CN115896611A - Austenite-ferrite dual-phase heat-resistant steel and preparation method and application thereof - Google Patents
Austenite-ferrite dual-phase heat-resistant steel and preparation method and application thereof Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
The invention aims to solve the technical problems of the existing grate plate material of the grate and provides austenite-ferrite dual-phase heat-resistant steel and a preparation method and application thereof. The heat-resistant steel comprises the following chemical components in percentage by mass: c:0.30 to 0.40 percent; si:0.5 to 1.0 percent; mn:3.0 to 4.0 percent; cr:24.0 to 28.0 percent; ni:3.0 to 4.5 percent; n:0.20 to 0.24 percent; nb:0.1 to 0.15 percent; p is less than or equal to 0.035%; less than or equal to 0.035 percent of S and the balance of Fe and inevitable impurities. The dual-phase heat-resistant steel greatly improves the high-temperature mechanical property and the high-temperature oxidation resistance, and can be stably used at the temperature of 100-1000 ℃.
Description
Technical Field
The invention belongs to the technical field of steel material manufacturing, and particularly relates to double-phase heat-resistant steel and a preparation method and application thereof.
Background
The dual-phase heat-resistant steel is taken as an important candidate high-temperature material, is widely applied to high-temperature working environments such as nuclear reactors, super heaters, coke dry quenching, chain grate machines and the like, has a structure consisting of ferrite and austenite, and has the characteristics of high strength, pitting corrosion resistance, good high-temperature oxidation resistance and the like of ferrite heat-resistant steel. At present, the dual-phase heat-resistant steel is mostly used for producing disposable parts which are in service in a high-temperature environment for a long time, and needs to be replaced periodically, so that the consumption is large and the cost is high.
Taking a grate-rotary kiln system for pellet production as an example, the working temperature of grate plates in the grate is changed alternately at 100-1000 ℃. The severe working condition and environment of the steel require the material to have excellent high-temperature performance, ZG20Cr26Ni5 dual-phase heat-resistant steel (from JB/T6403-2017 large heat-resistant steel casting technical conditions) is mostly adopted at present, the service life is usually 12-14 months, and spare parts need to be replaced regularly. The dosage of ZG20Cr26Ni5 dual-phase heat-resistant steel material parts in the chain grate is counted, the dosage is about 6000 tons in one year, and about 300 tons of nickel plates consuming 99.99 percent are consumed. Therefore, it is required to develop a dual phase heat resistant steel having a long life and excellent high temperature properties to replace ZG20Cr26Ni5 in order to save the consumption of resources.
In the prior art, the dual-phase heat-resistant steel is also researched.
1. Chinese patent application No. CN 201811651353.2: a corrosion-resistant austenite-ferrite dual-phase heat-resistant steel and a preparation method thereof. The invention provides corrosion-resistant austenite-ferrite dual-phase heat-resistant steel which comprises, by weight, 0.04-0.05% of carbon, 0.01-0.9% of silicon, 0-0.025% of sulfur, 0-0.03% of phosphorus, 0.1-1.5% of manganese, 18.2-18.8% of chromium, 9.1-12.5% of nickel, 7-8 times of niobium as much as carbon, and the balance of iron and inevitable impurities. The invention improves the high-temperature strength, the corrosion resistance and the oxidation resistance of the duplex stainless steel by adjusting the component proportion of the raw material steel and the process parameters in the preparation method, so that the duplex stainless steel has longer service life in application and meets the requirements of industries such as petroleum, chemical engineering, energy and the like on materials. However, this steel grade has a high nickel and chromium content, which leads to a high cost.
