good in corrosion resistance and
20 abrasion resistance and high strength.
Citation List
Patent Literatures
[0006]
PTL 1:JP Sho 61-243143 A
25 PTL 2: JP Hei 7-179967 A
5
Summary of the Invention
Technical Problem
[0007]
5 Cobalt based alloy materials as described in Patent
Literatures 1 and 2 would have higher mechanical
properties than cobalt-based alloys before the development
of the former alloys. However, it cannot be said that the
former alloys do not have sufficient mechanical properties
10 when compared with a precipitation strengthened Ni based
alloy materials in recent years. However, if the Co based
alloy materials can attain mechanical properties (such as
a 100000-hour creep durable temperature of 875 C or
higher at 58 MPa, and a tensile proof stress of 500 MPa or
15 more at room temperature) equivalent to or higher than
those of ’phase precipitation strengthened Ni based alloy
materials, the Co based alloy materials can turn to
materials suitable for turbine high-temperature members.
[0008]
20 The present invention has been made in light of
problems as described above; and an object thereof is to
provide a Co based alloy powder, a Co based alloy sintered
body, and a method for producing a Co based alloy sintered
body that each can provide a Co based alloy material
25 having mechanical properties equivalent to or higher than
6
those of precipitation strengthened Ni based alloy
materials.
Solution to Problem
5 [0009]
An embodiment of the Co based alloy powder of the
present invention for attaining the object is:
a cobalt-based alloy powder, including:
0.08 mass % or more and 0.25 mass % or less of
10 carbon;
0.1 mass % or less of boron;
10 mass % or more and 30 mass % or less of chromium;
5 mass % or less of iron; and
30 mass % or less of nickel,
15 including the iron and the nickel to be in a total
amount of 30 mass % or less,
including at least one selected from the group of
tungsten and molybdenum to be in a total amount of 5
mass % or more and 12 mass % or less,
20 including at least one selected from the group of
titanium, zirconium, niobium, tantalum, hafnium, and
vanadium to be in a total amount of 0.5 mass % or more and
2 mass % or less;
including:
25 0.5 mass % or less of silicon;
7
0.5 mass % or less of manganese; and
0.003 mass % or more and 0.04 mass % or less of
nitrogen; and including cobalt and impurities as the
balance of the powder, and crystal grains included in the
5 cobalt-based alloy powder having segregated cells, and the
segregated cells having an average size of 0.15 μm or more
and 4 μm or less.
[0010]
An embodiment of the Co based alloy sintered body of
10 the present invention for attaining the object is:
a cobalt-based alloy sintered body, including:
0.08 mass % or more and 0.25 mass % or less of
carbon;
0.1 mass % or less of boron;
15 10 mass % or more and 30 mass % or less of chromium;
5 mass % or less of iron; and
30 mass % or less of nickel,
including the iron and the nickel to be in a total
amount of 30 mass % or less,
20 including at least one selected from the group of
tungsten and molybdenum to be in a total amount of 5
mass % or more and 12 mass % or less,
including at least one selected from the group of
titanium, zirconium, niobium, tantalum, hafnium, and
8
vanadium to be in a total amount of 0.5 mass % or more and
2 mass % or less;
including:
0.5 mass % or less of silicon;
5 0.5 mass % or less of manganese; and
0.04 mass % or more and 0.1 mass % or less of
nitrogen; and including cobalt and impurities as the
balance of the sintered body, and crystal grains included
in the cobalt-based alloy sintered body having segregated
10 cells, and the segregated cells having an average size of
0.15 μm or more and 4 μm or less.
[0011]
An embodiment of the method, for producing a Co
based alloy sintered body, of the present invention for
15 attaining the object is a method for producing a cobaltbased alloy sintered body, including a raw-material mixing
and melting step of mixing raw materials of a cobalt-based
alloy powder having the abovementioned chemical
composition with each other, and melting the raw materials
20 to produce a molten metal, a molten-metal-pulverizing step
of producing a quenched and solidified alloy powder from
the molten metal, and a sintering step of sintering the
quenched and solidified alloy powder; the cobalt-based
alloy powder having the composition of the Co based alloy
25 powder of the present invention.
9
Advantageous Effects of Invention
[0012]
The present invention makes it possible to provide a
5 Co based alloy powder, a Co based alloy sintered body, and
a method for producing a Co based alloy sintered body that
each can provide a Co based alloy material having
mechanical properties equivalent to or higher than those
of precipitation strengthened Ni based alloy materials.
10
Brief Description of Drawings
[0013]
Figure 1 is a view illustrating schematically a
powdery surface of a Co based alloy powder of the present
15 invention.
Figure 2 is a flowchart showing an example of a
process of a method of the present invention for producing
a Co based alloy powder.
Figure 3 is a schematic perspective view
20 illustrating an example of a product in which a Co based
alloy sintered body of the present invention is used, the
product being a turbine static blade as a turbine hightemperature member.
Figure 4 is a schematic sectional view illustrating
25 an example of a gas turbine equipped with a product in
10
which a Co based alloy sintered body of the present
invention is used.
Figure 5 is respective SEM observed photographs of
Co based alloy sintered bodies of the present invention.
5 Figure 6 is a graph showing a relationship between
the average size of segregated cells in each of Co based
alloy sintered bodies and a cast body, and the 0.2% proof
stress thereof at 800 C.
10 Description of Embodiments
[0014]
[Basic Idea of the Present Invention]
As described above, about a Co based alloy material,
various researches and developments have been made about
15 the strengthening thereof by the precipitation of a
carbide phase. Examples of the carbide phase contributing
to the precipitation strengthening include respective MC
type carbide phases (“M” means transition metal element
and “C” means carbide) of Ti, Zr, Nb, Ta, Hf and V, and a
20 composite carbide phase of two or more of these metal
elements.
