CN116694978B - Low-cost heat-resistant stainless medium-entropy alloy and preparation method thereof - Google Patents
Low-cost heat-resistant stainless medium-entropy alloy and preparation method thereof Download PDFInfo
- Publication number
- CN116694978B CN116694978B CN202310981506.4A CN202310981506A CN116694978B CN 116694978 B CN116694978 B CN 116694978B CN 202310981506 A CN202310981506 A CN 202310981506A CN 116694978 B CN116694978 B CN 116694978B
- Authority
- CN
- China
- Prior art keywords
- entropy alloy
- medium
- alloy
- low
- smelting
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000956 alloy Substances 0.000 title claims abstract description 155
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 153
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 45
- 229910052742 iron Inorganic materials 0.000 claims abstract description 20
- 238000003723 Smelting Methods 0.000 claims description 47
- 229910052751 metal Inorganic materials 0.000 claims description 34
- 239000002184 metal Substances 0.000 claims description 34
- 238000010438 heat treatment Methods 0.000 claims description 22
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- 238000005096 rolling process Methods 0.000 claims description 20
- 238000000137 annealing Methods 0.000 claims description 19
- 238000000265 homogenisation Methods 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 10
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 abstract description 29
- 230000003647 oxidation Effects 0.000 abstract description 18
- 238000007254 oxidation reaction Methods 0.000 abstract description 18
- 238000010248 power generation Methods 0.000 abstract description 8
- 229910000963 austenitic stainless steel Inorganic materials 0.000 abstract description 7
- 238000005260 corrosion Methods 0.000 abstract description 7
- 230000007797 corrosion Effects 0.000 abstract description 7
- 239000011159 matrix material Substances 0.000 abstract description 4
- 239000003208 petroleum Substances 0.000 abstract description 4
- 238000001556 precipitation Methods 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 35
- 230000000052 comparative effect Effects 0.000 description 23
- 238000002844 melting Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- 238000005266 casting Methods 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 230000004584 weight gain Effects 0.000 description 5
- 235000019786 weight gain Nutrition 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229910000604 Ferrochrome Inorganic materials 0.000 description 1
- 229910000943 NiAl Inorganic materials 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention belongs to the technical field of medium-entropy alloy, and particularly relates to a low-cost heat-resistant medium-entropy alloy and a preparation method thereof. The low-cost heat-resistant medium-entropy alloy has a chemical formula of Fe y Cr y Ni y Al x Si x Where x=0.1 or 0.2, 2x+3y=1. The invention carries out the high concentration of main elements on austenitic stainless steel, designs three main components of Fe, cr and Ni in equal molar ratio, realizes the improvement of matrix strength, introduces Si and Al components, promotes the precipitation of sigma phase and BCC nano phase while improving the oxidation resistance and corrosion resistance of the alloy, and ensures that the alloy is highThe composite material has excellent strength and plasticity under low temperature, and simultaneously has high oxidation resistance and high corrosion resistance, and is suitable for the industrial energy fields of civil nuclear power, thermal power generation, gas power generation, chemical petroleum and the like.
Description
Technical Field
The invention belongs to the technical field of medium-entropy alloy, and particularly relates to a low-cost heat-resistant stainless medium-entropy alloy and a preparation method thereof.
Background
The heat-resistant stainless steel is used as a key structural material for nuclear power and thermal power pipelines, and the high-temperature creep strength and the structural stability of the heat-resistant stainless steel are key to ensuring the high-temperature service of the heat-resistant stainless steel. Fe. Cr and Ni are main elements of austenitic stainless steel, and the high Cr content not only can improve the corrosion resistance of the alloy, but also can obviously improve the high-temperature oxidation resistance of the alloy, for example, cr formed on the surface of the stainless steel below 873K 2 O 3 The oxide passivation film can well play an antioxidant role. However, cr in an environment above 873K, especially in the presence of water vapor 2 O 3 Is liable to form unstable or volatile hydroxide with water vapor, seriously deteriorating Cr 2 O 3 The stability of the layers, thereby restricting the use of conventional stainless steel in many high temperature environments.
At present, in the industrial energy fields of civil nuclear power, thermal power generation, gas power generation, chemical petroleum and the like, high-temperature-resistant 873-973K stainless alloy materials are needed, the conventional austenitic stainless steel can not meet the requirements of the fields, the performance improvement of the heat-resistant stainless steel is developed towards the research direction of high alloying, and the concept of medium-entropy alloy is put forward to exactly meet the thought of high alloying. In addition, austenitic stainless steel is low in general strength, particularly yield strength, which is also a main factor limiting the application of the austenitic stainless steel, and introduction of the concept of medium entropy alloy can improve the lattice distortion and the short-range order degree of the alloy, thereby playing an important role in improving the comprehensive performance.
