CN110527913B - Novel Fe-Ni-Cr-N alloy and preparation method thereof - Google Patents
Novel Fe-Ni-Cr-N alloy and preparation method thereof Download PDFInfo
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- 239000000956 alloy Substances 0.000 title claims abstract description 106
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 103
- 229910019590 Cr-N Inorganic materials 0.000 title claims abstract description 18
- 229910019588 Cr—N Inorganic materials 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 29
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 22
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 21
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 17
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 14
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 13
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 12
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 12
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 12
- 229910052802 copper Inorganic materials 0.000 claims abstract description 10
- 239000012535 impurity Substances 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims description 23
- 238000001816 cooling Methods 0.000 claims description 22
- 239000002994 raw material Substances 0.000 claims description 14
- 238000007670 refining Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 230000005611 electricity Effects 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 229910052720 vanadium Inorganic materials 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 3
- 239000012768 molten material Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 238000005275 alloying Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims 2
- 238000005260 corrosion Methods 0.000 abstract description 36
- 230000007797 corrosion Effects 0.000 abstract description 36
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract description 4
- 239000011780 sodium chloride Substances 0.000 abstract description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 35
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 29
- 239000011651 chromium Substances 0.000 description 18
- 239000006104 solid solution Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 229910000831 Steel Inorganic materials 0.000 description 8
- 229910001566 austenite Inorganic materials 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000010959 steel Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 229910000601 superalloy Inorganic materials 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- 238000004080 punching Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 229910000640 Fe alloy Inorganic materials 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910000734 martensite Inorganic materials 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910019589 Cr—Fe Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910000963 austenitic stainless steel Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
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- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/004—Heat treatment of ferrous alloys containing Cr and Ni
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- C21D6/00—Heat treatment of ferrous alloys
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Abstract
The invention belongs to the technical field of alloy materials, and particularly relates to a novel Fe-Ni-Cr-N alloy with excellent high-temperature strength and high-temperature corrosion resistanceGold and a preparation method thereof. The novel Fe-Ni-Cr-N alloy comprises the following chemical components in percentage by weight: c: 0.02wt% or less, Si: 0.6wt% or less, Mn: 1.0 to 4.0wt%, Cu: 1.5wt% or less, Ni: 26-33 wt%, Cr: 18-26 wt%, Mo: 2-5 wt%, Nb: 2-4 wt%, N: 0.4-0.8 wt%, Al: 0.1-0.5 wt%, Ti: 0.4-1.1 wt%, Ti/Al: 2.0 to 2.5 and Ti + Al: 1.2 to 1.8wt%, (Ti + Al)/N: 1.8-5.0, V: 0.06-0.10 wt%, and the balance Fe and unavoidable impurities. The corrosion current density of the novel Fe-Ni-Cr-N alloy prepared by the invention in 3.5 percent NaCl solution is 1.04 multiplied by 10‑7~7.65×10‑7mA/cm2, the alloy yield strength is 417.41-431.38 MPa, the tensile strength is 651.13-743.36 MPa, and the alloy has good yield strength, tensile strength and corrosion resistance in a temperature range of 600-700 ℃.
Description
Technical Field
The invention belongs to the technical field of alloy materials, and particularly relates to a novel Fe-Ni-Cr-N alloy with excellent high-temperature strength and high-temperature corrosion resistance and a preparation method thereof.
Technical Field
The nickel-based superalloy has excellent oxidation resistance, hot corrosion resistance, excellent creep resistance, thermal fatigue resistance and good structural stability in an environment higher than 600 ℃, so that the nickel-based superalloy is widely applied to key parts of aircraft engines and industrial ground combustion engines. In recent years, with the increasing requirements on the combustion efficiency and the thrust-weight ratio of the engine, the inlet temperature of the turbine is higher, and the temperature bearing level for adapting the material of the hot-end part of the engine with the high thrust-weight ratio is increased. Therefore, the combustion efficiency and the thrust-weight ratio of the engine can be improved only by continuously optimizing and improving the components and the production process of the alloy. On the other hand, because of the shortage of nickel resources in China, a large amount of imports are needed to maintain the demand, which leads to the increase of the cost and becomes the bottleneck of the development of the nickel-based superalloy industry. On the premise of ensuring the performance unchanged and reducing the cost, the search for new elements to replace nickel elements is the main development direction of the current industrial production.
