FIELD OF THE INVENTION
[0001] The present invention relates to a precipitation hardened Fe-Ni alloy. More specifically,
the invention relates to a precipitation hardened Fe-Ni alloy having high strength
and excellent corrosion resistance.
BACKGROUND OF THE INVENTION
[0002] A precipitation hardened stainless steel is a steel in which elements such as Cu,
Al, Ti, Nb, and Mo are added to achieve precipitation hardening and has both of high
corrosion resistance and high strength. Particularly, an austenite precipitation hardened
stainless steel represented by A286 alloy (SUH660) is an alloy excellent in both of
corrosion resistance and strength among Fe based alloys. However, for using the austenite
precipitation hardened stainless steel as a member requiring high strength in marine
environment, it is insufficient in both of corrosion resistance and strength.
[0003] On the other hand, in Fe-Ni alloys, alloys to which Ti, Al, and Nb are added have
been hitherto proposed.
[0004] For example, Patent Document 1 (Example 1) discloses a nickel-iron based alloy comprising,
in terms of % by weight, 0.027% of C, 0.08% of Mn, 0.10% of Si, 0.001% of P, 0.005%
of S, 15.81% of Cr, 39.89% ofNi, 2.83% of Nb, 1.61% of Ti, 0.3% of Al, and 0.0041
% of B, with the balance being Fe and unavoidable impurities.
[0005] Patent Document 2 (No. 1) discloses an Ni based alloy comprising, in terms of %
by weight, 0.017% of C, 0.15% of Si, 0.14% of Mn, 0.010% of P, 0.003% of S, 40.32%
ofNi, 16.20% of Cr, 1.02% of Mo, 0.25% of Al, 0.95% of Ti, and 2.71% of Nb, with the
balance being Fe and unavoidable impurities.
[0006] The document describes a fact that the alloy has high strength from room temperature
till extremely low temperature and can suppress HAZ cracking by such a composition.
[0007] Furthermore, Patent Document 3 (alloy #7) discloses a high-strength corrosion-resistant
alloy comprising, in terms of % by weight, 44.2% of Ni, 19.5% of Cr, 3.4% of Mo, 2.0%
of Cu, 0.006% of C, 0.3% of Al, 3.8% ofNb, and 1.6% of Ti, with the balance being
Fe.
[0008] The document describes a fact that high strength is obtained by precipitating predetermined
amounts of the y' phase and the y" phase by annealing and aging treatments.
[0009] In Patent Document 1, Mo and Cu are not added and corrosion resistance is insufficient.
In Patent Document 2, strength is insufficient owing to the balance among Ni, Nb,
Ti, and Al. In Patent Document 3, strength of Ni and Nb are high and the raw material
costs and the production costs thereof are high.
[Patent Document 1] JP-A-47-042414
[Patent Document 2] JP-A-03-097823
[Patent Document 3] JP-T-2009-515053 (the term "JP-T" as used herein means a published Japanese translation of a PCT patent
application)
SUMMARY OF THE INVENTION
[0010] A problem to be solved by the present invention is to provide a precipitation hardened
Fe-Ni alloy having both of high corrosion resistance and high hardness.
[0011] In order to solve the above problem, the gist of the invention is that the precipitation
hardened Fe-Ni alloy according to the invention has the following constitutions.
- (1) the precipitation hardened Fe-Ni alloy comprising:
from 0.01 to 0.08% by mass of C,
from 0.02 to 1.0% by mass of Si,
not more than 1.0% by mass of Mn,
from 36.0 to 41.0% by mass of Ni,
14.0 or more and less than 20.0% by mass of Cr,
from 0.01 to 3.0% by mass of Mo,
from 0.1 to 1.0% by mass of Al,
from 1.0 to 2.5% by mass of Ti, and
from 2.0 to 3.5% by mass of Nb,
with the balance being Fe and unavoidable impurities;
- (2) the precipitation hardened Fe-Ni alloy satisfying the following formulae (1) and
(2):


[0012] It is preferred that the precipitation hardened Fe-Ni alloy satisfies the following
formula (3):

[0013] When predetermined amounts of Nb, Al, and Ti are added to a precipitation hardened
Fe-Ni alloy, the y' phase (Ni
3(Al, Ti, Nb)) and the y" phase (Ni
3Nb) containing Nb as a constituent element are precipitated by a solution heat treatment
and an aging treatment.
[0014] At this time, when the Nb content is optimized so as to satisfy the formula (2),
the precipitation amount of the y" phase is increased. Therefore, high strength can
be obtained as compared with the conventional alloys.
[0015] On the other hand, as the addition amount of Nb increases, the Laves phase (Fe
2Nb) is prone to remain after the solution heat treatment. When the Laves phase remains
in a large amount, the Nb amount necessary for precipitation hardening in the matrix
decreases. As a result, necessary hardness cannot be obtained even when the aging
treatment is performed.