Disclosure of Invention
The purpose of the invention is that: the low-cost heat-resistant stainless medium-entropy alloy has excellent strength and plasticity under high and low temperature conditions, and simultaneously has high oxidation resistance and high corrosion resistance, and is suitable for the industrial energy fields of civil nuclear power, thermal power generation, gas power generation, chemical petroleum and the like; the invention also provides a preparation method, which has reasonable process and is simple and easy to implement.
The chemical formula of the low-cost heat-resistant stainless medium entropy alloy is Fe y Cr y Ni y Al x Si x Where x=0.1 or 0.2, 2x+3y=1.
According to the invention, a proper amount of Al element and Si element are added on the basis of FeCrNi and other atomic entropy alloy to form the heat-resistant entropy alloy, wherein Fe, cr and Ni adopt an equiatomic molar ratio and are of a single-phase face-centered cubic crystal structure, and the performance is stable; al (Al) 2 O 3 Growth rate ratio Cr of (2) 2 O 3 Is 1-2 orders of magnitude lower and Al 2 O 3 The high-temperature heat-resistant material has higher thermodynamic stability and better protection effect in a high-temperature working environment; si to Cr 2 O 3 Has a certain promoting effect on the formation of Si, and the affinity of Si to O is between Cr and Al, and a proper amount of Si can promote Al 2 O 3 Film formation and can reduce the distance of the NiAl depletion region between the oxide layer and the substrate, thereby extending the oxidation resistance time of the medium entropy alloy; in addition, the mechanical properties of the medium-entropy alloy can be obviously improved after the solid solution strengthening of the Al element and the Si element is obvious.
The preparation method of the low-cost heat-resistant stainless medium entropy alloy comprises the following steps:
and (3) mixing and smelting the Fe, cr, ni, al, si metal simple substances to obtain a medium entropy alloy plate, and then sequentially carrying out homogenization heat treatment, rolling and annealing treatment to obtain the low-cost heat-resistant stainless medium entropy alloy.
Preferably, the Fe, cr, ni, al, si elemental metal requires cleaning of the surface oxides prior to smelting.
Preferably, the purity of the Fe, cr, ni, al, si metal simple substance is more than or equal to 99.9 percent.
Preferably, in the metal simple substance raw material, the mole percentages of Al and Si are 10% or 20%, and the mole ratios of Fe, cr and Ni are equal.
Preferably, in the smelting process, a high-vacuum arc melting furnace is adopted, a Fe, cr, ni, al, si metal simple substance is smelted for 5-8 times under the protection of argon, an alloy button ingot is manufactured, and the alloy button ingot is sucked and cast into a copper mold to obtain the medium-entropy alloy plate.
Further preferably, the medium entropy alloy plate has dimensions of 2mm×10mm×100mm.
Preferably, the temperature of the homogenizing heat treatment is 1050-1150 ℃ and the time is 4-6 h.
Preferably, the rolling temperature is room temperature, and the thickness of the rolled stainless medium entropy alloy plate is reduced by 65-75%.
Preferably, the annealing treatment is performed at a temperature of 850-950 ℃ for 0.5-2 hours.
The low-cost heat-resistant stainless intermediate entropy alloy prepared by the invention has the quasi-static tensile yield strength of 650-860 MPa at 25 ℃, the ultimate tensile strength of 925-1350 MPa, and the oxidation weight gain after oxidation for 72h at 900 ℃ of 0.931-1.782 mg/cm 2 。
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention carries out the high concentration of main elements on austenitic stainless steel, designs three main components of Fe, cr and Ni in equal molar ratio, realizes the improvement of matrix strength, introduces Si and Al components, promotes the precipitation of sigma phase and BCC nano phase while improving the oxidation resistance and corrosion resistance of the alloy, ensures that the alloy shows excellent strength and plasticity under the conditions of high and low temperature, and Al 2 O 3 The protective film has better protective effect in the water vapor environment with the temperature of above 600 ℃, and Si is used for Cr 2 O 3 And Al 2 O 3 The formation of the passivation film has a certain promoting effect;
(2) The medium-entropy alloy of the invention precipitates two second phases in a face-centered cubic (FCC) matrix after homogenizing heat treatment, which are sigma phase with the size of 250nm and BCC phase with the size of 70nm, and the alloy shows excellent yield strength and plasticity under the condition of high and low temperature through the synergistic effect of the two second phases, and simultaneously has high oxidation resistance and high corrosion resistance, which is superior to the traditional heat-resistant steel, and is suitable for the industrial energy fields of civil nuclear power, thermal power generation, gas power generation, chemical petroleum and the like;