Like nickel, nitrogen is also an element that strongly forms austenite and expands the phase region, and its capacity is much greater than that of nickel. In duplex stainless steels, nitrogen also has a greater ability to stabilize austenite at high temperatures than nickel. Since nitrogen has an austenite forming ability comparable to that of carbon, which is 30 times that of nickel. In addition, nitrogen as a solid solution strengthening element increases the strength of the nickel-base alloy without significantly impairing the plasticity and toughness of the steel, while at the same time it increases the corrosion resistance of the steel, in particular the local corrosion resistance.
For example, patent document 1 discloses a method for further increasing the nitrogen content in steel based on the prior art, and provides a new idea for the production of high-nitrogen steel.
Further, patent document 2 discloses a high-hardness and corrosion-resistant Ni — Cr — Fe alloy and a method for producing the same.
[ Prior art documents ]
[ patent document ]
Patent document 1 discloses a method for producing a high nitrogen steel, which is applied to patent "a method for producing a high nitrogen steel" by Kunming university of science, patent No.: CN 104862447B.
Patent document 2 discloses a high-hardness and corrosion-resistant Ni-Cr-Fe alloy and a method for producing the same, which is applied by Jiangsu leap Pump group Limited, and the patent numbers: CN 109778048A.
However, the method for producing high nitrogen steel disclosed in patent document 1 is different from the design concept of the alloy for high temperature use of the present invention in that the design concept is not focused on the substitution of Ni with N, and the problem of occurrence of pores in the production process of high nitrogen steel is solved. In addition, although the high-hardness and corrosion-resistant Ni — Cr — Fe alloy disclosed in patent document 2 is similar in preparation method, the specific formulation and preparation details are different, and the alloy prepared in the patent document is different from the design idea of the present invention using N instead of Ni, and does not suggest that the use requirement under high temperature conditions is satisfied.
Disclosure of Invention
In view of the above circumstances, the present invention aims to provide a novel Fe-Ni-Cr-N alloy having excellent high-temperature strength and high-temperature corrosion resistance, and the alloy thus prepared has excellent yield strength, tensile strength and corrosion resistance in a high-temperature environment. Specifically, in the temperature range of 600-700 ℃, the high-temperature performance of the novel alloy is better than that of 316L austenitic stainless steel and part of nickel-based superalloy.
In order to achieve the purpose, the invention adopts the following technical scheme:
the novel Fe-Ni-Cr-N alloy comprises the following chemical components in percentage by weight: c: 0.02wt% or less, Si: 0.6wt% or less, Mn: 1.0 to 4.0wt%, Cu: 1.5wt% or less, Ni: 26-33 wt%, Cr: 18-26 wt%, Mo: 2-5 wt%, Nb: 2-4 wt%, N: 0.4-0.8 wt%, Al: 0.1-0.5 wt%, Ti: 0.4-1.1 wt%, Ti/Al: 2.0 to 2.5 and Ti + Al: 1.2 to 1.8wt%, (Ti + Al)/N: 1.8-5.0, V: 0.06-0.10 wt%, and the balance Fe and unavoidable impurities.
The preparation method of the novel Fe-Ni-Cr-N alloy comprises the following steps:
(1) calculating and weighing alloy element raw materials according to chemical components, wherein the N element is added in a form of MnN;
(2) mixing alloy element raw materials except MnN, vacuumizing until the vacuum degree is less than 10Pa, and starting to transmit the molten material;
(3) heating and refining after all the raw materials are melted to obtain alloy liquid A;
(4) cooling to the surface of the alloy liquid A to form a film, stopping vacuumizing, and filling inert gas;
(5) feeding electricity to punch a film to melt the film, and then adding MnN to obtain a synthetic uniformly-divided gold solution B;
(6) cooling the alloy liquid B to obtain an alloy ingot;
(7) and carrying out solution treatment on the alloy ingot, and then cooling.
The MnN is powder with the granularity of 100 meshes.
The raw materials of the alloy elements are powder, and the granularity is 100 meshes.
In the step (3), the refining temperature is 1600-.
In the step (4), the surface film formation means a state in which the surface of the alloy liquid starts to solidify to form a semi-solid film and the internal liquid is not solidified.
In the step (4), the inert gas is 96% Ar +4% N2And the vacuum degree in the furnace is 0.08-0.10 MPa.