[0015]
A C component essential for being combined with each
component of Ti, Zr, Nb, Ta, Hf and V to produce a carbide
25 phase has a nature of being remarkably segregated, at time
11
of melting and solidifying a Co based alloy, into a
finally solidified region (such as dendrite boundaries and
crystal grain boundaries) of the alloy. For this reason,
in any conventional Co based alloy material, carbide phase
5 grains thereof precipitate along dendrite boundaries and
crystal grain boundaries of the matrix. For example, in
an ordinal cast material of Co based alloy, the average
interval between its dendrite boundaries, and the average
crystal grain size of the material are each usually in the
10 order of 101 to 102 μm, so that the average interval
between grains of the carbide phase is also in the order
of 101 to 102 μm. Moreover, even according to laser
welding or any other process in which the solidifying
speed of the alloy is relatively high, in the solidified
15 regions, the average interval between the carbide phase
grains is about 5 μm.
[0016]
It is generally known that the degree of the
precipitation strengthening of alloy is in disproportion
20 with the average interval between precipitates therein.
Thus, it is reported that the precipitation strengthening
becomes effective in a case where the average interval
between the precipitates is about 2 μm or less. However,
according to the abovementioned conventional technique,
25 the average interval between the precipitates does not
12
reach the level described just above. Thus, the technique
does not produce a sufficient advantageous effect of
precipitation strengthening. In other words, in the prior
art, it has been difficult that carbide phase grains
5 contributing to alloy strengthening are finely dispersed
and precipitated. This matter is a main reason why it has
been said that Co based alloy material is insufficient in
mechanical properties when compared with precipitation
strengthened Ni based alloy material.
10 [0017]
For reference, another carbide phase which can
precipitate in Co based alloy is a Cr carbide phase. A Cr
component is high in solid-solution performance into the
Co based alloy matrix, so as not to be easily segregated
15 therein. Thus, the Cr carbide phase can be dispersed and
precipitated into crystal grains in the matrix. However,
it is known that the Cr carbide phase is low in latticematching with matrix crystals of the Co based alloy, so as
not to be very effective as a precipitation strengthening
20 phase.
[0018]
The inventors have conceived that if, in a Co based
alloy material, carbide phase grains contributing to
precipitation strengthening of the material can be
25 dispersed and precipitated into matrix crystal grains, the
13
Co based alloy material can be dramatically improved in
mechanical properties. The inventors have also conceived
that if this matter is combined with good corrosion and
abrasion resistances which the Co based alloy material
5 originally has, a heat resistant alloy material can be
produced which surpasses precipitation strengthened Ni
based alloy materials.
[0019]
Thus, the inventors have made eager researches about
10 an alloy composition and a producing method that each give
such a Co based alloy material. As a result, the
inventors have found out that carbide phase grains
contributing to alloy strengthening can be dispersed and
precipitated into matrix crystal grains of a Co based
15 alloy material by optimizing the composition of the alloy.
The present invention has been accomplished on the basis
of this finding.
[0020]
Hereinafter, embodiments of the present invention
20 will be described with reference to the drawings. However,
the present invention is never limited to the embodiment
referred to herein, and may be improved by combining any
one of the embodiments appropriately with a conventional
technique, or on the basis of a conventional technique as
14
far as the resultant does not depart from the technical
conception of the invention.
[0021]
[Chemical Composition of Co Based Alloy Powder]
5 Hereinafter, a description will be made about the
chemical composition of the Co based alloy powder of the
present invention.
[0022]
C: 0.08 mass % or more and 0.25 mass % or less
10 The C component is an important component for
constituting one or more MC type carbide phases (one or
more carbide phases of Ti, Zr, Nb, Ta, Hf and/or V, which
may be referred to as one or more strengthening carbide
phases), which become(s) one or more precipitation
15 strengthened phases. The content by percentage of the C
component is preferably 0.08 mass % or more and 0.25
mass % or less, more preferably 0.1 mass % or more and 0.2
mass % or less, and even more preferably 0.12 mass % or
more and 0.18 mass % or less. If the content is less than
20 0.08 mass %, the precipitation amount of the C
strengthening carbide phase is short so that the C
component does not sufficiently give an advantageous
effect of an improvement in mechanical properties of the
alloy. By contrast, if the C content is more than 0.25
25 mass %, the alloy is excessively hardened so that a
15
sintered body yielded by sintering the Co based alloy is
lowered in ductility and toughness.
[0023]
B: 0.1 mass % or less
5 The B component is a component contributing to an
improvement of crystal boundaries in bonding performance
(the so-called boundary strengthening). The B component
is not an essential component. When the component is
incorporated, the content by percentage thereof is
10 preferably 0.1 mass % or less, and more preferably 0.005
mass % or more and 0.05 mass % or less. If the content is
more than 0.1 mass %, at the time of the sintering of the
powder or a heat treatment subsequent thereto the
resultant Co based alloy is easily cracked or broken.
15 [0024]
Cr: 10 mass % or more and 30 mass % or less
The Cr component is a component contributing to an
improvement in the corrosion resistance and oxidation
resistance of the alloy. The content by percentage of the
20 Cr component is preferably 10 mass % or more and 30 mass %
or less, and more preferably 10 mass % or more and 25
mass % or less. When a corrosion resistant coating layer
is separately applied to the outermost surface of a Co
based alloy product, the content of the Cr component is
25 even more preferably 10 mass % or more and 18 mass % or
16
less. If the Cr content is less than 10 mass %, the
powder is insufficient in corrosion resistance and
oxidation resistance. By contrast, if the Cr content is
more than 30 mass %, a brittle  phase is produced or a Cr
5 carbide phase is produced to lower the alloy in mechanical
properties (toughness, ductility, and strength).
[0025]
Ni: 30 mass % or less
The Ni component has properties similar to those of
10 the Co component, and is lower in cost than Co. Thus, the
Ni component is a component which can be incorporated in
the form that the Co component is partially replaced by
this component. The Ni component is not an essential
component. When the Ni component is incorporated
15 thereinto, the content by percentage thereof is preferably
30 mass % or less, more preferably 20 mass % or less, and
even more preferably 5 mass % or more and 15 mass % or
less. If the Ni content is more than 30 mass %, the Co
based alloy is lowered in abrasion resistance and local
20 stress resistance which are characteristics of this alloy.