[0016] Contrarily, when the Ni content is optimized so as to satisfy the formula (1), the
remaining of the Laves phase can be suppressed after the solution heat treatment.
[0017] Furthermore, when predetermined amounts of Cr and Mo are added to the precipitation
hardened Fe-Ni alloy or predetermined amounts of Cr, Mo and Cu are added to the precipitation
hardened Fe-Ni alloy, high corrosion resistance is obtained with maintaining high
strength. Particularly, when the contents of Cr, Mo and Cu are optimized so as to
satisfy the formula (3), high corrosion resistance is obtained.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] Fig. 1 shows optical microscopic pictures of the materials after a solution heat
treatment obtained in Example 5 and Comparative Example 4.
DETAILED DESCRIPTION OF THE INVENTION
[0019] The following will describe one embodiment of the invention in detail.
[1. Precipitation Hardened Fe-Ni Alloy]
[1.1. Main Constituent Elements]
[0020] The precipitation hardened Fe-Ni alloy according to the invention contains the following
elements, with the balance being Fe and unavoidable impurities. Kinds of the addition
elements, composition ranges thereof, and reasons for the limitation thereof are as
follows.
(1) C: from 0.01 to 0.08% by mass
[0021] C is an element effective for forming a carbide together with Nb and Ti to enhance
the strength. Moreover, it suppresses crystal grain coarsening at a solution heat
treatment. For obtaining such effects, the C content is necessarily 0.01% by mass
or more. The C content is further preferably 0.04% by mass or more.
[0022] On the other hand, when the C content becomes excessive, toughness and ductility
are lowered. Moreover, when a large amount of the carbide is formed, corrosion resistance
is remarkably lowered. For suppressing the lowering of the toughness and ductility
and the corrosion resistance, the C content is necessarily 0.08% by mass or less.
The C content is preferably 0.07% by mass or less.
(2) Si: from 0.02 to 1.0% by mass
[0023] Si is effective as a deoxidizing element at the time of ingoting. For obtaining such
an effect, the Si content is necessarily 0.02% by mass or more.
[0024] On the other hand, when the Si content becomes excessive, the toughness is lowered.
Therefore, the Si content is necessarily 1.0% by mass or less.
(3) Mn: not more than 1.0% by mass
[0025] Similarly to Si, Mn is effective as a deoxidizing element at the time of ingoting.
However, when a large amount thereof is added, oxidation resistance at a high temperature
is lowered. Moreover, excessive Mn also lowers corrosion resistance. Therefore, the
Mn content is necessarily 1.0% by mass or less.
(4) Ni: from 36.0 to 41.0% by mass
[0026] Ni is essential as an austenite-forming element. Also, Ni makes the alloy age-hardened
through precipitation of the y' phase (Ni
3(Al, Ti, Nb)) and the y" phase (Ni
3Nb) together with Ti, Al, and Nb by the aging treatment. For obtaining such an effect,
the Ni content is necessarily 36.0% by mass or more. The Ni content is more preferably
37.0% by mass or more.
[0027] On the other hand, when the Ni content becomes excessive, the raw material costs
are increased. Therefore, the Ni content is necessarily 41.0% by mass or less. The
Ni content is more preferably 40.0% by mass or less, further preferably 39.0% by mass
or less.
(5) Cr: 14.0 or more and less than 20.0% by mass
[0028] Cr is an inevitable component for enhancing the corrosion resistance of the precipitation
hardened Fe-Ni alloy. For obtaining such an effect, the Cr content is necessarily
14.0% by mass or more.
[0029] However, Cr is a ferrite-forming element and, when the Cr content becomes excessive,
structural stability is lowered. Also, excessive Cr lowers hot workability. Therefore,
the Cr content is necessarily less than 20.0% by mass. The Cr content is more preferably
18.0% by mass or less, further preferably 17.0% by mass or less.
(6) Mo: from 0.01 to 3.0% by mass
[0030] Mo improves the corrosion resistance (particularly pitting resistance) through solution
into the parent phase. For obtaining such an effect, the Mo content is necessarily
0.01 % by mass or more.
[0031] On the other hand, when the Mo content becomes excessive, the Laves phase (Fe
2(Mo, Nb)) is precipitated at the time of the aging treatment and the precipitation
amounts of the y' phase and the y" phase are decreased. As a result, the strength
of the alloy is lowered. Therefore, the Mo content is necessarily 3.0% by mass or
less. The Mo content is preferably 2.0% by mass or less.
