JP3293254B2 - Co-based alloy with excellent high-temperature strength - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a Co-based alloy having excellent high-temperature strength, excellent high-temperature oxidation resistance, high-temperature fluid wear resistance and molten glass erosion resistance. is there.

[0002]

2. Description of the Related Art Conventionally, generally, for example, a glass fiber is charged with molten glass heated to about 1000 ° C. in a spinner, and the spinner is rotated at a high speed of about 1700 rpm to form a side wall of the spinner. It is well known that molten glass is formed by ejecting molten glass by centrifugal force from a large number of pores pierced radially along with the glass fiber. Since these materials are required to be chemically and erosion resistant to molten glass, their production requires, for example,
A Co-based alloy described in JP-A-3-30384 is used. In addition, structural members such as turbine nozzles and vanes of gas turbines are also required to have high-temperature strength and high-temperature oxidation resistance and wear resistance to high-temperature fluids such as high-temperature combustion gases, and thus have these characteristics. It is also known that a Co-based alloy described in, for example, Japanese Patent Publication No. 3-43813 is used.

[0003]

On the other hand, in recent years, for example, there has been a remarkable progress in increasing the output of gas turbines and increasing the speed of glass fiber forming processing. Spinners are required to have more excellent high-temperature strength, but the above-mentioned conventional Co-based alloys that constitute them,
Since many other Co-based alloys do not have a sufficiently high-temperature strength, at present, the service life is relatively short in practical use under severer high-temperature conditions.

[0004]

Means for Solving the Problems Accordingly, the present inventors have
From the above-mentioned viewpoints, as a result of researching to develop a Co-based alloy having particularly excellent high-temperature strength, C: 0.1 to 1.2% by weight (hereinafter,% indicates weight%). , Si
And one or two of Mn: 0.01 to 2%,
Cr: 22 to 37%, Ni: 5 to 15%, H
f: 0.1 to 5%, Re: 0.1 to 3.5%,
And optionally, (a) Ta and N
one or two of b: 0.1 to 12%, (b)
One or two of W and Mo: 0.1 to 10
%, (C) one or two of B and Zr:
0.005 to 0.1%, (d) one or more of the rare earth elements containing Y: 0.005 to 0.1%, (a) to
A Co-based alloy containing one or two or more of (d) and having a composition consisting of Co and unavoidable impurities has excellent high-temperature strength, high-temperature oxidation resistance, and high-temperature fluid. It has excellent abrasion resistance and resistance to molten glass erosion, so that it can be used under severe high temperature conditions, for example, when it is used for manufacturing gas turbine structural members or glass fiber molded spinners. The research results show that they exhibit excellent performance over a remarkably long period.

The present invention has been made on the basis of the above research results, and the reason for limiting the component composition as described above will be described below. (A) C The C component has a function of improving the high-temperature fluid abrasion resistance by forming a carbide in addition to forming a solid solution in the base material and strengthening it. The desired high temperature fluid abrasion resistance cannot be ensured, while the content is 1.
If it exceeds 2%, rapid embrittlement will occur.
The content was determined to be 0.1 to 1.2%.

(B) Si and Mn These components are indispensable components for the deoxidation of the molten alloy. Therefore, if the content is less than 0.01%, the desired deoxidizing effect cannot be secured. , While its content is 2
%, The alloy becomes embrittled, so the content was determined to be 0.01 to 2%.

(C) Cr The Cr component has a function of improving the high-temperature fluid wear resistance by forming a carbide as described above, and has the function of improving the high-temperature oxidation resistance by forming a solid solution in a base material. If the amount is less than 22%, the desired effect cannot be obtained, whereas if the content exceeds 37%, the high-temperature strength and toughness decrease, so the content is determined to be 22 to 37%. Was.

(D) Ni The Ni component has a function of improving the high-temperature strength in addition to improving the oxidation resistance in the coexistence of Co and Cr in a solid solution with the base material, but its content is less than 5%. In the above, the desired improvement effect cannot be obtained in the above-mentioned action. On the other hand, even if the content exceeds 15%, the action is saturated and the further improvement effect does not appear, so that the content is 5 to 15%. I decided.

(E) Hf The Hf component has the effect of forming carbides to improve the high-temperature fluid abrasion resistance, and has the effect of forming a solid solution in the substrate to improve the molten glass erosion resistance. If the content is less than 0.1%, the desired effect of improving the above effect cannot be obtained. On the other hand, if the content exceeds 5%, the toughness decreases, so the content is set to 0.1 to 5%. Was.