2. Chinese patent application No. CN 201010157343.0: the grate plate of the grate is made of heat-resistant steel. The heat-resistant steel for the grate plate of the chain grate comprises the following chemical components in percentage by weight: c:0.25% -0.35%, si:1.25% -1.75%, cr:27% -29%, mn:2.0% -3.0%, ni:7.0% -9.0%, mo:0.3% -0.5%, N: 0.15-0.25%, ti: 0.05-0.15%, cu: 0.20-0.40%, B:0.0024% -0.0026%, RE:0.04 to 0.05 percent of the total weight of the alloy, less than or equal to 0.04 percent of P, less than or equal to 0.007 percent of S and the balance of iron. For the grate of the pelletizing plant which operates at the working condition temperature of the alternate temperature change, on the basis of the traditional austenitic high-alloy heat-resistant steel (ZG 35Cr24Ni7 SDiN), the stability of the steel in an oxidizing medium can be improved, the heat resistance of the steel can be improved, and the requirement of the grate plate which operates at the working condition temperature of the alternate temperature change can be met by the combined action of changing the alloy components and adding a proper amount of Cu, mo, B and RE. However, the heat-resistant steel adopts rare earth elements, and the cost is high.
3. Chinese patent application with application number CN 201510625857.7: a high-strength and high-corrosion-resistant dual-phase heat-resistant steel. The invention relates to high-strength and high-corrosion-resistance dual-phase heat-resistant steel, which comprises the following chemical components: c:0 to 0.1; si:0.1 to 1.0; mn:0 to 0.5; cr:12 to 25; ni:15 to 22; mo:0 to 4.0; al:1.0 to 6.0; nb:0.1 to 1.0; b:0 to 0.05; p is not more than 0.03; s is not more than 0.02; the balance being Fe. The preparation method adopts a free forging mode, and the strain rate is controlled to be not less than 1s (-1) in the hot rolling process; the single-pass reduction is not less than 35%, and the size of the second phase is controlled by adopting rapid cooling. The invention realizes the matching of high-temperature corrosion resistance and high strength, is used in a high-temperature corrosive environment, and has the comprehensive performance obviously superior to that of the existing dual-phase heat-resistant steel. The preparation method of the heat-resistant steel is rolling, and a grid plate cannot be prepared.
Disclosure of Invention
The invention aims to solve the technical problems of the existing grate plate material of the grate and provides austenite-ferrite dual-phase heat-resistant steel and a preparation method and application thereof. The dual-phase heat-resistant steel greatly improves the high-temperature mechanical property and the high-temperature oxidation resistance, and can be stably used at the temperature of 100-1000 ℃.
One of the technical schemes of the invention is that the austenite-ferrite dual-phase heat-resistant steel comprises the following chemical components in percentage by mass: c:0.30 to 0.40 percent; si:0.5 to 1.0 percent; mn:3.0 to 4.0 percent; cr:24.0 to 28.0 percent; ni:3.0 to 4.5 percent; n:0.20 to 0.24 percent; nb:0.1 to 0.15 percent; p is less than or equal to 0.035%; less than or equal to 0.035 percent of S and the balance of Fe and inevitable impurities.
Preferably, the austenite-ferrite dual-phase heat-resistant steel comprises the following chemical components in percentage by mass: c:0.30 to 0.35 percent; si:0.8 to 1.0 percent; mn:3.0 to 3.2 percent; cr:26.0 to 27.0 percent; ni:4.0 to 4.2 percent; n:0.20 to 0.23 percent; nb:0.1 to 0.15 percent; p is less than or equal to 0.035%; less than or equal to 0.035 percent of S and the balance of Fe and inevitable impurities.
The effects of each alloy element and the specific content in the austenite-ferrite dual-phase heat-resistant steel are as follows:
carbon (C): 0.3 to 0.40 percent. Carbon is an element for enlarging a gamma phase region in an iron-carbon phase diagram, and when the carbon content in steel is too high, carbon can be combined with alloy elements such as chromium, molybdenum and the like in heat-resistant steel to form carbide, so that the heat-resistant steel has a chromium-poor phenomenon, the generation of a protective oxide film is slowed down, and the high-temperature corrosion performance of the heat-resistant steel is further reduced. On the other hand, however, carbides formed by carbon combined with alloying elements in the heat-resistant steel enhance the heat strength of the heat-resistant steel. Therefore, the heat-resistant steel generally contains a certain carbon content, and the carbon content is preferably 0.3 to 0.35%.