(7) Al: from 0.1 to 1.0% by mass
[0032] Al makes the alloy age-hardened through precipitation of the y' phase (Ni
3(Al, Ti, Nb)) together with Ni, Ti, and Nb. For obtaining such an effect, the Al content
is necessarily 0.1% by mass or more.
[0033] When the Al content becomes excessive, the hot workability is lowered. Therefore,
the Al content is necessarily 1.0% by mass or less. The Al content is preferably 0.5%
by mass or less.
(8) Ti: from 1.0 to 2.5% by mass
[0034] Ti makes the alloy age-hardened through precipitation of the y' phase (Ni
3(Al, Ti, Nb)) together with Ni, Al, and Nb. For obtaining such an effect, the Ti content
is necessarily 1.0% by mass or more. The Ti content is preferably 1.5% by mass or
more, more preferably 1.8% by mass or more.
[0035] On the other hand, when the Ti content becomes excessive, the hot workability is
lowered. Therefore, the Ti content is necessarily 2.5% by mass or less.
(9) Nb: from 2.0 to 3.5% by mass
[0036] Nb makes the alloy age-hardened through precipitation of the y' phase (Ni
3(Al, Ti, Nb)) and the y" phase (Ni
3Nb) together with Ni. For obtaining such an effect, the Nb content is necessarily
2.0% by mass or more.
[0037] On the other hand, when the Nb content becomes excessive, a coarse Laves phase remains
after the solution heat treatment and the precipitation amounts of the y' phase and
the y" phase are decreased. As a result, required strength and hardness are not obtained.
Therefore, the Nb content is necessarily 3.5% by mass or less. The Nb content is more
preferably 3.0% by mass or less.
[1.2. Auxiliary Constituent Elements]
[0038] The precipitation hardened Fe-Ni alloy according to the invention may further contain
one kind or two or more kinds of the following auxiliary constituent elements in addition
to the aforementioned main constituent elements. Kinds of the addition elements, composition
ranges thereof, and reasons for the limitation thereof are as follows.
(10) B: from 0.0005 to 0.01% by mass
[0039] B has an effect of enhancing the hot workability by adding B in a small amount. Also,
the precipitation of the η phase at a grain boundary can be suppressed by the presence
of B at the grain boundary. For obtaining such an effect, the B content is preferably
0.0005% by mass or more. The B content is further preferably 0.0010% by mass or more.
The B content is particularly preferably 0.0020% by mass or more.
[0040] On the other hand, when the Ni content becomes excessive, the hot workability is
lowered. Therefore, the B content is preferably 0.01% by mass or less. The B content
is further preferably 0.008% by mass or less.
(11) Cu: from 0.05 to 1.0% by mass
[0041] Cu has an effect of enhancing the corrosion resistance in a non-oxidative corrosive
environment. For obtaining such an effect, the Cu content is preferably 0.05% by mass
or more. The Cu content is further preferably 0.10% by mass or more.
[0042] On the other hand, when the Cu content becomes excessive, the hot workability is
lowered. Therefore, the Cu content is preferably 1.0% by mass or less.
(12) V: from 0.05 to 1.0% by mass
[0043] As is the case with Nb and Ti, V forms a carbide to enhance the strength. Also, the
precipitation amounts of the y' phase and the y" phase are increased through reducing
the ratio of Nb in the carbide. For obtaining such effects, the V content is preferably
0.05% by mass or more.
[0044] On the other hand, when the V content becomes excessive, the toughness and the processability
are lowered. Therefore, the V content is preferably 1.0% by mass or less.
(13) Zr, Ta, W, Hf, Mg, and/or REM: from 0.001 to 0.50% by mass
[0045] Zr, Ta, W, Hf, Mg, and REM (Rare Earth Metal) have an effect on micronization of
the carbide and micronization of crystal grains. For obtaining such an effect, a total
content of these elements is preferably 0.001% by mass or more.
[0046] On the other hand, when the content of these elements becomes excessive, the toughness
is lowered. Therefore, the total content of these elements is preferably 0.50% by
mass or less.
[0047] Incidentally, any one of these elements may be added or two or more thereof may be
used in combination.
(14) Ca: from 0.0005 to 0.01% by mass
[0048] Ca improves machinability. For obtaining such an effect, the Ca content is preferably
0.0005% by mass or more.
[0049] On the other hand, when the Ca content becomes excessive, the hot workability is
lowered. Therefore, the Ca content is preferably 0.01% by mass or less.
[1.3. Component Balance]
[0050] The precipitation hardened stainless steel according to the invention necessarily
satisfies the following formulae (1) and (2), in addition to the requirement that
the constituent elements are present in the aforementioned ranges.