In the step (5) above, MnN is added to provide all of the N element and part of the Mn element in the alloy.
In the step (7), the solid solution temperature is 1100 ℃, the temperature is kept for 2 hours, and the cooling mode is preferably water cooling.
The alloy composition of the invention has the following characteristics:
based on Fe-Ni-Cr-N alloy, Mo, Mn, V, Ti, Al, Nb, Si and Cu are added for alloying, so that the high-temperature performance and the corrosion resistance of the alloy are improved. From the action of a single element, N not only has the function of expanding an austenite phase region, but also has the capacity of stabilizing an austenite structure, nitrogen can be used for replacing a Ni element to achieve the effect of saving cost, and meanwhile, the nitrogen can inhibit the activation energy of martensite and deformed martensite, so that the alloy obtains a single austenite structure and the stability of the structure is ensured. N forms dispersed nitrides in the alloy with other elements, such as: cr (chromium) component2N、CrN、MnN、TiN、AlN、NbN、M23(C,N)6And the like. The precipitation of carbide and intermetallic compounds in the crystal boundary can be delayed by adding the N element, so that the heat treatment area is enlarged. Mo improves the local corrosion resistance and the chloride intergranular corrosion resistance of the alloy, and can be subjected to solid solution strengthening. Cu improves alloy and resists H2SO4And acidic environment properties including HF. Al, Nb and V improve the weld heat affected zone and the intergranular corrosion resistance. Si may also improve the corrosion resistance of the alloy. Most of Ni is dissolved in austenite in a solid solution mode, an austenite phase region is expanded, and the high-temperature performance of the alloy is improved; ni also has a significant tendency to passivate, either in oxidizing or reducing media, the element NiThe corrosion resistance of the alloy can be improved. Cr is the most important element for stabilizing the alloy surface, and forms an oxidation-resistant and corrosion-resistant protective layer on the surface of a base material, and is a key element for determining the corrosion resistance of the alloy.
Meanwhile, the added Ti and Al elements need to be kept in a certain proportion range: al: 0.1-0.5 wt%, Ti: 0.4-1.1 wt%, Ti/Al: 2.0 to 2.5 and Ti + Al: 1.2 to 1.8wt%, (Ti + Al)/N: 1.8 to 5.0; this is because Al is a main element forming the γ 'phase, and the γ' phase has high stability and strengthens the alloy. When the Al content is 0.1 wt%, sufficient strength cannot be obtained. On the other hand, if the Al content is more than 0.5wt%, the weld metal is deteriorated. Ti is a nitrogen fixation element, forms TiN phase which is dispersed and distributed in the matrix, and strengthens the alloy by influencing dislocation behavior. When the Ti content is less than 0.4 wt%, sufficient strength cannot be obtained. On the other hand, if the Ti content is more than 1.1wt%, grain boundaries are embrittled. The Ti/Al ratio has an influence on the high-temperature strength and the corrosion resistance of the weld metal. The ratio of Ti to Al is lower than 2.0, and the high-temperature corrosion resistance of the weld metal is poor. On the other hand, the ratio of Ti to Al is higher than 2.5, and the high-temperature creep property of the weld metal is poor. The total amount of Ti + Al added has an influence on the high-temperature strength and the corrosion resistance of the weld metal. When the total amount of Ti and Al is less than 1.2 wt%, the effect of improving the high-temperature performance of the weld metal is not obvious. On the other hand, if the total amount of Ti and Al is more than 1.8wt%, the high temperature performance of the weld metal is not good. The bonding capability of Ti, Al and N is strong, and the formed precipitation phases of TiN, AlN and the like are dispersed in crystal grains and on crystal boundaries, so that the strength of the weld metal is improved. The ratio of (Ti + Al)/N is less than 1.8, and the nitrogen fixation effect is not ideal. On the other hand, the ratio of (Ti + Al)/N is higher than 5.0, which is disadvantageous in high-temperature properties of weld metal.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the invention, on the basis of Fe-Ni-Cr-N alloy, elements such as Mo, Mn, V, Ti, Al, Nb, Si, Cu and the like are added, so that the high-temperature performance and the corrosion resistance of the alloy are improved.
(2) The corrosion current density of the alloy of the invention in 3.5 percent NaCl solution is 1.04 multiplied by 10-7～7.65×10-7mA/cm2, the alloy yield strength is 417.41-431.38 MPa, and the tensile strength is 417.41-431.38 MPa in the temperature range of 600-700 DEG CIs 651.13 to 743.36 MPa.