This would be caused by a difference in stacking fault
energy between Co and Ni.
[0026]
Fe: 5 mass % or less
17
The Fe component is far more inexpensive than Ni,
and further has similar in natures to the Ni component.
Thus, the Fe component is a component which can be
incorporated in the form that the Ni component is
5 partially replaced by this component. Specifically, the
total content by percentage of Fe and Ni is preferably 30
mass % or less, more preferably 20 mass % or less, and
even more preferably 5 mass % or more and 15 mass % or
less. The Fe component is not an essential component.
10 When the component is incorporated, the Fe content is
preferably 5 mass % or less, and more preferably 3 mass %
or less in the range of being lower than the Ni content.
If the Fe content is more than 5 mass %, this content
becomes a factor of lowering the corrosion resistance and
15 the mechanical properties.
[0027]
W and/or Mo: 5 mass % or more and 12 mass % or less
in total
The W component and the Mo component are components
20 contributing to the solution-strengthening of the matrix.
The content by percentage of the W component and/or the Mo
component is more preferably 5 mass % or more and 12
mass % or less, and more preferably 7 mass % or more and
10 mass % or less in total. If the total content of the W
25 component and the Mo component is less than 5 mass %, the
18
solution-strengthening of the matrix is insufficient. By
contrast, if the total content of the W component and the
Mo component is more than 12 mass %, a brittle  phase is
easily produced to lower the alloy in mechanical
5 properties (toughness and ductility).
[0028]
Re: 2 mass % or less
The Re component is a component contributing to
improvements on not only the solution-strengthening of the
10 matrix but also the corrosion resistance of the alloy.
The Re component is not an essential component. When this
component is incorporated, the Re content by percentage is
preferably 2 mass % or less in the form that the W or Mo
component is partially replaced by the Re component. The
15 Re content is more preferably 0.5 mass % or more and 1.5
mass % or less. If the Re content is more than 2 mass %,
the advantageous effects of the Re component are saturated
and further this component gives a disadvantage of an
increase in material costs.
20 [0029]
One or more of Ti, Zr, Nb, Ta, Hf, and V: 0.5 mass %
or more and 2 mass % or less in total
The Ti, Zr, Nb, Ta, Hf, and V components are each a
component important for constituting the strengthening
25 carbide phase (MC type carbide phase). The content by
19
percentage of one or more of the Ti, Zr, Nb, Ta, Hf and V
components is preferably 0.5 mass % or more and 2 mass %
or less, and more preferably 0.5 mass % or more and 1.8
mass % or less in total. If the total content is lower
5 than 0.5 mass %, the precipitation amount of the
strengthening carbide phase is short so that the
advantageous effect of the improvement in the mechanical
properties is not sufficiently obtained. By contrast, if
the total content is more than 2 mass %, the following are
10 caused: grains of the strengthening carbide phase become
coarse; production of a brittle phase (for example, a 
phase) is promoted; or oxide phase grains, which do not
contribute to the precipitation strengthening, are
produced. Thus, the mechanical properties are lowered.
15 [0030]
More specifically, when Ti is incorporated, the Ti
content by percentage is preferably 0.01 mass % or more
and 1 mass % or less, and more preferably 0.05 mass % or
more and 0.8 mass % or less. When Zr is incorporated
20 thereinto, the Zr content by percentage is preferably 0.05
mass % or more and 1.5 mass % or less, and more preferably
0.1 mass % or more and 1.2 mass % or less. When Nb is
incorporated thereinto, the Nb content by percentage is
preferably 0.02 mass % or more and 1 mass % or less, and
25 more preferably 0.05 mass % or more and 0.8 mass % or less.
20
When Ta is incorporated thereinto, the Ta content by
percentage is preferably 0.05 mass % or more and 1.5
mass % or less, and more preferably 0.1 mass % or more and
1.2 mass % or less. When Hf is incorporated thereinto,
5 the Hf content by percentage is preferably 0.01 mass % or
more and 0.5 mass % or less, and more preferably 0.02
mass % or more and 0.1 mass % or less. When V is
incorporated thereinto, the V content by percentage is
preferably 0.01 mass % or more and 0.5 mass % or less, and
10 more preferably 0.02 mass% or more and 0.1 mass % or less.
[0031]
Si: 0.5 mass % or less
The Si component is a component taking charge of
deoxidization to contribute to an improvement in the
15 mechanical properties. The Si component is not an
essential component. When this component is incorporated,
the Si content by percentage is preferably 0.5 mass % or
less, and more preferably 0.01 mass % or more and 0.3
mass % or less. If the Si content is more than 0.5 mass %,
20 coarse grains of oxides (for example, SiO2) are produced
to become a factor of lowering the mechanical properties.
[0032]
Mn: 0.5 mass % or less
The Mn component is a component taking charge of
25 deoxidization and desulfurization to contribute to an
21
improvement in the mechanical properties. The Mn
component is not an essential component. When this
component is incorporated, the Mn content by percentage is
preferably 0.5 mass % or less, and more preferably 0.01
5 mass % or more and 0.3 mass % or less. If the Mn content
is more than 0.5 mass %, coarse grains of sulfides (for
example, MnS) are produced to become a factor of lowering
the mechanical properties and the corrosion resistance.
[0033]
10 N: 0.003 mass % or more and 0.04 mass % or less, or
0.04 mass % or more and 0.1 mass % or less
The N component is varied in content by percentage
in accordance with an atmosphere for gas atomizing when
the Co based alloy powder is produced. When the gas
15 atomizing is performed in the argon atmosphere, the N
content percentage is lowered (N: 0.003 mass % or more and
0.04 mass % or less). When the gas atomizing is performed
in a nitrogen atmosphere, the N content is raised (N: 0.04
mass % or more and 0.1 mass % or less).