[1.3.1. Formula (1)]
[0052] The formula (1) is relevant to the amount of the Laves phase after the solution heat
treatment. When the Ni amount and the Nb amount are optimized so as to satisfy the
formula (1), the Laves phase (Fe
2Nb) can be completely dissolved after the solution heat treatment. As a result, the
precipitation amounts of the y' phase and the y" phase at the time of the aging treatment
are increased and thereby the strength of the alloy is enhanced.
[0053] The formula (1) is more preferably Ni≥6xNb+18.0, further preferably Ni≥6xNb+20.0.
[1.3.2. Formula (2)]
[0054] The formula (2) is relevant to the amount of the y" phase at the time of the aging
treatment. When the amounts of Nb, Ti, and Al are optimized so as to satisfy the formula
(2), the precipitation amount of the y" phase is increased and thereby further enhancing
the strength of the alloy.
[1.3.3. Formula (3)]
[0055] The formula (3) is relevant to the corrosion resistance of the precipitation hardened
Fe-Ni alloy. Cr, Mo, and Cu all have an effect of enhancing the corrosion resistance
of the precipitation hardened Fe-Ni alloy. Particularly, when the contents of these
elements are optimized so as to satisfy the formula (3), high corrosion resistance
is exhibited with maintaining high strength.
[1.4.0.2% Offset Yield Strength]
[0056] When individual components are optimized as mentioned above and a suitable solution
heat treatment is performed, the Laves phase is almost completely dissolved in the
matrix. When such a material is subjected to a suitable aging treatment, large amounts
of the y' phase and the y" phase are precipitated. As a result, the 0.2% offset yield
strength at room temperature becomes 850 MPa or more. When the components and the
heat treatment conditions are further optimized, the 0.2% offset yield strength at
room temperature becomes 900 MPa or more or 950 MPa or more.
[1.5. Area Percentage of Carbide]
[0057] The precipitation hardened Fe-Ni alloy according to the invention is preferably one
in which an area percentage of the carbide after the solution heat treatment is 0.4%
or more. At the time of the solution heat treatment, the coarsening of crystal grains
can be suppressed when a predetermined amount of the carbide is dispersed in the matrix.
[0058] Here, the "area percentage of the carbide" means a ratio of area of the carbide to
the total area of cross-sectional microstructure (0.034 mm
2 x 30 viewing fields).
[2. Method for Manufacturing Precipitation Hardened Fe-Ni Alloy]
[0059] The method for manufacturing the precipitation hardened Fe-Ni alloy according to
the invention comprises a melting and casting process, a hot working process, a solution
heat treatment process, and an aging treatment process.
[2.1. Melting and Casting Process]
[0060] The melting and casting process is a process of dissolving a raw material blended
in a predetermined composition and performing casting. The dissolving method and the
casting method are not particularly limited and various methods can be used according
to the purpose.
[2.2. Hot Working Process]
[0061] The hot working process is a process of hot-working an ingot obtained in the melting
and casting process. The hot working is performed for destroying cast structure and
casting defect. Hot working conditions are not particularly limited and most suitable
conditions can be selected according to the purpose.
[2.3. Solution Heat Treatment Process]
[0062] The solution heat treatment process is a process of heating a hot-worked material
at a predetermined temperature.
[0063] The solution heat treatment is performed mainly for dissolving a precipitate dispersed
in the steel. When heat treatment temperature is too low, solution of the precipitate
becomes insufficient. The heat treatment temperature is preferably 900°C or higher.
[0064] On the other hand, when the heat treatment temperature is too high, the crystal grains
are coarsened. The heat treatment temperature is preferably 1,200°C or lower.
[0065] Heat treatment time may be suitably a time sufficient for dissolving the precipitate.
Most suitable heat treatment time varies depending on the heat treatment temperature
but is usually from about 30 minutes to about 2 hours. After the heat treatment, the
material is quenched.
[2.4. Aging Treatment Process]
[0066] The aging treatment process is a process of subjecting the material after the solution
heat treatment to an aging treatment at a predetermined temperature.
[0067] In both cases where aging treatment temperature is too high and too low, an objective
precipitate is not precipitated and aging hardening cannot be achieved. The aging
treatment temperature is preferably from 600°C to 750°C.
[0068] Aging treatment time may be suitably a time sufficient for precipitating a sufficient
amount of the precipitate. Most suitable aging treatment time varies depending on
the aging treatment temperature but is usually from about 8 hours to about 24 hours.
[3. Action]
[0069] When a predetermined amount of Nb is added to the precipitation hardened Fe-Ni alloy,
the y' phase (Ni
3(Al, Ti, Nb)) and the y" phase (Ni
3Nb) containing Nb as a constituent element are precipitated by the solution heat treatment
and the aging treatment.
[0070] At this time, when the Nb content is optimized so as to satisfy the formula (2),
the precipitation amount of the y" phase is increased. Therefore, as compared with
conventional alloys, high strength can be obtained.