(3) Compared with the traditional high-entropy alloy, the medium-entropy alloy has fewer elements, does not contain noble metal elements such as Co, ti, V and the like, and has simpler preparation process and lower cost.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of the medium entropy alloys prepared in examples 1-2 and comparative example 1 of the present invention;
FIG. 2 is a transmission electron microscope (SEM) image of the medium entropy alloy prepared according to example 1 of the present invention;
FIG. 3 is a Transmission Electron Microscope (TEM) image of the medium entropy alloy prepared in example 1 of the present invention;
FIG. 4 is a graph showing the quasi-static tensile engineering stress-strain curves at 25℃for the intermediate entropy alloys prepared in examples 1-2 and comparative example 1 according to the present invention;
FIG. 5 is a graph showing the stress-strain curves of quasi-static tensile engineering at-196℃and 25℃and 600℃respectively for the intermediate-entropy alloy prepared in example 1 of the present invention;
FIG. 6 is a graph showing the quasi-static tensile engineering stress-strain curves at 25℃for the intermediate entropy alloys prepared in examples 1-2 and comparative examples 2-3 of the present invention;
FIG. 7 is a graph showing the comparison of the surface morphology of the intermediate entropy alloys prepared in examples 1-2 and comparative example 1 of the present invention after oxidation at 900℃for 72 hours;
in fig. 7, a1, b1 and c1 are the surface morphologies before oxidation of the intermediate entropy alloys prepared in comparative example 1, example 1 and example 2, respectively; a2, b2 and c2 are the surface morphologies of the intermediate entropy alloys prepared in comparative example 1, example 1 and example 2 after oxidation at 900 ℃ for 72 hours.
Detailed Description
The present invention is further illustrated by the following examples, which are given by way of illustration only and are not intended to limit the scope of the invention.
The metal raw material index used in the examples is shown in table 1.
TABLE 1
| Raw materials | Ni | Cr | Fe | Si | Al |
| Purity (%) | ≥99.9 | ≥99.9 | ≥99.9 | ≥99.9 | ≥99.9 |
| Density (g/cm 3) | 8.90 | 7.20 | 7.86 | 2.32 | 2.7 |
| Melting point (. Degree. C.) | 1453 | 1855 | 1539 | 1420 | 660 |
Example 1
An intermediate entropy alloy with a chemical formula of Fe y Cr y Ni y Al x Si x Wherein x=0.1, 2x+3y=1, the preparation method is as follows:
(1) Preparing raw materials: the adopted alloy smelting raw material is Ni, cr, fe, al, si metal simple substance, and the alloy smelting raw material is accurately weighed and proportioned according to the mole percentage of Al and Si of 10 percent and the mole ratio of Fe, cr and Ni of equal mole ratio for use in smelting and preparing alloy;
(2) Purifying metal simple substance: purifying Ni, cr, fe, al, si metal simple substance surface oxide;
(3) Smelting: smelting raw materials for 5 times by adopting a high-vacuum arc melting furnace under the protection of 99.99% high-purity argon, preparing alloy button ingots, and carrying out suction casting in a copper mold to obtain a medium-entropy alloy plate with the thickness of 2mm multiplied by 10mm multiplied by 100 mm;
(4) Homogenizing heat treatment: preserving the heat of the medium-entropy alloy plate at 1100 ℃ for 5 hours, and carrying out homogenization heat treatment;
(5) Rolling: rolling the homogenized intermediate entropy alloy plate at room temperature until the thickness is reduced by 70%;
(6) Annealing: and (3) preserving the heat of the rolled intermediate entropy alloy plate for 1h at 900 ℃ and carrying out annealing treatment to obtain the low-cost heat-resistant intermediate entropy alloy.
Example 2
An intermediate entropy alloy with a chemical formula of Fe y Cr y Ni y Al x Si x Wherein x=0.2, 2x+3y=1, the preparation method is as follows:
(1) Preparing raw materials: the adopted alloy smelting raw material is Ni, cr, fe, al, si metal simple substance, and the alloy smelting raw material is accurately weighed and proportioned according to the mole percentage of Al and Si of 20 percent and the mole ratio of Fe, cr and Ni of equal mole ratio for use in smelting and preparing alloy;
(2) Purifying metal simple substance: purifying Ni, cr, fe, al, si metal simple substance surface oxide;
(3) Smelting: smelting raw materials for 5 times by adopting a high-vacuum arc melting furnace under the protection of 99.99% high-purity argon, preparing alloy button ingots, and carrying out suction casting in a copper mold to obtain a medium-entropy alloy plate with the thickness of 2mm multiplied by 10mm multiplied by 100 mm;
(4) Homogenizing heat treatment: preserving the heat of the medium-entropy alloy plate at 1100 ℃ for 5 hours, and carrying out homogenization heat treatment;
(5) Rolling: rolling the homogenized intermediate entropy alloy plate at room temperature until the thickness is reduced by 70%;
(6) Annealing: and (3) preserving the heat of the rolled intermediate entropy alloy plate for 1h at 900 ℃ and carrying out annealing treatment to obtain the low-cost heat-resistant intermediate entropy alloy.