20 [0034]
The N component is a component contributing to
stabilizing of the strengthening carbide phase. If the N
content is less than 0.003 mass %, the advantageous effect
of the N component is not sufficiently obtained. By
25 contrast, if the N content is more than 0.1 mass %, coarse
22
grains of nitrides (for example, a Cr nitride) are
produced to become a factor of lowering the mechanical
properties.
[0035]
5 Balance: Co component + impurities
The Co component is a main component of the present
alloy and is a component which is the largest in content
by percentage. As described above, the Co based alloy
material has an advantage of having corrosion resistance
10 and abrasion resistance equivalent to or more than those
of Ni based alloy material.
[0036]
An Al component is one impurity of the present alloy,
and is not a component that should be intentionally
15 incorporated. However, when the Al content by percentage
is 0.5 mass % or less, the component does not produce a
large bad effect onto mechanical properties of the
resultant Co based alloy product. Thus, the incorporation
of Al is permissible. If the Al content is more than 0.5
20 mass %, coarse grains of oxides or nitrides (for example,
Al2O3 and AlN) are produced to become a factor of lowering
the mechanical properties.
[0037]
An O component is also one impurity of the present
25 alloy, and is not a component that should be intentionally
23
incorporated. However, when the O content by percentage
is 0.04 mass % or less, the component does not produce a
large bad effect onto mechanical properties of the
resultant Co based alloy product. Thus, the incorporation
5 of O is permissible. If the O content is more than 0.04
mass %, coarse grains of various oxides (for example, Ti
oxides, Zr oxides, Al oxides, Fe oxides, and Si oxides)
are produced to become a factor of lowering the mechanical
properties.
10 [0038]
[Methods for Producing Co Based Alloy Powder]
Figure 2 is a flowchart showing an example of steps
of a method of the present invention for producing a Co
based alloy powder and Co based alloy sintered body. As
15 shown in Figure 2, a raw-material mixing and melting step
(step 1: S1) is initially performed in which raw materials
of a Co based alloy powder of the present invention are
mixed with each other to give a composition of the Co
based alloy powder that has been described above, and then
20 molten to produce a molten metal 10. The method for the
melting is not particularly limited, and a conventional
method for highly heat-resistant alloy is preferably
usable (for example, an induction melting method, electron
beam melting method, or plasma arc melting method).
25 [0039]
24
In order to decrease the content by percentage of
impurity components further in the resultant alloy (or
heighten the alloy in purity), it is preferred in the rawmaterial mixing and melting step S1 to solidify the molten
5 metal 10 once after the production of this molten metal 10
to form a raw material alloy lump, and then remelt the raw
material alloy lump to produce a purified molten metal.
As far as the purity of the alloy is heightened, the
method for the remelting is not particularly limited. For
10 example, a vacuum arc remelting (VAR) method is preferably
usable.
[0040]
Next, a molten-metal-pulverizing step (step 2: S2)
is performed in which from the molten melt 10 (or the
15 purified molten metal), a quenched and solidified alloy
powder 20 is produced. The Co based alloy powder of the
present invention is produced by the quenching and
solidifying in which the cooling speed of the powder is
high. Thus, as illustrated in Figure 1, segregated cells
20 can be obtained which improve the strength of the
resultant Co based alloy product. The average size of the
segregated cells becomes smaller as the cooling speed is
higher.
[0041]
25
As far as the powder 20 can obtain a highly pure and
homogeneous composition, the method for the meltingpulverizing is not particularly limited, and a
conventional alloy-pulverizing method is preferably usable
5 (for example, an atomizing method (a gas atomizing method
or plasma atomizing method, a water atomizing method)).
[Microstructure of Co Based Alloy Powder]
[0042]
Figure 1 is a view illustrating schematically a
10 powdery surface of a Co based alloy powder of the present
invention. As illustrated in Figure 1, the Co based alloy
powder of the present invention, which is a powder 20, is
a polycrystal made of a powder 21 having an average powder
particle size of 5 μm or more and 150 μm or less, and
15 segregated cells 22 are formed in the surface and the
inside of the powder 21. The segregated cells 22 are
varied in shape by the cooling speed of the Co based alloy
powder in a step of producing this powder (pulverizing
step), this step being to be described later. When the
20 cooling speed is relatively high, spherical segregated
cells are produced. When the cooling speed is relatively
low, dendrite-form (tree branch form) segregated cells are
produced. In Figure 1 is illustrated an example in which
the segregated cells are in a dendrite form. It is
25 conceivable that after the Co based alloy powder 20 is
26
sintered, a carbide is precipitated along the segregated
cells.
[0043]
The average size of the segregated cells is
5 preferably 0.15 μm or more and 4 μm or less. The dendrite
microstructures 22 illustrated in Figure 1 each have a
primary branch 24 and secondary branches 25 extending from
the primary branch 24. The average size of the segregated
cells in the dendrite microstructures is the average width
10 (arm interval) 23 (portion shown by an arrow in Figure 1)
of the secondary branches 25.
[0044]
Note that the “average size of the segregated
cells” is a diameter in the case that the segregated cell
15 has spherical shape. The “average size of the segregated
cells” is defined as the average value of the respective
sizes of segregated cells in a predetermined region of an
observed image of a powder through an SEM (scanning
electron microscope) or the like.
20 [0045]
[Particle Size of Co Based Alloy Powder]
A particle size of the Co based alloy powder is
preferably from 5 to 85 μm, more preferably from 10 to 85
μm and most preferably from 5 to 25 μm.
25 [0046]
27
Preferred compositions of the Co based alloy powder
of the present invention are shown in Table 1 described
below.