[0071] On the other hand, as the addition amount of Nb increases, the Laves phase (Fe
2Nb) tends to remain after the solution heat treatment. When a large amount of the
Laves phase remains, the Nb amount in the matrix necessary for precipitation hardening
decreases. As a result, necessary hardness is not obtained even when the aging treatment
is performed.
[0072] In contrast, when the Ni content is optimized so as to satisfy the formula (1), the
remaining of the Laves phase after the solution heat treatment can be suppressed.
[0073] Furthermore, when predetermined amounts of Cr and Mo are added to the precipitation
hardened Fe-Ni alloy or predetermined amounts of Cr, Mo and Cu are added to the precipitation
hardened Fe-Ni alloy, high corrosion resistance is obtained with maintaining high
strength. Particularly, when the contents of Cr, Mo, and Cu are optimized so as to
satisfy the formula (3), high corrosion resistance is obtained.
EXAMPLES
(Examples 1 to 37, Comparative Examples 1 to 5)
[1. Preparation of Samples]
[0074] After each steel containing various components shown in Tables 1 and 2 was ingoted,
each steel was cooled to prepare an ingot. After hot working, the ingot was thermally
refined by a solution heat treatment and an aging treatment.
[0075] Solution heat treatment temperature was set to 900 to 1,200°C. Also, the aging treatment
temperature was set to 600 to 750°C.
Table 1
| |
Component composition (% by mass) |
Component balance |
| C |
Si |
Mn |
Ni |
Cr |
Mo |
Al |
Ti |
Nb |
B |
Cu |
V |
Others |
Formula (1') |
Formula (2') |
Formula (3') |
| Example 1 |
0.06 |
0.24 |
0.1 |
39.2 |
15.7 |
0.01 |
0.2 |
1.9 |
3.1 |
- |
|
- |
|
3.6 |
0.68 |
-3.27 |
| Example 2 |
0.05 |
0.41 |
0.5 |
36.9 |
15.4 |
0.03 |
0.2 |
2.3 |
2.7 |
0.0051 |
0.07 |
- |
|
3.7 |
0.28 |
-3.16 |
| Example 3 |
0.06 |
0.46 |
0.3 |
39.8 |
15.8 |
0.13 |
0.5 |
2.1 |
3.2 |
0.0099 |
0.06 |
- |
|
3.6 |
0.43 |
-2.51 |
| Example 4 |
0.04 |
0.35 |
0.3 |
39.8 |
15.4 |
1.54 |
0.3 |
2.4 |
2.7 |
0.0041 |
0.07 |
- |
|
6.6 |
0.20 |
1.37 |
| Example 5 |
0.04 |
0.35 |
0.3 |
39.8 |
15.4 |
0.52 |
0.3 |
2.4 |
2.7 |
0.0025 |
0.07 |
- |
|
6.6 |
0.20 |
-1.69 |
| Example 6 |
0.05 |
0.39 |
0.6 |
36.8 |
15.0 |
2.40 |
0.2 |
2.2 |
2.7 |
0.0046 |
0.06 |
- |
|
3.6 |
0.33 |
3.50 |
| Example 7 |
0.04 |
0.35 |
0.3 |
41.0 |
15.4 |
1.54 |
0.3 |
2.2 |
2.7 |
0.0063 |
0.07 |
- |
|
7.8 |
0.28 |
1.37 |
| Example 8 |
0.04 |
0.35 |
0.3 |
38.9 |
15.4 |
0.53 |
0.3 |
2.2 |
2.7 |
0.0006 |
0.52 |
- |
|
5.7 |
0.28 |
0.59 |
| Example 9 |
0.04 |
0.35 |
0.3 |
38.9 |
15.4 |
0.52 |
0.3 |
2.2 |
2.7 |
0.0051 |
0.07 |
0.5 |
|
5.7 |
0.28 |
-1.69 |
| Example 10 |
0.04 |
0.35 |
0.3 |
38.9 |
17.8 |
0.52 |
0.3 |
2.2 |
2.7 |
0.0099 |
0.07 |
- |
|
5.7 |
0.28 |
0.71 |
| Example 11 |
0.04 |
0.35 |
0.3 |
38.9 |
19.5 |
0.52 |
0.3 |
2.2 |
2.7 |
0.0041 |
0.07 |
- |
|
5.7 |
0.28 |