(3) The alloy prepared by the invention has good yield strength, tensile strength and corrosion resistance in the temperature range of 600-700 ℃.
Drawings
FIG. 1 is a structural morphology diagram of the Fe-Ni-Cr-N alloy with excellent high-temperature strength and high-temperature corrosion resistance prepared in example 1; wherein: (a) and (b) is a topography map magnified by different factors.
FIG. 2 is an X-ray diffraction analysis chart of the Fe-Ni-Cr-N alloy excellent in high-temperature strength and high-temperature corrosion resistance prepared in example 1.
Detailed Description
The novel Fe-Ni-Cr-N alloy comprises the following chemical components in percentage by weight: c: 0.02wt% or less, Si: 0.6wt% or less, Mn: 1.0 to 4.0wt%, Cu: 1.5wt% or less, Ni: 26-33 wt%, Cr: 18-26 wt%, Mo: 2-5 wt%, Nb: 2-4 wt%, N: 0.4-0.8 wt%, Al: 0.1-0.5 wt%, Ti: 0.4-1.1 wt%, Ti/Al: 2.0 to 2.5 and Ti + Al: 1.2 to 1.8wt%, (Ti + Al)/N: 1.8-5.0, V: 0.06-0.10 wt%, and the balance Fe and unavoidable impurities.
The preparation method of the novel Fe-Ni-Cr-N alloy comprises the following steps:
(1) calculating and weighing alloy element raw materials according to chemical components, wherein the N element is added in a form of MnN;
(2) mixing alloy element raw materials except MnN, vacuumizing until the vacuum degree is less than 10Pa, and starting to transmit the molten material;
(3) heating and refining after all the raw materials are melted to obtain alloy liquid A;
(4) cooling to the surface of the alloy liquid A to form a film, stopping vacuumizing, and filling inert gas;
(5) feeding electricity to punch a film to melt the film, and then adding MnN to obtain a synthetic uniformly-divided gold solution B;
(6) cooling the alloy liquid B to obtain an alloy ingot;
(7) and carrying out solution treatment on the alloy ingot, and then cooling.
The MnN is powder with the granularity of 100 meshes.
The raw materials of the alloy elements are powder, and the granularity is 100 meshes.
In the step (3), the refining temperature is 1600-.
In the step (4), the surface film formation means a state in which the surface of the alloy liquid starts to solidify to form a semi-solid film and the internal liquid is not solidified.
In the step (4), the inert gas is 96% Ar +4% N2And the vacuum degree in the furnace is 0.08-0.10 MPa.
In the step (5) above, MnN is added to provide all of the N element and part of the Mn element in the alloy.
In the step (7), the solid solution temperature is 1100 ℃, the temperature is kept for 2 hours, and the cooling mode is preferably water cooling.
The invention is further illustrated by the following examples:
example 1
The alloy of the experimental example comprises the following specific components (wt.%): c: 0.02wt%, 0.5wt% N, 32wt% Ni, 0.3wt% Si, 3wt% Mo, 2wt% Nb, 1.0wt% Cu, 18wt% Cr, 0.06wt% V, 1.0wt% Ti, 0.5wt% Al, 3.0wt% Mn, the balance Fe and unavoidable impurities. The preparation process comprises the following steps:
the weight of the powder is calculated according to the calculated proportion of each element by adopting an electronic balance, and the total weight is 50 g. Wherein N is added in the form of MnN. Cleaning the crucible with industrial alcohol, adding other alloy raw materials into the crucible of a vacuum induction furnace, sealing the furnace cover, vacuumizing, starting to transmit electricity to melt the alloy when the vacuum degree in the furnace is less than 10Pa, wherein the power transmission is 35kw, heating to 1610 ℃ after the alloy is completely melted, refining for 4min, stopping vacuumizing, filling 96% Ar +4% N into the crucible, stopping vacuum-pumping, and introducing 96% Ar +4% N2Feeding gas to the furnace with the vacuum degree of 0.10MPa, electrically punching the film, adding MnN into the film, cooling the alloy liquid in the furnace, taking out the alloy liquid, carrying out solid solution treatment on the alloy ingot with the solid solution temperature of 1100 ℃, preserving the heat for 2 hours, taking out the material, and carrying out water cooling.