Example 3
An intermediate entropy alloy with a chemical formula of Fe y Cr y Ni y Al x Si x Wherein x=0.1, 2x+3y=1, the preparation method is as follows:
(1) Preparing raw materials: the adopted alloy smelting raw material is Ni, cr, fe, al, si metal simple substance, and the alloy smelting raw material is accurately weighed and proportioned according to the mole percentage of Al and Si of 10 percent and the mole ratio of Fe, cr and Ni of equal mole ratio for use in smelting and preparing alloy;
(2) Purifying metal simple substance: purifying Ni, cr, fe, al, si metal simple substance surface oxide;
(3) Smelting: smelting raw materials for 8 times by adopting a high-vacuum arc melting furnace under the protection of 99.99% high-purity argon, preparing alloy button ingots, and carrying out suction casting in a copper mold to obtain a medium-entropy alloy plate with the thickness of 2mm multiplied by 10mm multiplied by 100 mm;
(4) Homogenizing heat treatment: preserving the temperature of the medium-entropy alloy plate at 1050 ℃ for 6 hours, and carrying out homogenization heat treatment;
(5) Rolling: rolling the homogenized intermediate entropy alloy plate at room temperature until the thickness is reduced by 65%;
(6) Annealing: and (3) preserving the heat of the rolled intermediate entropy alloy plate for 2 hours at the temperature of 850 ℃ and carrying out annealing treatment to obtain the low-cost heat-resistant intermediate entropy alloy.
Example 4
An intermediate entropy alloy with a chemical formula of Fe y Cr y Ni y Al x Si x Wherein x=0.2, 2x+3y=1, the preparation method is as follows:
(1) Preparing raw materials: the adopted alloy smelting raw material is Ni, cr, fe, al, si metal simple substance, and the alloy smelting raw material is accurately weighed and proportioned according to the mole percentage of Al and Si of 20 percent and the mole ratio of Fe, cr and Ni of equal mole ratio for use in smelting and preparing alloy;
(2) Purifying metal simple substance: purifying Ni, cr, fe, al, si metal simple substance surface oxide;
(3) Smelting: smelting raw materials for 6 times by adopting a high-vacuum arc melting furnace under the protection of 99.99% high-purity argon, preparing alloy button ingots, and carrying out suction casting in a copper mold to obtain a medium-entropy alloy plate with the thickness of 2mm multiplied by 10mm multiplied by 100 mm;
(4) Homogenizing heat treatment: preserving the temperature of the medium-entropy alloy plate at 1150 ℃ for 4 hours, and carrying out homogenization heat treatment;
(5) Rolling: rolling the homogenized intermediate entropy alloy plate at room temperature until the thickness is reduced by 75%;
(6) Annealing: and (3) preserving the heat of the rolled intermediate entropy alloy plate for 0.5h at the temperature of 950 ℃ and carrying out annealing treatment to obtain the low-cost heat-resistant intermediate entropy alloy.
Comparative example 1
An intermediate entropy alloy with a chemical formula of Fe y Cr y Ni y Wherein 3y=1, the preparation method is as follows:
(1) Preparing raw materials: the adopted alloy smelting raw materials are Ni, cr and Fe metal simple substances, and the alloy smelting raw materials are accurately weighed and proportioned according to the equimolar ratio of Fe, cr and Ni for use in smelting preparation of alloy;
(2) Purifying metal simple substance: purifying oxides on the surfaces of simple metals of Ni, cr and Fe;
(3) Smelting: smelting raw materials for 5 times by adopting a high-vacuum arc melting furnace under the protection of 99.99% high-purity argon, preparing alloy button ingots, and carrying out suction casting in a copper mold to obtain a medium-entropy alloy plate with the thickness of 2mm multiplied by 10mm multiplied by 100 mm;
(4) Homogenizing heat treatment: preserving the heat of the medium-entropy alloy plate at 1100 ℃ for 5 hours, and carrying out homogenization heat treatment;
(5) Rolling: rolling the homogenized intermediate entropy alloy plate at room temperature until the thickness is reduced by 70%;
(6) Annealing: and (3) preserving the heat of the rolled intermediate entropy alloy plate for 1h at 900 ℃ and carrying out annealing treatment to obtain the low-cost heat-resistant intermediate entropy alloy.
