WO2020038019A1 - Acier inoxydable à entropie moyenne en série fe-mn-cr-ni et son procédé de préparation - Google Patents

Acier inoxydable à entropie moyenne en série fe-mn-cr-ni et son procédé de préparation Download PDF

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Publication number
WO2020038019A1
WO2020038019A1 PCT/CN2019/085145 CN2019085145W WO2020038019A1 WO 2020038019 A1 WO2020038019 A1 WO 2020038019A1 CN 2019085145 W CN2019085145 W CN 2019085145W WO 2020038019 A1 WO2020038019 A1 WO 2020038019A1
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WO
WIPO (PCT)
Prior art keywords
stainless steel
entropy
steel
smelting
furnace
Prior art date
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PCT/CN2019/085145
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English (en)
Chinese (zh)
Inventor
乔珺威
边斌斌
石晓辉
张敏
杨慧君
郭瑞鹏
王重
吴玉程
Original Assignee
太原理工大学
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Publication date
Priority claimed from CN201810950173.8A external-priority patent/CN108660354B/zh
Priority claimed from CN201910239594.4A external-priority patent/CN109913769B/zh
Application filed by 太原理工大学 filed Critical 太原理工大学
Publication of WO2020038019A1 publication Critical patent/WO2020038019A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C22C1/03—Making non-ferrous alloys by melting using master alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent

Definitions

  • the invention relates to the composition, preparation and properties of an entropy stainless steel in the Fe-Mn-Cr-Ni series, and belongs to the technical field of steel.
  • the design principle of traditional steel is generally to select one or two elements as the main element, or to add several small amounts of steel elements to improve the comprehensive performance of the steel, such as: iron-based steel, cobalt-based steel, aluminum-based steel, etc.
  • multi-component high-entropy steel has many excellent properties, due to its use of a large amount of precious metal elements, its economic cost is very high compared to traditional steel materials, and it is actually difficult to realize industrial production.
  • high-entropy steel to the second generation of non-isoatomic ratio high-entropy steel, people's horizons and research scope have been further expanded.
  • the steel composition of the present invention uses this latest concept to design a medium-entropy stainless steel that does not contain precious elements. It can not only form a simple and stable phase structure, but also significantly reduce the economic cost. At the same time, it has better low-temperature tensile properties than high-entropy steel. In addition, this material has better corrosion resistance than stainless steel.
  • Corrosion is one of the main failure modes of structural materials.
  • corrosion resistance is an important factor that must be considered.
  • Studies have shown that the addition of easily passivating elements (such as Cr, Ni) can make steel have satisfactory corrosion resistance. Therefore, this material is expected to be used as a potential low-temperature material in practical conditions.
  • the invention provides a composition of a Fe-Mn-Cr-Ni series medium-entropy stainless steel and a preparation method thereof.
  • the purpose is to develop a non-isoatomic ratio Fe-Mn-Cr-Ni series medium-entropy stainless steel by using several inexpensive elements. , While improving performance while significantly reducing its production costs, laying a solid foundation for industrial production and applications.
  • the steel component of the entropy stainless steel in the present invention does not contain precious elements, which significantly reduces the production cost.
  • the medium-entropy stainless steel not only satisfies the formation of a simple and stable high-entropy phase structure, but also exhibits higher low-temperature performance than high-entropy steel, and also has better corrosion resistance than stainless steel.
  • the invention considers that pure Mn is easy to volatilize during the smelting process, resulting in too large a component deviation, and Fe-Mn steel having an Fe and Mn atomic ratio of 1: 1 is selected instead of pure Mn, and an additional 5% is added based on the chemical composition of the steel Of manganese was added as compensation.
  • the preparation process includes heat treatment and cold deformation. First, the plate-shaped sample of the suction casting is homogenized, and then cold-rolled, followed by stress relief annealing. The wire-like sample was cut into a tensile specimen using wire-cut EDM, and subjected to quasi-static stretching at room temperature and low temperature.
  • the invention provides a Fe-Mn-Cr-Ni series medium-entropy stainless steel, wherein the proportion of each element is: the atomic percentage of the elements Fe, Mn, Cr, and Ni is 40%: 20%: 20%: 20% .
  • the invention provides a method for preparing Fe-Mn-Cr-Ni series medium-entropy stainless steel, which includes the following steps:
  • Step 1 Raw material pre-treatment: The raw materials with high purity ( ⁇ 99.99%) of Fe, Ni, and Cr and Fe-Mn binary alloy with an atomic ratio of 1: 1 are respectively polished with a grinder and then placed on the surface. In a beaker filled with absolute ethanol, perform ultrasonic treatment for 10 minutes to remove impurities and dirt on the surface of the raw material, and then dry the raw material in a drying box;
  • Step 2 Weighing: According to the atomic percentage of Fe, Mn, Cr, and Ni in order of 40%: 20%: 20%: 20%, use the electronic balance with an accuracy of 0.001g to weigh the pre-treatment in step 1. Subsequent raw materials
  • the raw materials are placed in a copper crucible of a vacuum arc furnace in order from the lowest to the highest melting point, and the sponge titanium block is placed in another copper crucible of the vacuum arc furnace, and then the furnace door is closed tightly;
  • vacuum infusion is used to suck the steel ingot into the plate-shaped cavity for water cooling. After the system is completely cooled, open the mold and take out the plate-like sample;
  • Step 4 Post-processing: The sample obtained in Step 3 is subjected to 1200 ⁇ 5 ° C homogenization heat treatment for 2 hours, followed by water cooling, followed by cold rolling with 0%, 30%, 50%, and 70% reduction ratios, and finally Destress annealing at 650 ⁇ 5 °C for 10 minutes.
  • the product of the invention can be implemented in industrial production and has practicality.
  • the steel composition of the present invention does not contain precious and rare elements, has a simple and stable high-entropy phase structure while having a low cost, and exhibits higher low-temperature performance than high-entropy steel, and at the same time, it is more excellent than stainless steel. Resistance to seawater corrosion.
  • the medium-entropy stainless steel according to the present invention can greatly reduce the use cost of materials at low temperatures, and also improve the service life of materials.
  • This medium-entropy stainless steel has great potential as a structural material for use in low-temperature, high-salt environments.
  • the entropy stainless steel has a yield strength of 1182 MPa, a tensile strength of 1,320 MPa, and an elongation at break of about 24.74% at a liquid nitrogen temperature (77K).
  • the corrosion current density I corr of 304L stainless steel It is 9.2 ( ⁇ A / cm 2 ); the corrosion current density I corr of the entropy stainless steel in FeMnCrNi is 1.04 ( ⁇ A / cm 2 ). It can be seen that the corrosion resistance of the entropy stainless steel in FeMnCrNi is significantly better than that of 304L stainless steel.
  • Figure 1 is a schematic diagram of the purchased WK-II vacuum arc furnace
  • Example 4 is an electrochemical corrosion polarization curve of a sample and 304 stainless steel in a 3.5% sodium chloride solution after step 4 in Example 1;
  • FIG. 5 is an electrochemical corrosion resistance curve of the sample and 304 stainless steel in a 3.5% sodium chloride solution after the process of step 4 in Example 1.