The structural morphology of the Fe-Ni-Cr-N alloy prepared by the embodiment is shown in figure 1, and the X-ray diffraction analysis chart is shown in figure 2.
The alloy ingot prepared in this example had a high temperature yield strength of 418.51MPa, a tensile strength of 660MPa, and a corrosion current density of 2.63X 10-7mA/cm2。
Example 2
The alloy of the experimental example comprises the following specific components (wt.%): c: 0.02wt%, 0.6wt% N, 30 wt% Ni, 0.3wt% Si, 3wt% Mo, 2wt% Nb, 1.0wt% Cu, 19 wt% Cr, 0.05 wt% V, 1.1wt% Ti, 0.4 wt% Al, 3.5 wt% Mn, the balance Fe and unavoidable impurities. The preparation process comprises the following steps:
the weight of the powder is calculated according to the calculated proportion of each element by adopting an electronic balance, and the total weight is 50 g. Wherein N is added in the form of MnN. Cleaning the crucible with industrial alcohol, adding other alloy raw materials into the crucible of a vacuum induction furnace, sealing the furnace cover, vacuumizing, starting to electrify the material when the vacuum degree in the furnace is less than 9Pa, wherein the power is 35kw, heating to 1600 ℃ after the alloy is completely melted, refining for 3min, stopping vacuumizing until the surface of the alloy liquid is coated, and filling 96% Ar +4% N2Feeding gas to the furnace with the vacuum degree of 0.09MPa, punching a film by electricity, adding MnN into the film, cooling the alloy liquid in the furnace, taking out the alloy liquid, carrying out solid solution treatment on an alloy ingot with the solid solution temperature of 1100 ℃, preserving the heat for 2 hours, taking out the material, and carrying out water cooling.
The alloy ingot prepared in this example had a high temperature yield strength of 418.21MPa, a tensile strength of 661.08MPa, and a corrosion current density of 5.59X 10-7mA/cm2。
Example 3
The alloy of the experimental example comprises the following specific components (wt.%): c: 0.01 wt%, 0.7 wt% N, 29 wt% Ni, 0.2 wt% Si, 4wt% Mo, 3wt% Nb, 1.0wt% Cu, 20 wt% Cr, 0.06wt% V, 0.9 wt% Ti, 0.4 wt% Al, 4.0wt% Mn, the balance Fe and unavoidable impurities. The preparation process comprises the following steps:
the weight of the powder is calculated according to the calculated proportion of each element by adopting an electronic balance, and the total weight is 50 g. Wherein N is added in the form of MnN. Cleaning the crucible with industrial alcohol, adding other alloy materials into the crucible of a vacuum induction furnace, sealing the furnace cover, vacuumizing, and starting to transmit electricity and chemical materials when the vacuum degree in the furnace is less than 9Pa, wherein the power transmission power is 35kw, heating to 1590 deg.C after the alloy is completely melted, refining for 4min, stopping power supply, cooling to alloy liquid surface, forming film, stopping vacuumizing, and charging 96% Ar +4% N2Feeding gas to the furnace with the vacuum degree of 0.08MPa, punching a film by electricity, adding MnN into the film, cooling the alloy liquid in the furnace, taking out the alloy liquid, carrying out solid solution treatment on the alloy ingot with the solid solution temperature of 1100 ℃, preserving the heat for 2 hours, taking out the material, and carrying out water cooling.
The alloy ingot prepared in the example has a high-temperature yield strength of 412.28MPa, a tensile strength of 658.68MPa, and a corrosion current density of 4.65 × 10-7mA/cm2。
Examples 1, 2 and 3 show that the structure of example 1 is fine through metallographic comparison, the addition amount of N is moderate, a large amount of pores are not found, a plurality of fine particles are found on grain boundaries, and the fine particles are (Ti, Nb, Al) N through EDAX and XRD analysis, play a role in pinning on the grain boundaries and refine grains. In the examples 2 and 3, a large number of micropores are found in the metallographic phase, so that the mechanical property of the material is reduced.
Nitrogen and chromium combine to form nitride (Cr)2N) relative to formation of Cr23C6Compounds, which cause much lower losses for Cr, N reduces the extent of the chromium-depleted zone; on the other hand, the corrosion resistance of N is 20 times of that of Cr, and the segregation of N element on a grain boundary makes up the loss of Cr, so that the occurrence of material corrosion is effectively inhibited.