2.41 |
| Example 12 |
0.04 |
0.35 |
0.3 |
36.4 |
15.4 |
0.52 |
0.3 |
2.2 |
2.7 |
0.0025 |
0.07 |
- |
|
3.2 |
0.28 |
-1.69 |
| Example 13 |
0.04 |
0.35 |
0.3 |
38.9 |
15.4 |
0.52 |
0.3 |
2.2 |
2.2 |
0.0046 |
0.07 |
- |
|
8.7 |
0.08 |
-1.69 |
| Example 14 |
0.04 |
0.35 |
0.3 |
38.9 |
15.4 |
0.52 |
0.3 |
2.2 |
3.4 |
0.0063 |
0.07 |
- |
|
1.5 |
0.56 |
-1.69 |
| Example 15 |
0.04 |
0.35 |
0.3 |
38.9 |
15.4 |
0.52 |
0.9 |
2.2 |
2.7 |
0.0006 |
0.07 |
- |
|
5.7 |
0.07 |
-1.69 |
| Example 16 |
0.04 |
0.35 |
0.3 |
38.9 |
15.4 |
0.52 |
0.3 |
1.3 |
2.7 |
0.0051 |
0.07 |
- |
|
5.7 |
0.89 |
-1.69 |
| Example 17 |
0.04 |
0.35 |
0.3 |
38.9 |
15.4 |
0.52 |
0.3 |
2.4 |
2.7 |
0.0099 |
0.07 |
- |
|
5.7 |
0.20 |
-1.69 |
| Example 18 |
0.04 |
0.82 |
0.3 |
38.9 |
15.4 |
0.52 |
0.3 |
2.2 |
2.7 |
0.0041 |
0.07 |
- |
Zr:0.05 |
5.7 |
0.28 |
-1.69 |
| Example 19 |
0.04 |
0.35 |
0.3 |
38.9 |
15.4 |
0.52 |
0.3 |
2.2 |
2.7 |
0.0025 |
0.07 |
- |
Ta:0.15 |
5.7 |
0.28 |
-1.69 |
| Example 20 |
0.04 |
0.35 |
0.3 |
38.9 |
15.4 |
0.52 |
0.3 |
2.2 |
2.7 |
0.0046 |
0.07 |
- |
W:0.32 |
5.7 |
0.28 |
-1.69 |
| Example 21 |
0.04 |
0.35 |
0.3 |
38.9 |
15.4 |
0.52 |
0.3 |
2.2 |
2.7 |
0.0063 |
0.07 |
- |
Hf:0.21 |
5.7 |
0.28 |
-1.69 |
| * Formula (1') = Ni-(6xNb+17) Formula (2') = Nb/(Ti+Al)-0.8, Formula (3') = Cr+3Mo+5Cu-19 |
Table 2
| |
Component composition (% by mass) |
Component balance |
| C |
Si |
Mn |
Ni |
Cr |
Mo |
Al |
Ti |
Nb |
B |
Cu |
V |
Others |
Formula (1') |
Formula (2') |
Formula (3') |
| Example 22 |
0.04 |
0.35 |
0.3 |
38.9 |
15.4 |
0.52 |
0.3 |
2.2 |
2.7 |
0.0006 |
0.07 |
- |
Mg:0.02 |
5.7 |
0.28 |
-1.69 |
| Example 23 |
0.04 |
0.35 |
0.3 |
38.9 |
15.4 |
0.52 |
0.3 |
2.2 |
2.7 |
0.0046 |
0.07 |
- |
REM:0.03 |
5.7 |
0.28 |
-1.69 |
| Example 24 |
0.04 |
0.35 |
0.3 |
38.9 |
15.4 |
0.52 |
0.3 |
2.2 |
2.7 |
0.0063 |
0.07 |
- |
Ca:0.004 |
5.7 |
0.28 |
-1.69 |
| Example 25 |
0.04 |
0.35 |
0.3 |
38.9 |
15.4 |
1.62 |
0.3 |
2.2 |
2.7 |
0.0006 |
0.61 |
- |
|
5.7 |
0.28 |
4.31 |
| Example 26 |
0.04 |
0.35 |
0.3 |
38.0 |
15.7 |
0.01 |
0.2 |
2.2 |
2.7 |
0.0011 |
|
- |
|
4.8 |
0.33 |
-3.27 |
| Example 27 |
0.04 |
0.35 |
0.3 |
38.0 |
15.4 |
0.03 |
0.3 |
2.4 |
2.5 |
0.0023 |
|
- |
|
6.0 |
0.13 |
-3.51 |
| Example 28 |
0.04 |
0.35 |
0.6 |
38.0 |
15.8 |
0.13 |
0.2 |
2.2 |
2.7 |
0.0005 |
0.36 |
- |
|
4.8 |
0.33 |
-1.01 |
| Example 29 |
0.04 |
0.35 |
0.5 |
38.0 |
15.4 |
1.54 |
0.3 |
2.2 |
2.5 |
0.0042 |
0.09 |
- |
|
6.0 |
0.20 |
1.47 |
| Example 30 |
0.04 |
0.24 |
0.4 |
38.0 |
15.4 |
0.52 |
0.2 |
2.2 |
2.7 |
0.0051 |
|
- |
|
4.8 |
0.33 |
-2.04 |
| Example 31 |
0.04 |
0.24 |
0.5 |
38.0 |
17.8 |
0.53 |
0.3 |
2.2 |
2.5 |
0.0048 |
|
- |
|
6.0 |
0.20 |
0.39 |
| Example 32 |
0.05 |
0.24 |
0.6 |
38.0 |
19.5 |
0.52 |
0.2 |
1.5 |
2.7 |
0.0045 |
0.43 |
- |
|
4.8 |
0.79 |
4.21 |
| Example 33 |
0.05 |
0.46 |
0.3 |
38.0 |
15.4 |
0.52 |
0.3 |