Comparative example 2
An intermediate entropy alloy with a chemical formula of Fe y Cr y Ni y Si x Wherein x=0.1 and x+3y=1, the preparation method is as follows:
(1) Preparing raw materials: the adopted alloy smelting raw material is Ni, cr, fe, si metal simple substance, and the alloy smelting raw material is accurately weighed and proportioned according to the mole percentage of Si of 10 percent and the mole ratio of Fe, cr and Ni of equal mole ratio for use in smelting and preparing alloy;
(2) Purifying metal simple substance: purifying Ni, cr, fe, si metal simple substance surface oxide;
(3) Smelting: smelting raw materials for 5 times by adopting a high-vacuum arc melting furnace under the protection of 99.99% high-purity argon, preparing alloy button ingots, and carrying out suction casting in a copper mold to obtain a medium-entropy alloy plate with the thickness of 2mm multiplied by 10mm multiplied by 100 mm;
(4) Homogenizing heat treatment: preserving the heat of the medium-entropy alloy plate at 1100 ℃ for 5 hours, and carrying out homogenization heat treatment;
(5) Rolling: rolling the homogenized intermediate entropy alloy plate at room temperature until the thickness is reduced by 70%;
(6) Annealing: and (3) preserving the heat of the rolled intermediate entropy alloy plate for 1h at 900 ℃ and carrying out annealing treatment to obtain the low-cost heat-resistant intermediate entropy alloy.
Comparative example 3
An intermediate entropy alloy with a chemical formula of Fe y Cr y Ni y Si x Wherein x=0.2 and x+3y=1, the preparation method is as follows:
(1) Preparing raw materials: the adopted alloy smelting raw material is Ni, cr, fe, si metal simple substance, and the alloy smelting raw material is accurately weighed and proportioned according to the mole percentage of Si of 20 percent and the mole ratio of Fe, cr and Ni of equal mole ratio for use in smelting and preparing alloy;
(2) Purifying metal simple substance: purifying Ni, cr, fe, si metal simple substance surface oxide;
(3) Smelting: smelting raw materials for 5 times by adopting a high-vacuum arc melting furnace under the protection of 99.99% high-purity argon, preparing alloy button ingots, and carrying out suction casting in a copper mold to obtain a medium-entropy alloy plate with the thickness of 2mm multiplied by 10mm multiplied by 100 mm;
(4) Homogenizing heat treatment: preserving the heat of the medium-entropy alloy plate at 1100 ℃ for 5 hours, and carrying out homogenization heat treatment;
(5) Rolling: rolling the homogenized intermediate entropy alloy plate at room temperature until the thickness is reduced by 70%;
(6) Annealing: and (3) preserving the heat of the rolled intermediate entropy alloy plate for 1h at 900 ℃ and carrying out annealing treatment to obtain the low-cost heat-resistant intermediate entropy alloy.
Comparative example 4
An intermediate entropy alloy with a chemical formula of Fe y Cr y Ni y Al x Si x Wherein x=0.3, 2x+3y=1, the preparation method is as follows:
(1) Preparing raw materials: the adopted alloy smelting raw material is Ni, cr, fe, al, si metal simple substance, and the alloy smelting raw material is accurately weighed and proportioned according to the mole percentage of Al and Si of 30 percent and the mole ratio of Fe, cr and Ni of equal mole ratio for use in smelting and preparing alloy;
(2) Purifying metal simple substance: purifying Ni, cr, fe, al, si metal simple substance surface oxide;
(3) Smelting: smelting raw materials for 5 times by adopting a high-vacuum arc melting furnace under the protection of 99.99% high-purity argon, preparing alloy button ingots, and carrying out suction casting in a copper mold to obtain a medium-entropy alloy plate with the thickness of 2mm multiplied by 10mm multiplied by 100 mm;
(4) Homogenizing heat treatment: preserving the heat of the medium-entropy alloy plate at 1100 ℃ for 5 hours, and carrying out homogenization heat treatment;
(5) Rolling: the medium entropy alloy plate after homogenization heat treatment is rolled at room temperature, and the material is obviously embrittled due to the large addition of two elements of Al and Si, so that the medium entropy alloy plate is broken in the rolling process.
The medium entropy alloys prepared in examples and comparative examples were characterized and tested for performance as follows:
(1) The medium entropy alloys of examples 1-2 and comparative example 1 were subjected to X-ray diffraction (XRD) scanning at 20℃to 110℃and at a scanning speed of 5℃per minute, and the results are shown in FIG. 1.