  • FIG. 5 is an electrochemical corrosion resistance curve of the sample and 304 stainless steel in a 3.5% sodium chloride solution after the process of step 4 in Example 1.
  • This embodiment is a Fe-Mn-Cr-Ni series medium-entropy stainless steel composed of four elements: Fe, Mn, Cr, and Ni, and the atomic percentages of the elements of Fe, Mn, Cr, and Ni are 40%: 20%: 20%: 20%.
  • the raw materials are selected from pure Fe, pure Ni, pure Cr and FeMn binary alloy with an atomic ratio of 1: 1.
  • a method for preparing Fe-Mn-Cr-Ni series medium-entropy stainless steel includes the following steps:
  • Step 1 Pre-treatment: The raw materials with high purity ( ⁇ 99.99%) of Fe, Ni, and Cr and Fe-Mn binary alloy with an atomic ratio of 1: 1 are polished with a grinding machine, and then placed in the equipment. In a beaker with absolute ethanol, perform ultrasonic treatment for 10 minutes to remove impurities and dirt on the surface of the raw materials, and then dry the above raw materials in a drying box;
  • Step 2 Weighing: According to the atomic percentage of Fe, Mn, Cr, and Ni in order of 40%: 20%: 20%: 20%, use the electronic balance with an accuracy of 0.001g to weigh the pre-treatment in step 1. Subsequent raw materials
  • the raw materials are placed in a copper crucible of a vacuum arc furnace in order from the lowest to the highest melting point, and the sponge titanium block is placed in another copper crucible of the vacuum arc furnace, and then the furnace door is closed tightly;
  • vacuum infusion is used to suck the steel ingot into the plate-shaped cavity for water cooling. After the system is completely cooled, open the mold and take out the plate-like sample;
  • Step 4 Post-processing: The sample obtained in Step 3 is subjected to 1200 ⁇ 5 ° C homogenization heat treatment for 2 hours, followed by water cooling, followed by cold rolling with 0%, 30%, 50%, and 70% reduction ratios, and finally Annealed at 650 ⁇ 5 ° C for 10 minutes to obtain a cold-rolled plate-like sample. Structure and performance tests were performed on the obtained samples.
  • the WK-II non-consumable vacuum arc furnace is an off-the-shelf product.
  • WK-II non-consumable vacuum electric arc furnace includes furnace body, water-cooled crucible, vacuum device, cooling device and power supply device; the vacuum device part adopts mechanical pump and molecular pump to evacuate in stages, and the vacuum degree can be lowered to 10 -4 Pa
  • the furnace body adopts a double-layer water-cooled arrangement.
  • the inner and outer layers are made of stainless steel and steel, respectively, and are precision welded.
  • the copper mold is connected directly below the copper crucible, and the molten steel can be sucked into a plate shape.
  • an observation window is set on the front of the furnace, and a polarized glass plate is installed on the observation window. This part is used to protect the operator's eyes from being injured when the arc is operated; the control handle can move the electrode flexibly, and After the arc, move the arc to the designated position and smelt the steel;
  • FIG. 2 is an XRD pattern of the Fe 40 Mn 20 Cr 20 Ni 20 medium-entropy stainless steel after step 4. From the figure, it can be obtained that the material has a single-phase FCC structure after homogenization and deformation after casting;
  • Figure 3 is the room temperature and low temperature tensile curves of the entropy stainless steel of Fe 40 Mn 20 Cr 20 Ni 20 after step 4; the figure shows that the performance of the steel at each deformation is lower than that at room temperature, and As the amount of deformation increases, the properties of the material increase.
  • the medium-entropy stainless steel has a yield strength of 1182 MPa, a tensile strength of 1,320 MPa, and an elongation at break of about 24.74% at a liquid nitrogen temperature (77 K), which can be a good candidate material at low temperatures.
  • FIG. 4 is a polarization curve diagram of the entropy stainless steel in the 3.5% sodium chloride solution of the Fe 40 Mn 20 Cr 20 Ni 20 treated in step 4. It is shown that the corrosion current density I corr of 304L stainless steel in 3.5% sodium chloride solution is 9.2 ( ⁇ A / cm 2 ); and the corrosion current density I corr of entropy stainless steel in FeMnCrNi is 1.04 ( ⁇ A / cm 2 ), indicating that the medium entropy stainless steel The corrosion resistance is better than 304L stainless steel.
  • FIG. 5 is an impedance curve diagram of the entropy stainless steel in the 3.5% sodium chloride solution of the Fe 40 Mn 20 Cr 20 Ni 20 treated in step 4.
  • Figure 5 shows that the radius of the resistance curve of the entropy stainless steel in FeMnCrNi is significantly larger than that of 304L stainless steel. Further proves that its corrosion resistance is better than 304L stainless steel.
  • the medium-entropy stainless steel prepared in step 4 in this embodiment has a single-phase FCC structure, in which 70% of the cold-rolled material has the highest tensile properties at liquid nitrogen temperature, yield strength of 1182 MPa, tensile strength of 1320 MPa, and elongation at break. The rate is 24.74%. At the same time, it has better seawater corrosion resistance than 304L stainless steel.
  • the radius of the impedance curve of the entropy stainless steel in FeMnCrNi is significantly larger than that of 304L stainless steel.
  • Corrosion current density I corr of 304 stainless steel in 3.5% sodium chloride solution is 9.2 ( ⁇ A / cm 2 );
  • Corrosion current density I corr of stainless steel in FeMnCrNi is 1.04 ( ⁇ A / cm 2 ).
  • Corrosion performance is significantly better than 304L stainless steel.
  • the corrosion rate of FeMnCrNi medium entropy stainless steel is significantly lower than that of 304L stainless steel.
  • Example 2 The sample processed in step 4 of Example 1 was cut by wire cutting to obtain three standard tensile patterns. The gauge length was about 10 mm and the width was 3 mm. Then use 240 #, 600 #, 800 #, 1000 #, 1200 #, 1500 #, and 2000 # to perform mechanical polishing to ensure that the gauge section is flat, the direction of the scratch is consistent, and there are no macro defects. Use an INSTRON type mechanical testing machine to perform room temperature. Static and low temperature tensile experiments. The strain rate during the experiment is 1 ⁇ 10 -3 / s. In order to ensure the accuracy and repeatability of the experimental results, at least 3 samples of each material are tested. Finally, data with similar results are selected using Origin8.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Heat Treatment Of Articles (AREA)

