CN110564990A - nickel-based corrosion-resistant alloy and preparation method thereof - Google Patents
nickel-based corrosion-resistant alloy and preparation method thereof Download PDFInfo
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- CN110564990A CN110564990A CN201911044756.5A CN201911044756A CN110564990A CN 110564990 A CN110564990 A CN 110564990A CN 201911044756 A CN201911044756 A CN 201911044756A CN 110564990 A CN110564990 A CN 110564990A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/023—Alloys based on nickel
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
- C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
- C22C19/055—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 20% but less than 30%
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
- C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
- C22C19/056—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 10% but less than 20%
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Abstract
The invention relates to a nickel-based alloy, in particular to a nickel-based corrosion-resistant alloy and a preparation method thereof, aiming at the defect of poor corrosion resistance of Ni-Cr-Mo alloy in the environments of strong reducing medium and high oxidizing medium in the prior art, the invention provides the nickel-based corrosion-resistant alloy which comprises Cr, W, Mo, C, Mn, Si, V, Ti, Cu, Zr, Co, Fe, P, S and Ni2Above, the yield strength reaches 850N/mm2Above, the elongation at break reaches above 40%.
Description
Technical Field
the invention relates to a nickel-based alloy, in particular to a nickel-based corrosion-resistant alloy and a preparation method thereof.
Background
The nickel-based alloy not only can be widely applied to various industries as a high-temperature alloy, but also plays a vital role in the fields of aerospace, nuclear engineering, energy and power, transportation, oil and gas development, petrochemical industry, ocean engineering, metallurgy and the like as a corrosion-resistant alloy. With the increasingly complex and harsh service environment, especially the continuously improved engineering design standard, the requirements on the corrosion performance and the mechanical property of the material are higher and higher.
The Ni-Cr-Mo alloy is a typical commercialized Hastelloy C series alloy, the content of chromium (Cr) is 15%, but the problem that intergranular corrosion is easy to occur after welding is solved, in order to solve the problem, on the basis of alloy components, Hastelloy C-276 alloy is synthesized by properly reducing C, Si, but after long-term aging at 650-1000 ℃, carbide and a generated Co2Mo6 type intermetallic compound (mu phase) are precipitated at a grain boundary, so that the intergranular corrosion resistance of the alloy is reduced, the thermal stability is poor, and the mechanical property is reduced. Later, Hastelloy C-276 alloy was improved, and based on the alloy composition, the content of W was reduced to zero, the content of C was reduced to below 0.015%, and the addition of Ti to Fe was reduced, so that Hastelloy C-4 alloy was obtained, which improved the intergranular corrosion resistance and thermal stability of the alloy, but the Hastelloy C-4 alloy showed poor corrosion resistance in the environment of strong reducing media and high oxidizing media.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: aiming at the defect that the corrosion resistance of the Ni-Cr-Mo alloy in the prior art is poor in the environments of strong reducing media and high oxidizing media, the nickel-based corrosion-resistant alloy with excellent corrosion resistance and mechanical properties is provided.
the technical scheme adopted by the invention for solving the technical problems is as follows:
a nickel-based corrosion-resistant alloy comprises Cr, W, Mo, C, Mn, Si, V, Ti, Cu, Zr, Co, Fe, P, S and Ni, and is characterized in that: the weight percentages are respectively as follows: 18-20% of Cr, 3-5% of W, 10-12% of Mo, 0.01% of C, 0.3% of Mn, 0.3-0.5% of Si, 0.5-1% of V, 0.05-0.35% of Ti, 0.8-3.2% of Cu, 0.02-0.05% of Zr, 0.5-1% of Co, 1.5% of Fe, less than or equal to 0.02% of P, less than or equal to 0.03% of S and the balance of Ni;
preferably, the weight relationship among the Cr, the Mo and the W conforms to the formula: APF (4 Cr/(2Mo + W)) 2.8-3.2;
Preferably, said APF ═ 4Cr/(2Mo + W) ] -3.0;
preferably, the weight percentage of Cu is 3.0%;
Preferably, the mass percent of Zr is 0.03%;
preferably, the mass percentage of the Co is 0.5%;
The preparation method of the nickel-based corrosion-resistant alloy comprises the following steps:
(1) weighing raw materials of each alloy element according to the chemical components of the alloy;
(2) putting the alloy element raw materials into a crucible of a vacuum induction furnace, closing the furnace cover, starting vacuumizing, and starting to transmit the electrochemical material after the vacuum degree in the furnace is less than 10 Pa;
(3) heating and refining the alloy raw materials after the alloy raw materials are completely melted;
(4) stopping vacuumizing and filling high-purity argon after the alloy liquid surface is filmed after power failure and temperature reduction;
(5) Feeding electricity to punch the film;
(6) Adding a desulfurizing agent into the alloy liquid, vacuumizing, preserving heat under a vacuum condition to desulfurize the alloy liquid, and finally casting and molding to obtain the nickel-based alloy;
In the step (3): refining at 1500-1600 deg.C for 18-23 min;
In the step (4): filling high-purity argon until the vacuum degree in the furnace is 0.05-0.07 MPa;
in the step (6): the casting temperature is 1400-1500 ℃.