Therefore, in example 1, the content of N element is moderate, and the high temperature tensile strength and yield strength and corrosion resistance of the material are the best.
COMPARATIVE EXAMPLE 1 (Nickel-based alloy)
The difference from the embodiment 1 is that:
the alloy composition is (wt.%): c: 0.02wt%, 0.001 wt% N, 61.6 wt% Ni, 0.55 wt% Si, 8.7 wt% Mo, 3.7 wt% Nb, 22 wt% Cr, 0.4 wt% Ti, 0.1 wt% Al, 1.4 wt% Mn, and the balance Fe and unavoidable impurities.
The alloy ingot prepared by the embodiment has the high-temperature yield strength of 428.78MPa, the tensile strength of 680.98MPa and the corrosion current density of 6.51 multiplied by 10-7mA/cm2。
COMPARATIVE EXAMPLE 2(316L alloy)
The difference from the embodiment 1 is that:
the alloy composition is (wt.%): c: 0.01 wt%, 12.0 wt% Ni, 0.37 wt% Si, 2.5 wt% Mo, 17 wt% Cr, 1.8wt% Mn, the balance Fe and unavoidable impurities.
The alloy ingot prepared by the embodiment has the high-temperature yield strength of 132.52MPa, the tensile strength of 450.67MPa and the corrosion current density of 1.80 multiplied by 10-3mA/cm2。
Claims (10)
1. The Fe-Ni-Cr-N alloy is characterized by comprising the following components in percentage by weight: c: 0.02wt% or less, Si: 0.6wt% or less, Mn: 1.0 to 4.0wt%, Cu: 1.5wt% or less, Ni: 26-33 wt%, Cr: 18-26 wt%, Mo: 2-5 wt%, Nb: 2-4 wt%, N: 0.4-0.8 wt%, Al: 0.1-0.5 wt%, Ti: 0.4-1.1 wt%, Ti/Al: 2.0 to 2.5 and Ti + Al: 1.2 to 1.8wt%, (Ti + Al)/N: 1.8-5.0, V: 0.06-0.10 wt%, and the balance Fe and unavoidable impurities.
2. The method of claim 1, comprising the steps of:
(1) calculating and weighing alloy element raw materials according to chemical components, wherein the N element is added in a form of MnN;
(2) mixing alloy element raw materials except MnN, vacuumizing until the vacuum degree is less than 10Pa, and starting to transmit the molten material;
(3) heating and refining after all the raw materials are melted to obtain alloy liquid A;
(4) cooling to the surface of the alloy liquid A to form a film, stopping vacuumizing, and filling inert gas;
(5) feeding electricity to punch a film to melt the film, and then adding MnN to obtain alloy liquid B with uniform components;
(6) cooling the alloy liquid B to obtain an alloy ingot;
(7) and carrying out solution treatment on the alloy ingot, and then cooling.
3. The method of claim 2, wherein the MnN is a powder having a particle size of 100 mesh.
4. The method of claim 2, wherein the raw materials of the alloying elements are powders with a particle size of 100 mesh.
5. The method as claimed in claim 2, wherein the refining temperature in step (3) is 1600-1650 ℃, and the refining time is 2-4 min.
6. The method of claim 2, wherein in the step (4), the surface filming means that a semi-solid film is formed on the surface of the molten alloy and the internal liquid is not solidified.
7. The method of claim 2, wherein the inert gas is 96% Ar +4% N in the step (4)2And the vacuum degree in the furnace is 0.08-0.10 MPa.
8. The method of claim 2, wherein the MnN added in the step (5) is used to provide all N elements and part of Mn elements in the alloy.
9. The method of claim 2, wherein in the step (7), the solution temperature is 1100 ℃, the temperature is maintained for 2 hours, and the cooling mode is water cooling.
10. The Fe-Ni-Cr-N alloy is characterized by comprising the following components in percentage by weight: c: 0.02wt%, 0.5wt% N, 32wt% Ni, 0.3wt% Si, 3wt% Mo, 2wt% Nb, 1.0wt% Cu, 18wt% Cr, 0.06wt% V, 1.0wt% Ti, 0.5wt% Al, 3.0wt% Mn, the balance Fe and unavoidable impurities.
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