(F) Re The Re component has the effect of forming a solid solution in the substrate and significantly improving the high-temperature strength in the presence of the Hf component. High temperature strength cannot be ensured. On the other hand, if the content exceeds 3.5%, the toughness is reduced.
It was determined to be 3.5%.

(G) Ta and Nb These components form carbides to improve the high-temperature fluid abrasion resistance, and form a solid solution in the base to improve the high-temperature oxidation resistance and the molten glass erosion resistance. However, if necessary, the desired effect cannot be obtained if the content is less than 0.1%. On the other hand, if the content exceeds 12%, the toughness is reduced. From becoming
The content was determined to be 0.1 to 12%.

(H) W and Mo These components have the effect of forming carbides to improve the high-temperature fluid wear resistance, and also have the effect of forming a solid solution in the base material to improve the high-temperature strength. However, if the content is less than 0.1%, a desired effect cannot be obtained in the above-mentioned action, while if the content exceeds 10%, high-temperature oxidation resistance and toughness are reduced. Therefore, the content was determined to be 0.1 to 10%.

(I) B and Zr These components have the effect of strengthening the crystal grain boundaries and thereby improving the high-temperature strength, and are therefore contained as necessary. The content is 0.005%. If the content is less than 0.1%, the desired effect of improving the high-temperature strength cannot be obtained. On the other hand, if the content exceeds 0.1%, the toughness decreases, so the content is set to 0.005 to 0.1%. .

(J) Rare earth element containing Y Since the rare earth element containing Y has an effect of improving the high-temperature oxidation resistance, it is contained as necessary, but if the content is less than 0.005%, The effect of improving the high-temperature oxidation resistance is insufficient. On the other hand, if the content exceeds 0.1%, the castability and workability will be impaired. %.

(K) Fe In the Co-based alloy of the present invention, an Fe component may be contained as an unavoidable impurity.
% Does not have any adverse effect on the alloy properties, so it may be positively added up to 4% in consideration of economy.

[0016]

EXAMPLES Next, the Co-based alloy of the present invention will be specifically described with reference to examples. The Co-based alloy 1 of the present invention having the component compositions shown in Tables 1 to 7, respectively, by a normal melting method.
-61 and comparative Co-based alloys 1-10, respectively, and these alloy melts were subjected to creep rupture test specimen materials (diameter: 12 mm × Length: 120
mm bar), high-temperature oxidation test specimen material for evaluating high-temperature oxidation resistance (diameter: 12 mm × length: 120 mm round bar), high-temperature fluid wear test for evaluating high-temperature fluid wear resistance Test specimen material (diameter: 12 mm × length: 120 mm round bar) and test specimen material for molten glass nozzle ejection test for evaluating molten glass erosion resistance (diameter: 35 mm × thickness: 5 mm disc) ).

Each of the comparative Co-based alloys 1 to 10 has a component composition in which the content of any one of the basic components (marked with * in Table 7) is out of the range of the present invention. is there. In the creep rupture test, a test piece having a dimension of parallel part diameter: 6 mm × parallel part length: 32 mm × chuck (screw) part diameter: 12 mm × total length: 80 mm was cut out of the above-mentioned material, and this test piece was cut out. Use and atmosphere: in air,
Heating temperature: 950 ° C., load stress: 12 kg / mm ² , the breaking life (high temperature strength) was measured, and the elongation was measured for the purpose of evaluating the high temperature toughness.

In the above high-temperature oxidation test, a test piece having a size of 10 mm in diameter × 12 mm in height was cut out from the above-mentioned material, and the test piece was kept at a temperature of 1125 ° C. for 12 hours and then cooled. The descaling is one cycle, and this is 5
By repeating the cycle, the weight loss of the test piece after the test was measured, and the ratio to the weight of the test piece before the test (oxidation weight loss ratio) was calculated.

The high-temperature fluid abrasion test was carried out on the above-mentioned materials with a diameter of:
A test piece having a size of 10 mm × length: 100 mm was cut out, and this test piece was mixed with an alumina powder having an average particle size of 100 μm at a rate of 5 g / min in kerosene combustion gas (temperature: 900 ° C.). Was set up in a tube passing at a flow rate of about 90 m / sec, and this condition was maintained for 48 hours, and the wear depth of the fluid-facing surface at the center of the test piece after the test was measured.