[0047]
28
[Table 1] Chemical composition of each of alloy powders IA-1 to IA-7 and CA-1 to CA-5
Alloy
powder
Chemical composition (mass %)
C B Cr Ni Fe W Ti Zr Hf V Nb Ta Si Mn N Co Al O Ti+Zr+Hf+
V+Nb+Ta
IA-1 0.16 0.009 24.7 9.3 0.01 7.5 0.16 0.45 - - 0.20 0.15 0.01 0.01 0.005 Bal. 0.01 0.005 0.96
IA-2 0.25 0.011 26.5 10.5 0.90 7.4 0.30 0.60 - - 0.15 0.40 0.30 0.20 0.030 Bal. 0.05 0.020 1.45
IA-3 0.08 0.009 30.0 - - 5.0 - 0.35 - - 0.16 - 0.05 0.01 0.005 Bal. - 0.005 0.51
IA-4 0.10 0.010 25.0 8.0 0.02 7.5 0.25 0.05 - - 0.09 0.30 0.01 0.02 0.010 Bal. - 0.010 0.69
IA-5 0.18 0.009 24.9 9.2 0.01 7.6 0.17 0.45 0.02 0.04 0.21 0.16 0.01 0.01 0.015 Bal. 0.01 0.010 1.05
IA-6 0.24 0.011 25.5 10.3 0.90 7.4 0.20 0.60 0.05 0.02 0.15 0.40 0.30 0.20 0.08 Bal. 0.06 0.025 1.42
IA-7 0.08 0.009 29.5 - - 6.0 0.10 0.15 0.01 0.04 - 0.30 0.15 0.10 0.005 Bal. - 0.005 0.60
CA-1 0.35 0.009 32.5 9.5 0.01 7.3 0.15 0.40 - - 0.05 0.50 0.01 0.01 0.005 Bal. 0.01 0.005 1.10
CA-2 0.35 0.009 30.0 40.0 0.01 7.3 0.90 0.40 - - 1.0 1.0 0.01 0.01 0.005 Bal. 2.20 0.005 3.30
CA-3 0.40 0.010 29.0 10.0 0.20 7.5 0.20 0.10 - - 0.10 - 0.10 0.02 0.001 Bal. - 0.015 0.40
CA-4 0.25 0.010 29.0 10.0 0.10 7.5 - - - - - - - 0.01 00.10 Bal. - 0.010 0
CA-5 0.11 0.002 22.0 23.0 0.01 14.0 0.01 0.01 - - - - 0.50 0.003 0.006 Bal. 0.01 0.008 0.02
-: The symbol shows that the element concerned was not intentionally incorporated, or was not
detected.
Bal.: The symbol shows the balance including impurities other than Al and O
29
[0048]
[Method for Manufacturing Process of Co based alloy
sintered body]
A sintering step (step 3: S3) is performed in which
5 the quenched and solidified alloy powder 20 is sintered as
shown in the Figure 2. In this way, the Co based alloy
sintered body of the present invention can be gained. The
method for the sintering is not particularly limited. For
example, a hot isostatic pressing is usable.
10 [0049]
(Respective Productions of Sintered Body in Which
IA-2 Powder is Used and Sintered body in Which CA-5 Powder
is Used)
An alloy powder of each of the IA-2 and CA-5 shown
15 in the table 1 which had a purity S was used to form a
shaped body (a diameter of 8 mm  a height of 10 mm) by
HIP. Sintering conditions for the HIP were adjusted to a
temperature of 1150 C, a pressure of 150 MPa, and a
period of one hour. Thereafter, the shaped body was
20 subjected to heat treatment at 980 C for four hours to
produce a sintered body in which either of the IA-2 powder
and the CA-5 powder was used.
[0050]
(Respective Productions of Cast Alloy Product in
25 Which IA-2 Powder was Used and Cast Alloy Product in Which
CA-5 Powder was Used)
30
An alloy powder of each of the above-described IA-2
and CA-5 which has a particle size L was used to form a
cast body (a diameter of 8 mm  a height of 10 mm) by
precision casting, and subjected to the same solution heat
5 treatment and aging heat treatment as described above to
produce a cast alloy product (cast body) in which either
of the IA-2 powder and the CA-5 powder was used.
[0051]
(Microstructure Observation and Mechanical Property
10 Measurement)
From each of the sintered bodies and cast bodies
produced as described above, test pieces for
microstructure observation and mechanical property
measurements were collected, and then subjected to
15 microstructure observation and mechanical property
measurements.
[0052]
The microstructure observation was performed through
an SEM. Each of the obtained SEM observed images was
20 subjected to image analysis using an image processing
software (Public Domain Software developed by Image J,
National Institutes of Health (NIH)) to measure the
average size of segregated cells therein, the average
interval between micro segregations therein, and the
25 average distance between grains of carbide phase grains
therein.
31
[0053]
Regarding the mechanical property measurements, one
of the test pieces was subjected to a tensile test at 800
C to measure the 0.2% proof stress.
5 [0054]
Figure 5 is respective SEM observed photographs of
Co based alloy sintered bodies of the present invention.
Figure 5 shows photographs of the Co based alloy powder
having a three types of particle size (5 to 25 μm, 10 to
10 85 μm and 70μm or more) heated (982℃, 4 hours)
immediately after HIP or after HIP. It can be seen that a
microstructure of the sintered body is maintained before
and after the heat treatment. Further, the each of the Co
based alloy sintered bodies has a microstructure which
15 strengthening carbide phase particles precipitate. These
strengthening carbide phase particles are considered that
precipitating along the segregated cells by the sintering.
[0055]
Table 2 shows the 0.2% proof stress and the tensile
20 strength of each of the Co based alloy sintered bodies of
the present invention, and Table 3 shows the average
precipitate interval L and the tensile strength of each of
the Co based alloy sintered bodies. Table 2 also shows
results of the cast material. As shown in Table 2, each
25 of the particle sizes results in the attainment of a 0.2%
proof stress and a tensile strength which are higher than
32
those of the cast material. Moreover, it is understood
from Table 3 that an average precipitate interval L of 1
to 1.49 μm results in the attainment of an especially high
tensile strength (460 MPa or more).
