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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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 83
- 239000000956 alloy Substances 0.000 title claims abstract description 83
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 230000007797 corrosion Effects 0.000 title claims abstract description 30
- 238000005260 corrosion Methods 0.000 title claims abstract description 30
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 7
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 5
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 5
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 4
- 229910052802 copper Inorganic materials 0.000 claims abstract description 4
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 4
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 4
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 4
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 4
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims description 25
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 18
- 238000007670 refining Methods 0.000 claims description 15
- 229910052786 argon Inorganic materials 0.000 claims description 12
- 238000005266 casting Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 230000003009 desulfurizing effect Effects 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims description 3
- 239000006181 electrochemical material Substances 0.000 claims description 3
- 230000006698 induction Effects 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 abstract description 4
- 229910001182 Mo alloy Inorganic materials 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 2
- 239000011651 chromium Substances 0.000 description 7
- 229910000856 hastalloy Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000009835 boiling Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- WAIPAZQMEIHHTJ-UHFFFAOYSA-N [Cr].[Co] Chemical class [Cr].[Co] WAIPAZQMEIHHTJ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- 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
-
- 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%
-
- 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%
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
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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| CN201911044756.5A CN110564990A (en) | 2019-10-30 | 2019-10-30 | nickel-based corrosion-resistant alloy and preparation method thereof |
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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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2019
- 2019-10-30 CN CN201911044756.5A patent/CN110564990A/en active Pending
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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 |