Abstract

L'Invention concerne un acier inoxydable à entropie moyenne en série Fe-Mn-Cr-Ni dont les constituants chimiques sont Fe40Mn20Cr20Ni20, ayant une bonne résistance et une bonne aptitude à la déformation plastique à température ambiante, et ayant d'excellentes propriétés mécaniques et une excellente résistance à la corrosion à basses températures. Le procédé de préparation comprend le prétraitement de la matière première, la pesée, la fusion, le traitement thermique et l'usinage à froid.
PCT/CN2019/085145 2018-08-20 2019-04-30 Acier inoxydable à entropie moyenne en série fe-mn-cr-ni et son procédé de préparation WO2020038019A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CN201810950173.8 2018-08-20
CN201810950173.8A CN108660354B (zh) 2018-08-20 2018-08-20 一种Fe-Mn-Cr-Ni系高熵不锈钢及其制备方法
CN201910239594.4A CN109913769B (zh) 2019-03-27 2019-03-27 一种Fe-Mn-Cr-Ni系中熵不锈钢及其制备方法
CN201910239594.4 2019-03-27

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115976314A (zh) * 2022-12-30 2023-04-18 安徽工业大学 一种制备中熵奥氏体耐热钢的方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102787266A (zh) * 2012-09-04 2012-11-21 四川大学 基于高熵合金粘结相的碳氮化钛基金属陶瓷及其制备方法
US20170218480A1 (en) * 2016-01-29 2017-08-03 Seoul National University R&Db Foundation High-entropy alloy foam and manufacturing method for the foam
CN107760963A (zh) * 2017-10-26 2018-03-06 福建工程学院 一种含氮FeCoCrNiMn高熵合金及其制备方法
CN108660354A (zh) * 2018-08-20 2018-10-16 太原理工大学 一种Fe-Mn-Cr-Ni系高熵不锈钢及其制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102787266A (zh) * 2012-09-04 2012-11-21 四川大学 基于高熵合金粘结相的碳氮化钛基金属陶瓷及其制备方法
US20170218480A1 (en) * 2016-01-29 2017-08-03 Seoul National University R&Db Foundation High-entropy alloy foam and manufacturing method for the foam
CN107760963A (zh) * 2017-10-26 2018-03-06 福建工程学院 一种含氮FeCoCrNiMn高熵合金及其制备方法
CN108660354A (zh) * 2018-08-20 2018-10-16 太原理工大学 一种Fe-Mn-Cr-Ni系高熵不锈钢及其制备方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115976314A (zh) * 2022-12-30 2023-04-18 安徽工业大学 一种制备中熵奥氏体耐热钢的方法

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