5 [Table 2]
Powder
particle
size (m)
Test
temperature
(C)
0.2% Proof
stress
(MPa)
Tensile
strength
(MPa)
HIP
material
5-25 800 371 489
10-70 800 326 461
>70 800 306 453
Cast
material
- 800 200 300
[Table 3]
Powder particle
size (m)
Average
precipitate
interval L (m)
Tensile strength
(MPa)
5-25 1 489
10-70 1.49 461
>70 3.72 453
[0058]
10 Figure 6 is a graph showing a relationship between
the average size of segregated cells in each of Co based
alloy sintered bodies and a cast body, and the 0.2% proof
stress thereof at 800 C. In Figure 6, data about the cast
body is also shown for comparison. Moreover, in Figure 6,
15 the average interval between micro segregates is
substituted for the average size of segregated cells. In
Figure 6, “IA-2” and “CA-5” are Co based alloy powder
having the composition shown in the Table 1.
33
[0059]
As illustrated in Figure 6, the Co based alloy
sintered body produced using the CA-5 powder showed
substantially constant 0.2% proof stress without being
5 affected by the average size of the segregated cells. By
contrast, the Co based alloy sintered body produced using
the IA-2 powder was largely varied in 0.2% proof stress in
accordance with the average size of the segregated cells.
[0060]
10 The CA-5 powder is excessively small in total
content by percentage of “Ti + Zr + Nb + Ta + Hf + V” (the
powder hardly contains these elements). Thus, the
microstructure-observed result of the sintered body in
which the CA-5 powder is used has demonstrated that the
15 sintered body has a microstructure in which no
strengthening carbide phase precipitates but Cr carbide
grains precipitate. From this result, it has been
verified that the Cr carbide grains are not very effective
as precipitation strengthening grains. By contrast, the
20 sintered body in which the IA-2 powder was used has had a
microstructure in which strengthening carbide grains
precipitate. For this reason, it appears that the 0.2%
proof stress thereof has been largely varied in accordance
with the average size of the segregated cells (the average
25 grain distance between the carbide phase grains, this
distance being determined as a result of the average size).
34
[0061]
Considering requirement properties for turbine hightemperature members which are targets of the present
invention, the 0.2% proof stress of alloy at 800 C needs
5 to be 250 MPa or more. Thus, when a proof stress more
than 250 MPa is judged to be “acceptable” and a proof
stress less than 250 MPa is judged to be “unacceptable”,
it has been verified that allowable mechanical properties
are gained in such a range that the average size of
10 segregated cells (the average grain distance between the
carbide phase grains, this distance being determined as a
result of the average size) is in the range of 0.15 to 4
μm. In other words, one reason why a conventional
carbide-phase-precipitated Co based alloy material gains
15 no sufficient mechanical properties would be that the
average grain distance between strengthening carbide phase
grains cannot be controlled into a desired range.
[0062]
If the average interval between the segregated cells
20 is 0.1 μm or less, carbide on the segregated cells is
aggregated by heat treatment so that the average grain
distance between the carbide phase grains is unfavorably
enlarged. Thus, the 0.2% proof stress would be lowered.
Moreover, if the average interval is more than 4 μm or
25 more, an effect onto the 0.2% proof stress becomes small.
[0063]
35
From the abovementioned results, the average size of
segregated cells constituting the Co based alloy powder of
the present invention would also be preferably from 0.15
to 4 μm. The average size of the segregated cells is more
5 preferably from 0.15 to 2 μm, and even more preferably
from 0.15 to 1.5 μm. Also in a Co based alloy sintered
body obtained by sintering the Co based alloy powder of
the present invention, its segregated cells would have an
average size equivalent to that of the segregated cells in
10 the Co based alloy powder by an appropriate sintering of
the powder. A Co based alloy powder sintered body would
be gained in which carbide grains precipitate at an
interval of 0.15 to 4 μm.
[0064]
15 In addition, the raw materials of the Co based alloy
powder preferably contain the above-defined Co based alloy
powder in a proportion of 75 mass % or more, and more
preferably 90 mass % or more.
[0065]
20 [Product in Which Co Based Alloy Sintered Body is
Used]
Figure 3 is a schematic perspective view
illustrating an example of the Co based alloy product of
the present invention, the product being a turbine static
25 blade as a turbine high-temperature member. As
illustrated in Figure 3, the turbine static blade, which
36
is a blade 100, is roughly composed of an inner ring end
wall 101, a blade part 102, and an outer ring end wall 103.
Inside the blade part, a cooling structure is often formed.
In the case of, for example, a 30-MW-class gas turbine for
5 power generation, the length of a blade part of its
turbine static blade (the distance between both end walls
thereof) is about 170 mm.
[0066]
Figure 4 is a schematic sectional view illustrating
10 an example of a gas turbine equipped with a Co based alloy
product according to the present invention. As
illustrated in Figure 4, a gas turbine 200 is roughly
composed of a compressor part 210 for compressing an
intake gas and a turbine part 220 for blowing a fuel gas
15 of a fuel onto a turbine blade to give rotary power. The
turbine high-temperature member of the present invention
is favorably usable as a turbine nozzle 221 or the turbine
static blade 100 inside the turbine part 220. Note that
the turbine high-temperature member of the present
20 invention is not limited to any gas turbine article, and
may be used for any other turbine article (for example,
any steam turbine article).
[0067]
The abovementioned embodiments or experiments have
25 been described for the aid of the understanding of the
present invention. Thus, the present invention is not
37
limited only to the described specific structures. For
example, the structure of any one of the embodiments may
be partially replaced by a constitution according to
common knowledge of those skilled in the art. Moreover, a
5 constitution according to common knowledge of those
skilled in the art may be added to the structure of any
one of the embodiments. In other words, in the present
invention, the structure of any one of the embodiments or
experiments in the present specification may be partially
10 subjected to deletion, replacement by a different
constitution and/or addition of a different constitution
as far as the resultant does not depart from the technical
conception of the present invention.