As can be seen from fig. 1, the intermediate entropy alloy materials of examples 1-2 have FCC, σ phases and a small amount of BCC phases, and as the addition amount of Al and Si increases, the volume fractions of the two precipitated phases increase significantly, so that the yield strength and the fracture strength of the materials under high and low temperature conditions are improved.
(2) Coarse polishing the surface of the medium entropy alloy with 600, 800, 1000, 1500, 2000 and 3000 mesh metallographic sand paper, and further with HNO in volume ratio 3 :CH 4 The medium entropy alloy of example 1 was electropolished with o=1:4 electrolyte and then observed using Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) microstructure, the results of which are shown in fig. 2-3.
FIG. 3 is a Transmission Electron Microscope (TEM) image, from which it can be seen that there are significant differences in the size and morphology of the two precipitates; the sigma phase is a lath-like morphology of about 200nm in size and the BCC phase is a spherical morphology of about 70nm in size.
(3) Cutting the intermediate entropy alloys of examples 1-2 and comparative examples 1-3 into dog-bone shaped tensile samples with gauge length of 0.6mm×4mm×10mm by using a precision wire cutting machine, and performing quasi-static tensile test on the tensile samples by using an INSTRON mechanical experiment machine, wherein the strain rates are 1×10 -3 And/s, drawing a stress-strain curve of static stretching by using Origin software, wherein the stress-strain test results are shown in fig. 4-6 and table 2.
FIG. 4 is a graph showing the quasi-static tensile engineering stress-strain curves at 25deg.C for the intermediate entropy alloys prepared in examples 1-2 and comparative example 1, wherein the strength of the intermediate entropy alloy is increased as the content of Al and Si increases, as shown in the graph, feCrNiAl 0.2 Si 0.2 The yield strength and the ultimate tensile strength of the steel are respectively improved to 1.2GPa and 1.35GPa, and FeCrNiAl 0.1 Si 0.1 The ultimate tensile strength of (2) reaches 900MPa, which is improved by 30 percent compared with the FeCrNi medium entropy alloy, feCrNiAl 0.1 Si 0.1 The plasticity of (c) was kept at 20%.
FIG. 5 is a graph showing the quasi-static tensile engineering stress strain curves of the intermediate-entropy alloy prepared in example 1 of the present invention at-196℃and 25℃and 600℃respectively, wherein FeCr is reduced to liquid nitrogen temperature (-196 ℃) as the temperature is loweredNiAl 0.1 Si 0.1 The yield strength and the ultimate tensile strength of the steel are obviously improved to 1.1GPa and 1.2GPa respectively, and compared with the room temperature yield strength, the steel is improved by 65 percent and 33 percent, and the plasticity is kept by 18 percent; when the temperature reaches 600 ℃, feCrNiAl 0.1 Si 0.1 The yield strength of the steel is 650MPa, the ultimate tensile strength is 800MPa, no obvious softening occurs at the initial stage of deformation, and the plasticity is basically kept at about 18 percent; therefore, the material has good service performance at the temperature of between 196 ℃ below zero and 600 ℃ and can meet the use requirement of high and low temperature environments.
Fig. 6 shows quasi-static tensile engineering stress-strain curves at 25 ℃ of the intermediate-entropy alloys prepared in examples 1-2 and comparative examples 2-3 according to the present invention, and it can be seen from the graph that the yield strength and the breaking strength of the intermediate-entropy alloy corresponding to the simple addition of trace element Si are significantly lower than those of the present invention.
(4) The intermediate entropy alloys prepared in examples 1-2 and comparative example 1 were oxidized at 900 ℃ for 72 hours, and the surface morphology and the oxidation weight gain of the intermediate entropy alloys before and after oxidation were recorded, as shown in fig. 7 and table 2.
As can be seen from fig. 7, the oxidation resistance of the medium entropy alloy is significantly improved with the increase of the Al and Si contents.
Table 2 shows the results of stress strain tests at 25℃for the intermediate entropy alloys prepared in examples 1-2 and comparative examples 1-3, and the results of oxidation weight gain tests after oxidation at 900℃for 72 hours for the intermediate entropy alloys prepared in examples 1-2 and comparative example 1.
TABLE 2
| Project | Example 1 | Example 2 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Yield strength (MPa) | 650 | 860 | 400 | 450 | 500 |
| Tensile strength (MPa) | 900 | 1125 | 675 | 710 | 850 |
| Plasticity (%) | 20 | 10 | 42.5 | 35 | 25 |
| Oxidative weight gain (%) | 0.136 | 0.127 | 0.525 | / | / |
| Oxidative weight gain (mg/cm 2) | 1.782 | 0.931 | 3.392 | / | / |
As can be seen from Table 2, the invention introduces Si and Al components into the austenitic stainless steel main body, separates out two second phases in the face-centered cubic (FCC) matrix, which are sigma phase with the size of 250nm to 70nm and BCC phase with the size of 70nm, and ensures that the alloy shows excellent yield strength and plasticity and simultaneously has high oxidation resistance and high corrosion resistance through the synergistic effect of the two second phases; comparative example 1, without addition of Si, al, the resulting mid-entropy alloy has no sigma and BCC phases, and has lower yield strength and ultimate tensile strength; comparative examples 2-3 added only Si, without Al, where the entropy alloy yield strength and fracture strength were also significantly lower than the present invention.