2.2 |
2.5 |
0.0029 |
0.05 |
- |
|
6.0 |
0.20 |
-1.79 |
| Example 34 |
0.05 |
0.46 |
0.3 |
38.0 |
15.4 |
0.51 |
0.2 |
2.2 |
2.7 |
0.0055 |
|
0.3 |
|
4.8 |
0.33 |
-2.07 |
| Example 35 |
0.05 |
0.46 |
0.3 |
38.0 |
15.6 |
0.51 |
0.3 |
2.2 |
2.5 |
0.0061 |
|
0.4 |
|
6.0 |
0.20 |
-1.87 |
| Example 36 |
0.05 |
0.46 |
0.3 |
38.0 |
15.8 |
0.52 |
0.2 |
2.2 |
2.7 |
0.0053 |
0.57 |
0.4 |
|
4.8 |
0.33 |
1.21 |
| Example 37 |
0.05 |
0.46 |
0.3 |
38.0 |
15.9 |
0.52 |
0.3 |
2.2 |
2.5 |
0.0048 |
|
0.5 |
|
6.0 |
0.20 |
-1.54 |
| Comparative Example 1 |
0.03 |
0.31 |
0.2 |
25.1 |
15.0 |
1.1 |
0.2 |
2.2 |
- |
- |
|
0.3 |
|
|
|
|
| Comparative Example 2 |
0.04 |
0.35 |
0.3 |
33.8 |
15.4 |
0.52 |
0.3 |
2.2 |
2.7 |
0.0041 |
0.07 |
- |
|
0.6 |
0.28 |
-1.69 |
| Comparative Example 3 |
0.04 |
0.35 |
0.3 |
36.3 |
15.4 |
0.52 |
0.5 |
2.2 |
2.0 |
0.0041 |
0.07 |
- |
|
7.3 |
-0.06 |
-1.69 |
| Comparative Example 4 |
0.04 |
0.35 |
0.3 |
36.3 |
15.4 |
0.52 |
0.3 |
2.2 |
3.4 |
0.0041 |
0.07 |
- |
|
-1.1 |
0.56 |
-1.69 |
| Comparative Example 5 |
0.03 |
0.35 |
0.3 |
38.9 |
15.4 |
0.53 |
0.3 |
2.2 |
2.7 |
0.0045 |
0.07 |
- |
|
5.7 |
0.28 |
-1.66 |
| * Formula (1') = Ni-(6xNb+17), Formula (27) = Nb/(Ti+Al)-0.8, Formula (3') = Cr+3Mo+5Cu-19 |
[2. Test Methods]
[2.1. Tensile Test]
[0076] From each material after the aging treatment, a JIS No. 4 test piece was cut out.
A tensile test was performed at room temperature (20°C) to evaluate tensile strength
and 0.2% offset yield strength.
[2.2. Corrosion Resistance Test]
[0077] Evaluation of the corrosion resistance was performed on a corrosion rate at the time
of immersion for 6 h in 10% hydrochloric acid at 80°C. The case where the corrosion
rate was 100 g/m
2/h or less was designated as "A", the case where the rate was more than 100 g/m
2/h and 200 g/m
2/h or less was designated as "B", and the case where the rate was more than 200 g/m
2/h was designated as "C".
[2.3. Carbide Area Percentage]
[0078] For quantitative analysis of a carbide, area percentage was measured at 30 visual
fields on a microstructure photograph with a magnification of 400 times (1 visual
field: 0.034 mm
2) using an image-analyzing software.
[3. Results]
[0079] Table 3 shows results. From Table 3, the following are realized.
- (1) In Comparative Example 1 (corresponding to A286 alloy), the tensile strength and
the 0.2% offset yield strength are low. This is because Nb is not added and the y"
phase is not precipitated. Also, in Comparative Example 1, the corrosion resistance
is low. This is because the Ni amount is small.
- (2) In Comparative Example 2, the 0.2% offset yield strength is slightly low. This
is because the Ni content is small and hence a sufficient amount of the y" phase is
not obtained. Also, in Comparative Example 2, the corrosion resistance is low. This
is because the Ni amount is small.