15 Reference Signs List
[0068]
20: Co based alloy powder, 21: crystal grain of Co
based alloy powder, 22: dendrite microstructure, 100:
turbine static blade, 101: inner side end wall, 102: blade
20 part, 103: outer side end wall, 200: gas turbine, 210:
compressor part, 220: turbine part, 221: turbine nozzle.

WE CLAIM

A cobalt-based alloy powder, comprising:
0.08 mass % or more and 0.25 mass % or less of
5 carbon;
0.1 mass % or less of boron;
10 mass % or more and 30 mass % or less of chromium;
5 mass % or less of iron; and
30 mass % or less of nickel,
10 comprising the iron and the nickel to be in a total
amount of 30 mass % or less,
comprising at least one selected from the group of
tungsten and molybdenum to be in a total amount of 5
mass % or more and 12 mass % or less,
15 comprising at least one selected from the group of
titanium, zirconium, niobium, tantalum, hafnium, and
vanadium to be in a total amount of 0.5 mass % or more and
2 mass % or less,
comprising:
20 0.5 mass % or less of silicon;
0.5 mass % or less of manganese; and
0.003 mass % or more and 0.04 mass % or less of
nitrogen; and comprising cobalt and impurities as the
balance of the powder, and
39
crystal grains comprised in the cobalt-based alloy
powder having segregated cells, and the segregated cells
having an average size of 0.15 μm or more and 4 μm or less.
[Claim 2]
5 A cobalt-based alloy powder, comprising:
0.08 mass % or more and 0.25 mass % or less of
carbon;
0.1 mass % or less of boron;
10 mass % or more and 30 mass % or less of chromium;
10 5 mass % or less of iron; and
30 mass % or less of nickel,
comprising the iron and the nickel to be in a total
amount of 30 mass % or less,
comprising at least one selected from the group of
15 tungsten and molybdenum to be in a total amount of 5
mass % or more and 12 mass % or less,
comprising at least one selected from the group of
titanium, zirconium, niobium, tantalum, hafnium, and
vanadium to be in a total amount of 0.5 mass % or more and
20 2 mass % or less,
comprising:
0.5 mass % or less of silicon;
0.5 mass % or less of manganese; and
more than 0.04 mass % and 0.1 mass % or less of
25 nitrogen, and comprising cobalt and impurities as the
balance of the powder, and
40
crystal grains comprised in the cobalt-based alloy
powder having segregated cells, and the segregated cells
having an average size of 0.15 μm or more and 4 μm or less.
[Claim 3]
5 A cobalt-based alloy powder, comprising:
0.08 mass % or more and 0.25 mass % or less of
carbon;
0.1 mass % or less of boron;
10 mass % or more and 30 mass % or less of chromium;
10 5 mass % or less of iron; and
30 mass % or less of nickel,
comprising the iron and the nickel to be in a total
amount of 30 mass % or less,
comprising at least one selected from the group of
15 tungsten and molybdenum to be in a total amount of 5
mass % or more and 12 mass % or less,
comprising at least one selected from the group of
titanium, zirconium, niobium, tantalum, hafnium, and
vanadium to be in a total amount of 0.5 mass % or more and
20 2 mass % or less,
comprising:
0.5 mass % or less of silicon;
0.5 mass % or less of manganese; and
more than 0.04 mass % and 0.1 mass % or less of
25 nitrogen, and comprising cobalt and impurities as the
balance of the powder, and
41
the cobalt-based alloy powder having a grain size of
5 μm or more and 85 μm or less.
[Claim 4]
The cobalt-based alloy powder according to claim 1
5 or 2, having a particle size of 5 μm or more and 85 μm or
less.
[Claim 5]
The cobalt-based alloy powder according to any one
of claims 1 to 3, having a particle size of 5 to 25 μm.
10 [Claim 6]
The cobalt-based alloy powder according to any one
of claims 1 to 3, having a particle size of 10 to 85 μm.
[Claim 7]
The cobalt-based alloy powder according to any one
15 of claims 1 to 3,
wherein when the powder comprises the titanium, the
titanium is in an amount of 0.01 mass % or more and 1
mass % or less,
when the powder comprises the zirconium, the
20 zirconium is in an amount of 0.05 mass % or more and 1.5
mass % or less,
when the powder comprises the niobium, the niobium
is in an amount of 0.02 mass % or more and 1 mass % or
less, and
42
when the powder comprises the tantalum, the tantalum
is in an amount of 0.05 mass % or more and 1.5 mass % or
less,
when the powder comprises the hafnium, the hafnium
5 is in an amount of 0.01 mass % or more and 0.5 mass % or
less,
when the powder comprises the vanadium, the vanadium
is in an amount of 0.01 mass % or more and 0.5 mass % or
less.
10 [Claim 8]
The cobalt-based alloy powder according to any one
of claims 1 to 3, comprising, as impurities, 0.5 mass % or
less of aluminum and 0.04 mass % or less of oxygen.
[Claim 9]
15 A cobalt-based alloy sintered body, comprising:
0.08 mass % or more and 0.25 mass % or less of
carbon;
0.1 mass % or less of boron;
10 mass % or more and 30 mass % or less of chromium;
20 5 mass % or less of iron; and
30 mass % or less of nickel,
comprising the iron and the nickel to be in a total
amount of 30 mass % or less,
comprising at least one selected from the group of
25 tungsten and molybdenum to be in a total amount of 5
mass % or more and 12 mass % or less,
43
comprising at least one selected from the group of
titanium, zirconium, niobium, tantalum, hafnium, and
vanadium to be in a total amount of 0.5 mass % or more and
2 mass % or less,
5 comprising:
0.5 mass % or less of silicon;
0.5 mass % or less of manganese; and
0.003 mass % or more and 0.04 mass % or less of
nitrogen; and comprising cobalt and impurities as the
10 balance of the sintered body, and
crystal grains comprised in the cobalt-based alloy
sintered body having segregated cells, and the segregated
cells having an average size of 0.15 μm or more and 4 μm
or less.