In the molten glass nozzle ejection test, the center of the above material was reduced in thickness by cutting to a thickness of 1 mm, a hole having a diameter of 0.5 mm was formed in the reduced thickness portion, and the hole was formed into an inner diameter of 20 mm.
In the crucible, a soda glass in which WC powder having an average particle size of 5 μm was mixed at a ratio of 3% by volume was melted in the air, and the molten glass was heated to 1050 ° C.
The test was performed by applying a pressure of 3 atm to the molten glass from above the crucible and ejecting the molten glass from the hole in the bottom plate of the crucible for 48 hours while maintaining the temperature of the molten glass. The hole diameter after the test was measured, and the hole diameter change rate, that is, [(hole diameter after the test) − (hole diameter before the test)] ÷ (hole diameter before the test) × 100, was obtained from the measurement result.
% Was calculated. The results are shown in Tables 8 to 11.

[0021]

[Table 1]

[0022]

[Table 2]

[0023]

[Table 3]

[0024]

[Table 4]

[0025]

[Table 5]

[0026]

[Table 6]

[0027]

[Table 7]

[0028]

[Table 8]

[0029]

[Table 9]

[0030]

[Table 10]

[0031]

[Table 11]

[0032]

From the results shown in Tables 1 to 11, all of the Co-based alloys 1 to 61 of the present invention have remarkably excellent high-temperature strength, high-temperature toughness, high-temperature oxidation resistance, and high-temperature fluid wear resistance. , And also excellent in molten glass erosion resistance, as seen in Comparative Co-based alloys 1 to 10, when the content of any of the constituents is out of the range of the present invention, It is clear that at least one of the above properties is inferior. As described above, the Co-based alloy of the present invention has particularly excellent high-temperature strength and excellent high-temperature oxidation resistance, high-temperature fluid abrasion resistance, and molten glass erosion resistance. For example, when it is used as a structural member of a gas turbine or a glass fiber forming spinner, it has industrially useful properties such as exhibiting excellent performance over a long period of time even in practical use under more severe conditions. It has.

Continuation of the front page (56) References JP-A-61-183432 (JP, A) JP-A-61-549 (JP, A) JP-A-60-262935 (JP, A) JP-A-60-224732 (JP) JP-A-55-82743 (JP, A) JP-A-55-82741 (JP, A) JP-A-3-120327 (JP, A) JP-A-64-42545 (JP, A) 62-3221 (JP, B1) (58) Fields investigated (Int. Cl. ⁷ , DB name) C22C 19/07 C03B 37/04

Claims (16)