Silicon (Si): 0.5 to 1.0 percent. Silicon is a beneficial element for high-temperature corrosion of heat-resistant steel, and can improve the working performance of the heat-resistant steel at room temperature. Under the high-temperature working state, a layer of compact silicon oxide film can be formed on the surface of the steel by silicon elements in the heat-resistant steel. When the silicon content is 1 to 2%, the oxidation resistance effect is more remarkable, but too high silicon content causes deterioration of mechanical properties of the heat resistant steel, and the content thereof should preferably be 0.8 to 1.0%.
Manganese (Mn): 3.0 to 4.0 percent. Manganese can promote nitrogen to be fused in austenite, belongs to weak austenite growth promoting elements, and at present, mn and N are mostly adopted to replace Ni elements in order to reduce casting cost. When the Mn content is as low as 0.5%, a layer of Mn-Cr spinel may be formed on the surface, but too high a Mn element may impair the high-temperature strength of the heat-resistant steel, so that the content thereof should preferably be 3.0 to 3.2%.
Chromium (Cr): 24.0 to 28.0 percent. Chromium element can form a layer of compact Cr on the surface of heat-resistant steel 2 O 3 The protective film can prevent the diffusion of corrosive gases such as oxygen, sulfur and nitrogen into the steel to some extent. Cr is easily combined with C to form M in heat-resistant steel 23 C 6 The type compound plays roles of precipitation strengthening and grain boundary strengthening, but the increase of the chromium content can cause the refractory steel to generate sigma phase at high temperature, and the sigma phase has brittle damage to a matrix. Therefore, the content thereof should preferably be 26 to 27%.
Nickel (Ni): 3.0 to 4.5 percent. The nickel element can enlarge austenite phase region, raise recrystallization temperature of heat-resisting steel, along with the increase of nickel element content, a portion of nickel element is solid-dissolved in matrix, and a portion of nickel is formed into gamma' high-temp. strengthening phase (Ni) 3 (Al, M)), further enhancing the high-temperature strength of the heat-resistant steel. The nickel element can also slow down Cr by improving the composition and constitution of the oxide film 2 The cracking and peeling of the O oxide film improves the oxidation resistance of the heat-resistant steel, but it is expensive. Therefore, the content thereof should preferably be 4.0 to 4.2%.
Nitrogen (N): 0.2 to 0.24 percent. The nitrogen element is mainly present in a compound state in the heat-resistant steel, and a small amount thereof is solid-dissolved in the heat-resistant steel in an atomic state. The nitrogen element can improve the stability of high-temperature austenite, and the effect of promoting and stabilizing the austenite is about 30 times that of nickel. As the nitrogen content increases, the amount of solid solution nitrogen and the amount of combined nitrogen gradually increase, and the high-temperature endurance strength of the heat-resistant steel increases. However, when the mass fraction of nitrogen is more than 0.16%, the oxidation resistance of the steel is deteriorated, so that the content thereof should preferably be 0.2 to 0.23%.
Niobium (Nb): 0.1 to 0.15 percent. Nb is taken as a microalloy element and is usually added into heat-resistant steel to improve high-temperature strength and creep resistance, and Nb taken as a strong carbide forming element can replace Cr and C to form stable NbC and is taken as a heterogeneous nucleation core to refine grains and improve the comprehensive performance of the steel. However, an excessive amount of Nb reduces the high-temperature oxidation resistance of the heat-resistant steel, so that the Nb content should preferably be 0.1 to 0.15%.
The second technical scheme of the invention is that the preparation method of the austenite-ferrite dual-phase heat-resistant steel comprises the following steps:
(1) Proportioning the raw materials of the components of the dual-phase heat-resistant steel in proportion;
(2) Smelting the raw materials by using an induction smelting furnace with negative pressure, wherein the smelting temperature is more than or equal to 1600 ℃, and then adding aluminum for pre-deoxidation;
(3) Adding ferrosilicon and electrolytic manganese to perform Si and Mn alloying, fully deoxidizing by adopting a silicon-calcium alloy, then adding a nitrogen-containing alloy in batches, and keeping the temperature of molten steel to be more than or equal to 1600 ℃ during the period;
(4) Transferring the molten steel into a pouring crucible, wherein an iron-chromium wire filter screen is arranged above the crucible, and filtering the molten steel;
(5) Pouring is started after filtering is finished, the temperature of the molten steel is controlled to be 1500-1550 ℃ during pouring, the poured shell is supported by the negative pressure of a vacuum pump, and after the molten steel pouring is finished, the pressure is maintained for 8-15 min and the pressure is removed;
(6) And cutting off a casting riser and a pouring gate to finish casting.