15 [Claim 10]
A cobalt-based alloy sintered body, comprising:
0.08 mass % or more and 0.25 mass % or less of
carbon;
0.1 mass % or less of boron;
20 10 mass % or more and 30 mass % or less of chromium;
5 mass % or less of iron; and
30 mass % or less of nickel,
comprising the iron and the nickel to be in a total
amount of 30 mass % or less,
44
comprising at least one selected from the group of
tungsten and molybdenum to be in a total amount of 5
mass % or more and 12 mass % or less,
comprising at least one selected from the group of
5 titanium, zirconium, niobium, tantalum, hafnium, and
vanadium to be in a total amount of 0.5 mass % or more and
2 mass % or less,
comprising:
0.5 mass % or less of silicon;
10 0.5 mass % or less of manganese; and
more than 0.04 mass % and 0.1 mass % or less of
nitrogen, and comprising cobalt and impurities as the
balance of the sintered body, and
crystal grains comprised in the cobalt-based alloy
15 sintered body having segregated cells, and the segregated
cells having an average size of 0.15 μm or more and 4 μm
or less.
[Claim 11]
A cobalt-based alloy sintered body, comprising:
20 0.08 mass % or more and 0.25 mass % or less of
carbon;
0.1 mass % or less of boron;
10 mass % or more and 30 mass % or less of chromium;
5 mass % or less of iron; and
25 30 mass % or less of nickel,
45
comprising the iron and the nickel to be in a total
amount of 30 mass % or less,
comprising at least one selected from the group of
tungsten and molybdenum to be in a total amount of 5
5 mass % or more and 12 mass % or less,
comprising at least one selected from the group of
titanium, zirconium, niobium, tantalum, hafnium, and
vanadium to be in a total amount of 0.5 mass % or more and
2 mass % or less,
10 comprising:
0.5 mass % or less of silicon;
0.5 mass % or less of manganese; and
more than 0.04 mass % and 0.1 mass % or less of
nitrogen, and comprising cobalt and impurities as the
15 balance of the sintered body, and
the cobalt-based alloy sintered body having a grain
size of 5 μm or more and 85 μm or less.
[Claim 12]
The cobalt-based alloy sintered body according to
20 claim 9 or 10, having a grain size of 5 μm or more and 85
μm or less.
[Claim 13]
The cobalt-based alloy sintered body according to
any one of claims 9 to 11, having a grain size of 5 μm or
25 more and 25 μm or less.
[Claim 14]
46
The cobalt-based alloy sintered body according to
any one of claims 9 to 11, having a grain size of 10 μm or
more and 85 μm or less.
[Claim 15]
5 The cobalt-based alloy sintered body according to
any one of claims 9 to 11,
wherein when the sintered body comprises the
titanium, the titanium is in an amount of 0.01 mass % or
more and 1 mass % or less,
10 when the sintered body comprises the zirconium, the
zirconium is in an amount of 0.05 mass % or more and 1.5
mass % or less,
when the sintered body comprises the niobium, the
niobium is in an amount of 0.02 mass % or more and 1
15 mass % or less, and
when the sintered body comprises the tantalum, the
tantalum is in an amount of 0.05 mass % or more and 1.5
mass % or less,
when the powder comprises the hafnium, the hafnium
20 is in an amount of 0.01 mass % or more and 0.5 mass % or
less,
when the powder comprises the vanadium, the vanadium
is in an amount of 0.01 mass % or more and 0.5 mass % or
less.
25 [Claim 16]
47
The cobalt-based alloy sintered body according to
any one of claims 9 to 11, comprising, as impurities, 0.5
mass % or less of aluminum and 0.04 mass % or less of
oxygen.
5 [Claim 17]
The cobalt-based alloy sintered body according to
any one of claims 9 to 11, wherein a carbide is
precipitated in the segregated cell.
[Claim 18]
10 A method for producing a cobalt-based alloy sintered
body, comprising:
a raw-material mixing and melting step of mixing raw
materials of a cobalt-based alloy powder having a
predetermined chemical composition with each other, and
15 melting the raw materials to produce a molten metal;
a molten-metal-pulverizing step of producing a
quenched and solidified alloy powder from the molten
metal; and
a sintering step of sintering the quenched and
20 solidified alloy powder,
the cobalt-based alloy powder comprising:
0.08 mass % or more and 0.25 mass % or less of
carbon;
0.1 mass % or less of boron;
25 10 mass % or more and 30 mass % or less of chromium;
5 mass % or less of iron; and
48
30 mass % or less of nickel,
comprising the iron and the nickel to be in a total
amount of 30 mass % or less,
comprising at least one selected from the group of
5 tungsten and molybdenum to be in a total amount of 5
mass % or more and 12 mass % or less,
comprising at least one selected from the group of
titanium, zirconium, niobium, tantalum, hafnium, and
vanadium to be in a total amount of 0.5 mass % or more and
10 2 mass % or less,
comprising:
0.5 mass % or less of silicon;
0.5 mass % or less of manganese; and
0.003 mass % or more and 0.04 mass % or less of
15 nitrogen, and comprising cobalt and impurities as the
balance of the powder, and crystal grains comprised in the
cobalt-based alloy powder having segregated cells, and the
segregated cells having an average size of 0.15 μm or more
and 4 μm or less.
20 [Claim 19]
The method for producing a cobalt-based alloy
sintered body according to claim 18, wherein in the
molten-metal-pulverizing step, the quenched and solidified
alloy powder is produced by gas atomizing or plasma
25 atomizing.
[Claim 20]
49
The method for producing a cobalt-based alloy
sintered body according to claim 18 or 19, wherein the raw
materials of the cobalt-based alloy sintered body
comprises the cobalt-based alloy powder in an amount of 75
5 mass % or more.