- (3) In Comparative Example 3, the 0.2% offset yield strength is slightly low. This
is because a sufficient amount of the y" phase is not obtained owing to a low value
of Nb/(Ti+Al)-0.8.
- (4) In Comparative Example 4, the 0.2% offset yield strength is slightly low. This
is because a coarse Laves phase remains owing to a low value of Ni-(6xNb+17) and,
as a result, the Nb amount in the matrix is decreased and hence the precipitation
amounts of the y' phase and the y" phase at the time of the aging treatment are decreased.
- (5) In Comparative Example 5, the 0.2% offset yield strength is slightly low. This
is because the crystal grains are coarsened owing to the small carbide area percentage,
i.e., the small amount of the carbide which suppresses crystal grain coarsening at
the time of the solution heat treatment.
- (6) In all of Examples 1 to 37, the 0.2% offset yield strength is more than 850 MPa
and good corrosion resistance is exhibited.
- (7) Among Examples, the materials satisfying the formula (3) particularly exhibit
high corrosion resistance.
Table 3
| |
Tensile strength (MPa) |
0.2% offset yield strength (MPa) |
Corrosion resistance |
Carbide area percentage (%) |
| Example 1 |
1168 |
972 |
B |
0.73 |
| Example 2 |
1160 |
929 |
B |
0.68 |
| Example 3 |
1191 |
990 |
B |
0.74 |
| Example 4 |
1153 |
961 |
A |
0.51 |
| Example 5 |
1196 |
946 |
B |
0.53 |
| Example 6 |
1137 |
894 |
A |
0.59 |
| Example 7 |
1163 |
972 |
A |
0.48 |
| Example 8 |
1160 |
969 |
A |
0.49 |
| Example 9 |
1193 |
945 |
B |
0.54 |
| Example 10 |
1162 |
931 |
A |
0.50 |
| Example 11 |
1142 |
924 |
A |
0.55 |
| Example 12 |
1132 |
866 |
B |
0.52 |
| Example 13 |
1175 |
888 |
B |
0.47 |
| Example 14 |
1227 |
997 |
B |
0.61 |
| Example 15 |
1197 |
948 |
B |
0.45 |
| Example 16 |
1173 |
857 |
B |
0.41 |
| Example 17 |
1206 |
937 |
B |
0.60 |
| Example 18 |
1198 |
948 |
B |
0.52 |
| Example 19 |
1187 |
936 |
B |
0.54 |
| Example 20 |
1203 |
952 |
B |
0.53 |
| Example 21 |
1193 |
942 |
B |
0.58 |
| Example 22 |
1186 |
941 |
B |
0.51 |
| Example 23 |
1188 |
937 |
B |
0.54 |
| Example 24 |
1192 |
945 |
B |
0.49 |
| Example 25 |
1137 |
894 |
A |
0.55 |
| Example 26 |
1152 |
963 |
B |
0.53 |
| Example 27 |
1163 |
984 |
B |
0.58 |
| Example 28 |
1155 |
966 |
A |
0.42 |
| Example 29 |
1148 |
957 |
B |
0.47 |
| Example 30 |
1166 |
987 |
B |
0.54 |
| Example 31 |
1152 |
964 |
A |
0.61 |
| Example 32 |
1141 |
887 |
A |
0.68 |
| Example 33 |
1159 |
989 |
B |
0.72 |
| Example 34 |
1164 |
977 |
B |
0.71 |
| Example 35 |
1161 |
983 |
B |
0.66 |
| Example 36 |
1142 |
850 |
A |
0.65 |
| Example 37 |
1172 |
887 |
B |
0.69 |
| Comparative Example 1 |
1052 |
651 |
C |
0.35 |
| Comparative Example 2 |
1166 |
850 |
C |
0.53 |
| Comparative Example 3 |
1004 |
843 |
C |
0.52 |
| Comparative Example 4 |
1018 |
827 |
C |
0.55 |
| Comparative Example 5 |
1115 |
846 |
B |
0.38 |
[0080] Fig. 1 shows optical microscopic photographs of materials after solution heat treatment
obtained in Example 5 and Comparative Example 4. From Fig. 1, it is realized that
the Laves phase is observed besides the carbide in Comparative Example 4 but the Laves
phase is not observed in Example 5.
[0081] While the mode for carrying out the present invention has been described in detail
above, the present invention is not limited to these embodiments, and various changes
and modifications can be made therein without departing from the purport of the present
invention.
INDUSTRIAL APPLICABILITY
[0083] The precipitation hardened Fe-Ni alloy according to the invention can be used as
members for excavation, automobile engine parts, thermal power generation plant members,
and the like.