(57) [Claims] C .: 0.1 to 1.2% by weight, one or two of Si and Mn: 0.01 to 2
%, Cr: 22 to 37%, Ni: 5 to 15%, Hf: 0.1 to 5%, Re: 0.1 to 3.5
%, With the balance being a composition comprising Co and inevitable impurities. 2. In% by weight, C: 0.1 to 1.2%, one or two of Si and Mn: 0.01 to 2
%, Cr: 22 to 37%, Ni: 5 to 15%, Hf: 0.1 to 5%, Re: 0.1 to 3.5
%, And one or two of Ta and Nb: 0.1 to 12
%, With the balance being a composition comprising Co and inevitable impurities. 3. C .: 0.1 to 1.2% by weight, one or two of Si and Mn: 0.01 to 2.
%, Cr: 22 to 37%, Ni: 5 to 15%, Hf: 0.1 to 5%, Re: 0.1 to 3.5
%, And one or two of W and Mo: 0.1 to 10
%, With the balance being a composition comprising Co and inevitable impurities. 4. In% by weight, C: 0.1 to 1.2%, one or two of Si and Mn: 0.01 to 2
%, Cr: 22 to 37%, Ni: 5 to 15%, Hf: 0.1 to 5%, Re: 0.1 to 3.5
%, And one or two of B and Zr: 0.005 to
0.1%, with the balance being Co and unavoidable impurities.
o-based alloy. 5.% by weight, C: 0.1 to 1.2%, one or two of Si and Mn: 0.01 to 2
%, Cr: 22 to 37%, Ni: 5 to 15%, Hf: 0.1 to 5%, Re: 0.1 to 3.5
%, And at least one of the rare earth elements containing Y: 0.005 to
0.1%, with the balance being Co and unavoidable impurities.
o-based alloy. 6. In% by weight, C: 0.1 to 1.2%, one or two of Si and Mn: 0.01 to 2
%, Cr: 22 to 37%, Ni: 5 to 15%, Hf: 0.1 to 5%, Re: 0.1 to 3.5
%, And one or two of Ta and Nb: 0.1 to 12
%, One or two of W and Mo: 0.1 to 10
%, With the balance being a composition comprising Co and inevitable impurities. 7. In% by weight, C: 0.1 to 1.2%, one or two of Si and Mn: 0.01 to 2
%, Cr: 22 to 37%, Ni: 5 to 15%, Hf: 0.1 to 5%, Re: 0.1 to 3.5
%, And one or two of Ta and Nb: 0.1 to 12
%, One or two of B and Zr: 0.005 to
0.1%, with the balance being Co and unavoidable impurities.
o-based alloy. 8. In% by weight, C: 0.1 to 1.2%, one or two of Si and Mn: 0.01 to 2
%, Cr: 22 to 37%, Ni: 5 to 15%, Hf: 0.1 to 5%, Re: 0.1 to 3.5
%, And one or two of Ta and Nb: 0.1 to 12
%, One or more of the rare earth elements containing Y: 0.005 to
0.1%, with the balance being Co and unavoidable impurities.
o-based alloy. 9. In% by weight, C: 0.1 to 1.2%, one or two of Si and Mn: 0.01 to 2
%, Cr: 22 to 37%, Ni: 5 to 15%, Hf: 0.1 to 5%, Re: 0.1 to 3.5
%, And one or two of W and Mo: 0.1 to 10
%, One or two of B and Zr: 0.005 to
0.1%, with the balance being Co and unavoidable impurities.
o-based alloy. 10. In% by weight, C: 0.1 to 1.2%, one or two of Si and Mn: 0.01 to 2
%, Cr: 22 to 37%, Ni: 5 to 15%, Hf: 0.1 to 5%, Re: 0.1 to 3.5
%, And one or two of W and Mo: 0.1 to 10
%, One or more of the rare earth elements containing Y: 0.005 to
0.1%, with the balance being Co and unavoidable impurities.
o-based alloy. 11. In% by weight, C: 0.1-1.2%, one or two of Si and Mn: 0.01-2.
%, Cr: 22 to 37%, Ni: 5 to 15%, Hf: 0.1 to 5%, Re: 0.1 to 3.5
%, And one or two of B and Zr: 0.005 to
0.1%, at least one of rare earth elements containing Y: 0.005 to
0.1%, with the balance being Co and unavoidable impurities.
o-based alloy. 12.% by weight: C: 0.1 to 1.2%, one or two of Si and Mn: 0.01 to 2
%, Cr: 22 to 37%, Ni: 5 to 15%, Hf: 0.1 to 5%, Re: 0.1 to 3.5
%, And one or two of Ta and Nb: 0.1 to 12
%, One or two of W and Mo: 0.1 to 10
%, One or two of B and Zr: 0.005 to
0.1%, with the balance being Co and unavoidable impurities.
o-based alloy. 13.% by weight, C: 0.1 to 1.2%, one or two of Si and Mn: 0.01 to 2
%, Cr: 22 to 37%, Ni: 5 to 15%, Hf: 0.1 to 5%, Re: 0.1 to 3.5
%, And one or two of Ta and Nb: 0.1 to 12
%, One or two of W and Mo: 0.1 to 10
%, One or more of the rare earth elements containing Y: 0.005 to
0.1%, with the balance being Co and unavoidable impurities.
o-based alloy. 14. C .: 0.1-1.2% by weight, one or two of Si and Mn: 0.01-2.
%, Cr: 22 to 37%, Ni: 5 to 15%, Hf: 0.1 to 5%, Re: 0.1 to 3.5
%, And one or two of Ta and Nb: 0.1 to 12
%, One or two of B and Zr: 0.005 to
0.1%, at least one of rare earth elements containing Y: 0.005 to
0.1%, with the balance being Co and unavoidable impurities.
o-based alloy. 15. In% by weight, C: 0.1-1.2%, one or two of Si and Mn: 0.01-2.
%, Cr: 22 to 37%, Ni: 5 to 15%, Hf: 0.1 to 5%, Re: 0.1 to 3.5
%, And one or two of W and Mo: 0.1 to 10
%, One or two of B and Zr: 0.005 to
0.1%, at least one of rare earth elements containing Y: 0.005 to
0.1%, with the balance being Co and unavoidable impurities.
o-based alloy. 16. C: 0.1 to 1.2% by weight, one or two of Si and Mn: 0.01 to 2.
%, Cr: 22 to 37%, Ni: 5 to 15%, Hf: 0.1 to 5%, Re: 0.1 to 3.5
%, And one or two of Ta and Nb: 0.1 to 12
%, One or two of W and Mo: 0.1 to 10
%, One or two of B and Zr: 0.005 to
0.1%, at least one of rare earth elements containing Y: 0.005 to
0.1%, with the balance being Co and unavoidable impurities.
o-based alloy.