The invention has the beneficial effects that:
(1) the alloy prepared by the method has good corrosion resistance in an acidic reducing medium and an oxidizing medium by balancing the contents of Ni, Co and Mo and adding a proper amount of other alloy elements such as Cu, Zr, Mn, Si, V, Ti and the like.
(2) the alloy prepared by the method not only has good corrosion resistance, but also has good mechanical strength, and the tensile strength of the alloy reaches 980N/mm2above, the yield strength reaches 850N/mm2above, the elongation at break reaches above 40%.
Detailed Description
The present invention will now be described in further detail with reference to examples.
example 1
(1) Weighing raw materials of various alloy elements according to the chemical composition of the alloy, namely Cr (18%), W (3%), Mo (10%), C (0.01%), Mn (0.3%), Si (0.3%), V (0.5%), Ti (0.05%), Cu (0.8%), Zr (0.02%), Co (1%), Fe (1.5%), P (0.02%), S (0.03%) and the balance of Ni;
(2) putting the alloy element raw materials into a crucible of a vacuum induction furnace, closing the furnace cover, starting vacuumizing, and starting to transmit the electrochemical material after the vacuum degree in the furnace is less than 10 Pa;
(3) Heating and refining the alloy raw materials after the alloy raw materials are completely melted;
(4) stopping vacuumizing and filling high-purity argon after the alloy liquid surface is filmed after power failure and temperature reduction;
(5) feeding electricity to punch the film;
(6) adding a desulfurizing agent into the alloy liquid, vacuumizing, preserving heat under a vacuum condition to desulfurize the alloy liquid, and finally casting and molding to obtain the nickel-based alloy;
In the step (3): the refining temperature is 1600 ℃, and the refining time is 18 min;
In the step (4): filling high-purity argon until the vacuum degree in the furnace is 0.05 MPa;
In the step (6): the casting temperature was 1500 ℃.
Example 2
the rest of the process was the same as example 1 except that: cr (18%), W (4%), Mo (10%), Si (0.4%), V (0.5%), Ti (0.1%), Cu (1.2%), Zr (0.03%) and Co (0.5%) in the raw materials of the alloy elements; the alloy preparation method comprises the following steps: in the step (1), the refining temperature is 1600 ℃, and the refining time is 20 min; filling high-purity argon into the furnace until the vacuum degree in the furnace is 0.06 MPa; the temperature for casting in step (6) was 1500 ℃.
Example 3
The rest of the process was the same as example 1 except that: cr (18%), W (5%), Mo (10%), Si (0.5%), V (0.5%), Ti (0.2%), Cu (1.6%), Zr (0.04%), Co (0.6%) in the raw materials of the alloy elements; the alloy preparation method comprises the following steps: in the step (3): the refining temperature is 1500 ℃, and the refining time is 23 min; in the step (4): filling high-purity argon until the vacuum degree in the furnace is 0.07 MPa; in the step (6): the casting temperature was 1500 ℃.
Example 4
The rest of the process was the same as example 1 except that: cr (18%), W (3%), Mo (11%), Si (0.3%), V (0.5%), Ti (0.3%), Cu (2%), Zr (0.05%) and Co (0.8%) in the raw materials of the alloy elements; the alloy preparation method comprises the following steps: in the step (3): refining at 1500 deg.C for 20 min; in the step (4): filling high-purity argon until the vacuum degree in the furnace is 0.06 MPa; in the step (6): the casting temperature was 1400 ℃.
example 5
The rest of the process was the same as example 1 except that: cr (19%), W (4%), Mo (10%), Si (0.5%), V (1%), Ti (0.25%), Cu (2.4%), Zr (0.02%) and Co (0.5%) in the raw materials of the alloy elements; the alloy preparation method comprises the following steps: in the step (3): refining at 1500 deg.C for 20 min; in the step (4): filling high-purity argon until the vacuum degree in the furnace is 0.06 MPa; in the step (6): the casting temperature was 1400 ℃.
Example 6
The rest of the process was the same as example 1 except that: cr (19%), W (5%), Mo (10%), Si (0.4%), V (0.5%), Ti (0.35%), Cu (3%), Zr (0.02%) and Co (0.5%) in the raw materials of the alloy elements; the alloy preparation method comprises the following steps: in the step (3): refining at 1500 deg.C for 18 min; in the step (4): filling high-purity argon until the vacuum degree in the furnace is 0.06 MPa; in the step (6): the casting temperature was 1400 ℃.
Example 7
the rest of the process was the same as example 1 except that: cr (18%), W (3%), Mo (11%), Si (0.4%), V (0.5%), Ti (0.35%), Cu (3.2%), Zr (0.02%) and Co (0.5%) in the raw materials of the alloy elements; the alloy preparation method comprises the following steps: in the step (3): refining at 1500 deg.C for 20 min; in the step (4): filling high-purity argon until the vacuum degree in the furnace is 0.06 MPa; in the step (6): the casting temperature was 1400 ℃.