Furthermore, the heat-resistant steel prepared by the preparation method has an austenite and ferrite structure, and the proportion of austenite in the structure reaches more than 70%.
Furthermore, the yield strength of the heat-resistant steel prepared by the preparation method reaches 130-150 MPa at the high temperature of 900 ℃, and the tensile strength reaches 165-200 MPa.
The third technical scheme of the invention is the application of the austenite-ferrite dual-phase heat-resistant steel in the grate plate of the grate.
Compared with the prior art, the invention has the advantages that:
1. the chemical composition design of the invention fully considers the premise of lower nickel element content, improves the austenite proportion in the dual-phase heat-resistant steel by improving Mn and N elements so as to improve the high-temperature oxidation resistance of the heat-resistant steel and ensure that the cost cannot be greatly improved; the content of the C element is improved, the austenite proportion is improved, the number of carbides in the heat-resistant steel is also increased, and the high-temperature strength of the heat-resistant steel is improved.
2. The invention provides the long-life and high-performance austenite-ferrite dual-phase heat-resistant steel which can be stably used under the working condition that the temperature is changed between 100 and 1000 ℃, and the service life of the grid plate made of the heat-resistant steel can reach more than 17 months.
3. The steel has excellent high-temperature mechanical property and high-temperature oxidation resistance, the yield strength at high temperature can reach 130-150 MPa, and the tensile strength can reach 165-200 MPa; the high-temperature oxidation resistance level reaches the complete oxidation resistance level.
Drawings
FIG. 1 is a scanning electron microscope photograph of the tissue of example 1 of the present invention.
FIG. 2 is a scanning electron microscope photograph of the tissue of example 2 of the present invention.
FIG. 3 is a SEM image of the tissue of example 3 of the present invention.
FIG. 4 is a scanning electron microscope photograph of the tissue of example 4 of the present invention.
FIG. 5 is a scanning electron microscope photograph of the structure of comparative material ZG20Cr26Ni 5.
Detailed Description
For a further understanding of the invention, its nature and function, reference should be made to the following detailed description of the invention, taken in conjunction with the accompanying drawings, which are set forth to illustrate, but are not to be construed as limiting the invention.
The invention relates to austenite-ferrite dual-phase heat-resistant steel, which comprises the following components in percentage by mass: c:0.3 to 0.40 percent; si:0.5 to 1.0 percent; mn:3.0 to 4.0 percent; cr:24.0 to 28.0 percent; ni:3.0 to 4.5 percent; n:0.20 to 0.24 percent; nb:0.1 to 0.15 percent; p is less than or equal to 0.035%; less than or equal to 0.035 percent of S, and the balance of Fe and inevitable impurities.
The steel is cast and molded by adopting a high-efficiency and environment-friendly casting mode, and the manufacturing process comprises the following steps: batching → smelting in a negative pressure induction furnace → filtering molten steel → casting molten steel → cutting off a riser and a pouring gate. The detailed process comprises the following steps: (1) Carrying out batching calculation according to the preferable components of the steel; (2) Smelting the raw materials by using an induction smelting furnace with negative pressure, wherein the smelting temperature is more than or equal to 1600 ℃; (3) After smelting, transferring the molten steel to a crucible for pouring, wherein an iron-chromium wire filter screen is arranged above the crucible to filter the molten steel, and pouring is started after the molten steel is completely poured, wherein the temperature of the molten steel is controlled to be 1500-1550 ℃ during pouring; (4) The casting shell adopts an EVA plastic film and a steel sandbox to form a closed space, negative pressure is pumped by a vacuum pump to support, and after the molten steel is cast, the pressure is maintained for 8-15 min and is removed; (5) And cutting off a casting riser and a pouring gate to finish the manufacture of the workpiece.
Specific chemical compositions and comparative materials (mass fraction%) of examples of the present invention are shown in table 1 below, and the balance is Fe and inevitable impurities.
TABLE 1 chemical composition of various steel materials (% by mass)
The comparative material is heat-resistant steel, and the grade is ZG20Cr26Ni5 (JB/T6403-2017 large heat-resistant steel casting technical conditions).
To further illustrate the properties of the invention, the invention is tested in comparison with the comparative material ZG20Cr26Ni5 in examples 1, 2, 3 and 4, as follows:
1: microstructure of matrix
The test method comprises the following steps: the steel and the comparative material are manufactured into samples by the casting forming method, the smelting temperature is more than or equal to 1600 ℃, the pouring temperature is controlled between 1500 ℃ and 1550 ℃, and small test blocks of 10mm multiplied by 10mm are manufactured by a linear cutting mode. After the surface of the small test block is ground and polished, aqua regia (75% hydrochloric acid +25% nitric acid) is used for erosion, and an Optical Microscope (OM) is used for analyzing the tissue of the small test block, wherein the structure is shown in figures 1-5 respectively.
OM analysis showed that the structures of examples 1, 2, 3 and 4 and the comparative materials were austenite and ferrite, and the content of nickel and carbon in examples 1, 2, 3 and 4 was higher than that in the comparative materials, which resulted in a higher austenite proportion and more carbides.
2: high temperature mechanical properties
The high temperature mechanical property tests of the steel of the present invention and the comparative material were carried out at 900 ℃ according to the standard GB/T4338-2006 high temperature tensile test method for metallic materials, the results of which are shown in Table 2.
TABLE 2 high-temperature mechanical properties of various steel materials
| Tensile strength/MPa | Yield strength/MPa | Elongation after break/% | Reduction of area/%) | |
| Example 1 | 169.2 | 133.0 | 38.6 | 42.6 |
| Example 2 | 165.1 | 130.1 | 37.5 | 39.5 |
| Example 3 | 167.5 | 135.4 | 38.4 | 41.5 |
| Example 4 | 168.5 | 132.4 | 38.2 | 38.9 |
| Contrast material | 69.7 | 52.0 | 50.3 | 59.0 |
From the tensile results, it can be seen that the yield strengths of examples 1, 2, 3 and 4 are all 2 times or more higher than those of the comparative materials, the tensile strength is also improved by about 100MPa, and the elongation after fracture is slightly reduced. The contents of the C element in the examples 1, 2, 3 and 4 are higher than those of the comparative materials, and the heat strength of the samples is improved.
3: high temperature oxidation resistance
The test method comprises the following steps: taking a small square block with the thickness of 30mm multiplied by 10mm multiplied by 5mm, adopting sand paper with different meshes to polish each surface of the small square block until the roughness Ra is 0.8 mu m, putting the small square block into a drying box with the temperature of 150-200 ℃ for heat preservation for 1h, weighing the sample for multiple times, taking the average value of the samples, and counting the surface area of the sample. The sample was heated in a heating furnace and the weight was measured after 100 hours at 900 ℃. The samples were rated for oxidation resistance according to the standard GB/T13303-91 method for measuring the oxidation resistance of Steel, as shown in Table 3.
TABLE 3 high-temperature oxidation resistance of various steel materials
According to the oxidation resistance level, the oxidation resistance of the examples 1, 2, 3 and 4 is better than that of the comparative material, and the nickel, manganese and nitrogen elements of the examples 1, 2, 3 and 4 are higher than those of the comparative material, so that the high-temperature oxidation resistance is excellent.
4: cold and hot fatigue resistance
The experimental method comprises the following steps: a sample with the specification of 40mm multiplied by 20mm multiplied by 5mm is taken, a V-shaped notch is arranged on the short side of the rectangle, and the length of the notch is 3mm. One end of the non-drilled hole of the sample is used as a base surface, and the hole is used for fixing the sample on a clamp so that the sample is heated and the water inlet position is consistent. Before testing, the sample is ground and polished by sand paper to eliminate the influence of the surface factors of the sample on the test result. And a resistance heating self-restraint thermal fatigue testing machine is adopted to carry out thermal fatigue tests. The sample was subjected to a thermal cycle of heating and cooling at 20 ℃ to 800 ℃ in a furnace at 800 ℃ and at 20 ℃ in running tap water. The heating and cooling were performed once as one cycle until the predetermined number of cycles was 200 times, and the specimens were removed and the lengths of cracks were measured, and the results are shown in table 4.