Claims (4)
1. A low cost heat resistant stainless medium entropy alloy characterized by: the chemical formula is Fe y Cr y Ni y Al x Si x Where x=0.1, 2x+3y=1;
the preparation method of the low-cost heat-resistant stainless medium entropy alloy comprises the following steps:
mixing and smelting Fe, cr, ni, al, si metal simple substances to obtain a stainless intermediate entropy alloy plate, and then sequentially carrying out homogenization heat treatment, rolling and annealing treatment to obtain the low-cost heat-resistant stainless intermediate entropy alloy;
the temperature of the homogenizing heat treatment is 1050-1150 ℃ and the time is 4-6 hours;
the rolling temperature is room temperature, and the thickness of the rolled stainless medium entropy alloy plate is reduced by 65-75%;
the annealing treatment temperature is 850-950 ℃ and the annealing treatment time is 0.5-2 h.
2. The low cost heat resistant stainless medium entropy alloy according to claim 1, wherein: fe. Cr, ni, al, si elemental metal requires surface oxide cleaning prior to smelting.
3. The low cost heat resistant stainless medium entropy alloy according to claim 1, wherein: fe. The purity of the Cr, ni, al, si metal simple substance is more than or equal to 99.9 percent.
4. The low cost heat resistant stainless medium entropy alloy according to claim 1, wherein: and in the smelting process, a high-vacuum arc smelting furnace is adopted, a Fe, cr, ni, al, si metal simple substance is smelted for 5-8 times under the protection of argon, an alloy button ingot is manufactured, and the alloy button ingot is sucked and cast into a copper mold to obtain the stainless intermediate entropy alloy plate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310981506.4A CN116694978B (en) | 2023-08-07 | 2023-08-07 | Low-cost heat-resistant stainless medium-entropy alloy and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310981506.4A CN116694978B (en) | 2023-08-07 | 2023-08-07 | Low-cost heat-resistant stainless medium-entropy alloy and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116694978A CN116694978A (en) | 2023-09-05 |
| CN116694978B true CN116694978B (en) | 2023-11-07 |
Family
ID=87841758
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310981506.4A Active CN116694978B (en) | 2023-08-07 | 2023-08-07 | Low-cost heat-resistant stainless medium-entropy alloy and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116694978B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116970824B (en) * | 2023-09-25 | 2023-12-12 | 太原理工大学 | Entropy alloy in trans-scale body-centered cubic precipitated phase mosaic structure and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5779153A (en) * | 1980-10-31 | 1982-05-18 | Nippon Steel Corp | Burning resistant iron alloy for oxygen duct |
| CN113684425A (en) * | 2021-08-31 | 2021-11-23 | 西北工业大学 | High-performance iron-based medium-entropy alloy and heat treatment method thereof |
| CN113862544A (en) * | 2021-12-03 | 2021-12-31 | 西安稀有金属材料研究院有限公司 | High-entropy alloy wave-absorbing material and preparation method thereof |
| CN115233077A (en) * | 2022-09-19 | 2022-10-25 | 太原理工大学 | CoCrNi-based medium entropy alloy with high aluminum content and high titanium content and strengthened nano coherent precipitation and preparation method thereof |
-
2023
- 2023-08-07 CN CN202310981506.4A patent/CN116694978B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5779153A (en) * | 1980-10-31 | 1982-05-18 | Nippon Steel Corp | Burning resistant iron alloy for oxygen duct |
| CN113684425A (en) * | 2021-08-31 | 2021-11-23 | 西北工业大学 | High-performance iron-based medium-entropy alloy and heat treatment method thereof |
| CN113862544A (en) * | 2021-12-03 | 2021-12-31 | 西安稀有金属材料研究院有限公司 | High-entropy alloy wave-absorbing material and preparation method thereof |
| CN115233077A (en) * | 2022-09-19 | 2022-10-25 | 太原理工大学 | CoCrNi-based medium entropy alloy with high aluminum content and high titanium content and strengthened nano coherent precipitation and preparation method thereof |
Non-Patent Citations (8)
| Title |
|---|
| A Co-free Cr-Fe-Ni-Al-Si high entropy alloy with outstanding corrosion resistance and high hardness fabricated by laser surface melting;Chen Chen、Shuhan Yuan等;Materials Letters;第314卷;1-5 * |