Example 8
The rest of the process was the same as example 1 except that: cr (18%), W (4%) and Mo (11%) in the raw materials of alloy elements.
Example 9
The rest of the process was the same as example 1 except that: cr (18%), W (5%) and Mo (11%) in the raw materials of alloy elements.
Example 10
The rest of the process was the same as example 1 except that: cr (20%), W (5%) and Mo (10%) in the raw materials of alloy elements.
Example 11
The rest of the process was the same as example 1 except that: cr (20%), W (5%) and Mo (11%) in the raw materials of the alloy elements.
Example 12
The rest of the process was the same as example 1 except that: cr (20%), W (4%) and Mo (11%) in the raw materials of alloy elements.
example 13
The rest of the process was the same as example 1 except that: cr (20%), W (3%) and Mo (12%) in the raw materials of alloy elements.
Example 14
The rest of the process was the same as example 1 except that: cr (18%), W (4%) and Mo (12%) in the raw materials of alloy elements.
Comparative example 1
The rest of the process was the same as example 1 except that: cr (18%), W (5%), Mo (11%), Cu (0.5%).
Comparative example 2
The rest of the process was the same as example 1 except that: cr (18%), W (1%), Mo (11%), Cu (3.5%).
Performance evaluation: the alloy prepared in the examples 1 to 14 and the comparative examples 1 to 2 is subjected to a performance test, and the material is processed into a sheet-shaped test sample with the thickness of 3X 20X 30mm after heat treatment, and the surface smoothness is 7.
test medium and test method
Full immersion corrosion experiment: the test time is 24 h;
Medium: (1) boiling 50% H2SO4+42g/L Fe2(SO4)3(test Standard ASTMG28)
(2) Boiling 40% HF
TABLE 1
TABLE 2
in light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (10)
1. a nickel-based corrosion-resistant alloy comprises Cr, W, Mo, C, Mn, Si, V, Ti, Cu, Zr, Co, Fe, P, S and Ni, and is characterized in that: the weight percentages are respectively as follows: 20-23% of Cr, 3-5% of W, 10-12% of Mo, 0.01% of C, 0.3% of Mn, 0.3-0.5% of Si, 0.5-1% of V, 0.05-0.35% of Ti, 0.8-3.2% of Cu, 0.02-0.05% of Zr, 0.5-1% of Co, 1.5% of Fe, less than or equal to 0.02% of P, less than or equal to 0.03% of S and the balance of Ni.
2. the nickel ~ based corrosion ~ resistant alloy according to claim 1, wherein the weight relationship among Cr, Mo and W is defined by APF = [4Cr/(2Mo + W) ] =2.8 ~ 3.2.
3. The nickel-base corrosion-resistant alloy of claim 2, wherein: the APF = [4Cr/(2Mo + W) ] = 3.0.
4. the nickel-base corrosion-resistant alloy according to any of claims 1 to 3, wherein: the weight percentage of Cu is 3.0%.
5. The nickel-base corrosion-resistant alloy of claim 4, wherein: the mass percent of Zr is 0.03%.
6. the nickel-base corrosion-resistant alloy of claim 5, wherein: the mass percent of Zr is 0.03%.
7. the nickel-base corrosion-resistant alloy of claim 6, wherein: the mass percent of the Co is 0.5%.
8. The nickel-base corrosion-resistant alloy according to claims 1-3, wherein: the mass percent of the Co is 0.5%.
9. The nickel-base corrosion-resistant alloy according to any one of claims 1 to 3, 5 and 7, wherein: the preparation method comprises the following steps:
(1) weighing raw materials of each alloy element according to the chemical components of the alloy;
(2) Putting the alloy element raw materials into a crucible of a vacuum induction furnace, closing the furnace cover, starting vacuumizing, and starting to transmit the electrochemical material after the vacuum degree in the furnace is less than 10 Pa;
(3) Heating and refining the alloy raw materials after the alloy raw materials are completely melted;
(4) stopping vacuumizing and filling high-purity argon after the alloy liquid surface is filmed after power failure and temperature reduction;
(5) Feeding electricity to punch the film;
(6) Adding a desulfurizing agent into the alloy liquid, vacuumizing, preserving heat under a vacuum condition to desulfurize the alloy liquid, and finally casting and molding to obtain the nickel-based alloy.
10. The method of preparing a nickel-base corrosion-resistant alloy according to claim 9, wherein:
In the step (3): refining at 1500-1600 deg.C for 18-23 min;
In the step (4): filling high-purity argon until the vacuum degree in the furnace is 0.05-0.07 MPa;
In the step (6): the casting temperature is 1400-1500 ℃.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112030041A (en) * | 2020-09-07 | 2020-12-04 | 沈阳金纳新材料股份有限公司 | MonelK500A alloy with corrosion resistance in oxygen-containing hydrofluoric acid |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112030041A (en) * | 2020-09-07 | 2020-12-04 | 沈阳金纳新材料股份有限公司 | MonelK500A alloy with corrosion resistance in oxygen-containing hydrofluoric acid |
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Application publication date: 20191213 |