TABLE 4 Cold and Heat fatigue resistance of various steel materials
| Example 1 | Example 2 | Example 3 | Example 4 | Comparative materials | |
| Crack length (mm) | 0.56 | 0.58 | 0.54 | 0.51 | 2.82 |
According to the crack length, the cold and hot fatigue resistance of the embodiment is far better than that of the comparative material, mainly because the austenite structure proportion in the embodiment is higher, so that the embodiment has good cold and hot fatigue resistance.
The heat-resistant steel integrates the characteristics, so that the service life of the grate plate cast by the heat-resistant steel can reach more than 17 months.
Claims (7)
1. An austenite-ferrite dual-phase heat-resistant steel is characterized by comprising the following chemical components in percentage by mass: c:0.30 to 0.40 percent; si:0.5 to 1.0 percent; mn:3.0 to 4.0 percent; cr:24.0 to 28.0 percent; ni:3.0 to 4.5 percent; n:0.20 to 0.24 percent; nb:0.1 to 0.15 percent; p is less than or equal to 0.035%; less than or equal to 0.035 percent of S and the balance of Fe and inevitable impurities.
2. The austenitic-ferritic duplex heat-resistant steel according to claim 1, wherein the chemical components are, in mass percent: c:0.30 to 0.35 percent; si:0.8 to 1.0 percent; mn:3.0 to 3.2 percent; cr:26.0 to 27.0 percent; ni:4.0 to 4.2 percent; n:0.20 to 0.23 percent; nb:0.1 to 0.15 percent; p is less than or equal to 0.035%; less than or equal to 0.035 percent of S and the balance of Fe and inevitable impurities.
3. A method for producing an austenitic-ferritic dual phase heat resistant steel according to claim 1 or 2, characterized by comprising the steps of:
(1) Proportioning the raw materials of the components of the dual-phase heat-resistant steel according to a proportion;
(2) Smelting the raw materials by using an induction smelting furnace with negative pressure, wherein the smelting temperature is more than or equal to 1600 ℃, and then adding aluminum for pre-deoxidation;
(3) Adding ferrosilicon and electrolytic manganese to perform Si and Mn alloying, fully deoxidizing by adopting a silicon-calcium alloy, then adding a nitrogen-containing alloy in batches, and keeping the temperature of molten steel to be more than or equal to 1600 ℃ during the period;
(4) Transferring the molten steel into a pouring crucible, wherein an iron-chromium wire filter screen is arranged above the crucible, and filtering the molten steel;
(5) Pouring is started after filtering is finished, the temperature of the molten steel is controlled to be 1500-1550 ℃ during pouring, the poured shell is supported by the negative pressure of a vacuum pump, and after the molten steel pouring is finished, the pressure is maintained for 8-15 min and the pressure is removed;
(6) And cutting off a casting riser and a pouring gate to finish casting.
4. A method for producing an austenitic-ferritic dual phase heat resistant steel as claimed in claim 3, characterized in that the heat resistant steel structure is austenite and ferrite, and the ratio of austenite in the structure is 70% or more.
5. The method for preparing austenitic-ferritic dual phase heat resistant steel according to claim 3, wherein the yield strength of the prepared heat resistant steel at 900 ℃ reaches 130-150 MPa, and the tensile strength reaches 165-200 MPa.
6. The method for preparing austenitic-ferritic dual phase heat resistant steel according to claim 3, wherein the obtained heat resistant steel has a high temperature oxidation resistance level of 900 ℃ reaching a complete oxidation resistance level and has good cold and hot fatigue resistance.
7. Use of an austenitic-ferritic dual phase heat resistant steel according to claim 1 or 2, characterized in that the austenitic-ferritic dual phase heat resistant steel is used on grate plates.
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| CN116804257A (en) * | 2023-06-21 | 2023-09-26 | 鞍钢集团矿业有限公司 | Low-cost austenitic-ferritic dual-phase heat-resistant steel and preparation method thereof |
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