| A novel Fe-rich Fe-Cr-Ni-Si-Al high-entropy alloy with low-cost and outstanding as-cast mechanical properties;Nuo Lei , Guangzeng Zhang等;Materials Letters;第344卷;1-4 * |
| AlxCrFeNi medium entropy alloys with high damping capacity;Hongding Wang、Wei Zhang等;Journal of Alloys and Compounds;第876卷;1-8 * |
| Azmi Erdogan、Sefa Emre Sunbul等.Microstructure, wear and oxidation behavior of AlCrFeNiX (X = Cu, Si, Co) high entropy alloys produced by powder metallurgy.Vacuum.2021,第187卷1-11. * |
| Effect of Aluminum on the Friction and Wear Behavior of Al xCrFeNi Medium-Entropy Alloys;Ling Qiao, Raju V. Ramanujan等;Advanced Engineering Materials;第24卷;1-10 * |
| Extra Strengthening and Work Hardening in Novel Precipitation-Hardened FeCrNiSix Medium-Entropy Alloys;Tuanwei Zhang、Zhihua Wang等;Advanced Engineering Materials;第23卷;1-7 * |
| Microstructure, wear and oxidation behavior of AlCrFeNiX (X = Cu, Si, Co) high entropy alloys produced by powder metallurgy;Azmi Erdogan、Sefa Emre Sunbul等;Vacuum;第187卷;1-11 * |
| Tuning Cr-rich nanoprecipitation and heterogeneous structure in equiatomic CrFeNi medium-entropy stainless alloys;Kai Wang、Tuan-wei Zhang等;Journal of Iron and Steel Research International;1-9 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116694978A (en) | 2023-09-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100460346B1 (en) | Super duplex stainless steel with a suppressed formation of intermetallic phases and having an excellent corrosion resistance, embrittlement resistance, castability and hot workability | |
| CN115141984B (en) | High-entropy austenitic stainless steel and preparation method thereof | |
| CN110106428B (en) | High-entropy alloy with banded precipitated phases and preparation method thereof | |
| WO2006109727A1 (en) | Austenitic stainless steel | |
| JP4221518B2 (en) | Ferritic heat resistant steel | |
| CN114836700B (en) | Large-size zirconium-based amorphous alloy with high strength and high hardness and preparation method thereof | |
| JP6675846B2 (en) | Fe-Cr-Ni alloy with excellent high-temperature strength | |
| CN104878248B (en) | High temperature alloy 625H and its manufacturing process | |
| CN109023002B (en) | Silicon solid solution reinforced VNbMoTaSi high-entropy alloy and preparation method thereof | |
| CN102041450A (en) | Ferrite heat resisting steel and manufacture method thereof | |
| CN116694978B (en) | Low-cost heat-resistant stainless medium-entropy alloy and preparation method thereof | |
| Lu et al. | Bulk Glass Formation in an Fe-Based Fe–Y–Zr–M (M= Cr, Co, Al)–Mo–B System | |
| CN115558833B (en) | High-strength and high-toughness FeNiCrAlTi high-entropy alloy with graded precipitation phase strengthening function and preparation method thereof | |
| CN113981328B (en) | Aluminum-containing austenitic stainless steel with surface spontaneously and continuously generating aluminum oxide film and preparation method thereof | |
| CN102086496A (en) | Fe-Ni base precipitation-strengthened austenite alloy and preparation method thereof | |
| CN111676409B (en) | Preparation method of low-density low-cost Fe-Mn-Al-C intermediate entropy alloy | |
| KR101929138B1 (en) | Steel for solid oxide fuel cells and method for porducing same | |
| CN117265360A (en) | Composite precipitation strengthening type high-entropy alloy and preparation method thereof | |
| CN117107138A (en) | Method for improving toughness of refractory high-entropy alloy by doping rare earth Ce | |
| JP2007197779A (en) | Manufacturing method of cr-containing steel sheet having excellent high-temperature strength and toughness, and cr-containing steel sheet | |
| JP5554180B2 (en) | Austenitic stainless steel | |
| Zhang et al. | Annealing effects on structure and mechanical properties of CoCrFeNiTiAlx high-entropy alloys | |
| CN110541130A (en) | Stainless steel for medical instruments and preparation method thereof | |
| CN111304555A (en) | In-situ endogenously precipitated ceramic particle reinforced Cr-Mn-Ni-C-N austenitic heat-resistant steel and preparation method and application thereof | |
| CN115478192B (en) | Preparation method and application of oxygen-doped BCC structure Ti-Zr-Nb alloy |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |